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Molar Group Contributions to the Heat of Combustion

September 2001 DOT/FAA/AR-TN01/75 This document is available to the public through the National Technical Information Service (NTIS), Springfield, Virginia 22161.

U.S. Department of Transportation Federal Aviation Administration

S. This document does not constitute FAA certification policy.NOTICE This document is disseminated under the sponsorship of the U. Consult your local FAA aircraft certification office as to its use. Department of Transportation in the interest of information exchange. Hughes Technical Center’s Full-Text Technical Reports page: actlibrary.gov in Adobe Acrobat portable document form (PDF). . The United States Government does not endorse products or manufacturers. The United States Government assumes no liability for the contents or use thereof.faa. Trade or manufacturer's names appear herein solely because they are considered essential to the objective of this report.tc. This report is available at the Federal Aviation Administration William J.

. Key Words 18. 21. DOT/FAA/AR-TN01/75 4. Contract or Grant No. 13. 3. No. Department of Transportation Federal Aviation Administration Office of Aviation Research Washington. Flammability 19. Performing Organization Name and Address 10. Abstract Experimental results for the gross heat of combustion of over 140 commercial and developmental polymers and small molecules of known chemical structure were used to derive additive molar group contributions. Walters 9. Work Unit No. Report Date MOLAR GROUP CONTRIBUTIONS TO THE HEAT OF COMBUSTION September 2001 6. Price 20. Supplementary Notes Technical Report 14. Security Classif. Hughes Technical Center COTR is Richard Lyon 16. C Egg Harbor Township. Bldg. Fire. Type of Report and Period Covered U. Performing Organization Code 7. 2. DC 20591 15. Predicted gross heats of combustion were within 2. (of this report) This document is available to the public through the National Technical Information Service (NTIS). (of this page) Unclassified Form DOT F1700. 17. Security Classif. Virginia 22161. Combustion. Distribution Statement Polymer. Sponsoring Agency Name and Address 11.7 (8-72) Unclassified Reproduction of completed page authorized 14 .Technical Report Documentation Page 1. Author(s) 8. Springfield. Performing Organization Report No. Title and Subtitle 5.S. Group contributions.5 percent of the values measured by oxygen bomb calorimetry. Report No. NJ 08234 12. of Pages 22. Richard N. Government Accession No. (TRAIS) Galaxy Scientific Corporation 2500 English Creek Ave. Sponsoring Agency Code AIR-120 The FAA William J. Recipient's Catalog No.

iii/iv .ACKNOWLEDGEMENT The author would like to thank Dr. Stanislav Stoliarov of the University of Massachusetts (Amherst) for his input and help with the analysis of the group contribution values and the FAA for supporting this work.

TABLE OF CONTENTS Page EXECUTIVE SUMMARY INTRODUCTION EXPERIMENTAL Materials Methods Theory RESULTS CONCLUSION REFERENCES vii 1 2 2 2 3 5 7 7 LIST OF FIGURES Figure 1 Plot of the Calculated Versus the Measured Heat of Combustion for 66 Polymers and 78 Small Molecules Page 5 LIST OF TABLES Table 1 2 Structural Groups and Their Molar Contributions to the Gross Heat of Combustion Calculation of Heat of Combustion of Bisphenol-A Epoxy Page 4 6 v/vi .

sulfur. and silicon in linear.EXECUTIVE SUMMARY Experimental results for the gross heat of combustion of over 140 commercial and developmental polymers and small molecules of known chemical structure were used to derive additive molar group contributions to the heat of combustion. The materials examined contained carbon. phosphorous. This new method provides an accurate single step method for calculating the heat of combustion. fluorine. hydrogen. The average relative error of the calculated gross heats of combustion is 2. nitrogen. branched and cyclic structures. Values for the molar group contributions are summed and divided by the molecular weight of the molecule or polymer repeat unit to yield the gross heat of combustion as determined by oxygen bomb calorimetry. oxygen. vii/viii .5 percent. chlorine.

the quantity ro = [nO2M O2/npMp] is the stoichiometric oxygen-to-fuel mass ratio. A simpler approach to correlating polymer chemical structure with properties is to group the atomic contributions into characteristic structural elements (e. !h c = E n O2M O2 = Er o n pM p (2) The additivity of molar group contributions to the physical and chemical properties of materials is the basis of an empirical methodology for relating chemical structure to properties [1-3]. chemical. Another method for obtaining the heat of combustion is by using the heats of formation of the products and the reactants [7-9]. A simpler. and MO2 = 32 g/mol is the molecular weight of diatomic oxygen. These different methods have been examined by the author [10 and 11] and found to agree to within ±5%. The early work in this area focused on calculating heats of combustion from the individual atoms comprising small molecules. In equation 1. with excellent results [1-3]. respectively. and 11] to determine E from known atomic compositions and measured heats of combustion. This method for deriving the heat of combustion is very accurate but difficult to perform and is only applicable to linear hydrocarbon molecules. However. performing calculations for large (polymer) molecules based on the interactions of the individual atoms can prove to be very difficult. as well as flammability. Heats of combustion calculated from oxygen consumption rely on the empirical observation that a wide range of organic compounds.. and add these group contributions according to their mole fraction in the polymer repeat unit. This method has been used to relate the chemical structure of polymers to their thermal. This calculation was performed for polymers in several studies [5. 10. –CH3). Oxygen consumption is a commonly used method for calculating the heat of combustion from known chemical structures [4] and for measuring heat release rates in flaming combustion tests [5 and 6].1 ± 0.7 kJ /g–O2 n O2M O2 o (1) where !hc is the net heat of complete combustion of the sample with all products in their gaseous state. Inverting equation 1 shows that the net heat of complete combustion of a polymer is simply calculated if the atomic composition of the polymer is known so that the balanced thermochemical reaction equation can be written.g. including polymers. and mechanical properties. have approximately the same heat of complete combustion per gram of diatomic oxygen consumed E = !h c n pM p !h c = r = 13. nO2 is the number of moles of O2 consumed in the balanced thermochemical equation. np and M p are the number of moles and molecular weight of the molecule or polymer repeat unit. Other methods involve compiling structural group contributions and correction factors for their adjacent bonds [12]. optical. determine the value of the group contribution to the property of interest parametrically. more 1 .INTRODUCTION Several approaches have been taken to calculate the heat of combustion based on the molecular structure of a material [1-3].

the latent heat of water at 298 K is subtracted from the gross heat of combustion because this amount of heat is required to maintain the combustion product water in the gaseous state. natural. !hc in kJ/g. For polymeric reactants the molar heat of formation can be estimated from the tabulated molar contributions of the chemical groups which constitute the monomer or repeat unit. In practice. The calculation of the heat of the combustion can also be carried out using the principle of molar additivity of the heats of formation of the combustion products and reactants [13]. METHODS. 298 K.99% purity grade obtained from Matheson Gas Products. The oxygen gas used for testing was dry.51 kJ/mol. The net or lower heat of combustion is relevant to flaming combustion. Illinois) according to a standard procedure ASTM D 2382-88 [14]. Scientific Polymer Products. EXPERIMENTAL MATERIALS. The gross heat of combustion was measured in an oxygen bomb calorimeter (Model 1341..r (3) where p and r denote products and reactants. or virgin-grade resins obtained from Aldrich Chemical Company. The average standard error for this technique is 0. Plain Jacket Oxygen Bomb Calorimeter. Thus. The concept is derived from the fact that enthalpy (H) is a state function and therefore its change in any process is independent of the path from reactants to products. Polymer samples were unfilled. in the standard state at temperature. w H is the weight fraction of hydrogen in the sample. Moline. the heat of combustion of the reaction can be calculated by subtracting the heat of formation of the products from the heat of formation of the reactants !h c = "n i p !h o f . The gross heat of combustion measured by the procedure stated above is corrected for the heat of vaporization of the water formed during the combustion to give the net heat of combustion. where water is in the gaseous state at flame temperatures of ! 1000 K.accurate method has been developed for calculating the heat of combustion under standard conditions using molar group additivity. Parr Instrument Co. using the relation [16] "hc = Qc – 21. As a result. with corrections for the heat of solution of any acid gases that may have been formed [15]. p – " n !h i r o f . the overall enthalpy of a reaction is simply the sum of the enthalpies of the component reactions. 2 . >99. There are no direct methods for measuring the net heat of combustion#which is the gross heat of combustion minus the latent heat of vaporization of the water produced during the reaction. respectively. or directly from manufacturers.96wH (4) where Qc is the gross heat of combustion in kJ/g.

The molar heat of complete combustion !Hc is a thermodynamic property and should be calculable from the molar group contributions of the structural components. the molar heat of combustion of component i. The sum of the molar group contributions is divided by the molecular weight of the molecule or polymer repeat unit to yield the specific heat of combustion. the largest chemical groups listed in the table 1 are used to calculate the heat of combustion of the molecule. respectively.THEORY. ni = Ni " Ni i and M = "n i i Mi = "N M "N i i i i i (6) where Ni and Mi are the number of moles and molar mass. Assume that there is a molar heat of combustion. H. in which each chemical group i in the polymer contributes according to its mole fraction. the heat of combustion can be expressed on a mass basis. in the repeat unit. An empirical approach was taken to derive values for the structural group contributions to the heat of combustion. 3 . ni. of group i in the polymer having repeat unit of molar mass M. !h c = H = M "nH "n M i i i i i i = "N "N i i i Hi Mi i (7) In practice. with units of kJ/mol. H = "nH i i i (5) with Hi. Since.

i O N O N O N Hi (kJ/mol) 939 781 775 Structural Group. STRUCTURAL GROUPS AND THEIR MOLAR CONTRIBUTIONS TO THE GROSS HEAT OF COMBUSTION Structural Group.TABLE 1. i CF3 Hi (kJ/mol) 213 190 112 C C CH3 H O C O O N O O N O 4343* 3964* 3725* CH2 670 548 522* NH 77 0 -43 N O N O C N NO 2 C O H N N CH2 O Cl O 3444* 3186 3130 2871 CH 518 431 338 328 311 O C O -78* -100 -108 -132 -230 C O S O N OH O CF2 O N O 2746 S O F Cl Cl C C N 2653 CH3 C CH3 C 259 219 N NA N 2294 Si NA 4 . i O P Hi (kJ/mol) 9845* 4955* 4889 Structural Group.

which were independent of initial estimates.RESULTS Measured heat of combustion values for 66 polymers [10 and 11] and 78 small molecules [16 and 17] with known chemical structure have been used to generate the additive molar group contributions shown in table 1. The calculation converged rapidly to the unique H i. listed in table 1. Measured and calculated heats of combustion for the 66 polymers and 78 small molecules are plotted against one another in figure 1. The optimization calculation continued until the sum of the squares of the relative error between the measured ! hc and calculated values was a minimum. PLOT OF THE CALCULATED VERSUS THE MEASURED HEAT OF COMBUSTION FOR 66 POLYMERS AND 78 SMALL MOLECULES 5 . Calculated Heat of Combustion (kJ/g) 60 Polymers Small Molecules 50 40 30 20 10 0 0 10 20 30 40 50 60 Measured Heat of Combustion (kJ/g) FIGURE 1. The molar group contributions were obtained by treating the Hi as adjustable parameters in the linear system of equations for materials with known chemical structures and measured !hc. Molar group contributions derived from a single material are marked with an asterisk (*) to indicate that these are not average values.

0347 76.797 g Mi Hi Molecules that can be described by several different group combinations should use the largest groups listed for calculating the heat of combustion.9988 267. Hi (kJ/mole) 431 518 670 775 2653 -132 Total: Ni Mi (g) 12. calculated and measured heats of combustion for over 140 compounds differ by only ±2. 6 .5036 30.0694 152. This polymer has the repeat unit structure: CH3 C CH3 O CH2 CH CH2 O The polymer repeat unit is comprised of six basic chemical groups and the heat of combustion is calculated from the associated Ni.011 13. Mi.1952 31.5% on average.16 kJ/g compares well with the measured value of 32. !H c = "N "N i i i i = 8881 kJ = 33. obtained by summing the group contributions according to their mole fraction is then divided by the molar mass of the repeat unit to give the heat of combustion in units of kJ/g.50 kJ/g for this particular polymer. i C Ni 1 1 2 2 2 Mi (g/mole) 12. Since the molar group contributions are derived from experimental data they should correlate well with measured heats of combustion. CALCULATION OF HEAT OF COMBUSTION OF BISPHENOL-A EPOXY Structural Group. TABLE 2.Table 2 shows an example of the thermochemical calculation of the heat of combustion from additive molar group contributions for a ring-opening polymerization of the diglycidyl ether of bisphenol-A (BPA epoxy).0189 28.011 13. and Hi as follows. The predicted value of 33.16 kJ / g 267.9994 Group Value.7969 Ni Hi (kJ) 431 518 1340 1550 5306 -264 8881 CH CH2 CH3 O 2 The molar heat of combustion.0189 14.0268 15.0976 15. In fact.

2. No. Lyon.CONCLUSION Additive molar contributions to the gross heat of complete combustion for 37 structural groups have been determined from data for 66 polymers and 78 small molecules with known chemical structure. Inc. Graf. D. and S. Painter. Amsterdam. 3. V.L. 6.” Thermochemical Kinetics. 9.” AIChE Journal. 1980. R..M. Hshieh. Parker. Janssens and W.J. M. Hackett.. 1968. Walters. 12. Marcel Dekker.C. 8. “Heats of Combustion of High-Temperature Polymers. Properties of Polymers.” Philosophical Magazine and Journal of Science. Bensen. “Estimation of Rate of Heat Release by Means of Oxygen Consumption Measurements. S. 4 (2). REFERENCES 1. 11.” Heat Release in Fires.” Fire & Materials. PA. NY. J.” Journal of Ningxia University (Natural Science Edition).” Fire and Materials. R. September 2000.” Fire & Materials. “Heats of Combustion of High-Temperature Polymers. Cardozo.J.” DOT/FAA/AR-TN97/8. 1992.” Technomic Publishing Co. 1999. 1996. 2000. 3rd Ed. 23. 5. LI Qin. eds. and P. “The Role of Oxygen to the Heat of Combustion of Organic Compounds. M.. Inc. Jozef Bicerano. The group contribution method improves upon previous techniques by providing a direct. 1991. 3.. 10. WANG Ke-qiang. W. No. 7 .M. single step method for calculating the heat of combustion of chemical compounds. 32. 4.. 21. London. Elsevier Applied Science. Coleman. pp.N. 1990.Y. R.M.E. “Oxygen Consumption Calorimetry. Hackett. “Prediction of the Enthalpy of Combustion of Organic Compounds.F. pp. “A New Method for Predicting the Heat of Combustion of Liquid Alkanes by Using the Group-Bond Contribution Method. 7. F. New York. 844-848. Prediction of Polymer Properties. S. Babrauskas. 2nd Edition. 5. Clayton Hugget. “Predicting Heats of Combustion and Lower Flammability Limits of Organosilicon Compounds. 1998. and R. Thornton. Van Krevelen.E. 1917. May 1986. Vol.W. Vol. 24. “Specific Interactions and the Miscibility of Polymer Blends. NY. Lancaster. Elsevier. Walters. R. John Wiley. “Methods for the Estimation of Thermochemical Data and Rate Parameters.W. Lyon. Chapter 3. Grayson.N. New York. S. 31-59. 33(196).

14..M. Grayson.. 3rd Ed. Hirschler. pp. 15. 207232.” Properties of Polymers. M.” ASTM Fire Test Standards. Babrauskas. Chapter 8. D.. pp.W. Van Krevelen. Philadelphia. Babrauskas and S. 16. “Thermochemical Properties: Calculation of the Free Enthalpy of Reaction from Group Contributions. 230-238. 17. Rossini. “Experimental Thermochemistry. 3rd Edition.” Heat Release in Fires. 1956.J. pp. Interscience.” V. Amsterdam. PA.” F. 1990. V. eds. “Heat Release in Fires.. 629-639. American Society for Testing of Materials.13. 1992. Elsevier Applied Science. London 1992. ed. NY. Grayson. New York. 1990. S.D. “Heat of Combustion and Potential Heat. 207-223. “D2382-88: Standard Test Method for Heat of Combustion of Hydrocarbon Fuels by Bomb Calorimeter (High Precision Method). Elsevier. pp. Elsevier Applied Science. Chapter 20. 8 . eds. Babrauskas. V.