i ii iiiiiiiiiiiiiiii i
TRANSCRIPT
WITTEN BY
-R.W . Burkhardt ATOMICS INTERNATIONAL
TOR NO .
wernw 267 1A division of North American Aviation Inc .
Organic Reactors
,CO
7500
UN IT Process DevelopmentTECHNICAL DATA RECORD LEDGER ACCT .
362 1APPROVED BY : PROGRAM SUB-ACCT , 1812
ONR Research and Development TYR
jV !, 1 .v~ . .PROJECT DATE April 17, 1958
Purification System Development PACE1 11.
TO: D . W. Bareis
COPIES TO, 0MR - OMRE Distribution10 copies to 791-2 3W.C . Burke
SUBJECT :
LATENT HEAT OF VAPORIZATION AND VAPOR PRESSURE DATA FOR ORGANIC COOLAJJTS :
CONTENTS :I STATEMENT OF PROBLEM . . . . . . . . . . . . . . . . . . . . . PACE t 4111 SUMMARY OF RESULTS AND RECOMMENDATIONS . . . . . . . . . . . . PAGE 2
111 METHOD USED , DESCRIPTION OF EQUIPMENT , SAMPLE CALCULATIONS . . . PAGE 2
IV REFERENCES AND APPENDICES . . . . . . . . . . . . . . . . . . . PACE 8
I STATEMENT OF PROBLEM
In order to estimate the performance of flash distillation equipment for th epurification of organic coolants, heat of vaporization and vapor pressure data for th ecoolant components are needed . Under contract with Atomics International, the Smith -Emery Company of Los Angeles obtained heat of vaporization data for isopropyl diphenyl ,orthoterphenyl, metaterphenyl, paraterphenyl and diphenyl at absolute pressures of four ,two, one and one-half inches of mercury . The corresponding equilibrium temperature sprovided additional vapor pressure data . The data were correlated for interpolation andlimited extrapolation, and for estimation of the vapor pressure and heat of vaporizationof Santowax R .
730-0- a
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TECHNICAL DATA RECORDOMR Research
PROGRAM and DevelopmentPurification
PROJECT System DPve1 opmPnt
II. SUMMARY OF RESULTS AND RECOMMENDATIONS
TOR NO . 2671
DATE April 17, 1958
PACE 2 OF 14
The vapor pressure data and heat of vaporization data from the Smith-Emery reportlare correlated herein . Thscr.etical calculations t .,-. check the experimental data andestimates of the properties of Santowax R are also included .
The vapor pressure data obtained from the Smith-Emery Company are plotted on areference -substance plot in Figure 1 using mercury as the reference substance . Theplotted data are in Table II . The low pressure data are reasonably well correlated bya straight line through the atmospheric boiling points,5,6 thereby giving confidence to
the interpolation of the intermediate vapor pressures and allowing a limited extrapola-tion above atmospheric pressure. The vapor pressure obtained at the lowest pressure(0.5 inch Hg) for each compound was disregarded due to the difficulty of obtaining ., .. ;` .pressure measurements in this low pressure region . An estimate of the vapor Or.essire' .0fSantowax R is also shown in Figure 1 .
Heat of vaporization data for the same compounds at absolute pressurelt of , .titone and one-half inches of mercury are recorded in Table I and correlated in'Figure2 :_ona reference-substance plot. The correlating lines are best fit estimates only, a'do-norepresent the calculated values . An estimate of the latent heat of vaporization is alsoshown in Figure 2 .
Calculation of the heat of vaporization from the reference -substance vaporpressure plot gives estimates which deviate less than 6 per cent from the experimentalvalues for all compounds except isopropyl diphenyl . The experimental and calculatedvalues for the latent heat of vaporization of isopropyl diphenyl differ by as much as35 per cent, thereby casting some doubt on the reliability of the experimental data .Calculation from a benzene -referenced vapor pressure plot (not shown in this TDR)yielded a similar discrepancy.
III . METHOD USED, DESCRIPTION OF EQUIPMENT, SAMPLE CALCULATIONS
Smith-Eme t rihe the equipment and method used as follows :
"The apparaetd6 .. u6ed . was a modification of that developed by Mathew &Fehlandt, discussed on Page 3212 of Volume 53 of the Journal of the AmericanChemical Society (1931) . The modifications we made include the substitutionof a calibrated burette for the suspended vaporizer tube and the provision ofNichrome heating coils with a capacity of 1500 watts in the boiler . Theapparatus was also adapted for operation in a partial vacuum as required byyour order.
730_0_ A
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TECHNICAL DATA RECORDMR Resea4rch.
PROGRAM and :T1a3►iil't►Purification
PROJECT System Developm nt
TOR NO . 267 1
DATE April 17, 1958
PACE 3 OF :
Itr`t1 A, Raiarp to provide insulation against radiant heat'ih temperatures required. This was done bylosses i
wrapping the. vaport'ter"tube with aluminum foil and, in the case of the highest
temperatures involved, it was also found necessary to wrap the entire apparatus
with this material and to provide asbestos insulation in addition.
1rior to adding the substances under test to the apparatus, all
components were thoroughly cleaned by re#luxing with xylol. After cooling,
the xylol was drained off and the entire apparatus rinsed with reagent grade
acetone. The residual acetone was then removed from the apparatus with
filtered compressed air . To avoid uneven boiling in the vaporizer tube, a
current of 0 .38 amperes was passed through the empty vaporizer heating coil
for two hours . The apparatus was then assembled and a granule of Micro-
Porous Boiling Chips, produced by Todd Scientific Co . of Springfield, Pa . ,
was placed in the vaporizer tube .
The procedure followed was to add a weighed amount of approximately-50 grams of the material to be tested in crystal form to the vaporizer ttiibe...
and to add sufficient melted material to the boiler to adequately cov: th .heating coils . The apparatus was then sealed and the required vacuum' .' :
applied, after which the boiler coils were energized . When the contents
of the vaporizer tube had melted, the volume was noted to enable us to`
calculate its density at the operating temperature . As soon as equilibrium
had been attained in the still, a current of one ampere was passed through
the vaporizer heater coil and the quantity of material evaporated in
exactly eight minutes was Voted . Since the vaporizer heating coil is pure
platinum wire, 0 .0015 inches in diameter and 32 .4 centimeters long, its
resistance can be calculated at any temperature . From this information,
the quantity of heat applied was calculated.
Considerable difficulty was experienced in separating the large ground
glass joints at the termination of each run . After the material in the
boiler had been drained off, we allowed the apparatus to cool and then
refluxed pure dibutyl phthalate in the still at atmospheric pressure.
Since the boiling point of dibutyl phthalate is higher than the melting
points of all the substances tested, it was possible by this means to.~`Munt of test substance which had lodged betweeninsuretk~ i '
the su . glass joints was in a liquid state. In this
cond. ssible to disassemble the apparatus with a few
light:
if-Proi r• run in triplicate and, in the event one
determination differed from the remainder by more than 2 calories, the
whole procedure was repeated .
The apparatus was found to behave satisfactorily with all the samples
submitted except paraterphenyl . Paraterphenyl sublimes heavily under the
conditions of the test and gave considerable trouble due to blockage of
condensers and vacuum lines . "
The vapor pressure data in the Smith-Emery report1 can be correlated for purposes
of interpolation and extrapolation by a reference substance plot . Mercury was found to
be a satisfactory reference in view of the relatively high temperatures involved and the
volume of vapor pressure data available ,
Too-a- 4
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TECHNICAL DATA RECORDOMR Research
PROGRAM anc naze1l nMnn+ificatio
PROJECT tPTn Tlasvaiapm rt.
TDR R0 .
DATE _
PACE -
2671
April 17, 1958
L of 14
Justificat a2 for this;: plot comes from the Clausius-Clapeyron equation -
dP - -XdT T vg-v1,
where P - Vapor Pressure (PSIA )T - Absolute Temperature (OF )7! - Molal Heat of Vaporization (Btu/lb . mole )
v - Molal Specific Volume of the Gas Phase (cij ft./mols )vg- - Molal Specific Volume of the Liquid Phase (cu.ft ./mole )
Neglecting v in comparison to v and expressing v in terms of the ideal gas Law ..,_givesreadily integrable expression g g
dPdT -TRT
P
or
where R - Universal Gas Constant (10-73 PSI-cu ./ft ./°F-lb. mole )
R --ff -d(lnP)T
Equation (3) written fora reference substance at the same temperature gives
d(ln Pr) - R a2T
quation (3) divided by uatrion (4) becomes
I
Eq. (5 )
where M --Molecular weight (lb ./lb. mole)
Integration of Equation (5) give s
lnP - XM 1nPr+Cr r
where C - constant of integration
log P - c at log Pr + C'r
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Eq. (3 )
Eq. (4)
Eq. (6)
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TECHNICAL DATA RECORDOMR Research
PROGRAM and nioMS]O;0"~:r fic don
PROJECT va Pm PVRI npmPn±.
TOR NO. 2671
DATE April 17, 1958
PACE c OF 14
This indicates ttOMa, .plot .of log P versus log P will give a straight line (See Figure 1It also yields a`iaethoc# of:'piedicting heats of vaporization which was used in this paperto check the experimental values .
An example of the data arrangement for the reference substance plot is as follows :
Smith-Emery data (Table I) gives the boiling point of diphenyl at 411 Hg(1 .96 PSI) to be 35Z F (18O .5°C) . The Handbook gives the vapor pressureof mercury at 180.5 C as 191.0 mm Hg (3 .70 PSI) . On log-log coordinates,1.96 PSI is plotted versus 3 .70 PSI . The plotted data are tabulated inTable II . In Figure 1 the reference abscissa was converted to temperaturefor convenience .
The vapor pressure reference substance plot, as well as yielding reliable extra-polations of the vapor pressure data, affords an estimate of heat of vaporization . : . FromJquation /7) the scope or the rererenc i
X M Then (Slope)-A
r r% rMr M
For example, using the same diphenyl point as in the above illustrat d t(357°F at V Hg), Smith -Emery determined the heat of vaporization to be '82 .9 cal/gm (149 .1 Btu/lb) . The slope of the diphenyl line in Figure 1 4is 0.87 . The heat of vaporization for mercury at 3570F is 129 .2 Btu/lb .
Then _ .870 ( 129 .2) 200 .6I M72
-X - 116.0 Btu/lb
The percent deviation from the Smith-Emery value is
U46.0 - 1119 .1) loo = 2 1 %..19
The theoretical,".Vv ` o .fated in this way- are compared to experimental data inTable lt .
1j
Heat ofp are shown on an equal temperature, reference substanceplot in Figure,_, '' eat of vaporization of the organic in question was plottedagainst the heat of vaporization of mercury at the camp temperature. The referenceabscissa was converted to temperature for convenience .
The Santowax R vapor pressure line in Figure 1 represents the sum of the productsof each component vapor pressure times its mole fraction in liquid Santowax R . Thiscomposition is as follows
Orthoterphenyl 10 %
Metaterphenyl 60%
Paraterphenyl 30%
»o=4- s
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TECHNICAL DATA RECORDOMR Reis earth. .
PROGRAMPurification
PROJECTSy t. e n ne1T91 ^t
TOR NO . 2671
DATE April 17, 1958
PACE 6 OF 1-4
Whereas the comp C Eton of ` antowax R varies from batch to batch, the above is taken asa rough average from analyses at Atomics International .
Santowax R vapor pressure is estimated as the sum of the partial pressures of thecomponents as calculated by Raoult' s Law . . The following points were used to establishthe Santowax R line in Figure 1 .
Tempgrature Vapor Pressure
(Ur) (PSI )
4400 0 .18500 1 .16
600 4 .69
Similarly the heat of vaporization for Santowax R is assumed to be the sunrf` theBighted contributions from each component .
Latent Heat ofTempBF}tur e
(Vaporization
Btu/lb . )
1100 131
500 127
y ih
~ 3 x't'~~ kro +~ ~ w s
ii kT
770- -♦
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ATOMICS INTERNATIONALA Division of North Amodcon Aviation, Inc.
TECHNI QATA RECORDese
DetAOr ke~rc
PROGRAM an t~liPurification
PROJECT System Development
NOMENCLATURE
TOR NO .
DATE _
PAGE _
2671
April 17, 1958
OF lh
T = Absolute Temperature (°R )
= Molal Heat of Vaporization (Btu/lb mole)
Heat of Vaporization (Btu/lb)
P = Vapor Pressure (PSIA )
v Molal Specific Volume (cuft./mole)
R = Universal Gas Constant (10 .73 PSI-cutft ./°R-lb mole)
M Molecular Weight (lb/mole )
HBR High Boiler Residue
Subscripts :
r = reference substance (Mercury)
g = gas
1 = liquid
720.5-s
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TECHNICAL DATA RECORDOMR Research ,
PROGRAM and IA1a ,nl~
IV . REPERENCEF7
1 . Laborato
TOR NO . 267 1
DATE April 17, 1958
PROJECTPurificationSgatem Pavel npinant PAGE 8 OF 111
ry Report 4416117-51, Smith- Emery Company , Los Angeles , California(2-28-58) .
2 . 'ireybal, R .W ., Mass Transfer Operations , pp 152-3, New York : McGraw-HillBook Company (1 9
3 . Handbook of Chemistry and Physics , C . S . Hodgman, Editor, 30th Edition, p 1832,Cleveland : Chemical Rubber Publishing Company (19L8) .
Monsanto Chemical Company, Phosphate Division (1950) .
L . Ibid ., p 1900 .
5 . "Monsanto Terphanyls " Monsanto Technical Bulletin No . P106, St . .Louis : .
Monsanto Chemical Company (1956) .6. "Isopropyl Diphenyl" Monsanto Technical Data Sheet No . 1500, St .,'I.ou
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ECHNICAL DATA RECORD DATE April 17 . 1958TOMR Res ear, c. l
PROGRAM anti flwaw7 nni n K-Purification
PROJECT Sy4tPm DAVR1 opcent PAGE 9 OF 14
TABLE I
Latent Heat of Vaporization Data
Boiling SystemObserved Latent
Temperature PressureHeat of
Vaporizatio n tian( F) (Inches Hg) (Calories/gram)
Isopropyl Diphenyl 420 14 .0 lOtT. =`~f {~` .380 2 . 0348 1A 7 «$ T330 0 . 5 . 10 r-A
Ortho Terphenyl 489 4 .0Yi`t h
67..5" ..443 2 .0 69 . 5396 1.0 69 .9367 0 .5 70 . 3
Meta Terphenyl 545 14 .0 70 .11502 2 .0 70 . 9451 1.0 72 . 1
428 0 .5 72 .4
Para Terphenyl 551 4.0 70 . 2508 2 .0 70 . 8
162 1 .0 71. 6439 0 .5 72 .0
Diphe :,~ ire 357 4.0 82 .9
ti a317279
2 .01.0
83 . 0811 . 2
243 0 .5 85 . 8
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TECHN11 DATA RECORD DATE April 17, 1958Research . Purification
PROGRAM Deyeloj pt PROJECT _ ystRm Devel op ent PACE 10 OF 144
TABLE II
Reference-Substance Vapor Pressure for Figure 1
Vapor Pressure Vapor Pressure3Substance Tested Temp rature
~F)of Organic of Mercury
(PSIA) (PSIA)
Isopropyl Diphenyl 1120 1 .96 0.53380 0 .98 0 .25,,_,348 0 .491 0r `"~ v
330 0 .246Y x
a.`~n
570 14.7.
3IA iffi~
Ortho Terphenyl 489 1 .96 1..,_443 0.98 0 .8O'396 0 .491 0 .357367 0 .246 0 .211
637 14.7 10 . 8
Meta Terphenyl 545 1 .96 3 .34502 0 .98 1.91
451 0 .491 0 .90428 0 .246 0 .62
703 14.7 19 .6
Para Terphe 551 1.96 3 .70508462
0 .9 80 .491
2 .101.07
439 0.246 0 .7 5
727 14•
7 23•
4yt.'S:Y ~t.4kr
Diphenyl 357 1.96 0 .173317 0 .98 0 .076279 0 .491 0.0319243 0 .246 0 .0128
491 111.7 1.64
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PROGRAM .-A 'n"" riPurification
DATE April 17, 1958
PROJECT System navelenmant PACE 11 OF 14
TABLE III
Normal Boiling Points
CompoundAtmospheric Boiling
Referenc ePoint ( oC )
Isopropyl Diphenyl 295 to 300 6
Ortho Terphenyl 336 5
Meta Terphenyl 373 5
Para Terphenyl 386 5
Diphenyl 255 5
730-4-6
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TECHNIC DATA RECORDese ch
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PROJECT System DPVal n man .
TABLE IV
TOR NO . 267 1
DATE April 17 it 19 158
PACE 12 OF 14
Comparison of Experimental Heats of Vaporization
with those Calculated from Vapor Pressure Data
Temperature
(°F)
Calculated Heat Experimental Heat 1of Vaporization of Vaporization
(Btu/Ib) (Btu/lb)
Isopropyl Diphenyl : ( Slope - 0 .963 )
420 125. 7380 126 .3348 127 . 3330 127. 7
Ortho Terphenyl : ( Slope - 1.019)
1189 128 .711113 129 .7396 130 . 8367 131 . 2
Meta Terphenyl: (Slope - 1.130 )
545 122 .7502 123 .61151 1211 . 81128 125.3
180.6181.6183.3183.9
121 .4125 .1125 .9126 .6
126 .8127 .7129 .8130 . 3
1.109)
120.3 126.3121.2 127.5122.2 128.9122.8 129.6
Diphenyl : ( Slope - 0.870)
357 146.0 149.1317 147.0 1119.3279 1148.0 151.72143 7119.0 154.3
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(VISd) HUnSS1Hd WdV A
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2671April 17, 1958
11; of 114
I i
Q Isopropyl diphenylO DiphenylL OrthoterohenylO Metaterphenyl❑ Paraterphenyl
Data from Ref . 1
The correlating li nes are best fitestimates only and do not representthe calculated values in Table IV
ln..~'Ahe~Y'.Z
`b~Te MSit e I'I`Cc$1 -c ,~
°,T Iu
ated)
200 300 100 500
TEMPERATURE (°F)
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FIGURE 2 . LATENT HEAT OF VAPORIZATION OF POLYPHENYLS(Reference-Substance Plot )
190 ; :
180
170
160
150
1140
130
120
110
600
I
700
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