EPA" 
 
 450 / 3 - 
 
 84 - 01 ? 
 
 SEPA 
 
 United States 
 Environmental Protection 
 Agency 
 
 Office of Air Quality 
 Planning and Standards 
 Research Triangle Park NC 27711 
 
 Air 
 
 Procedures for 
 Certifying 
 Quantity of 
 Volatile Organic 
 Compounds 
 Emitted by Paint, 
 Ink, and Other 
 Coatings 
 
 EPA-450/3-84-019 
 December 1984 
 
 PB 85-159044 
 
 9*° v , r V> 
 
 
 REPRODUCED BY 
 
 U.S. DEPARTMENT OF COMMERCE 
 NATIONAL TECHNICAL 
 INFORMATION SERVICE 
 SPRNGFELD.VA 22161 
 
TECHNICAL REPORT DATA 
 
 ( Please read Instructions on the reverse before completing) 
 
 1. REPORT NO. 2. 
 
 EPA 450/3-84-019 
 
 3. RECIPIENT'S ACC 
 
 PBS 5 1 5 S 
 
 ESSI.ON NO.. . 
 
 0 4 4 /AS 
 
 4. TITLE AND SUBTITLE 
 
 Procedures for Certifying Quantity of Volatile Organic 
 Compounds Emitted by Paint, Ink, and Other Coatings 
 
 5. REPORT DATE 
 
 December 1984 
 
 6. PERFORMING ORGANIZATION CODE 
 
 7. AUTHOR(S) 
 
 8. PERFORMING ORGANIZATION REPORT NO. 
 
 9. PERFORMING ORGANIZATION NAME AND ADDRESS 
 
 Office of Air Quality Planning and Standards 
 
 U. S. Environmental Protection Agency (MD-13) 
 
 Research Triangle Park, NC 27711 
 
 * 
 
 10. PROGRAM ELEMENT NO. 
 
 11. CONTRACT/GRANT NO. 
 
 12. SPONSORING AGENCY NAME AND ADDRESS 
 
 SAME AS BOX 9 
 
 13. TYPE OF REPORT AND PERIOD COVERED 
 
 14. SPONSORING AGENCY CODE 
 
 E PA/200/04 
 
 15. SUPPLEMENTARY NOTES 
 
 16 ABSTRACT 
 
 This manual provides procedures by which firms may voluntarily 
 certify the quantity of volatile organic compounds which will be emitted 
 by a paint, ink, or other coating. Two data sheets are provided. One 
 is to be used by the manufacturer of the coating, the other by the user. 
 Analytical test methods and procedures for preparing the data sheets are 
 included, as are the equations and instructions necessary to convert the 
 analytical results into a format suitable for determining compliance with 
 
 State or Federal regulations. 
 
 • ... 
 
 17. KEY WORDS AND DOCUMENT ANALYSIS 
 
 a. DESCRIPTORS 
 
 b.IDENTIFIERS/OPEN ENDED TERMS 
 
 c. COSATi Held/Group 
 
 Air Pollution 
 
 Coatings 
 
 Compliance Calculations 
 
 Pollution Control 
 
 Reference Method 24 
 
 Test Methods 
 
 Volatile Organic Compounds 
 
 Air Pollution Control 
 
 1 3-B 
 
 18. DISTRIBUTION STATEMENT 
 
 19 . SECURITY CLASS (This Report) 
 
 Unclassified 
 
 21. NO. OF PAGES 
 
 15 
 
 20. SECURITY CLASS (This page) 
 
 Unclassified 
 
 22. PRICE 
 
 1 
 
 EPA F orm 2220^1 (Rev. 4-77) previous edition is obsolete 
 
 4 
 
 1 
 
EPA-450/3-84-019 
 
 Procedure for Certifying Quantity of 
 Volatile Organic Compounds Emitted 
 By Paint, Ink, and Other Coatings 
 
 Emission Standards and Engineering Division 
 
 U.S. ENVIRONMENTAL PROTECTION AGENCY 
 Office of Air and Radiation 
 Office of Air Quality Planning and Standards 
 Research Triangle Park, North Carolina 2771 1 
 
 December 1984 
 
This report has been reviewed by the Emission Standards and Engineering Division of the Office of Air Quality 
 Planning and Standards, EPA, and approved for publication. Mention of trade names or commercial products is not 
 intended to constitute endorsement or recommendation for use. Copies of this report are available through the 
 Library Services Office (MD-35), U.S. Environmental Protection Agency, Research Triangle Park, N.C. 27711, or 
 from the National Technical Information Services, 5285 Port Royal Road, Springfield, Virginia 221 61. 
 
 ii 
 
PREFACE 
 
 This manual was conceived as a way to provide simple step-by-step 
 instructions for certifying the quantity of volatile organic compounds 
 (VOC) that will be released by a coating. It has not turned out that 
 way. The guidance is here, but in spite of great diligence, the 
 instructions remain imposing. 
 
 The manual was prepared for several reasons. First, the coatings 
 industry, as represented by the National Paint and Coatings Association, 
 had requested a certification procedure which would relieve their custom¬ 
 ers the expense of analysis. Second, the complexity of the calculations 
 necessary to determine compliance, for example, when dilution solvent is 
 added to a coating, continue to confound Federal, State and Local enforce 
 ment personnel. Finally, results of a recent review of the Agency's 
 reference method for determining VOC reemphasized the importance of 
 analytical procedures to verify VOC content. 
 
 In response to the results of the review of the test methods, this 
 manual reaffirms that Reference Method 24 or its constituent methods 
 developed by the American Society for Testing and Materials (ASTM), 
 are the procedures by which the VOC content of a coating will be deter¬ 
 mined for compliance with Federal regulations. The earliest guidance 
 was not so specific. In 1977, the first report 1 , written to assist 
 States in developing regulations for sources of VOC emissions, provided 
 recommendations for the maximum allowable VOC content for complying 
 coatings in a variety of industries. These values were expressed in 
 mass of VOC per unit volume of coating. In deriving the recommended 
 limitation, the VOC content of a coating was calculated based on the 
 solids content provided by the coating manufacturer. The Agency calcu¬ 
 lated the mass of VOC in the coating by assuming the VOC had a density 
 of 7.36 pounds per gallon. 
 
 Solvent and VOC were used somewhat interchangebly even though it 
 was recognized that organics such as resin monomer, oligimers, and 
 reaction by-products could be released by a coating during the cure. 
 
 There was no accepted analytical method available for measuring the 
 total VOC which would be released by a coating. The initial guidance 1 
 provided an analytical method for use only for air-dry coatings, those 
 where all VOC emissions would be expected to come as a result of evapor¬ 
 ation of solvent. On a volume basis, air dry coatings constituted the 
 largest catagory of coatings then in use. 
 
 The Agency subsequently developed a more general analytical proce¬ 
 dure that could be used to determine the total VOC in a coating. On 
 October 3, 1980, the Agency published "Reference Method 24 (RM-24) - 
 
 Control of Volatile Organic Emissions from Stationary Sources - 
 Volume II: Surface Caoting of Cans, Coils, Paper, Fabrics, Automobiles, 
 and Light-duty Trucks, Document No. EPA-450/2-77-008. 
 
 in 
 
Determination of Volatile Matter Content, Density, Volume Solids, and 
 Weight Solids of Surface Coatings," in the Federal Register (45 FR 65958). 
 For the first time the Agency formally specified an analytical method 
 for the VOC content of those coatings that cure by chemical reaction. 
 
 Even then, the-announcement continued to allow the manufacturer's formu¬ 
 lation to be used to calculate the VOC content but specified that the 
 analytical technique, RM-24, would be the reference in any conflict 
 between the two. 
 
 During 1981 and 1982, as more State and Federal regulations were 
 established, the demand for low-solvent coatings began a continuing 
 increase in the sales volume of reaction-cure coatings. There was some 
 concern voiced by the industry in how appropriate the reference method 
 was for these type coatings. To find out, the Agency began a review of 
 RM-24 to determine the effect of temperature and exposure time on the 
 indicated VOC "content". It was concluded that the maximum effect of 
 those time-temperature combinations that were examined amounted to only 
 about a 10 percent variation. Somewhat more surprising was that the 
 solvent sometimes accounted for only 50 to 70 percent of the total 
 VOC measured by the reference method. 
 
 The obvious conclusion was that RM-24 is a better measure of the 
 total organics freed by a coating than is the solvent. This manual 
 implements a policy based on that conclusion. Certification of VOC 
 content on the attached Data Sheets must be based on an analysis using 
 RM-24. No longer will solvent content be permitted as a surrogate for 
 VOC unless a showing is first made that its use is a reasonable alter¬ 
 native or equivalent method of determining the VOC content of that 
 particular coating. 
 
 One final comment. Since VOC is not always syionomous with solvent, 
 it follows that the amount of solids in a coating cannot be obtained by 
 subtracting the solvent from the total volume of coating. The original 
 Federal Register proposal for RM-24, published on October 3, 1980, recom¬ 
 mended the American Society of Test Materials test Number D2697 as the 
 appropriate method of determining solids content. Subsequent comments 
 from the industry maintained that this test is unreliable. As a result, 
 when promulgated in 1980, RM-24 specified that the solids content of a 
 coating can be obtained only from the manufacturer's formulation of the 
 coating. 
 
 Dennis Crumpler 
 December 14, 1984 
 
 iv 
 
TABLE OF CONTENTS 
 
 CHAPTER Page 
 
 PREFACE.:.Ill 
 
 GLOSSARY OF TERMS AND SYMBOLS.vi 
 
 1 INTRODUCTION . 1-1 
 
 2 VOC CONTENT OF PAINT, INK, AND OTHER COATINGS 
 
 "AS SUPPLIED" BY THE COATING MANUFACTURER . II-l 
 
 2.1 VOC DATA SHEET FOR "AS SUPPLIED" COATINGS .... 11-2 
 
 2.2 IMPLEMENTING INSTRUCTIONS . I1-3 
 
 3 VOC CONTENT OF PAINT, INK AND OTHER COATINGS 
 
 "AS APPLIED" TO THE SUBSTRATE BY THE USER.III-l 
 
 3.1 VOC DATA SHEET FOR "AS APPLIED" COATINGS . II1-2 
 
 3.2 IMPLEMENTING INSTRUCTIONS.111-4 
 
 v 
 
glossary of terms 
 
 "As Applied" 
 
 the condition of a coating after dilution by the user 
 just prior to application to the substrate. 
 
 "As Supplied" 
 
 the condition of a coating before dilution, as sold 
 and delivered by the coating manufacturer to the user. 
 
 (D c )a 
 
 coating density "as applied" 
 
 (o c ) s 
 
 coating density, "as supplied" 
 
 ^d 
 
 density of dilution solvent 
 
 
 density of organic sol vent/water mixture 
 
 “w 
 
 density of water (8.33 lb/gal) 
 
 ^d 
 
 dilution solvent ratio, equals the volume of VOC added 
 per unit volume of coating "as supplied" 
 
 V 
 
 equals the volume of premixed water and VUG added per 
 unit volume of coating "as supplied" 
 
 (V n )a 
 
 Volume percent solids of coating "as app'iieu" 
 
 ^n^s 
 
 Volume percent solids of coating "as supplied" 
 
 (VOC) a 
 
 VOC content of "as applied" coating, expressed as mass 
 of VOC per unit volume of coating less water or as mass 
 of VoC per unit volume of solids 
 
 (VOC) s 
 
 VOC content of "as supplied" coating, expressed as mass 
 of VOC per unit volume of coating less water or as mass 
 of VOC per unit volume of solids 
 
 
 tne water content, in volume percent, of coating "as applied" 
 
 ^w^d 
 
 the water content, in volume percent, of the dilution solvent 
 added to the "as supplied" coating 
 
 
 the water content, in volume percent, of the coating 
 "as supplied" 
 
 ( w o^a 
 
 the organic volatile content, in weight percent, of the 
 coating "as applied" 
 
 (Wq)s 
 
 the organic volatile content, in weight percent, of the 
 coating "as supplied" 
 
 
 vi 
 
(w v ) a 
 
 the weight percent 
 
 
 "as applied" 
 
 (W v )$ 
 
 the weight percent 
 
 
 "as supplied" 
 
 (^w^a 
 
 the weight percent 
 
 (W w ) d 
 
 the weight percent 
 
 ( w wU 
 
 the weight percent 
 
 of total volatiles in the coating 
 
 of total volatiles in the coating 
 
 water in the coating "as applied" 
 water in the dilution solvent 
 water in the coating "as supplied" 
 

 
 
 
 
 
 
 
 
 
 
 
 \ 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
1. INTRODUCTION 
 
 This Manual provides step-by-step instruction for preparation of two 
 data sheets developed by the Environmental Protection Agency which may be 
 used by coating manufacturers and users to present information on the 
 quantity of volatile organic compounds* (VOC) emitted from a coating. 
 
 One of the data sheets may be prepared by the manufacturer of the coating; 
 the second would be used by the company that applies the coating to a 
 substrate. 
 
 The first VOC data sheet, which would be prepared by the manufacturer, 
 provides information on the volatile organic content of a coating as it is 
 delivered to a customer. This is referred to as the VOC content of the 
 coating "as supplied" (by the manufacturer to the user). 
 
 The second VOC data sheet, which would be prepared by the user or coater, 
 provides information on the quantity of volatile organic compounds present as 
 the coating is used or applied to the substrate and includes the effect 
 of any dilution solvent added before application. This is referred to as the 
 VOC content of the coating "as applied" (to the substrate). 
 
 The coating user may submit, and the Agency enforcing a regulation may 
 accept, these data sheets as prima facie evidence of the actual VOC content 
 of a coating. The referee method for ultimate determination of compliance, 
 however, will continue to be the method specified in the applicable regula¬ 
 tion (for example, tPA Reference Method k:4 or individual aSTM methods). 
 
 ^Volatile Organic Compound (VOC) - Any organic compound which participates 
 in atmospheric photochemical reactions; that is, any organic compound 
 other than those which the Administrator designates as having negligible 
 photochemical reactivity. VOC may be measured by a reference method, 
 an equivalent method, an alternative method, or by procedures specified 
 under any regulation. 
 
 1-1 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
2. VOC CONTENT OF PAINT, INK AND OTHER COATINGS 
 
 "AS SUPPLIED" BY THE COATING MANUFACTURER TO THE USER 
 
 II-l 
 

 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 
 
 VQC DATA SHEET : 
 
 PROPERTIES OF THE COATING H AS SUPPLIED" BY THE MANUFACTURER 
 
 Coating Manufacturer:_ 
 
 Coating Identification:_ 
 
 Batch Identification:_ 
 
 Supplied To:__ 
 
 Properties of the coating as supplied!- to the customer: 
 
 A. 
 
 Coating Density (D c ) s : 
 
 
 1b/gal 
 
 kg/1 
 
 
 / 7 ASTM D1476 
 
 / 
 
 ~T Other 2 
 
 
 B. 
 
 Total Volatiles (W v ) s : 
 
 
 Weight 
 
 Percent 
 
 
 / 7 ASTM D2359 
 
 / 
 
 / Otner 2 
 
 
 C. 
 
 Water Content: 1. (W w 
 
 )s 
 
 Weight 
 
 Percent 
 
 
 l~T ASTM U3792 
 
 / 
 
 / ASTM D4017 
 
 / / Other 2 
 
 
 2. (V w 
 
 )s 
 
 Volume 
 
 Percent 
 
 
 / / Calculated 
 
 / J Other 2 
 
 
 u. 
 
 Organic Volatiles (w 0 ) s 
 
 • 
 
 • 
 
 Weight Percent 
 
 E. Nonvolatiles Content (V n ) s : _Volume Percent 
 
 F. VOC Content (V0C) s : 1. _lb/gal coating less water 
 
 or___kg/1 coating less water 
 
 2. _lb/gal solids 
 
 or_kg/1 solids 
 
 Remarks: (use reverse side) 
 
 lThe subscript "s" denotes each value is for the coating "as supplied" 
 by the manufacturer. 
 
 ^Explain the other method used under "Remarks". 
 
 Signed:_Date_ 
 
 
 .w. 
 
 (J 
 
 %— w J 
 
 *1 men* 0 
 
 11-2 
 
2.2 IMPLEMENTING INSTRUCTIONS FOR THE VOC DATA SHEET FOR "AS SUPPLIED" COATINGS 
 
 This DATA SHEET is normally completed by the coating manufacturer and 
 provided to the user.l It will henceforth be referred to as the "AS SUPPLIED" 
 VUC DATA SHEET. 
 
 A. The "as supplied" coating density, (D c ) s 2 , is determined using 
 "ASTM D1475 - Standard Test Method for Density of Paint, Lacquer, 
 and Related Products." 
 
 B. The weight percent of total volatiles in a coating, (W v ) s , is determined 
 by "ASTM D2559 - 81 Standard Method for Volatile Content of Coatings." 
 drying conditions to be used are 11G°C for 1 hour^. 
 
 C. Water Content 
 
 1. The weight percent water, (W w ) s , is determined by "ASTM D3792 - 
 Standard Test Method for Water Content of Water-ReduciDle Paints 
 by Direct Injection Into a Gas Chromatograph," or "aSTM D4017 - 
 Standard Test Metnod for Water in Paints and Paint Materials by 
 the Karl Fischer Method."^>4 An acceptable alternative to these 
 procedures for purposes of preparing the data sheet would be to 
 calculate the weight percent water from the manufacturer's coating 
 formulation. 
 
 l-EPA's Reference Method 24 (40 C.F.R. Part 50, App. A), contains the 
 ASTM methods referenced in these instructions. 
 
 ^The subscript "s" denotes those parameters of a coating when measured 
 in the "as supplied" condition, before dilution by the user. 
 
 ^If the manufacturer believes a specified method does not give results 
 that are representative of the actual cure mechanism, he may petition the 
 enforcement authority for approval of an alternate analytical method. Any 
 alternate method or alteration to the methods and procedures in these instruc¬ 
 tions or in any applicable regulation would be subject to review and approval 
 by the appropriate State and Federal enforcement agency. 
 
 ^Volatile compounds classified by EPA as having negligible photochemical 
 reactivity such as 1,1,1-trichloroethane and methylene chloride, etc., and 
 listed as exempt in the applicable Federal and State VOC regulation should 
 be treated in the same manner as water. The weight percent.of negligibly 
 reactive compounds in a coating should be determined from the manufacturer's 
 formulation. The volume percent can then be calculated using equation 11-1 
 when the weight percent and density of the negligibly reactive compounas are 
 substituted for those of water. The weight and volume percent can be used in 
 Equations 11-2 and 11-6, respectively, in place of (W w ) s and (V w ) s . 
 
 11-3 
 
2. The water content, in volume percent, (V w ) s , can be calculated 
 by the equation: 
 
 (Vw)s 
 
 ( W w)S( D c)s, 
 
 -IT 
 
 w 
 
 II-l 
 
 where D w is the density of water, 8.33 lbs/gal. 
 
 D. The organic volatiles content, (W 0 ) s , i.e., the 
 expressed as a percent by weight, is determined 
 equation^: 
 
 VOC content 
 by the following 
 
 (W 0 ) s = (W v ) s - (W w ) s 11-2 
 
 If the coating contains no water the weight percent of organic 
 volatiles is equal to the weight percent of total volatiles. 
 
 In other words: 
 
 (W w ) s = 0 and 
 
 (W 0 ) s = (W v ) s 11-3 
 
 E. The volume percent solids (nonvolatiles), (V n ) s , should be derived 
 from the coating formulation using the following equation: 
 
 P 
 
 (v n ) s = £ (v n ) s . n-4 
 
 i-i 1 
 
 where (V n ) s denotes the volume percent of each 
 1 
 
 nonvolatile component in an "as suppl ied" coating, 
 and "p" is the number of nonvolatile components in 
 that coating. (Also see Footnote 1, Pg. I1-3.) 
 
 5 The precision limit adjustments permitted by Reference Method 24 for 
 experimentally determined mean W w and W v values may be made only by 
 enforcement agencies for determination of compliance. The adjustment 
 is not toTe used for the purposes of completing the "AS SUPPLIED" 
 WCTTOTA SHEET. 
 
 11-4 
 
F. The VOC content of the "as supplied" coating (V0C) s can now be calculated 
 and thereby expressed in terms used by most State or Federal regulations. 
 
 1. The mass of VOC per unit volume of coating less water: 
 
 a. If the coating contains no water, the equation is calculated 
 as follows: 
 
 (V0C) s 
 
 ^ w o^s ^ D c^s 
 
 -TODS- 
 
 b. If the coating contains water, Equation 11-5 becomes: 
 
 11-5 
 
 (VOC) s 
 
 <Vs 
 
 ^ D c^s 
 
 m% - (v w y s - 
 
 11-6 
 
 2. The VOC content may also be calculated in terms of mass of VOC per 
 unit volume of solids (nonvolatiles). For both solvent-borne and 
 waterborne coatings, the equation is: 
 
 (VOC) s 
 
 (Vs 
 
 <Vs 
 
 
 11-7 
 
 11-5 
 

 * 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
 
3. VOC CONTENT OF PAINT, INK AND OTHER COATINGS 
 "AS APPLIED" TO THE SUBSTRATE BY THE USER 
 
 III-l 
 

 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 
 
 VOC DATA SHEET : 
 
 PROPERTIES OF THE COATING "AS APPLIED 11 TO THE SUBSTRATE 
 
 Coating Manufacturer:_ 
 
 Coating Identification:_ 
 
 Batch Identification:_ 
 
 User:_ 
 
 User's Coating Identification:_ 
 
 Properties of the coating as applied* by the User: 
 
 A. Coating Density (D c ) a : _kg/1, or _ lb/gal 
 
 / 7 ASTM D1475 / 1 Other * 2 
 
 B. Total Volatiles (W v ) a : _ Weight Percent 
 
 / 7 ASTM D2369 / 1 Other? 
 
 C. Water Content: 1. (W w ) a _Weight Percent 
 
 / 7 ASTM D3792 /~7 ASTM D4017 /~7 Other? 
 
 2. (V w ) a _ Volume Percent 
 
 / / Calculated / / Other 2 
 
 D. Weighted Average Density of the dilution solvent (D d ) 3 : _lb/gal 
 
 / / ASTM D1475 / / Handbook / / Formulation 
 
 (Continued on Reverse Side) 
 
 *The subscript "a" denotes each value is for the coating "as applied" to the 
 substrate. 
 
 2 Explain the other method used under "Remarks" on reverse side 
 
 2 The subscript "d" denotes values are for the dilution solvent 
 
 111-2 
 
E. 
 
 Dilution Solvent Ratio (R^): 
 
 F. 
 
 G. 
 
 H. 
 
 Organic Volatiles Content 4 5 (W Q ) a : 
 Non-Volatiles Content (V n ) a : 
 
 VOC Content (V0C) a : 1. 
 
 or 
 
 2 . 
 
 or 
 
 _ gal diluent 
 
 (gal coating)^ 
 
 or 
 
 _ liter diluent 
 
 (liter coating)4 
 
 _ Weight Percent 
 
 _ Volume Percent 
 
 lb/gal of coating less water 
 kg/1 of coating less water 
 Ib/gal solids 
 kg/1 solids 
 
 REMARKS: 
 
 Signea: 
 
 Date: 
 
 4 The subscript "s" denotes values are for the coating "as supplied" by the 
 manufacturer. 
 
 ^This terminology is used to be consistent with Method 24. It refers to 
 all photochemically reactive organic compounds emitted from the coating 
 including reactive by-products of the cure reaction, exactly the same 
 matter as indicated in Paragraph H, i.e., volatile organic compounds, 
 or VOC. 
 
 111-3 
 
3.2. IMPLEMENTING INSTRUCTIONS FOR THE YOC DATA SHEET FOR "AS APPLIED" COATINGS 
 
 This DATA SHEET, henceforth referred to as the "AS APPLIED" VOC DATA 
 SHEET, is to be completed by the company which applies a coating. It 
 provides information on the amount of volatile organic compounds (VOC) in 
 the coating "as applied" to the substrate by accounting for the quantity of 
 diluent solvent added to a coating prior to application. There are two 
 avenues available for the coater to certify the VOC content. One is to 
 analyze each diluted coating with the same'method used to generate the data 
 provided by the coating manufacturer on the "AS SUPPLIED" VOC DATA SHEET. 
 
 (See Chapter 2 of this Manual.) In this case begin with Step A. 1 The other 
 is to maintain adequate records of how much organic solvent is added to each 
 coating and use that information and the "AS SUPPLIED" VOC DATA SHEET^ to 
 calculate the VOC content "as applied." (The user may choose to analyze an 
 "As Supplied" coating using Reference Method 24 and complete the "AS SUPPLIED" 
 VOC DATA SHEET rather than have the coating manufacturer complete it. The 
 volume percent solids, however, will necessarily continue to be supplied by 
 the coating manufacturer.) In this case begin with Step D. If a coating is 
 diluted only with water or a solvent of negligible photochemical reactivity, 
 skip Steps A through D below and proceed directly to t. (Also see Footnote 
 4, Pg. 111—5.) 
 
 A. The "as applied" coating density, (D_) a ^, is determined using "asTM U1475- 
 Stanaard Test Method for Density of Paint, Lacquer, and Related Products." 
 
 B. The weight percent of total volatiles in the coating, (W v ) a is determined 
 by "asTM b23b9-Ul Standard Method for Volatile Content of Coatings." 
 
 The drying conditions to be used are 110°C for 1 hour*. 
 
 i-EPA's Reference Method 24 (40 C.F.R. Part 60, App. A), contains the 
 ASTM methods referenced in these instructions. 
 
 ^The subscript "a" denotes those parameters of a coating in the 
 "as applied" condition, i.e., after dilution by the user. The subscript 
 "s" denotes the parameters of a coating in the "as supplied" condition, 
 before dilution by the user. 
 
 ^If the manufacturer believes the specified method gives results that 
 are not representative of the VOC released during the normal cure, he 
 may petition the enforcement authority for approval of an.alternative 
 analytical method. Any alternate method or alteration to the methods 
 and procedures in these instructions or in any applicable regulation 
 would be subject to review and approval by the appropriate State and/or 
 Federal enforcement agency. 
 
 111-4 
 
C. The water content is necessary only if the coating has been diluted 
 with a mixture of organic solvent and water.4,5 if th e dilution 
 solvent is 100 percent organic, or if the weight and volume percent 
 water in the mixture is known, proceed directly to Step D. 
 
 The weight percent water, (W w ) a , is determined by "ASTM u 3792 - 
 Standard Test Method for Water Content of Water-Reducible 
 Paints by Direct Injection Into a Gas Chromatograph," or "ASTM D4017 
 - Standard Test Method for Water in Paints and Paint Materials by 
 the Karl Fischer Method." (Also see Footnote 3, Pg. III-4.)' 
 
 The water content, in volume percent, (V w ) a , can be calculated by 
 the equation: 
 
 ( v w^a “ 
 where b w 
 
 ^w^a ^c^a 
 
 U w 
 
 is the density of water, 8.33 lb/gal. 
 
 I1I-1 
 
 ^Volatile compounds classified by EPA as having negligible photochemical 
 reactivity such as 1,1,1-trichloroethane and methylene chloride, etc., and 
 listed as exempt in the applicable Federal and State VuC regulation, should 
 be treated in the same manner as water. The weight percent of negligibly 
 reactive compounds in the dilution solvent must be known either from the 
 coater's mixing records or the dilution solvent supplier's formulation. 
 
 The volume percent can then be calculated using Equations III-l or III-5 
 when the weight percent and density of the negligibly reactive organics 
 are substituted for those of water. The weight and volume percent of 
 the negligibly reactive compounds can be substituted in all equations 
 where the weight and volume percent water, (W w ) and (V w ), respectively, 
 are used. 
 
 ^The precision limit adjustments permitted by Reference Method 24 for 
 experimentally determined mean weight percent water and total volatiles, 
 
 W w and W v respectively, may be made only by enforcement agencies for 
 determination of compliance. The adjustment is not to be used for the 
 purposes of completing the "AS APPLIED" VUC DATA SHEET. 
 
 111-5 
 
D. If the dilution solvent consists of a single compound the density 
 may be obtained from the literature. 
 
 If the dilution solvent is a mixture of organic compounds, the 
 density, D^, can be determined analytically via ASTM U1475, or 
 an average density can be estimated from the solvent formulation 
 as shown below. This estimation assumes that volumes are additive. 
 
 or 
 
 Dj = 
 
 100 % 
 
 m w, 
 
 E 4 
 
 j=i J 
 
 TuU% 
 
 rn 
 
 E v j u j 
 
 j=l 
 
 111-2 
 
 111-3 
 
 where: Dj, Wj, and V, denote the density, weight percent, 
 and volume percent of each solvent in the dilution solvent 
 mixture and "in" is the number of organic solvents in the 
 dilution solvent mixture. 
 
 If the dilution solvent is a mixture of photochemically reactive 
 organics and water, the coater must know the weight percent, (W w ), 
 or volume percent, (V w )^, of water from his mixing records or the 
 supplier's formulation, or he must analytically determine the weight 
 fraction of water in the dilution solvent using ASTM D3792 or A5TM 
 D4017. The density, U^, of the dilution solvent may then be deter¬ 
 mined by analytically measuring the density of the organic solvent/ 
 water mixture, D^', using AoTM U1475 and adjusting it for the water 
 content using the following equation. (See also Footnote 4, Pg. 111-5.) 
 
 n - n t nOW - <W w > d ] 
 
 d d LIoo% - (v w ) d j 
 
 II1-4 
 
 Note: If either the weight or volume percent water in the 
 dilution solvent is known, the other can be calculated by the 
 equation: 
 
 (W w )d 
 —U 
 
 111 — 5 
 
 where "D w " is the density of water. 
 
 ^The subscript "d" denotes a parameter that pertains to that solvent 
 used by the coater to dilute the "as supplied" coating. 
 
 II1-6 
 
E. The dilution solvent ratio, R^, is defined as the volume of 
 
 photochemically reactive organic solvent, (VOC), added per unit 
 volume of "as supplied" coating. Stated mathematically, 
 
 R = Volume photochemically reactive dilution solvent added 
 d Volume of "as supplied" coating 
 
 1. -If the "as supplied" coating is subsequently diluted with 
 water or a solvent which is of negligible photochemical 
 reactivity, the VOC content will be unchanged from that reported 
 on the "AS SUPPLIED" VOC DATA SHEET. This should be reported on 
 the "AS APPLIED" VOC DATA SHEET by entering "0" for the dilution 
 solvent ratio, R^. 
 
 2. In the absence of adequate dilution records, R<j can be 
 calculated from entries on the VOC DATA SHEETS by one of the 
 following equations: 
 
 a. When the dilution solvent consists only of VOC, 
 
 _ ^c^s “ ^ c ) a III-O 
 
 d ' ‘Va - < u d> 
 
 b. When the dilution solvent is a mixture of water and 
 photochemically reactive organic solvent. Equation Ii1-6 
 may be expressed as: 
 
 D t ^c^s “ ^c^a 111-7 
 
 R d = - T 
 
 (u c ) a - (D d ) t 
 
 where: is the ratio of the volume of water 
 
 and organic dilution solvent to the volume of "as 
 supplied" coating to which it is added. (Also see 
 Footnote 4, Pg. 111-5.) 
 
 The dilution solvent ratio, Rd> may now be calculated from 
 R^' by the following equation: 
 
 ^w^d 
 
 TUD¥" 
 
 111-8 
 
 111 - 7 
 
F. The organic volatile content (W 0 ) a , i.e. the VOC content expressed 
 as a percent by weight of the diluted coating, can now be calculated 
 by either of two ways: 
 
 1. From analyses of the coating using the following equation: 
 
 (W 0 ) a = <W v ) a - (W w ) a IH-9 
 
 (See Footnotes 4 and 5, Pg. III-S.) 
 
 If the coating does not contain water, the weight percent of 
 organic volatiles is equal to the weight percent of total 
 volatiles, or 
 
 ^o^a 
 
 III-10 
 
 2. By using the data from the "AS SUPPLIED" VOC DATA SHEET, the 
 dilution solvent ratio, and the density of the dilution solvent 
 with tiie following equation: 
 
 (W 0 ), 
 
 [(D c ) s (W o ) s /100« + (R d u d ) 
 
 ■^7 
 
 + 
 
 x 1U0» 
 
 III-ll 
 
 G. The volume percent solids, or nonvolatiles, (V n ) a , must be calculated 
 from the following equation where (V n ) s is obtained from the "AS 
 
 supplied" voc data sheet. 
 
 = ( Vs 111-12 
 
 H. The VOC content of the "as applied" coating (VOC) a , can now be 
 
 calculated and thereby expressed in terms used in most State or Federal 
 regulations. 
 
 1. The mass of VOC per unit volume of coating, less water, is 
 calculated in either of two ways. 
 
 a. Using the results obtained by analyzing the coating with EPA 
 Reference Method 24 or its constituent aSTM Methods: 
 
 (1). If the coating contains no water the equation is: 
 (VOC) 
 
 ^ w o7 
 
 ^c^a 
 
 II1-13 
 
 1UU% 
 
 111-8 
 
(2). If the coating contains water the following equation 
 must be used: 
 
 (VOC)a 
 
 ( w o^a (°c^a 
 
 - <Va 
 
 111-14 
 
 b. Using the VOC content of the "as supplied" coating, (V0C s ), 
 the dilution solvent ratio, and the density of the solvent, 
 the equation is: 
 
 (VOC)a 
 
 [(V0C) s (100% - (V w ) s )/100%] + (R d D d ) 
 
 r+ir^ 
 
 111 - 15 
 
 Where (VOC) s in this case must be in units of 
 lbs VOC/gal coating less water. 
 
 2. The VOC content may also be calculated in terms of mass of VOC 
 per unit volume of solids (nonvolatiles). 
 
 a. Using the results obtained by analyzing the coating with EPA 
 Reference Method 24 or its constituent ASTM methods, 
 the equation for both sol vent-borne and waterborne coatings, 
 i s: 
 
 {VOC) a * (w °lg ! Dc) * nl - 16 
 
 ' v n J a 
 
 b. Using dilution information and calculation procedures only, 
 the equation is: 
 
 (VOC) a = 
 
 C(V0C) s (100% - (V w ) s )/100%] + (R d D d ) 
 
 111-17 
 
 (v n ) s /loo% 
 
 Where (VOC) s in this case must be in units of 
 lbs VOC/gal coating less water. 
 
 II1-9 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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