unclassified ad number - dtic6. the heats of formation (ah.) required for hypothetical explosive...

UNCLASSIFIED

AD NUMBER

AD374171

NEW LIMITATION CHANGE

TOApproved for public release, distributionunlimited

FROMDistribution authorized to U.S. Gov't.agencies and their contractors;Administrative/Operational Use; 10 JUN1966. Other requests shall be referred toX.

AUTHORITY

THIS PAGE IS UNCLASSIFIED

UNCLASSIFIED

AD NUMBER

AD374171

CLASSIFICATION CHANGES

TO

unclassified

FROM

confidential

AUTHORITY

30 Jun 1978, Gp-4 & OCA.

THIS PAGE IS UNCLASSIFIED

GENERALSECLASSIFICATION

SCHEDULEIN ACCORDANCE WITH

POD 5200.-R & EXECUTIVE ORDER 11652

SECURITYMARKING

The classified or limited status of this repoil applies

to each page, unless otherwise) marked.Separate page printoutsMUST marked accordingly.

THIS DOCUMENT CONTAINS INFORMATION AFFECTING THE NATIONAL DEFENSE OFTHE UNITED STATES WITHIN THE MEANING OF THE ESPIONAGE LAWS, TITLE 18,U.S.C., SECTIONS 793 AND 794. THE TRANSMISSION OR THE REVELATION OFITS CONTENTS IN ANY MANNER TO AN UNAUTHORIZED PERSON IS PROHIBITED BYLAW.

NOTICE: When government or other drawings, specifications or otherdata are used for any purpose other than in connection with a defi-nitely related government procurement operation, the U. S. Governmentthereby incurs no responsibility, nor any obligation whatsoever; andthe fact that the Government may have formulated, furnished, or in anyway supplied the said drawings, specifications, or other data is notto be regarded by implication or otherwise as in any manner licensingthe holder or any other person or corporation, or conveying any rightsor permission to manufacture, use or sell any patented inrention thatmay in any way he related thereto.

'[

!I[/

CONFIDENTIAL NOLTR 65-217

CQMPUTATION OF DETONATION PROPERTIESN OF FLUOROEXPLOSIVES (U)

I10 JUNE 1966

UITED STATES NAVAL ORDNANCE LABORAIORY, WHITE OAIK, IMARYLAND

NOTICE: Thk merlal contains information affecting the nationaldefenso of the United Stales with;n the meaning of the Espionage Laws,

I-. Title 18, U.S.C. Sectio, 793 and 794, the transmission or revelationVof which in any-manner to an unauthorized person is prohibited by low.

IIn addiion to security e.'*quxrementswhich mu;t be rnet, rch tr n . rntta

of thls. Aocument outside of the Dc arJt:raent of Dofense rnust have prior ap-

0i proval of INOL.

Downgraded at 3 Year Irervals

CONFIDENTIAL Dickossified after 12 Yea;,, D0D Vir $20$.10O

NOLTR 65-217CONF IDENTIAL

COMPUTATION OF DETONATION PROPERTIESOF FLUOROEXPLOSIVES (U)

ByHarold Hurwitz

ABSTRACT: The RUBY code has been used to compute detonationproperties for a number of fluorinated explosives. Results aregiven for fluorinated TNB, RDX, tetryl, TNT, DATB, and trinitro-benzotrifluoride, and for Eluorodinitropropare and fluoro-dinitromethane. When necessary densities and heats of formationof the explosives were estimated for input to RUBY. Ingeneral, the calculated detonation properties of the fluorinatedexplosives, compared with the properties of the non-fluorinatedparent compounds, showed increased detonation velocity, increaseddetonation pressure, and decreased _etonation energy. It shouldbe noted that if lower densities had been assumed,the computeddetonation pressures and velocities would have been lower. Forexample, the computed detonation velocity for 2,2,4,6-tetrafluoro-RDX at the initial density p. = 2.17 gm/cc is 9.25 vm/usec(compared with 8.80 for RDX at TMD), and the computed detonationpressure is 0.409 megabars (compared with 0.344 for RDX). AtS' = 2.05 gm/cc, the values computed for the same compound are.65 i /psec and 0.352 megabars. Computed detonation velocities

of the fluorinated TNB's at measured densities show an averagedeviation of 2.1% from literature values.

EXPLOSION DYNAMICS DIVISIONEXPLOSIONS RESEARCH DEPARTMENT

U. S. NAVAL ORDNANCE LABORATORYWHITE OAK, MARYLAND

iCONFIDENTIAL

CONFIDENTIAL

NOLTR 65-217 10 June 1966

COMPUTATION OF DETONATION PROPERTIES OF FLUOROEXPLOSIVES (U)

The work described in this report was carried out under Eglin Air Force BaseMIPR PG-3-19, dated September 1963. The purpose of the work was to calculatethe detonation properties of a number of fluoroexplosives. This makespossible a preliminary evaluation of the compowuds, thus serving as a guidefor possible experimental effort.

J. A. DARE-Captain, TfSNCommander

C. J. ARONSONBy directon

iiCO)NFiDFNTIAL

CONFIDENTIAL

NOLTR 65-217

TABLE OF CONTENTSPage

INTRcJDCTION -- ATA---------------------------------------------------- 1SOURCES OF INPUT DATA ------------------------------------------- 2RESULTS OF COMPUTATIONS ----------------------- 4

COMPARISON WITH OTHER VALUES ----------------------------------------- 5CONCLUSIONS --------------------------------------------------------- 6REFERENCES ----------------------------------------------------------- 8APPENDIX ------------------------------------------------------------- 38

TABLES

1. DEFINITION OF NAMES USED FOR CHEMiCAL COMPOUNDS ----------------- 102. ESTIMATED HEATS GY FORMATION ------------------------------------- 153. DENSITIES OF EXPLOSIVE MATERIALS USED FOR RUBY CAY.ULATIONS ----- 164. COVOIUMES (ki) USED IN THE RUBY COMPUTATIONS --------------------- 175. COMPUTED DETONATION PROP.CRTIES FOR MFTNT, USING DIFFERENT

AHf's AND EQUATION,.OF-STATE PARAMETERS ------------------------- 86. COMPUTED DETONATION PROPERTIES FOR FLUORINATED RDX's

(Using RDX-Type Parameters) -------------------------------------- 197. COMPJTED DETONATION PROPERTIES FOR FLUORINATED TN's ------------- 208. COMFJTED DETONATION PROPERTIES FOR FLUORINATED TETRYLS ----------- 219. COMPUTED DETONATION PROPERTIES FOR FLUORINATED TNT's AND DATB --- 2210, COMPUTED DETONATION PROPERTIES FOR RING-FLUORINATED TNBTF's ----- 2311. COMPUTED DETONATION PROPERTIES FOR FDNP/FTNM MIXTURES

(Using RDX-Type Parameters) -------------------------------------- 2412. LITERATURE VALUES FOR DETONATION VELOCITIES ---------------------- 25

ILLUSTRATIONS

Figure 1. COMPUTED D FOR MMIT., VARYING AHf AND EQUATION OFSTATE PARAMETERS ------------------------------------------- 26

Figure 2. COMPUTED P FOR MFTNT, VARYING AHf AND EQUATION OFSTATE PARA RS ------------------------------------------- 27

Figure 3. COMPUTED AE FOR MFTNT, VARYING AHf AND EQUATIONOF STATE PARMTERS ---------------------------------------- 28

Figure 4. OOM11UTED DETONATION VELOCITY VS. NUMBER OF FLUORINEATOMS FOR FLUORINATED RDX'S -------------------------------- 29

Figure 5. COMPUTED CJ PRESSURE VS NUMBER OF FLUORINE ATOMSFOR FLUORINATED RDX'S -------------------------------------- 30

Figure 6. COMPUTED CHEMICAL ENERGY VS NUMBER OF FLUORINE ATOMSFOR FLUORINATED RDX'S -------------------------------------- 31

Figure 7. COMPUTED DETONATION VELOCITY VS NUMBER OF FLUORINE ATCIASFOR FLUORINATED TNB'S -------------------------------------- 32

Figure 8. COMPUTED CJ PRESSURE VS NUMBER OF FLUORINE ATOMS FORFLUORINATED TNB'S ------------------------------------------ 33

iiiCONFIDENTIAL

CONFIDENTIALmmLTR 65-217

ILLUSTRATIONS CONTINUEDPage

Figure 9. COMPUVED CHEMICAL ENERGY VS NUMBER OF FLUORINE ATOMSFOR FUJORINATED TNB'S ............ 34

Figure 10. DETONATION VELOCITIES FOR DFTNB, FROM NOL AND OTHERSOURCES --------------------------------------------------- 35

Figure 11. DETONATION VELOCITIES FOR MFTNBJ% FROM NOL AND OTHERSOURCES --------------------------------------------------- 36

Figure 12. DETONATION VELOCITIES FOR TINFF, FROM NOL AND OTHERSOURCES --------------------------------------------------- 37

ivCONFIDENTIAL

CONFIDENTIALNOLTR 65-217

COPTATION OF DETONATION PROPERTIES OF FLUOROEXPLOSIVES (U)

INTRODUCTION

1. The research described in this report was conducted by the Naval OrdnanceLaboratory for the Air Force under Eglin Air Force Base MIPR PG-3-19, dateiSeptember 1963. Under this contract NOL was to calculate the detonationproperties of a number of fluorinated explosive compounds. Previously, theDenver o1esearch Institute on an Air Force contract had shown by chemicalsynthesis and subseluent measurements that the replacement of hydrogen atomsby fluorine atoms in explosive materials could lead to improvements indesirable propertie; (Ref. l).* The need for actual synthesis and measure-ment, however, could be kept to a minimum by the use of available computa-tional methods that predict the properties of hypothetical compounds.

2. Detonation characteri3tics of explosive compositions can be estimatedusing the RUBY code, a digital computer program develoled at the LawrenceRadiation Laboratories (Ref. 2) and now in use at NOL (Refs. 3,4). Animportant feature of RUBY is the use of the Kistiakowsky-Wilson equat-on ofstate (which may be written as in Equation (1))to represent the behavior ofthe explosion product gases.

PV/RT = 1 + x exp(ox)

x = k/V(T + 0) (1)

k E~x, ki

In Equation (1), V is the molar gas volume, P is the pressure, T is theabsolute temperature, and xi is the mole fraction of component i. Thequantities i, 03, h, e, and ki are constants, the ki being covolumes. Theuse of this equation of state for representing gaseous explosion productshas been discussed by Mader (Ref. 5).

3. Certain properties of the explosive material (HE) and the product speciesare required as input to RUBY. For the HE these are chemical composition,density, and heat of formation. The input quantities required for the gaseousproduct species are chemical composition, thermodynamic properties, andcovolumes (ki). The only condensed product considered in the present workis solid graphite, and the information on graphite required as input to RUBYincludes thermodynamic properties, molar volume, and constants for anappropriate equation of state (note that Equation (1) applies only to gases).The equation of state used for this purpose is

P = -2.4673 + 6.7692Y - 6.9555Y2 + 3.0405Y 3 - 0.3869?

+(-.9534 + 2.3368Y) x 10-5T

+(6.142 - 5.794 + 2.271 /y 2 ) x 1o1T2

V0

*References py be found 1CONFIDENTIAL


where P is in megabars, and T in degrees Kelvin, as given in Refs. 2 and 6.

4. In this report, lengthy chemical names have been abbreviated to shortsymbols for convenience. These shor' names are defined in Table 1, whichalso includes definitions of co'entional HE nrames (RDX, DCB, etc.). Theexplosives investigated were mono-, di-, and trifluorinated TNB; mono-, di-,and tetrafluorinated RDX; mono- and difluorLnated tetryl; mono- anddifluorinated TNT; fluorinated DATB; trinitrobenzotrifluoride, and its mono-and difluoro derivatives; and fluorodinitropropane, fluorodinitromethane,and mixtures of the two. In general, the calculated detonation properties,compared with the properties of the non-fluorinated parent explosivecompounds, show increased. detonation velocity and detonation pressure, anddecreased detonation energy.

SOURCES OF INPUT DATA

5. The thermodynamic properties--enthalpy of formation, Gibbs free energy offormation, and constants giving the constant-pressure heat capacity as afunction of temperature--required for the product species, were obtained fromthe JANAF Thermochemical Tables (Ref. 7). Covolumes used for the gaseousproducts were those given in Ref. 8, with the revisions fur U20 and 002suggested in Ref. 5.

6. The heats of formation (AH.) required for hypothetical explosivecompositions had to be estimated. There are a number of useful methods(e.g. Refs. 9 and 10) for estimating heats of formation by sum-aing thecontributions of various structural features over the entire molecule.However, since the compounds treated in the present work are simple deriva-tives of known chemical species, the estimation of their heats of formationwas approached by taking as a starting point molecules whose heats offormation were already known. The method may be illustrated by takingmonofluorodiamintotrinitrobenzene (FDATB) as an example:

FC6H6(I) CA

Az = +11.7 kcal/mole 6Hf = -3.8

AH = -34.8-.1.7 = -46.5

DATB (s) F FDATB(s)

AHf = -29.2 ,% = ?

AHf(FDATB) = -29.2 + (-46.5) = -75.7 kcal/mo.be

The difference in heat of formation between benzene and monofluorobenzeneis -46.5 kcal/mole. When this is added to the heat of formation of DATB(-29.2 kcal/mole) the result is -75.7 kcal/mole, the estimvted heat. offormation of FDATB. In this procedure, the AHf difference due to

2CONFIDENTIAL


fluorination of a liquid to form a liquid is assumed to be approximatelyequal to the Alf difference due to fluorination of a solid tu form anothersolid. Appendix A shows the computation of the AHf estimates for thevarious compounds treated in this report. The resulting estimated AHlfvaluez -e listel ir. Table 2.

7. In making the detonation ca:, -ulins for the hypothetical compositionsit is also necessary to estimate densities. Pavlath and Leffler (Ref. ll)suggest that densities be estimated by examining the molar volumes ofsimilar compounds rather than from densities of similar compounds directly.Although these authors stress that their method is strictly applicable onlyto liquids, in the present work it was considered to give an adequate approxi-mation for solids when no other information was available. It should be notedthat the computed detonation properties are strongly influenced by thesedensity estimates. Consideration of other factors which sometimes aff .ct thedensities of solids (such as charge distribution and symmetry) might have ledto lower densities and lower detonation velocities and pressures.

8. Table 3 gives the densitias used for the RUBY calculations. In the caseof the fluorinated trinitrobenzenes, only one density for each compouna isgiven in the table although RUBY computations were also carried out for otherdensities for comparison with results reported by other investigators. Twoseparate densities are listed as estimated for each fluorinated RDX, andcomputations were carried out for each value. This was done because thevolume increment derived by Pavlath and Letfler for aromatic compounds couldnot be applied with confidence to the aliphatic RDX's. For the TNBTF's themethod of applying the theory to the side-chain fluorine atoms was uncertain,and the estimates are con3equently given to 'ily two significant figures.

9. The values of the equation-of-state parameters cy, 5, x, and 9 arethose given by Mader in Ref. 5. The values of k. were those given in Ref. 8with the changes suggested in Ref. 5. The quantities a and B are dimension-less, the ki have the dimensions of volume, 8 has tho dimensions of tempera-ture, and n has the dimensions of temperature raised to the o( power. For8 and 4, Mader recommended two sets of values. One set (called here RDX-type)is fitted to the properties of RDX, but then adjusted so that (6P/aT)v willalways be positive. The other set (ca led here TNT-type) is fitted to theproperties of TNT and recommended for dense explosives whose products containrelatively large amounts of solid graphite. The values of y, 6, x, and aare as follows:

0.50

B = 4000K

Parameter Type 5 (°K6)

TNT 0.0958) 12.685

RDX O. 16 10.91

3CONFIDENTIAL

CONFIDNTIALNOIMR 65-217

Mie values of the k are given in Tsble 4. It should be noted that con-sistency with the use of cubic centimeters as the units for other volumequantities in the computation requires that the units of the k be consideredas cubic centimeters. However, as is usual in RUBY-type computations, thenumerical values of Mader's ki, which are computed in terms of cubic angstromsper molecule, have been used here without application of the approprittefactor (0.602) to convert to cuLic centimeters per mole. This is equivalentto multiplying each ki by 1.66, which is the reciprocal of the conversionfactor.

RESUPS OF COMTATIOS

10. Because of the uncertainty in some of the heat of formation estimates,it was of interest to observe the effect of changes in the heat of formationof the explosive composition on RUBY results. Por this purpose, and also tocompare the effects of the two sets of values of 0 and A, computations werecarried out for MT assuming the AHf to be -50, -75, and -100 kcal/mole andusing both sets of the equation of state parameters. The results are shownin Table 5, and in Figures 1, 2, and 3. In Tables 5-11, P, T, p, E, and S arepressure, temperature, density, energy, and entropy, respectively. The sub-script J indicates the detonation products in the (hapman-Jouguet state, andthe subscript o indicates the unreacted explosive at 298°K and 1 atm. pressure.AEchem is the detonation energy, defined as the energy increase while goingfrom the unreacted explosive at 298°K and 1 atm. pressure, to the Chanman-Jouguet gas mixture reduced to 298°K and 1 atm. pressure.

11. Decreasing the AHf of the MFTNT from -50 to -100 kcal/mole, using theTNT-type parameters, caused a 3.0% decrease in the computed detonationvelocity, an 8.1% decrease in the Chapman-Jouquet (CJ) pressure, and a l510K(or 16.%) drop in the W temperature. The energy change for the chemicalreaction (AEhem) increased by 200 cal/gm or 49.0 kcal/mole, a value whichsuggests an immediate derivation from the decrease in AHf of the explosive.The change in composition of the product mixture can be considered toresult from a shift to the right of the equilibrium reaction

4HF+8C0 F4+ 3002 + C + 2H2 0. (2)

Such a shift would be expected to be associated with the decrease intemperature, although it would be opposed by the decrease in pressure.

12. When the computations using the two sets of equation-of-stateparameters are compared (both for A o = -50 kcal/mole), it is seen thatwith the RDX-type parameters the detonation velocity is 5.4 higher, theCJ pressure is 5.2% higher, and the CJ temperature is 6.2% lower. Thedifference in AEchem is negligible (0.16%). The difference in chemicalcomposition of the product mixture can again be described as a righthandshift in Equation 2 (for a change from TNT-type parameters to ADX-typeparameters), with the increase in pressure and decrease in temperature nowacting in the same direction.

4CONFIDNIAL

CONFIDENTIALNom 65-217

13. RUBY computations were carried out for a series of fluorinated RDX's.The results are given in Table 6 for 0,1,2, and 4 fluorine atoms per molecule.The program wald not converge for the trifluoro-DX's. The detonationvelocities, CJ pressures, and chemical energies are plotted in Figures 4, 5,and 6, respectively, the points for the difluoro and tetrafluoro compoundsbeing plotted for the more probable higher densities (see paragraph 8).

14. It can be seen from the graphs that as the numLar of fluorine atoms permolecule increases, tle detonation velocity increases, the CJ pressureincreases, and the detonation energy (-AEchem) decreases. Although theAEchem (Figure 6) seems to be strictly monotonic, the D and Pj curves(Figures 4 and 5) have humps at the two-fluorine-atom position. However,the estimated density of the difluoro-RDX is likely a few tenths of apercent too high, and a correction of this magnitude would smooth out theD and Pi curves. For the disubstituted and tetrasubstituted compounds, thedifferences between isomers are presented to RUBY simply as differences inheat of formation. Accordingly, the c-nsequent differences in computedresults are analogous to those discussed in paragraph 11.

15. Computed detonation parameters for fluorinated TNB, tetryl, TNT, TNBTF,and DATB are given in Tables 7-10, along with values computed for theunfluorinated materials for comparison. (See Figures 7-9 for plots of TNBresults.) Since it was not clear which set of equation-of-state parameterswas applicable in each case, computations were carried out using both sets,and both are listed in the tables.

16. Table 11 gives the ..esults of computa ions suggested by Dr. J. M. Rosenof this Laborptory. for FD 3P, FTNM, and mixtures of the two. As predicted byRosen (Ref. 12) the maximum dotonation energy is computed for a mixturecontaining approximately 50.3% FDNP, which is balanced for complete reactionto H20, C02, CF2, and N2 . The Pj maximum is at about the same composition,while the mixture with maximm detonation velocity seems to contain a littlemore FDNP.

COMPARISON WITH OTHER VALUES

17. Experimentally determined detonation velocities for several of thecompounds treated here have been repoi-ted by other workers (Refs. 1, 13, )4).These values are given in Table 12, along with values computed by Amcel usingRUBY (Ref. 14), and NOL RUBY results. The same information is presentedgraphically for DFTNB, MFTNB, and TNBTF in Figures 10, 11, and 12.

18. For MFMB, DI . and TFffB, computations were carried out at the sameloading densities (Poi at which experimental detonation velocities had beenreported by Schmidt-Collerus et al of the Denver Research Institute (Ref. 1).The RDX parameters were used for this comparison because, as seen in theTable, they seemed to give results that were closer to the experimentalvalues.

5CONFIDENTIJL

CONFIDENTIALNOIR 65-217

19. For NB at 0 = 1.512, 1.615, and 1.802 gm/cc, the deviations of theNOL computed valuee from the DRI experimental values are +0.14%, -1.6%, andq0.17%. Deviation from the Picatinny value (Ref. 23) at p = 1.80 is +4.8%.If the value computed at NOL for p0 = 1.8383 (RDX parameters) is comparedwith the experimental value reported by Amcel for po = 1.83, the deviationis +0.026%.

20. For DFM the deviations from the DRI experimental values are not quiteas good. For p0 = 1.695, 1.768, and 1.841, the deviations are -3.7%, -3.5%,and -3.0%, respectively. The deviation from the Picatinny value at p0 = 1.84is -0.94%. The deviation of the NOL computed value at po = 1.8564(RDX parameters) from the Amcel experimental value at p = 1.855 is -2.1%.It should be noted that the NOL-estimated heat of formation of DYTNB is100% greater than that found by Amcel. If the Amcel value is correct, thiswould account for the relatively large deviations for this compound, recallingthat for MM a similar difference in the heat of formation used for inputproduced a 2.1% decrease in the computed value of D (using RDX parameters).

21. For TFMIB at p0 = 1.964, the deviation from the DRI experimental valueis +1.3%. Literature values for TNBTF, MFTNBTF, and DFTNBTF are listed inthe Table, but NOL computations were not carried out at densities appropriatefor comparison.

22. In the Amcel comprtations (results listed in Table 12) the older valuesof the equation of state parameters were used, and the carbon formed in thereaction was assumed incompressible. The resulting computed detonationproperties may be useful for intercomparison of certain compounds, whetheror not they are considered valid predictions of absolute values. Since theAmcel and NOL RUBY comput ations are based on different assumptions, theresults necessarily disagree.

CONCLUSIONS

23. According to the computed results presented in this report, fluorinationof C-H-N-O explosives promises improved performance in applicationswhere alatively high detonation velocities and pressures are desirable buthigh energy is not "equlred. (This is not consistent with the high energyoutputs referred to in Ref. 1.) The RUBY computations for progressivelyfluorinated RDX, TRY, cmd DATB all show an increase in detonation velocityand Chapman-Jouguet pressure as the number of F atoms in the molecule isincreased, with an aee-:irpnying decrease in the detonation energy (assumingeach compound is at crystal density). For tetryl and TNBTF, the computationsshow an increase ir F. azd D when RDX-type parameters are used, althoughwhen TNT-type parawm.tes are used the computed values of these propertiesdecrease on addition of the first F atom, with subsequent increase onadditional fluorination. This suggests that the RDX-type parameters givethe more valid results for these two series of compounds. The computationsfor the fluorinated TfBts show an irregular effect on Pj and D of progressivefluorination, but this nay actually result from the difficulty of estimatingheats of formation and densities. The computed -AEchem for the fluorinatedTNB's shows the "usual steady decrease.

6CONFIDENTIAL


24. The contract under which the present work was carried out (seeparagraph 1) suggests that the most promising materials might be thosewith a stoichiometric balance to HF. If the results for the fluorinatedRDX's (Figures 4-6) are examined from this standpoint, an apparent changein slope can be observed near the HF balance point. (3 fluorine atoms inthe molecule). This feature of the RDX curves, however, can be explainedwith equal validity as being related to the HF balance or as resulting fromerrors in the estimates of densities and heats of formation. The ranges offluorination of the other series of compounds treate did not include theHF balance point.

7CONFIDENTIAL

NOLTR 65-217

REFERENCES

1. Josef J. Schmidt-Collerus, John A. Young, John A. Drimmel, et al,(Denver Research Institute), Research on Fluoroexplosives ReportATL-TDR-64-45 Contract No. AF 08(635)-2109. Directorate of ArmamentDevelopment, Det 4, Research and Technology Division, Air Force SystemsCommand, Eglin Air Force Base, Florida, July 1964.

2. Howard B. Levine and Robert E. Sharples, Operator's Manual for RUBY.Report UCRL 6815, University of California, Ernest 0. Lawrence RadiationLaboratory, Livermore, California, March 20, 1962.

3. H. Hurwitz, Calculation of Detonation Parameters with the RUBY Code,NOITR 63-205. U. S. Naval Ordnance Laboratory, White Oak, Silver Spring,Maryland, March 31, 1965.

4. Donna Price and I1rold Hurwitz, RUBY Code Calculation of DetonationProperties I. C-H-N-O Systems, NOLTR 63-216. U. S. Naval OrdnanceLaboratory, Silver Spring, Maryland, November 1, 1963.

5. Charles L, Mader, vetonation Properties of Condensed Explosive ComputedUsing the Becker-Kistiakovsky-Wilson Equation of State. Report IA-2900.Los Alamos Scientific Laboratory of the University of California, LosAlamos, New Mexico. Written February 19, 1963. Distributed July 17, 1963.

6. R. D. Cowan and W. Fickett, Calculation of the Detonation Properties ofSolid Explosives with the Kistiakowsky-Wilson Equation of State. J. Chem.Phys. 24, 932 (1956).

7. JANAF Thermochemical Tables, as Suuplemented, 1962. (Walter H. Jones,Chairman, JANAF Thermochemical Panel) Dow Chemical Company, Midland, Mich.

8. Charles L. Mader, Detonation Performance Calculations Using theKistiakowsky-Wilson Equstion of State. Report IA-2613. Los Alamos ScientificLaboratory of the University of California, Los Alamos, New Mexico. WrittenJanuary 1961. Distributed October 9, 1961.

9. Keith J. Laidler, A System of Molecular Thermochemistry for Organic Gasesand Liquids. Can. J. Chem. 34, 626-48 (1956).

10. G. Richard andrick, Heats of Combustion of Organic Compounds, I&E Chem.48 1366 (1956).

11. Attila E. Pavlath and Amos J. Leffler, Aromatic Fluorine Compounds. ACSMonograph No. 155. (Reinhold Publ. Co., New York, 1962).

12. J. M. Rosen Private Comnication, U. S. Naval Ordnance Laboratory,White Oak, Maryland.

8

REFERENCES

13. Picatinny Arsenal Monthly Progress Report No. 1, MIPR PG-3-201 November 1963. (Cited in Reference 1).

14. Fred M. Hudson and Staff (Amcel Propulsion Company), Evaluation of NewExplosive Mixtures. Technical Report No. ATL-TDR-64-12, Contract No. AF 08(635)-3650. Directorate of Armament Development, Det. 4, Research andTechnology Division, Air Force Systems Ccmmand, Eglin Air Force Base,Florida, October 1964.

15. W. D. Good, D. W. Scott, and Guy Waddington, Combustion Calorimetry ofOrganic Fluorine Compounds by a Rotating Bomb Method. J. Phys. Chem. 60,lO8O (1956).

16. F. D. Rossini, et al, Selected Values of Properties of Hydrocarbons.

Circular of the Natl. Bureau of Standards C-461. November 1947.

17. W. D. Good, et al, Combustion Calorimetry of Or[,anic Fluorine Compounds.The Heats of Combustion and Formation of the Difluorobenzenes, 4-Fluorotoluene,and m-Trifluorotoluic Acid. Z. Phys. Chem. 66, 1529 (1962).

18. W. D. Good, et al, Thermochemistry and Vapor Pressure of Aliphatic

Fluorocarbons. A Comparison of the C-F and C-H Thermochemical Bond Energies.

J. Phys. Chem. 63, 1133 (1959).

9

CONFIDENiTIAL

NoILrR 65-21T

TABLE 1. DEFINRPION OF NAMES USED FOR CHEMICAL COtAPOUMD

TNB Trinitrobenzene

02N 0O2 C6H3N306

MW = 213.11.

MFTUBMonofluorotrinitrobenzene

02N1 NO2 C6H2 306F

Q F MW = 231.10NO2

DFM Difluorotrinitrobenzene

02N][: _N02 C6113 0F 2

FK< F mw = 2419.09NO2

TFTNB Trifluorotrinitrobenzene

F

021N NO2 CeN306F3

F 0 F MW -267.08

NO2TNBTF Trinitrobenzotrifluoride

CF302N NO 102 C7i2N30F 3

MW = 281.l11NO2

MFTUBTFMonofluorotrinitrobenzotrifluoride

02NOr}N02 C7 HN3 6 F

F ~ MW -299.10

NO2DFTNBTF Difluorotrinitrobenvotrifluoride

00 N2 C7 N 3 06 5

N02 M~W = 317.09

10CONMXEINTIAL

NomL~ 65-217

TABLE 1 Contd

TNT Trinitrotoluene

02N0 NO2 7"5 s 3O6

W= 227. 13NO2

IFTNT Mono? luorotrinitrotoluene

ON H NO 2 C.THN 3O6

iF MW =2I5-12

DFI'NT N0ifluorotrinitrotolueneCH3

0O NO2 C71 3 3 % 2MW =263.12

NO2DATB Disnmintrinitrobenzene

02N C6 5N506

NO2 MW = 2143.141

FDATB FluorodieminotrinitrobenzeneFO2 N.<AK ~%%N C6 J 506F

MW = 261.13NO

2

RDX H 1,3, 5-Trinitrohexahydro-.s -triazinec 2 (or Cyclotrimethylenetrinitramine)

02 N-N-. '-N-NO2 C 3 H6 606

"2 14!2 M = 222.12

NO2

CONFIDENTIlAL

F CO~1NFIiTIAIJ

IIOLTR 65-217

CIL4 Table 1 Contd

MFRDX 021! -11 "fro2 2-Fluoro-1, 3, 5-trinitrohexahydro-s-triazine

*2c" TI 01v C3 5116 O6 F

Nf.- = 24o1i.*

22DFRDX 2,2-Difluoro-1, 3, 5-triniLtrohexahydro-s-triazine

02 N-PNOp C3H4N 606F2

H2C~N I-'C2 MW = 258.10

NO224~DFRDX 2,4-Difluoro-1, 3, 5-trinitrohexahydro-

CH2 s-triazine

02 "w" NO 2 C 3 HN 6O6 F 2Hj' r-"I'- MW = 258.10

11O2

224TFRDx 2,2,4i-Trifluoro-1, 3,5-trinitrohexahydro-CE2 s-triazine

021 0 3 3P6o?3F11 r MW =276.09

INO2

246TFRDX 2,4,6-Trifluoro-1, 3, 5-trinitrohexahydro-s-triazine

2N -N02 C 3 H 3N6 6 3H, I MW= 76o

F IN-N,-'2MW 2b9

NO 22244TriDx 2,2,4I,4-Tetrafluoro-1, 3, 5-trinitrohexahydro-

s-triazineCH,

0pI "j I ~ u C3H2N6O6F4

V2 N,, L2W = 294. o8

12CONTFI DM!TIAL

CONFIDENTIALNOLTiR 65-217

Table 1 Contd

2246TTFRDx 2,2.4,6-Tetrafluoro-l, 3,5-trinitrohexahydro-

H Fs-triazine

Oi 2 1 -- , N0 2 C 3 H2N6O6 F4

MW = 2941.o8

/2

10

Tetryl TrinitrphenylmethylnitramineHI3 C-N-N02 C7 H 5N508

0 O MW = 287.15

NO0

MET MonoluorotrinitrophenylnmthylnitraianeH-DC-N-NO2.

ol 11% C 7 H4N 508F

0 F MW =3O5.14NO 2

DET Difluorotrinitrophenylmthylnitranine

H3 C~-NO02 C7H3N508F2

02N1 1102 MW = 323.13

FO FN102

TFNA CF71,1, l-Trif'laoro-3, 5, 5-trinitro-3-azahexane1 3

N-NO2 C..NO-F 3

CH 111 = 276.13

NO 2

CH 3

13CONFID12TIAI.

CONFIDENTIAL

iNoLRm 65-217

Table 1 Contd

TFE(A H-N-NO 2 Trifluoroethyl nitramine

C 2 FV3 C2113N2 02F3

mw= 144.05

FDNP F FluorodiLnitropropane

02N-C..NO2 C3H5N1204FCH2

1 MW = 152-05C"3

FMF Fluorotrinitromthane

02N-C-N0 2 cN 306F

NO2 4W =169.-03

CONFIDENTIAL

CONFIDENTIALNom 65-217

TABLE 2.* ESTIMATED HMTS OF FORMATION

tAHf AHfHE (Kcal/mole) HE (Kcal/mole)

-58 MBDX -26

DF B -103 22DFRDX -76

TFTNB -148 24DFRDX -66

TNBF -171 224TFRDX -U6

MFTNBTF -216 246TFRDX -io6

DFInBF -262 2244TMMDX -166

M-64 2246TTFRDX -156

DFIT -109 MFT -42

FDATB -76 DFT -87

15CONFIDENTIAL

CONFIDEMIALNoiL 65-217

TABLE 3. DENSITIES OF EXPLOSIVE MATERIALS USED ORRUBY CALCULATIONS

HE (gm/cc) Reference

.'FTUB 1.8383 1DPNB 1.856 1

TNB1.9477 1TNTF 1.9 Estimated

MMBTF 2.0 Estimated

DFTIBTF 2.1 Estimated

METwT 1.79 Estimated

DPTWT 1.88 Estimated

FDATB 1.97 Estimated

MFRDX 1.90,1.87 Estimated22DFRDX 2.00,1.94 Estimated

24DFRDX 2.00,1.94 Estimated224TFRDX 2.09,2.00 Estimated

246TFRDX 2.09,2.00 Estimated

2244TTFRDX 2.17,2.05 Estimated2246TTFRDX 2.17,2.05 Estimated

1.84 EstimatedDMv 1.92 Estimated

TFN2A 1.6925TFENA 1.523 5FDNF 1.35 12

FTNM 1.586 12

16CONFIDENTIAL


TABLE 4 COVOLUMES (k,) USED IN THE RUBY COMPUTATIONS

Species (cc/nole) Species (cc/le) Species (cc/iole)

CF2 1330 002 6o0 N2 380

CF3 1330 COF2 1300 N20 &O0

IF4 1330 F 108 NH3 476

CH2F2 1330 F2 387 NO 386

CH3F 1920 H 76 No2 6oo

CH4 528 H2 180 0 120

3 1920 H20 250 02 350

00 390 1.F 389 OH 413

17CONFIDENTIAL

CONFIDENTIALNOIT 65-217

TABLE 5. COMPUTED DETONATION PROPERTIES FOR MFTNT, USINGDIFFERENT AOf's AND EQUATION-OF-STATE PARMMERS

Property Units

(Parameter Type) TNT TNT TNT RDX RDX RDX

Of kca1/mole -50 -75 -1O0 -50 -75 -100

PO gms/cc 1.80 1.80 1.80 1.80 1.80 1.80D .=A/psec 7.292 7.186 7.079 7.668 7.588 7.510

pi megb 0.2465 0.2366 0.2266 0.2592 0.2500 o.241o

Tj OK 2818. 2593. 2367. 2643. 2413. 2182.pi gMs/cc 2.425 2.414 2.404 2.384 2,372 2.360

y 2.882 2.930 2.981 3.083 3.146 3.212

Ej-Eo cal/gm HE 421.7 399.7 377.8 421.5 400.4 379.9AEchem cal/gm HE -1265. -166. -1o65. -1267. -1167. -lO66.SS o 0cal /OK/gm/iEO.05853 0.01639 -0.02947 0.06576 0.02199 -0.02596

compo- cF2 i0 - .!oles/sition gm E * * * * * *

of CF , , , * , ,Product 341xture CF4 0.9379 0.9544 0.9698 0.9651 0.9805 0.9936

CH2F2 * . * * * ,H3 F * * * * * .

cm4 * * * * * *

CHF 3 * . . .

CO 0.3960 0.2422 0.1340 0.2488 o.1434 o.o62oCo2 8.045 8.105 8.143 8.090 8.132 8.154COF 2 * * . . *F * * * * * *

F2 * * * *H * * * * * *

H2 * * * * * *

H20 7.991 8.025 8.057 8.049 8.080 8.106

HF 0.3272 0.2616 0.2004 0.2186 0.1574 0.1050N2 6.118 6.118 6.119 6.119 6.119 6.119

N20 * , * * * ,NH3 *.* **,

NO* * * *

0* * * * * *02*.* * ,OH*** ***

C(graphite) 19.18 19.26 19.31 19.25 19.31 19.35

moles as 103 moles/gmHE 23.82 23.71 23.62 23.69 23.60 23.54

vg cc/mole 14.18 14.29 14.39 14.58 14.70 14.81vs cc/mole 3.892 3.913 3.936 3.847 3.864 3.881

*Mole fraction in gas mixture less than 10-4.

18OONFID 31IAL

COThIDMNIkLNoLTR 65-217

g o o coc

*cgiOD0 11cv~~ In CA0 ci C\ 0 00 0 O5 s-CV

o 0o

0 Hr 0' C\,UG\1 *1 -* 3*

8*2* 0 \ 0

' I CU~0 0Ji. C\ o '.0 cr1 m'. H- 0 66 -

CVJ entsH HP 0. (r1 0 '

'.0 IIn-A 10 ooCU'! *'C6 ~ 0. 0A CI r. I. ms 51Cr1

0 CJ1 '.0 C\0r H 0 OC mr

0 H

.6 m :'s Q- Is I I !'.e OCUj co t- co1 mr

0, co 031'u I 1 . 0 H cH cu

'R CU

0 \.R u

n 4cUo (5OcUlcm r\ 1 H OC- m-

0) C-J cn a sc

* , H C U M - H

'.a 0~ \t M3 ~84 _: * * * I* . 00

H . . l0 Cr1j ntf

\00

5~ CA >)Lr+ H c6 > ' )0I

~R N

~ ~~-~3) i

Cs2 .0

.191

COMIT~IAL

CONFIDMIALNOLTR 65-217

TABLE 7. CO%,MTED DETONATION PROPERTIES FOR FLUORI21ATED TNB's

Property Units TNB MFTNB DFTB TFTNB I .-'NB DFTNB TPTNB

(1,arameter Type) RDX RDX RDX RDX TNT TNT T

AHf kcal/mole -11.40 -58. -103. -148. -58. -103. -148.

00 grs/cc 1.688 1.8383 1.8564 1.9477 1.8383 1.8564 1.9477D m/psec 7.371 7.657 7.459 7.541 7-242 7.009 6.982

Pimogb 0.2299 0.2647 0.2525 0.2640 0.2500 0.2365 0.2418

TI °K 2990. 2703. 2625. 2423. 2914. 2862 2723.pj gms/cc 2.253 2.437 2.457 2.557 2 482 2.506 2.613

y 2.989 3.071 3.090 3.196 2.856 2.856 2.926

Ej-E° cal/gm HE 408.1 422.7 397.5 385,9 421.5 394.9 377.8

AEchem cal/gm HE -1340. -1261. -1188. -1125. -3257. -1184. -1122.Sj-So Cal/°K/gm HE o.i464 0.07526 0.05387 0.0423 0.06991 0.05091 0.00652

Compo- 'F2 10-3mole/gm HE - * * * * * *sition CF . ,,of 3

Product CF4 - 1.050 1.987 2.808 1.030 1.970 2.808Mixture c2F2 - , , _ * , .

CHF - * * _ , * .

CH4 * , * - * , .

H- * * - . *

CO 1.005 0.2629 0.1865 0.06090 o46o9 0.3702 0.1847CO2 1o.o6 10.72 10.97 11.20 10.64 10.89 11..4COF2 - * * * * , *F - * * * * * *

F2 - * * * * * *H - * * - * * -

H2 * * . * *

120 7.036 4.264 1.966 - ".... 1.932

Hr - 0.1257 0.08100 - 0.2069 o.1476 -

1N2 7.038 6.49o 6.022 5.616 6.490 6.021 5.616

N20 - * * * * * *

NH3 * * * _ * * -

NO - * * * * * *NO2 * * * * , ,

0 - * * * * * *

02 * * , , ,

OH - * * - * * -

C(graphite) 17.09 13.93 10.95 8.394 13.83 10.85 8.332

moles gas 10-3moles/tp 12 25.14 22.91 21.21 19.69 23.05 21.34 19.49

Vj cc/mole 14.97 15.58 17.19 18.23 15.15 16.To 17.73

Vs cc/mole 3.953 3.833 3.866 3.824 3.886 3.925 3.902

*I,1le fraction in gas mixture less than 10-

0ONFIDMTXAL


TABLE 8. COMPUTED DETONATION PROPERTIE& FOR FLUORINATED TETRYLS

Property Units Tetryl MFT DET MBT DFT

Parameter Type) RDX RDX RDX TNT TNT

Aaf kcal/mLe +4.67 -42. -87. -42. -87.

Po gms/cc 1.73 1.84 1.92 1.84 1.92D mm/Psec 7.817 8.031 8.129 7.596 7.599Pi megb 0.2644 0.2927 0.3065 0.2765 0.2852

Tj OK 2971. 2734. 2543. 2964. 2831.

Pi gms/cc 2.307 2.442 2.532 2.488 2.585Y 2.999 ).055 3.139 2.839 2.887

Ej-20 cal/gm HE 456.7 468.8 460.9 467.8 456.7

AEchem cal/gm HE -1422. -1355. -1295. -1351. -1292.

Si-So ca!/OK/gm HE +0.07156 +0.02059 -0.01841 +0.01466 -0.01905

Compo- CF2 10 3 moles/gm HE - * * * *sition C

of CF - * * * *

Product CF4 - 0.7902 1.536 0.7684 1.520Mixture 2F2 _ ,

CH 3F - , , , ,

CH4 * * * * *

CHF3 - * . .

CO 0.7063 0.2461 0.09655 0.4537 0.2502

C02 9.225 9.738 10.02 9.657 9.961COF2 - * , , ,F - * * * *

F2 " * * * *

H - * * * *

H20 8.705 6.496 4.619 6.449 4.585HF - 0.1157 0.04515 0.2028 0.1104N2 8.706 8.193 7.737 8.191 7.736N20 - . * . .

NH3 * * * ,NO - * * * *NO2 - * * . .

0 - * * * *02 - * * . .

OH * * * *

C(graphite) 14.45 12.17 10.01 12.06 9.932

Z moles gas lO 3 moles/gm HE 27.34 25.58 24.06 25.'13 24.16

Vg cc/mole 13.82 14.22 14.87 13.84 14.45

Vs cc/mole 3.846 3.760 3.7,8 3.811 3.783

*Mole fraction in gas mixture less than 10 -4

21CONFIDENTIAL

CONFIDEnTIALNOLTR 65-217

TABLE 9. COMFTED DSTOATI{O PROPERTISS FOR FLUORINATED TNT's AND DATB

Property Units TNT M'INT DFTNB MFIWT DFTT DATB FDATB FDATB

(Paramter Type) TNT TNT TNT RDX RDX TNT TNT RDXAHf kca/mole -17.81 -64. -109. -64. -109. -29.23 -76. -76.0o grs/cc 1.651 1.79 1.88 1.79 1.88 1.837 1.97 1.97D =/psec 7.000 7.204 7.208 7.586 7.695 7.661 7.823 8.498P0 megb 0.2071 0.233 0.2466 O.25:1 C.2644 0.2679 0.2953 0.3256Tj 2884. 2704. 2568. 2529. 2339. 2373. 2151. 1843.P s/c 2.219 2.408 2.515 2.367 2.466 2.444 2.609 2.555Y 2.907 2.898 2.961 3.104 3.210 3.025 3.082 3.370

• cal/gm 1E 383.7 408.1 395.7 408.2 399.2 432.9 438.8 451.9MAchem cal/a HE -1280. -1209. -n44. -1211. -1146. -1165. -1096. -i096.Sj-s o cal/K/gm HE +0.09679 +0.03903 -0.00105 0.04574 0.O0085 -0.1204 -0.1789 -0.1904Compo- CF2 1o 3moles/gm ILI -, . , ,sition CF ,o f 3 - * 1 0 .9 6 9 4 *Product CF4 0.9419 1.862 0.9694 1.883 - 0.9507 0.9564

Mixt ure CM V 2 - , , , . , ,C H 3 F - * , . . . ,CH F3 * , . . * , ,

00 0.8523 0.3233 0.1582 o.19qi 0.o6625 0.1058 0.02596 0.003553C02 7.282 8.077 8.511 8.113 8.536 7.145 7.653 7.658COF2 - * * * * * *F - * * , , , ,

H2 - * * * * * *H - * * * * , ,

- * * * * -* *

H2 0 11.00 7.999 5.623 8.057 5.666 10.28 7.645 7.657HF - 0.3116 0.1515 0.2018 0.06982 - 0.02670 0.004118N2 r ,2 6.118 5.700 6.119 5.701 10.28 9.574 9.5741120 - * , * , , ,NH3 0.003797 * * * * * , ,NO . * * . - , ,HO2 * . * .* _ ,* ,0 - 4* * * ,* 4* ,

02 - * * *

OH - ,

C(graphite) 22.68 19.21 16.07 ___9.28 16.12 17.43 14 5 1436P moles gas O3 em/gm Hr 25.74 23.7 22.01 23.66 21.92 27., 25.&i 25.85cc e/mole 13 96 14 31 15 23 14 71 15 605 12 32 12.74 13 11

s cc/mole 4.028 3.913 3.NtI 3.866 3.R19 3.AI 3.731 364'

*Hole fraction in gas mixture lose than 10-4

OZ:FDR,*.YAL

CONFIDENTIAL

NOLTR 65-217

TABLE 10. COMPUTED DETONATION PROPETIES FOR RING-FLUORINATED TNBTF's

Property [ Units TNBTF MFTNBTF M TNBTF 'IBTF MFTNBTF DFTN]2F

Paremter Type) RDX RDX RDX TNT TNT TNT

AHf kcal/mole -171. -216. -261. -171. -216. -261.Po /cc 1.9 2.0 2.1 1.9 2.0 2.1

D =/sec 7.506 7.696 7.911 6.956 7.010 7.070

Pi meab 0.2507 0.2707 0.2931 0.2303 0.2425 0.2557

Tj OK 2115. 1909. 1699. 2372. 2233. 2094.Pi gms/cc 2.481 2.593 2.703 2.535 2.655 2.776

Y 3.271 3.375 3.485 2.992 3.052 3.104Ej-Eo Cal/gm HE 369.2 369.7 371.9 362.8 357.5 354.66Echem Cal/gm HE -1027. -979.4 -936.8 -1026. -979.0 -936.6s_ _ _ _ cal/OK/gm HE -0.04528 -0.09342 -0.1453 -0.04165 -0.08129 -0.1228

COmpO- CF2 1O-3mole/gm HE * * * * * *sition 3* * * * * *of

Product CF4 2.660 3.342 3 .9 12 2.646 3.337 3.942MixtureOH 2F2 * * * * -

CHF * * * * -

*K3 * .- . .*C 0.02367 0.004256 * 0.08013 0.03019 O.009924

C02 8.889 9.193 9.461 8.876 9.1.86 9.456COF 2 * * * . * *F * * * * * *

F2 * * * * * *H * * -* * -H2 * * -* * -

H20 3.542 1.670 - 3.511 1.659 -

HF 0.03o83 o.oo4286 o.08948 0.02495 -N2 5.336 5.015 4.731 5.336 5.015 4.73120* * * *

NH3 * . . _

NO * * * * * *NO2 * * * . . .

0 * * * * * *2* * * - * * *

OH * * -* * -C(graphite) 13.33 10.86 8.672 13.30 10.85 8.668

Z no1es gas zo-iles/gm HE 20.48 19.23 18.13 20.54 19.25 18.14V c/zmole 17.17 17.92 18.63 16.67 17.38 18.02

V6 c/oe 3.849 3.785 3.719 3.924 3.879 3.834

*MOle fraction in gas mixtre less than 10 "

23

C FID TIAL

CONFIDfaTIALoin 65-217

TABLE 11. CCMVTED DETONATZIC PROPERTIES FOR FIf-P/FTHM HMJ(Using RDX-Type Parameters)

Property Units FDP FrP/M-M FWP/FTM FMP/FW M55.0/45.0 50.3/49.7 45.0/55.0

AHf cal/gm -528.7 -390.1 -375.6 -359.3 .220.7AHT kcal/mole -80.4 - - - -37.3Po /cc 1.35 1.4469 1.4578 1.4703 1.56D MM/Asec 6.848 7.258 7.211 7.108 6.089Pi mgb 0.1809 0.216o 0.2165 0.2103 o.1116TT 0K 2817. 3417. 3614. 3414. 1289.Pi g/cc 1.890 2.019 2.041 2.051 2.089y 2.500 2.528 2.501 2.532 3.152Ej-Eo cal/gm HE 457.5 505.7 506.9 484.0 257.1AEchem cal/gm HE -1253. -1455. -1508. -1409. -531.7S_-S_ _cal/°K/gm HE -0.02247 +0.05126 +O.O4768 +0.o2622 -0.3784

Compo- CF2 103moles/gm HE * * * * .sition co CF * * * * *

Product CF4 0.8976 1.129 1.084 1.122 1.479Mixture CH2F2 * . . . .

CH? * . . . -

3CHF3 * . . . -

Co 1.115 2.480 0.2557 0.02987 *

C02 5.128 9.901 11.52 10.98 4.437COF2 * * . . .F 0.003654 0.01543 0.08283 0.1190 *F2 * * 0.005129 0.01535 *H * * * *

H2 0.008791 0.007511 * *1120 14.93 8.153 7.359 6.610 -

RF 2.981 1.743 1.816 1.573 -N2 6.572 7.605 7.664 7.587 8.635

N20 * * 0.008053 0.03166 *NH3 0.005459 0.004899 * *

NO * 0.003636 0.08568 0.3190 0.003748NO2 * * 0.006171 0.1230 0.47100 * * * * *

02 * * 0.05269 1.082 12.84OH * . . .C(graphite) 12.58 0. 0. 0. 0.

E moles gas lO'3moles/gm HE 31.64 31.05 29.94 29.59 27.87

Vg cc/mole 15.08 15.95 16.36 16.48 17.18Vs cc/mole 4.128 4.021 4.029 4.042 4.228

*Mole fraction in gas mixture less than 10- 4

24COFIDENTIAL

CONFIDETIAL

NOJER 65-217

TABLE 12. LITERATURE VALUES FOR DETONATION VELOCITIES

9OL (Calculated) Literature

Po arH D[RDX/TNT3 J D

HE (gm/cc) (Kcal/mole) (mlu/sec) Ref. (Kcal/mole) (nm/Psec)

DFIB 1.695 -103. 6.924 a 7.190

1.768 -103. 7.155 a 7.4151.841 -103. 7.404 a 7.636

1.855(extrap) a 7.750

1.84 b 7.4741.855 c(Expt) 7.618

1.873 c(Calc) -51.3 7.6181.8564 -103. 7.459/7.009

DMMIT BTF 1.937 c(Calc) (sic)225.0 6.799

2.1 -261. 7.911/7.070

MFMB 1.512 -58. 6.659 a 6.650

1.615 -58. 6.936 a 7.0501.802 -58. 7.526 a 7.5151.80 b 7.1821.83 c(Expt) 7.655

1.802 c(Calc) -47.1 7.7661.8383 -58. 7.657/7.242

MFTffBJF 1.887 c(Calc) -184.2 7.050

2.0 -216. 7.696/7.010

TF M 1.964 -148. 7.603 a 7.5021.920 c(Calc) -135.1 7.0851.9477 -148. 7.541/6.982

TNHPF 1.82 a 7.1701.82 b 6.919

1.805 c(Expt) 7.1851.816 c(Cac) -142.2 7.249

1.9 -171. 7.506/6.956

References:a. Denver Research Institute (Ref. 1)b. Picatinny Arsenal (Ref. 13)c. Amcel Propulsion Company (Ref. 14)

250CFIDEDIAL


LU

0'

0

-10A

z

0

02

-J-

O &nw w

LL-J

<~I w c. (9z

ui uj o

LA LA

LoC) CD

ci C0

LUUJ~/vvq a

26~

CONFIEN-IA

CON FIDENT IALNOLTR 65-217

LU

ol

0'0

0

D

U-i-i

0 0

z

zI-

w we

0-

-n

LU W I--0- CL-

x 0

0 z u-

0

o0 0n 00

(203W) rd

27CONFIDENTIAL


______ _____

uiC>-

u-i

0'0

0

ui

0 0

z>V-.

ozI--u-i

-J 0

10

w u-iZ- D

L to

4) 04(yqC/,V:) wao3 V

28~

CONFIENTIA


2246TTFRDX2244TTFRDX*

9.20

A 24DFRDX9.10-

A 22DFRDX

LUZL

9.00-

A MFRDX

8.90-

8.80 RDX

0 1 23 4NUMBER OF F'S

FIG. 4 COMPUTED DETONATION VELOCITY VS. NUMBER OF FLUORINE ATOMSFOR FLUORINATED RDX'S

29CONFIDENTIAL


0.410 2246TTFRDX A

2244TTFRDX A

0.400

A 24DFRDX

0.390A 22DFRDX

0.380

0.370

0 MFRDX

0.360

0.350

RDX

0.340--0 1 t

0 3 4

NUMBER OF F'S

FIG. 5 COMPUTED CJ PRESSURE VS NUMBER OF FLUORINE ATOMS FOR FLUORINATED RDX'S

30CONFIDENTIAL


1500 4 RDX

A MFRDX

1400

A 24DFRDX

A22DFRDX

1300

0

u

E-

Lu

1200

1100

2246TTFRDXA

2244TTFRDXA

0000 1 2 34

NUMBER OF F'S

FIG. 6 COMPUTED CHEMICAL ENERGY VS. NUMBER OF FLUORINE ATOMS FOR FLUORINATED RDX'S

31CONFIDENTIAL

CONFIDENTIAL

NOLTR 65-217

7.8

A RDX-TYPE PARAMETERS

* TNT-TYPE PARAMETERS

A MFTNB

7.6-

ATFTNB

A DFTNB

U.1

. 7.4-

TNB

0 MFTNB

7.2

7.0- 0 DFTNB

o TFTNB

NUMBER OF F'S

FIG. 7 COMPUTED DETONATION VELOCITY VS. NUMBER OF FLUORINE ATOMSFOR FLUORINATED TNB'S

32CONFIDENTIAL

CONFIDENTIALNOLTP 65-217

0.27-

A RDX-TYPE PARAMETERS

* TNT-TYPE PARAMETERS

A MFTNBA TFTNB

0.26

ADFTNB

. 0.25 *MFTNB

a,.

®TFTNB

0.24-

0 DFTNB

TNB0.23 I

0 1 2 3NUMBER OF F'S

FIG. 8 COMPUTED CJ PRESSURE VS. NUMBER OF FLUORINE ATOMS FOR FLUORINATED TNB'S

33CONFIDENTIAL


1350

TNBA RDX- TYPE PARAMETERS

0 TNT - TYPE PARAMETERS

1300-

0 MFTNB•

" 1250-

Eu"

I-

1200

DFTNB

1150

O TFTNB

0 1 2 3

NUMBER OF F'S

FIG. 9 COMPUTED CHEMICAL ENERGY VS. NUMBER OF FLUORINE ATOMS FOR FLUORINATED TNBS

34CONFIDENTIAL


7.75 - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

7.50-

L

N.7.25-

A NOL CALC. (RDX PARAMS.)*NOL CALC (TNT PARAMS.)

7.00-U AMCEL CALC (OLD PARAMS.)

y DRI EXPTL.+ PICATINNY EXPTL.

)K AMCEL EPL

6.75- .

1 .70 1.75 1.80 1.85

P0 (GM/CC)

FIG. 10. DETONATION VELOCITIES FOR DFTNB, FROM NOL AND OTHER SOURCES

35CONFIDENTIAL

CONFIDENTIAL

NOLTR 65-217

7.75-

7.50'..

LU

:L

' 7.25-

¥+

7.00

A NOL CALC. (RDX PARAMS.)

0 NOL CALC. (TNT PARAMS.)*AMCEL CALC. (OLD PARAMS.)y'DRI EXPTL.

+ PICATINNY EXPTL.

6.75-~ AMCEL EXPTL.

1.50 1.60 .70 1.80

P, (GM/CC)

FIG. I]. DETONATION VELOCITIES FOR MFTNB, FROM NOL AND OTHER SOURCES

36CONFIDENTIAL

CONFIDENTIAL

NOLTR 65-217

8.0-

7.5 A

uj

7.0

+A

A NOL CALC. (RDX PARAMS.)* NOL CALC. (TNT PARAMS.)

6.5 - AMCEL CALC. (OLD PARAMS.)

'Y' DRI EXPTL.

+ PICATINNY EXPTL.

UJ AMCEL EXPTL.

6.041.80 1.85 1.90 1.95*

Po (G M/CC)

FIG. 12. DEIONATION VELOCITIES FOR TNBTF, FROM NOL AND OTHER SOURCES

37CONFI DENTIAL

ONFIDENTIAL

Norm 65-217

APPENDIX

ESTIMATION OF HEATS OF FORMATION (AHf)

Af (kcal/mole) F1eference

MFTNBC4HrF(A) -34.8 15

C6 6(1) +3.2 j6

(Fluoro-) -46.5 (Difference)

TNB(s) -11.4 4

MFTNB(B) -57.9 (Soum)

IYINBm-C6 HF 2(t) -79.64 17

c6H6(l) +11.72 16

(Difluoro-) -91.36 (Difference)

TNB(s) -1.4o 4

DFM (s) -102.76 (sum)

TFTNBm-C06 F2(l) -79.64 17

C6H5F(l) -34.8 15


DFTHB(s) -103.0

TF M (s) -148.o (sum)

TNDPTN(S) -11.4fo 14

C6H6(L) +1.7 16

(Trinitro) -23.12 (Difference)

C6H5CF3(L) -147.8 15

TNB(s) -170.9 (sum)

STB(s) -u.40 4

c6E6(l) +1.72 16

(Trinitro-) -23.12 (Difference)

m-FC6H1 CF3 (L) -193.2 18

MF~rP(s) -216.3 (sum)

38CONFIDENTIAL


APPENDIX Contd

AHf (kcal/mole) Reference

MFTNWBTF(s) -216.1 (Estimated)

TNBTF(s) -170.9 (Estimated)


MFTNBTF(s) -216.3

DFnINM(s) -261.7 (sum)

MFTNTTNT(s) -17.81 4C6H5CH3 (1) +2.867 16

(Trinitro-) -20.68 (Difference)

p-FC6HCH() .43.43 17

MFTNT(s) -64.11 (sum)

nmrMFNT(s) -64 (Estimated)FMB (s) -58 (Estimated)

(Methyl-) -6 (Difference)

DYM (s) -103 (Estimated)

DFTNT(s) -109 (sum)

FDATBC6115F(At) -.34.8 15C6H6(.) +11.7 16


DATB(s) -29.2 4FDATB(s) -75.7 (sum)

MFRDXRDX +14.71 4* -4o.4 (See Ref. 18)

MFRDX -25.7 (sum)

*Heats of formation of the fluorinated RDX's were estimated by using the

increments for substitution of a fluorine atom for a hydrogen atom inaliphatic hydrocarbons given by Good et al in reference 18. The incrementsvary with the number of other fluorines attached to the same carbon atom andare therefore listed separately in this table.

39CONFIDENTIAL

CONFIDENTIALNOInR 65-217

APPENDIX Contd


22DRXRDX +14.71 4

.-40.4 (See Ref. 18)

MFRDX -25.7 (Sum)

22DFRDXPDX +14.71 4* -90.4 (See Ref. 18)

22DFD -75.7 (sum)

24DFRDXRDX +14.71 4. 2(-40.4) (See Ref. 18)

24mFRDx -66.1 (sum)

224TmRDXRDX +14.71 4* -90.4 (See Ref. 18)

-4o.4

224m x -16.1 (Sum)

246,mDxRtDX +14.71 4* 3(-4o.4) (See Ref. 18)

246MFRDX -lO6.5 (sum)

2244T'FRDXRDx +14.71 4

* 2(-90.4) (See Ref. 18)

2244TTFRnX -166.1 (SAm)

2246TMDpX +14.71 4* -90.4 (See Ref. 18)

2246TF M -156.5 (sum)

40CONFIrMINTIAL

CONFIDENTIALNOm 65-217

APPENDIX Contd


C06 5F (1) -34.8 15

C6 H6 (M) +1.7 16

(Fluoro-) -46.5 (Difference)Tetryl(s) 44.7 4

mn(s) -41.8 (sum)DFT

m-C6H4F2(A) -79.6 17C6H6 (1) +11-7 16(Difluoro-) -91.3 (Difference)

Tetryl(s) +4.7 4

DFT(s) -86.6 (sum)

41

CONFIDMTIAL

UNC.ASIFIEDSecurity Classification

DOCUMENT CONTROL DATA- R&D(Security classification of title, body of abstract and indexing annotation must be entered when the overall report is classified)

ORIGINATING ' 'TIVI Y (Co.porate author) 2. RCFIORT SECURITY C LASSIFICATION

U. S. Naval Ordnance Laboratory ondentialWhite Oak, Silver Spring, Maryland I2b OUP

3 REPORT TITLE

Computation of Detonation Properties of Fluoroexplosives (u)

4 DESCRIPTIVE NOTES (Type of report and inclusive date&)

S AUTHOR(S) (Last name, first name, initial)

Hurwitz, Harold

6. REPORT DATE 7a TOTAL HO OF PAGES 7b NO OF RE S

10 June 1966 41. 188e CONTRACT OR GRANT NO 9a ORIGINATOR'S REIORT NUMBER(S)

b PAOJECT No. NOmPR 65-217

MIPR PG-3-9, Eglin AFB, Fla. Sb THER RPORT NO(S) (Any other numbero that may be assignad

d10 AV A IL ABILITY/LIMITATION NOTICES

In addition to security requirements, which apply to thf (bcument and mustbe met, each transmittal outside the agencies of the U.S. Covernnent musthnvp nrion. an.v1n l T [ SPNOINOIITRT-TV

II SUPPLEMENTARY NOTES 12 SPONSORING MILITARY ACTIVIT'

U. S. Air ForceEglin AFB, Fla.

13. ABSTRACT

The RUBY code has been used to compute detonation properties for a number offluorinated explosives. Results are given for fluorinatea I!B, RDX, tetryl,TNT, DATB, and trinitrobenzotrifluoride, and for fluorodinitroprcpane andfluorodinitromelhane, When necessary densities and heats of formition of theexplosives were estimated for input to RUBY.

D D ,FR0 1473 __ _ _ __ __ _

Security Classification

UICLMSSIIESecurity Classi.ication

14. LINK A LINK 8 LINK CKEY WORDS ROLE WT ROLE WT ROLE NT

DetonationFluoroexplosivesExplosivesRUBY

INSTRUCTIONS1. ORIGINATING ACTIVITY. Enter the name and address imposed by sccurity classification, using standard statementsof the contractor, subcontractor, grantee, Department of De- such as:fense activity or other organization (corporate author) issuing (1) "Qualified requesters may obtain copies 3f thisthe report. report from DDC."2a. REPORT SECUITY CLASSIFICATION: Enter the over- (2) "Foreign announcement and dissemination of thisall security classification of the report. Indicate whether"Restricted Data" is included. Marking is to be in accord- reiort by DDC is not authorized."ance with appropriate security regulations. (3) "U. S. Government agencies may obtain copies of

this report directly from DDC. Other qualified DDC2b. GROUP: Automatic downgrading is specified in DoD Di- users shall request throughrective 5200. 10 and Armed Forces Industrial Manual. Enterthe group number. Also, when applicable, show that optionalmarkings have been used for Group 3 and Group 4 as author- (4) "U. S. military agencies may obtain copies of thisized, report directly from DDC. Other qualified users

3. REPORT TITLE: Enter the complete report title in all shall request throughcapital letters. Tatles in all cases should be unclassified.If a meaningful title cannot be selected without classifica-tion, show title classification in all capitals in parenthesis (5) "All distribution of this report is controlled. Qual-immediately following the title. ified DDC users shall request through4. DESCRIPTIVE NOTES. If appropriate, enter the type of __report, e.g., interim, progress, summary, annual, or final. If the report has been furnished to the Office of TechnicalGive the inclusive dates when a specific reporting period is Services, Department of Commerce, for sale to the public, mdi-covered. cate this fact and enter the price, if known.S. AUTHIOR(S). Enter the name(s) of author(s) as shown on 11. SUPPLEMENTARY NOTES: Use for additional explana-or in the report. Enter last name, first name, middle initial, tory notes.If military, show rank and branch of service. The name ofthe principal author ib an ahsolute minimum requrement. 12. S _)NSORING MILITARY ACTIVITY. Enter the name of

the departmental project office or laboratory sponsoring (pay-6. REPORT DATE. Enter the date of the report as day. Ing for) the research and development. Include address.mcwi -ar or month, year. if wore than one date appearson the ie',ort, use date of publication. 13 ABSTRACT: Enter an abstract giving a brief and factual

summary of the document indicative of the report, even though7a. T3rAL NUMBER OF PAGES, The total page count it may also appear elsewhere in the body of the technical ro-should follow normal pagination proceditres, i.e., enter the port. If additional space is required, a continuation sheet shallnumber of pages containing information. be attached.7b. NUMBER OF REFERENCES Enter the total number of It is highly desirable that th., abstract of classified reportsreferences cited in the report. be unclassified. Each paragraph of the abstract shall end with8a CONTRACT OR GRANT NUMBER. If appropriate, enter an indiation of tie military security (,lassification of the in-the applicable number of the contract or grant under which tormation in the paragraph, represented as (TS). (5). (C), o, (U)the report was written. There is no limitation on the length of the abstract How-8b, 8c, & 8d. PROJECT NUMBER: Enter the appropriate ever. the suggested length is from 150 to 225 wordsmilitary dq'artment identification, such as project number,subproject number, system numbers, task number, etc. 14 KEY WORDS. Key words are technically meanngful terms

or short phrases that chaacterize a report and may be used as9a, ORIGINATOR'S REPORT NUMBER(S). Enter the offi- index entries for cataloging the report. Key words must becial report number by which the document will be identified selected so that no security classification is required Identi-and controlled by the originating activity. This number must fiers. such es -quipment model designation, trade name, militarybe unique to this report. project coe name, geographic location, may be used as key9b. OTIIER REPORT NUMBER(S). If the report has been words but vili be followed by an indication of technical con-assigned any other report numbers (either by th'ie originator text The assignment of links, roles, and weights is optionalor by the sponsor), also enter this number(s).

10. AVAILABILITY/LiMITATION NOTICES: Enter any lm-Rations on turther dissemination of the report, other than those

UNCLBBIFIXDSecurity Classification

I I '

00 0 0

1 4-, N 4, N 4

a 0 0 1-4H 0 rI.fi 0 F: ,

as 0 H 0 n sA1

to 0,0

~0 I0 4 P. A 4, P. a;4 0 > 0 . N V, 4 Io :1 41 dof 41 W)+)A rI9411

tH It It 0d0~- 4 a~ c044 .4 p 4" I..04-4.

o0~' 0 o) *H ID 0 0 0 ~.,-0 0r~~ U 0 - 4, I i0 U oi ~ 4

40- 1 0- -P r. 1. 9 0 4 o4 CLoP.q 14 H d ~ C 0 0. wi

0 P .4 04 0 0 3

IV %0 $.a4 Z,1 %1 .91 4 fI11 4-1 S-

.4003 *'o o-~ t4 40 ' oS 04C) . g4 00ri 4* 4 43

A4 H -I- d0'~P r-? H 43,

.4~~~~~ 0 o H 0t H 0 P. 0 0 I 00i 43 A *"0 q o t4. 0

at A H 0 43 v4o .4 HO' 10 4 t C

k4O'5 H , o 4- X 1asXHo 0

.a 0 0 Pk 1 , o 4 ZI4

0!o0 -1 HZO- .0.)dn H "N '5'

'OP.4 .4 PiO at I 0 0~O

r.4 N 3 P Ic 1or

at .90 O N+

HO r 0 -IH 4".s IU1%1%1I -. P.

a 0

* H .3 H4s

0- 0 4 ~~~~ 040 P

4314 P.42lo X

0.400 *.1

04 P,4.64345 d

.4 ~~~ ~ ~ 1 M-~ ~~uo-u I .435 0 43..40 04 F,' 43 0 .4 0 I

z , - s "1 43 0 0 1 '0 -406 :3 ~ r-4.C-% 4,> 4 1r41 3"4C) I m ,-

L.0dOC.4 d rHP.t4 00P03

~40O a 4 04

43 0 43 0~ '1a. 0 o H 0.4 0

.P 43 44 0 p~ 43 .'U4,

043 A2 ~ 'O 04

0C. . . I6 . ~ - . cc H 4

06 00 't5A I.. A V . * ' 0- 0 ' pk0L0 m r4 r0 30 "44d

n ,/5C - 1044 w 43 "04Cl. d m .. ,. - 0 4 L. c a *4 P

4)~ 40 rI toa o 4 Ht

0c It 0 > 0

r-4 #4 0 0

Z f'.H PoE-..oaJH 0 0. flE.L '03

- -P1

00 0 0 0

01209 0 ,-40 0~ 011 0 r

HD P*. H 11XO-~ 2 1. 1

-PH S4 o P0 H4W 4 H

K 004

04 1 404 40'1 I- :j M 0 k 3d -H c o~0 k'r -P 12 04 0 ' Ck 04H.0 4 0.- r231

o ~ 0 0 ~.4.,-4000 0 .4.O0 ~ ~ 4- --. -) T3 ~'.0 p g S: C)4. H: o~" 1 r. Ht - 0 0 -r.9

43, 043 It,0 0 :5

'00) k 4). "-q4 ~

43 10 1

~0 . 0 E-1 1 A 040.0404A I no~ Z.- 9 '43 AS ZH 40$4- 4 J..2'o

tao H 1 0t 1C44 ' r. 00 f 0 sodAHOr, 1 43 0.H 00 lo +IC' C4~'0

120 . .20 0 1 - 0 10 0 & >- 1 0 H O , v9-+ 40 .- 4ooo It' C4

0 rrAH4 0 0 0-P.~ 'A 000 4. 4>.a0.t G 1 o f IH -Hd "NH

IDS 0 ID 0 aHcH -iO H

r0 00 ~ .C.K -- --- - - - - -

I, VI ID 12r44., 04 43-i 4

HO 4H 0-' I ),'?

*4.1,4

0*H 0 Ic (I H H .014

0.

'41 0 V). 4d 21 0 X.4kS.) 4I 0 P-. 0 .4 C do4CI.3 ~ 0 4 - 43Sr- 0 4S r. P.2H 4 124 0 0' FH4...d0.-4*

Id * 00. 41O -.L 0 in 0 0 S.43 0 0.40 o C-. 1 03 H 0 (3 4. 5a.. H 0 0-t. Vr M.- E 2,

I A -. 0., 00 d 2 4X0.4 -0o 43 -79 % 3-to2 43 - 5

&-- 5: 0~ 4- 43d

LA. 4- I 12)c * -00 o.OP $4 04 00 * .0 X -i 0 4)64 oo 1.-4Ad0 43 0*~ 42343.d9

.DS..2~'...0 .4 F4'.* li 4. 00 4- 0.4-

09 Xf.,~ I -0 vO4A

.0 12 F/ 43 OC. 2-4 -o 12d'' 05. -P P12oor-. cd 25.)- 40 dA-4' so r-4 k

a 43 j0 .0o01 H v m 0--2 >-0 Lv 0CI00 0 04-.A-V..-I COOX -4'-4.-

(n2- 0.-I " 0 12 rO 2 . . 4 " V 2

40 I 0 d garI cc N 4

-H 2'H 0 0. 3 1- 4i' a -C 0

unclassified ad number - dtic6. the heats of formation (ah.) required for hypothetical explosive...

Documents