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1L162706 A553I 1 TITLE (include Security Clanil cation)Vapor Pressure of Methyiphosphonic Dichloride: A Compendium

12 PERSONAL AUTHOR(SBrozena, Anad Fielder, Donald

13aTYP OFREPRT 3b.TIMRVAED14. DAYR OF REPORT (Year, Month, Day) S. PAGE COUNT

AI AGS I'RACT (Contlnu, on rev.,se it necessary and Identify by block number)apor-pressure data for methyl phosphonic dichloride from many sources are reviewed and

analyzed to obtain a b:est-fit predictive Antoine equation. Also given are the heat ofvaporization and volatility at various temperatures.

SAMESRBTINVALBLIYO ABSTRC USER BSTRACTSI~U.iTY.C$*FlICATION

W~ UNCLASSI FIE D/UNLIMITED C3SM SRPT. s.j TICUSR22a NAME OF RESPONSIBLE INDIVIDUAL 22b .TEL9M"Q'EO Area C* 122c. OPFF1 .YNQ,

BRENDA C. ECKSTEIN ciUI)ýPS.-

DD FORM 1473, 84 MAR 83 APR edition may be used until #xhsu~e4. EUIYCASFCAINO HSPGAll other editions are obsolete SCRT JýIM sPG

PREFACP

The work described in this report was authorized underProlect lt162706A553, Deterrent Systems. This work was started inMay 1984 and completel August 1984. The experimental data are re-corded in laboratory notebook 83-0149.

The use of trade names or manufacturer's names in thisreport does not constitute endorsement of any commercial products.This report may not be cited for purposes of advertisement.

Reproduction of this document in whole or in part is pro-hibited except with permission of the Commander, U.S. Army ChemicalResearch and Development Center.,,ATTNo SMCCR-SPS-IR, AberdeenProving Ground, Maryland 21010-5423. However, the Defense Tech-nical Information Center and the National Technical InformationService are authorized to reproduce the document for U.S. Govern-ment purposes,

This report has been approved for release to the public.

Acknowledgment

Appreciation is extended to Audrey A. Steelman for hereditorial assistance and to Carmela V. Kaufman for her excellenttyping of the report.

NTIS G1{A&IDTIC TAB,

- Unannounooed f] - *s•bELECTE justi t

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... ... .... . ar /o -Diat, S..oial

A AV 1.1

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CONTENTS

Page

1. INTRODUCTION........................ ..... 7 ,

2. DATA SOURCE .7................... 7

3. EVALUATION OF DATAvoe*.,,..,. . ...... ..... .... . .. ... 7

4 DISCUSSION OF DATA 8... .. .. . 8

5. CONCLUSIONo s .............. e. .9

LITERATURE 13

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o'

VAPOR PRESSURE OF METHYLPHOSPHONIC DICHLORIDE:A COMPENDIUM

*1

1. INTRODUCTION

Vapor pressure data for the compound methylphosphonicdichloride (hereafter called d&c•'or) can be found in many sources,both open literature and unpub 1ied reports. This report attemptsto consolidate all available data, evaluate it, and develop a best-fit predictive Antoine equation for the combined data.

2. DATA SOURCE

SfZe ferfpublished an Antoine equation for dichlor in 1960.-However, no experimental gaa were given in the report. SeveralBritish technical reportsewwuontamned some experimental vapor-pressure ta for dichlor, and several Edgewood Arsenal contractorreports •--t'also contained vapor-pressure data for the compound.The data from these various sources ~,e combined into a set andevaluated, using Penski and Latour's method of computation.Zeffert's equation was used to calculate values for his experi-mental data and these values were used when all data were combinedinto a se

3. EVALUATION OP DATA

When the combined data were evaluated by Penski andLatour's method, an arbitrary limit of 10-percent difference betweenthe experimental and the calculated value was chosen as the criteriafor excluding a member from the set. Using this criteria, 10 membersof the set were deleted as being out of range. The final set con-tained 57 members of which 14 were calculated from Zeffert's equation.This set of values was then used to calculate the Antoine vapor-pressure equation of the form.

BloglOP - A -(C-- (1)

(c+t)

where

P - vapor pressure in torrt - temperature in degrees centigrade

A, 8, C w constants

The standard deviation, SD, was calculated for the Antoine equationusing the following equation:

; 1/2

S*S.D. - (2)7 n-1

7RI t V~Iv u S PA CK -"

1 I| 8LANK

where

' (log P log P 2s ~.10 calc 10 exp

The logarithmic values were used since it has been reported 1 2 thatthis procedure prevents excess weighting of the higher vapor-pres-sure data.

The constants derived for the Antoine equation were usedto calculate the heat of vaporization in kcal/mole and the volatilityin g/m 3 at various temperatures from the following respective equa-tions.:

AHvap 2.303 RB T) (3)

PMVolatility m (4)

76ORlT

where

B & C - Antoine equation constantst = temperature in degrees centigradeT w temperature in degrees KelvinP - vapor pressure in torrM - molecular weight in g/moleR w gas constint

- 1.987xgs -o kcal/g-mole6KR1 , gas constanta 82.05xl0- a&tm-m 3 /g-moleOK

4. DISCUSSION

"4 At the top of table 1 are shown the A, B, and C Antoineconstants, the standard deviation of the equation, and the calcula-ted boiling point. This table lists the experimental and calculated

IN vapor pressures and the percent difference between the two fordichlor at various temperatures. Table 2 contains the calculatedvolatility and heat of vaporization as a function of temperature.The figure shows a plot of the vapor pressure (torr) versus l/T KI

*" the line is calculated and the points are experimental. The dataare in good agreement considering that they are from many sources.Additionally, the boiling point calculated from this data compila-tvon closely agrees with that obtained by Hofmann 1 3 in 1873 (1650i versus 1630C).

8

Ir

5. CONCLUSION

Vapor-pressure data for dichlor from many sources hasbeen reviewed and analyzed to obtain a best-fit predictive Antoineequation. The data shows internal consistency and no large devia-tions.

Table 1. Experimental and Calculated Vapor Pressuresfor Dichlor

Antoine Constants

A - 7.51821B - 1831.49"C - 229.687

Standard Deviation 0.0103

Calculated Boiling Point 165.30C

Vapor Pressure (torr) PercentTemperature (*C) Experimental Calculated Difference

39 5.0 5.03 0.6547 8 7.92 -0.9750 9.3 9.33 0.3250 10.1 9.33 -7.6360 15.7 15.70 0.0060 15.5 15.70 1.2960.5 15 16.10 7.3362 18 17.35 -3.6264.5 18.5 19.62 6.0365 20 20.10 0.5070 25 25.52 2.0870 25.6 25.52 -0.3270 26.7 25.52 -4.4274 30 30.72 2.3880 40 40.20 0.5080 40.3 40.20 -0.2584.0 47.0 47.82 1.7585.5 50 50.98 1.9690 61.6 61.55 -0.0990 63.1 61.55 -2.4692.0 67.0 66.81 -0.2995 75 75.41 0.5599.0 88.0 88.32 0.37

100 91 91.83 0.91100 91.6 91.83 0.25100 92 91.83 -0.19102.5 100 101.11 1.11

,105.5 113.0 113.27 0.24

108 125 124.33 -0.54

9I,"

I*

k "~~ .~ 5

Table 1. (Continued)

Vapor Pressure (torr) PercentTemperature (*-C). Experimental Calculated Difference

110 133.0 133.82 0.61110 137.4 133.82 -2.61111.5 144.0 141.32 -1.86112.5 150 146.52 -2.32117.5 175 174.98 -0.01118.0 179.0 178.06 -0.52120 188.9 190.85 1.03120 192 190.85 -0.60121.5 200 200.94 0.47122 210.6 204.40 -2.94124.0 218.0 218.74 0.34128 250 249.94 -0.02130 262.9 266.88 1.51130 265 266.88 0.71132.0 282.0 284.75 0.98133 300 294.06 -1.98140 359.2 366.48 2.03142 400 389.68 -2.58150 500 494.91 -1.02150 482.4 494.91 2.59150 519.3 494.91 -4.70156 600 588.26 -1.96160 637.8 658.13 3.19162 700 695.52 -0.64165 750.5 754.83 0.58165 758 754.83 -0.42165.5 760 765.10 0.67167 768.8 796.61 3.62

10

Table 2. Calculated Volatility and Heat of Vaporizationat Selected Temperatures

Temperature Volatility Heat of Vaporization("C) (g/m*.) (kcallmole)

35.0 27.46 11.3640.0 36.30 11.3045.0 47.50 11.2450.0 61.53 11.1955.0 78.97 11.1460.0 100.44 11.0865.0 126.68 11.0470.0 158.50 10.9975.0 196.81 10.9480.0 242.60 10.9085.0 297.00 10.8690.0 361.21 10.8195.0 436.57 10.77

100.0 524.49 10.74105.0 626.54 10.70"110.0 744.38 10.66

"" 115.0 879.78 10.63120.0 1034.64 10.59125.0 1210.97 10.56130.0 1410.89 10.53135.0 1636.64 10.50140.0 1890.55 10.47145.0 2175.08 10.44150.0 2492.77 10.41155.0 2846.27 10.38160.0 3238.33 10.35165.0 3671.78 10.33

.ar

m,.

•4,t

,', 11

a.m

I:I": TEMPERAITURE DEGREES CENTIGRADEb 29.8 49.43 7,1.68 97.2 126.8 ,61 Ff

-A- -A i 0:0Co- .-4-

CO'-

U3- _WO livew. m - -m L., -

w

33L -0-3 0-9- z2sb -23 U

I-_ *j EIRCLTME 7 1A1-j JN RNCJRCr)- -Cr)

-0.33 -0.31 -b.29 -0.27 -0.25 -0.23MINUS RECIPROCAL TEMPERATURE( 1/K ) O"

Figure. Plot of Vapor Pressure of MethylphosphonicDichloride

12

p,

*%, ~* ;*: ¶ 4

*', ¶ \~ * P%% **** *. * " '~* **

LITERATURE CITED

1. Zeffert, B.M., Coulter, P.B., and Tannenbaum, H. Properties,Interaction and Esterification of Methylphosphonic Dihalides.J. Am. Chem Soc. 82, 3843. 1960.

2. Burnop, V.C.E., and McGrath, L.B. Sutton Oak Report 775.Development of Processes for Preparing 'G' Compounds, Part III.The Preparation of Methane Phosphonyl Dichloride from DimethylPhosphite by the Salt Process, p. 7. January 1948.

3. Gulwell, T. Sutton Oak Report 810. Development of the Pro-cesses for Manufacturing 'G' Compounds, Part XXX. The Preparationof Methylphosphonyl Difluoride and Ethylphosphonyl Difluoride on aLarge Laboratory and Semi-Technical Scale. Appendix p. 2. September1951.

4. Brown, R. Sutton Oak Report 800. The Development of Processesfor Manufacturing 'G' Compounds, Part XXIII. The Laboratory Prepara-tion of Methyl-Phosphonyl Dichloride by the Aluminum Chloride Process,Appendix p. 2. November 1951.

5. Perry, B.J. Porton Technical Paper 166. The Chemistry of AlkylFliiorophosphonites and Related Compounds, Part XI. The Mechanism ofthe Di-Di Reaction. Appendix p. 4. April 1950.

6. Neale, E. Porton Technical Paper 277. The Heats of Hydrolysisof Phosphorus Oxychloride, Phosphorus Trichloride, and Some AlkylSubstituted Derivatives, p. 1. April 1952.

7. Tennessee Valley Authority, Div. Chem. Eng., Rach. and Dev. Br.,Edgewood Technical File 153.61-1. Functional Support Program forthe More Efficient Utilization of Byproducts from Phosphate Develop-ment Works: Initial Progress Report Through March 31, 1951,TVAJOS33A, p. 18. UNCLASSIFIED Report.

8. Monsanto Chemical Company., Edgewood Technical File 107.61.1.* Preliminary Design Data on Facilities for Manufacture of GB Inter-

mediate, Vol V. Manufacture of Methyl Difluoro Phosphine Oxide(Step IV), p. 18. June 1950. UNCLASSIFIED Report.

9. Tolkmith, H. Dow Report. New German Combat Gases During WWII.July 1949. UNCLASSIFIED Report.

10. Westvaco, Chlor-Alkali Div. Edgewood Technical File 107.61-*• 19/48. Final Report VI, Pilot Developmeot of HTM Process for Pro-

duction of Methanephosphonyl Dichloride, UOP 48, Appendix LA,p. L35. February 1955.

"11. Penski, E.C., and Latour, L.I. EATR 4491. ConversationalComputation Method for Fitting the Antoine Equation to VaporPressure-Temperature Data. F'ebruary 1971. UNCLASSIFIED Report.

13

-4

12. Thomson, G.W. Physical Methods of Organic Chemistvy, Part I.p. 193. Weissberger, Ed. Interscience Publishers, New Y,-rk.New York. 1949.

13. Hofmann, h.W. Chem. Ber. 6, 303. 1873.

1

14