July. 191j
T H E JOl-RS.IL OF ISDl-.STRI.IL . I S D ESGISEERIAI-GCHEMISTRE'
\yere t h e n further fractionated from a 2 0 0 0 cc. roundliottomed flask provided with a glass 12-bulb pear still-head and an .lnschutz normal thermometer. The fractions 13j ot o 1 4 j O were collected and mixed. .X total of 1170 cc. were obtained originating from the > $ I , ' ? gals. transformation distillate. This was again fractionated, as before, collecting this time b e t r e e n 138, j o and 142. jo. Of this last fraction, only 1 2 j cc. were obtained. A little of this was treated n-ith concentrated nitric acid, first coldc finally boiling. h u t it yielded no nitro compounds. Hence, no xylene is present. Since xylene is absent. it is assumed t h a t no aromatic hydrocarbons are present. %\-era1 distillations were made of t h e tars obtained in these experiments v-ith t h e object in x-iew of isolating a n y viscous hydrocarbons of value as lubricating oils t h a t might be present. This was always done w i t h lil-e open s t e a p , with t h e simultaneous application of fire heat t o the bottom of t h e still in t h e manner usual in t h e petroleum industry. I n one case, 30 gals. of :ar were subjected t o this treatment. I t is unnecessary t o go into details about these trials. since nothing of value was found. T h e high heat and great pressure seems not only t o have broken down whatel-er \-iscous hydrocarbons were originally present > but also t o h a r e prevented t h e formation of others. either b y balanced reactions or otherwise. The original tars were all of heavier gravity t h a n t h e oils frcm which t h e y were made. of good cold test. and very thin i n viscosity. -411 t h e residual oils left after steam distillation were similar, b u t t h e cold test was not so good: t h a t is t o say, there was present sufficient crystallizable paraffine t o render t h e oil more susceptible t o cold. 411 t h a t is said above applies equally t o t a r s derived from light original oils---namely, 300 oil and kerosene, and t o those from heavy, waxy origina! oils--namely, wax distillate. etc. The original cryst:tllizable paraffine, when present. was almost 1.otally tlestroyed by t h e heat and pressure and so were all viscous components. Credit is due t o my son, James -1.Bjerregaard, f o r constructing and operating this apparatus. 11y thanks are clue t o the Canfield Oil Company. of Cleveland. Ohio, for permission t o publish this report. C'LEVBLAKD, OHIO
THE TEMPERATURE COEFFICIENT OF EXPANSION OF PETROLEUM RESIDUUMS R y H. ROSSBACHER Received March 29. 1915
I n the purchase of residuum oil the measurement oi \-olume is usually made a t a n elevated temperature a n d t h e volume is then reduced t o some s t a n d ard temperature, usually 60" F. Englerl has shown t h a t this coefficient is not a constant for all ranges of temperature b u t must be determined for ranges closely approximating those t o which it is t o be a p plied. Even for a defined temperature range t h e value will vary with t h e consistency of t h e material and the t y p e of crude petroleum from which it is prepared. A closer attention t o this value might prove of commercial advantage in many cases. K i t h this '
"Das Erdoel," Vol. I , p 95.
- * I
31 I
idea, the following description is given of an easily applied method for determining t h e temperature coefficient of espansion of a petroleum residuum over any desired temperature range. DESCRIPTIOX-TO consider the most complicated case, it is assumed t h a t t h e sample is semi-solid 3t t h e standard temperature. When t h e sample is sufficiently fluid t o allow the seating of t h e stopper a t this temR perature, the following operations and calculations can be somewhat simplified. The specific gravity a t t h e standard temperature is determined in a Hubbard pycnometer.' The pycnometer is then filled with t h e sample, warmed sufficiently t o allow the stopper t o be seated. and suspended in a wire sling in a glycerine bath. the top of the stopper projecting slightly from t h e surface of t h e glycerine. -1thermometer is placed in t h e bath Tvith its bulb opposite t h e middle of t h e pycnometer. T h e r z b a t h is heated slowly, with stirring, the stopper being kept firmly seated and wiped clean as t h e residuum expands. When the desired temperature is reached i t is kept constant until t h e absence of further exudation of the sample from t h e capillary indicates t h a t the sample has reached t h e temperature of t h e bath. The pycnometer is then removed, wiped clean, allowed t o cool and weighed.
n
C.%LCL'LhTION
Let u = Weight of pycnometer, empty. b = 1Veight of pycnometer, 1 . water a t standard temperature. c = Weight of pycnometer i sample a t standard temperature. d = Weight of pycnometer sample f water a t standard temperature. i. = Weight of pycnometer 4-sample a t elevated temperature. f = Coefficient of cubical expansion of pycnometer, assumed 0.0000156 per "F. in this case.1 1 "Chemiker Kalendar," vol. I1 ( I Y I ? ) , p. 89.
+
From values a. b and c , calculate ITs, the weight of sample in t h e pycnometer a t the standard temperature. The specific gravity of water a t T,may be taken a s unity for t h e purposes of this calculation. From n and b find ITy,t h e volume of the pycnometer a t t h e standard temperature. Applying f , find the volume a t the elevated temper.zture. I-?, in terms of 1 - s . 3Te(.f)I' \-e -- I -1 I 3TJj) From u and e find We, t h e weight of sample in the ~~~
pycnometer a t T,.
IT ~
VCe'
I
+ +
~
- Wts. weight
volume corresponding t o Vs.
Yes
- IT,
____--~-
1V.S loss in weight of ITsin increasing T, in t e ni p er a t ure . 1,
Tk
Te-
=
a t T, for - I,, the
T, degrees
nt, coefficient of expansion in t h e formula
+
\-e = 1-s[1 m ( T , - Ts)] Some results obtained b y this method are of interest in illustrating t h e effect of temperature range on the coefficient. 1
"Dust Preventives and Road Binders." pp. 329-30.
T H E JOrRLV.4L O F I N D U S T R I A L A N D ENGIh'EERING C H E M I S T R Y
578
"STANOLITE"
5'01. 7 , No. 7
Received January 4, 1915
t h e limits of experimental error no m a t t e r what device is employed t o secure t h e m . Viscosity coefficients for crude oils a n d refined products are commonly determined. M a n y chemists measure refractive indices, though t h e use of t h i s raluable method of identification is r a t h e r limited. Other physical constants such as surface tension, capillary rise a n d molecular weight have been determined in only a limited number of cases a n d their practical applications have not been given extensive consideration b y petroleum technologists. For t h e purpose of determining possible simple relationships, measurements were made of t h e following series of constants: A-Distillation range E--Surface tension B-Specific gravity F-Capillary constant C-Refractive index G-Molecular weight D-Viscosit y H-ULtimate analysis
I n t h e industrial s t u d y of petroleum a n d petroleum products strictly chemical methods of identification are of secondary importance. T h e number of reactions in use is limited, a n d these processes are n o t particularly convenient a n d satisfactory. T h e y fail t o give t h e sort of information most needed. F o r instance, t h e sulfonation test for olefines gives t h e s a m e results whether t h e hydrocarbons have a boiling point of 100' or 300°, a n d indicates little regarding t h e commercial use or possibilities of a n oil. Likewise a liquid sulfur dioxide extraction does not aid in differentiating a gasoline from a kerosene. T h e i m p o r t a n t information i n t h e s t u d y of petroleum distillates is obtained from determinations of
As t h e present work deals with a comparsion of constants, rather t h a n oils, i t was n o t considered necessary t o secure a n absolutely comprehensive series of samples. Representative oils from a n u m ber of different fields were obtained, a n d t h e selection was made with t h e view of including crude petroleums of different types. T h e list includes five carefully selected samples of California crude oils, five from Oklahoma, four from Pennsylvania, t w o from Russia a n d one from Mexico. F r o m t h e works of Mabery a n d other investigators, it is known t h a t wide differences exist among t h e t y p e s of hydrocarbons found in oils from t h e different
COEFFICIENT OF EXPANSION PER O F . 60-212' F. 0.000364 60-264" F. 0.000378
SPECIFIC GRAVITY 60/60° F. 1 ,0957 77/77' F. 1 ,0887
77-212' F. 77-264O F.
0.000337 0.000343
B y Weiss' method of calculation' t h e coefficient of expansion for t h e range 60-77' F. on this sample is 0.0004I 2 . A sample of Mexican residuum having a specific gravity of 1.0104 a t 7 7 / 7 7 ' F. gave t h e coefficient 0.00032 for t h e range 77-160" F. CHEMICAL
1,ABORATORY
O F A I O R R I S 82
COMPANY
CHICAGO
RELATIONS AMONG THE PHYSICAL CONSTANTS OF THE PETROLEUM DISTILLATES By WALTERF. RITTMANA N D GUSTAVECLOFF
SAMPLES AXD D E T E R M I N A T I O N S
TABLEI-SOURCES A N D PHYSICAL CONSTANTS OF CRUDEOIL SAMPLES LEASE WELL No. PHYSICAL CONSTANTS OF C R U D E PETROLEIIMS FIELDDISTRICT SAMPLEDLOCATIONSTATECOUNTY ARRANGED I N ORDEROF THEIR 15 269 Cal. Piru 12/ 6/07 T 3 N , R l 8 W Cal. Ventura Union Oil Co. SPECIFIC GRAVITIES 12/ 4/07 T 4 N , R18W Cal. Ventura Modella, 7, 19.21, 22, 28, 29 273 Cal. Piru
No.
587 Cal. 591 Cal. Heald 764 P a . I 765 Pa. I 815 P a . 816 Pa. 1280 Okla. 1281 Okla. 13.36 Okla. 1339 Okla.
1
Midway Midwav
J. S. Sloan Farm Branden Farm Collinsville Collinsville Collinsville Collinsville
IO/ 8/10 T31S. R22E Cal. lO/l8/10 T31S. R22E Cal.
{ 9/7/11 9/7/11 {
S. Maria R . R. Russian-Provided R. M. Russian-Provided M e x . Mexican-Provided
9/21/11 9/21/11 May/l3 May/l3 5/24/13 5/24/13
Emlenton Emlenton Pleasantville Pleasantville TZZN, R15E T22N, R I S E T14N. R I S E T14N. R18E
Kern Kern
Manchuria, Midway Bear Creek
I 0
;
Pa. Venango Boulder Sand: 1195 f t . Pa. Venango Second Sand: 1050 f t . Pa. First Sand: 580 f t . II Pa. Second Sand: 650 i t . ' 6 Okla. Claremore Pool .. Okla. Sellers Lease, Claremore Pool 1 Okla. G. Callahan Lease, Muskogee Pool 3 Okla. Stevens cease, Muskogee Pool 1
by the kindness of C. I. Robinson of the Standard Oil C o . of K.J. b y the kindness of Prof. C. F. Mabery The Case School Cleveland, 0 . b y the kindness of Dr. D. T. Day, U. 8. Bureau of Mine's. Washington, D. C.
various physical constants. I n view of t h e convenience with which t h e y can be measured, a n d t h e wide utility of these constants, it has been t h o u g h t desirable t o s t u d y relations existing among t h e m . T h e work described in t h i s communication deals with a comprehensive series of measurements a n d furnishes d a t a which are helpful in indicating how t h e results of various experiments may be interpreted. The t w o processes most universally employed and best understood are distillation a n d measurement of specific gravity. Distillation figures are more or less relative, depending upon t h e method used.3 Gravity measurements are absolute a n d agree within 1 John Morris Weiss, "The Coefficient of Expansion of Tar," J Frank Inst., Sept., 1911. 2 Published with the permission of the Director of the Bureau of Mines See Rittman and Dean, THISJOURNAL, 7 (1915), 185
Sample 815 764 816 765 1336 1339 1280 Heald 1281 269 R. R . R. M. 273 s. M.
Sp. Gr. 0.799 0.800 0.808 0.816 n, 825 0.838 0.846 0,865 0.870 0.876 0.876 0.878 0.891 0.901
Viscosities Spec. Sec. I .30 67.5 67 1.29 I .32 68.5 1.40 73 I .44 7.5 1.71 89 1.70 88.5 2.77 I44 3.35 I i 4 2 31 I20 2 . 6 1 136 3.22 167.5 2.11 I I O 4.92 256
Surf. Tens. 24.0i 25.12 24.81 25.44 24.78 26. 19 25.03 26.59 26.59 2s. in 27 55 27.82 76.08 26. I3
Cap. Conet. 6. I 7 6.44 6.30 6.38 6.I S 6.40 6.06 6.30 6.26 6.no 6.43 6.49 5.99 5.94
fields. Table I gives t h e sources a n d physical cons t a n t s of t h e oils studied. VISCOSITIES of t h e crude oils were measured in t h e S t a n d a r d Engler Viscosimeter at a temperature of 20' C. Results are expressed in Engler degrees, which represent ratios of t h e r a t e s of flow of t h e oil a n d water. When expressed in this manner t h e results indicate specific viscosity. This is in contrast t o empirical refinery practice using t h e Saybolt machine, which shows t h e time required for a given q u a n t i t y of oil to pass a given orifice a n d omits comparison with t h e s t a n d a r d liquid, water. T h e conversion factors from Engler' t o Redwood a n d Saybolt are:
+ 4 + e4) KZ
TR = I ~ Z . Z K ( I 1
I
Chem. R e s . Fell-Hare. Ind.. 19 (30, ,331, (44 to 49).
