Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Technologic Papers
OF THE
Bureau of Standards
S.
W.
STRATTON, Director
No. 77
H. W.
BEARCE,
Assistant Physicist
and
E. L.
PEFFER,
Laboratory Assistant
Bureau of Standards
ISSUED AUGUST
26, 1616
WASHINGTON
GOVERNMENT PRINTING OFFICE
1916
ADDITIONAL COPIES
OF THIS PUBLICATION MAY BE PROCUKED FROM
THE SUPERINTENDENT OF DOCUMENTS
GOVERNMENT PRINTING OFFICE
WASHINGTON, D. C.
AT
10
A complete list of
be obtained
the Bureau
free
of
Standards, Washington, D. C,
PETROLEUM
By H. W.
OILS
CONTENTS
Page
I.
Introduction
Object of investigation
Material used
1.
II.
III.
Methods
of
4
4
4
6
measurement employed
V. Calibration of apparatus
VI. Temperature range of density determinations
VII. Method of procedure
1
By the method of hydrostatic weighing
6
6
XIV.
XV.
8
10
10
11
12
12
14
and volumetric
17
18
tables
18
19
21
XVI. Rate of expansion of fuel oils and lubricating oils at high temperatures
XVII. Comparison of results with previous work
XVIII. Conclusion
I.
1.
22
23
25
INTRODUCTION
OBJECT OF INVESTIGATION
MATERIAL USED
II.
The
States
Pennsylvania,
of
New
York,
oil in
Ohio,
various
from the
Louisiana,
Texas,
California.
origin,
lubricating
oils.
APPARATUS USED
of the
in Fig. 3.
1
Bureau
of
Standards Bulletin, 9,
p. 371;
9, P- !
The
sinker
of 99.9630 g,
and the
5
follow-
TABLE
Volume
of Sinker No. 7
Tempera-
Volume
ture in
degrees
centigrade
in milliliters
47.
6882
10
47.
6998
20
47.
7113
25
47.
7170
30
47.
7227
40
47.
7339
50
47.
7450
TABLE
Tempera-
Internal volume in
milliliters
ture in
degrees
centigrade
No.
108.
3803
No.
109.
0834
25
108. 4543
109. 1545
109. 2335
50
108. 5378
75
108.
6283
109.
3216
95
108.
6906
109.
3954
range in the same regular order and with occasional determinations of the ice point, the temperature observations are very consistent and are believed to be reliable to o?oi or o?02 C.
The
temperatures were nearly always read with a stationary or slowly
rising meniscus, as a falling meniscus is known to be unsteady and
unreliable.
V.
The density
use of pure,
CALIBRATION OF APPARATUS
sinker
air-free, twice-distilled
Calibrations were
which
temperature
at
densities
were
made at each
to be determined.
Throughout this paper all densities are expressed in grams per
milliliter and all weights are reduced to vacuo.
The densities are,
therefore, in all cases numerically the same as true specific gravities at the various temperatures referred to water at 4 C as unity.
VI.
Density determinations
TIONS
were made on most
On
25
of the samples at
30
40
and 50
C.
85
and 95
VII.
1.
The
C.
METHOD OF PROCEDURE
P. Chappuis, Bureau International des Poids et Mesures, Travaux et Memoires, XIII; 1907.
Fig.
i.
Densimeter
sinker
tube,
and thermometers in
temperature-control bath
44904 16
Fig.
2.
Densimeter tube
and sinker
made with
is
oils
described
is
applica-
up a position of static equilibrium when susWith the more viscous oils the sensibility of
the balance is greatly reduced and the weighings become more
For such oils it is
difficult to make, and of doubtful accuracy.
therefore necessary, or at least desirable, to use some other
method. The method usually resorted to is that of the picnomto readily take
pended in the
oil.
For the work here described, special picnometers were designed and constructed somewhat similar to those previously
used in alcoholometric determinations. 3 The essential features
stopcock.
nometer when
When
caps
joints.
it is
desired to introduce a
new
sample.
filling is
Bull.
Bureau
of
Standards,
9, p. 405.
the reservoir /
is
Fig.
3.
Special picnometer
by means of a pipette, filter paper, and gasoThe temperature is then observed and the picnometer
removed from the bath, dried on the outside, allowed to come to
room temperature, and then weighed.
The density of the oil at each temperature is calculated by dividing the mass by the volume; that is, by the internal volume of
carefully cleaned
line.
IO
in
CQ
>>"20
3.2^.
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-<->
cu
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w
p
s.2-^0"ii
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3.5g
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3 3
D.
cq
>
o
ii
12
IX.
CALCULATION OF RESULTS
By
the
method
of hydrostatic weighing:
D = density
t
__
Dt
S = mass of sinker
w = apparent mass of sinker in oil at temperature
p = density of air
8.4 = density of brass weights
V% = volume of sinker at temperature /
sinker
(2)
D%
D = density
t
^(i-^+^-p M
-p.
w = apparent mass
p = density of air
8.4 = density of brass weights
v = external volume of picnometer
P = mass of empty picnometer
V = internal volume of picnometer at temperature
=mass of oil contained in picnometer.
t
X.
REDUCTION OF OBSERVATIONS
sample.
of the
method
made on each
is
D = D T + a(t-T) +(3(t-T)
13
may
be repre-
in which,
D = density
at
Dt = density
and
(3
any temperature
sample.
error.
A similar reduction
TABLE
Sample
c2
Ci*
Ci
10
-25
-15
20
225
-225
25
-250
-225
40
15
225
50
25
625
25
30
140625
0.79494
375
625
.78735
+1125
50625
.77978
62500
.77599
50625
.77217
375
625
.76453
+9375
140625
.75683
446250
.77594
-1125
25
375
Ch
-9375
25
25
of Reduction of Observations
CiCs
375
625
7)1750
CiN
-0.47500
+7.12500
.01885
.84825
.17115
.28525
.47775
-7.16625
.01141
.00384
.01141
.01911
.01920
.00000
.00005
.00377
.17115
-1.33310
SC 2 a + SC C 8 = SC iV
SC C2 a + SC22 8 = SC2iV
2
xm + 2Cn p D l
1
2i
in
which
C = tm
C = C, - [C ]m
N = - [D ]m
1
n = number
of
(t
m = mean temperature)
= mean C,
([A]m = mean D )
([Cfln
measured temperatures
+0.01900
+
+
+
-
250
25
in series
=7
.28525
.86400
.01250
.06950
14
By
of a,
and
25
are obtained
a=
0.000762
/3= 0.00000016
25
0.77598
TABLE
a (t-25)
(t-25)2
t-25
10
-25
-15
20
0(t-25)2
625
+0.01904
-0.00010
225
+
+
25
25
5
25
40
15
225
50
25
625
30
Difference
(calculated)
(observed)
(obs.-cal.)
0.79492
0.79494
.00004
.78737
.78735
.00381
.00000
.77979
.77978
-2
-1
.00000
.00000
.77598
.77599
.00381
.00000
.77217
.77217
.00004
.76451
.76453
.00010
.75684
.75683
-1
.01143
.01143
.01904
The above reductions are for a sample of " Texaco spirits " from
Oklahoma crude.
The density determination made on the individual samples, and
the calculated thermal density coefficient for each sample are shown
The samples in each group are arranged
in the following pages.
in increasing order of their densities at 25 C.
XI.
RESULTS IN DETAIL
TABLE
Refined Oils
Density (g/ml) at
Locality
produced
Nature
of oil
0.
20
6388
25
0.
30
40
50
6131
X105 0X10'
103
.....do
.6410
.6164
98
do
.6564
.6321
97
do
.6562
.7002
Gasoline
.7193
Naphtha
Texas
Pennsylvania
10
do
.6324
0.
6914 0.6825
.6781
95
0.
6736
0.
6647
0.
6558
89
.7107
.7020
.6975
.6933
.6845
.6757
87
.7237
.7150
.7062
.7019
.6975
.6887
.6798
88
.7506
.7422
.7339
.7296
.7256
.7172
.7087
84
.7515
.7433
.7351
.7310
.7270
.7188
.7105
82
2
2
1
1
15
TABLE 7 Continued
Refined Oils
produced
Locality
Nature
Continued
Density (g/ml)
at-
25
30
40
50
of oil
10
20
aX10-5
Gasoline (treated)
7532
7447
.7362
7319
.7277
.7190
.7104
86
Benzine (treated)
7641
7556
.7473
,7431
.7389
.7305
.7220
84
Indiana
Naphtha
7657
7575
.7493
,7453
.7411
.7328
.7244
82
California
Do
California
Engine distillate..
7879
7799
.7719
,7679
.7639
.7559
.7478
80
Oklahoma
Gasoline
7949
7874
.7798
,7760
.7722
.7645
.7568
76
Pennsylvania.
Kerosene
7981
7908
.7835
,7799
.7762
.7689
.7615
73
....do
7990
7918
.7845
,7809
.7772
.7700
.7627
73
Do
Do
....do
Louisiana
Lighthouse
Pennsylvania.
Kerosene
Do
oil.
7994
7921
.7848
,7812
.7775
.7702
.7629
73
8017
7944
.7872
,7835
.7799
.7726
.7650
73
8040
7968
.7896
,7860
.7824
.7753
.7681
72
/3X10?
3
1
2
1
2
1
....do
8054
7982
.7910
,7874
.7838
.7766
.7694
72
Ohio
....do....
8096
8023
.7949
,7913
.7876
.7802
.7729
73
Indiana
Refined..
8128
8054
.7979
,7942
.7905
.7830
.7756
74
Oklahoma
Kerosene.
8136
8062
.7989
,7953
.7916
.7842
.7769
73
Mid -continent
....do....
8177
8104
.8030
,7994
.7957
.7883
.7809
74
California
....do
8249
8175
.8101
,8064
.8027
.7953
.7878
74
....do
8301
8228
.8155
,8119
.8009
.7935
73
.8053
67
68
Do
Burning
oil
(high
,8220
F.T.)
Louisiana
Mineral Seal
8390
8322
.8254
8221
,8187
.8119
.8052
Pennsylvania.
Refined
8573
8507
.8440
,8407
,8374
.8308
.8243
66
8614
,8546
.8478
,8444
,8410
.8343
.8275
68
.8317
66
do
Indiana
Neutral
8646
....do
,8714
California
,8763
Pennsylvania.
Refined
Dynamo
Do
Do
,8481
.8620
,8585
8550
8479
8703
.8538
,8606
8574
8510
.8447
64
71
8800
8736
.8672
.8639
8607
8542
.8478
64
8802
8735
.8671
.8639
8607
8544
.8481
64
Louisiana
....do
8832
.8498
67
Neutral
8834
.8512
65
Pennsylvania.
Refined
8841
.8531
62
Marine engine
Gas engine
Refined
Louisiana.
Cylinder
Paraffin
Indiana
oil
66
8974
.8810
.8651
65
9007
.8838
.8678
66
9108
,8910
.8730
a 76
.8786
66
,8947
8850
.8786
65
Engine
9124
9053
.8956
8924
8859
.8794
a 66
oil
oil
oil
do
9153
.8971
.8803
70
9205
.9036
.8876
66
.8912
a 75
9285
oil
Gas engine
Refined
.8609
8915
9385
do
Do.
.8766
,8948
Cylinder
Texas.
8594
9045
Refined
Indiana
8657
8938
9118
oil
,8688
9111
Paraffin
,8672
8718
Refined
Cylinder
Texas.
,8661
8782
oil...
.9086
9319
9252
.9219
1
1
65
,8551
8692
Refined
oil
+
+
9186
9119
.9054
66
a 74
9421
.9221
.9052
,9470
.9306
.9145
65
9497
,9333
.9173
65
9551
,9389
.9230
64
+
+
+14
-1
TABLE
Crude Oils
Do
Locality produced
g/ml
Pennsylvania
Ohio
Do
Texas
25
g/ml
D50
g/ml
8253
0.
00074
8067
0.
00070
7892
00076
.8118
00071
7940
.8425
00074
.8241
00072
.8432
00072
.8251
00069
8078
.8526
00065
.8363
00065
8200
.8648
00076
.8459
00068
8288
.8726
00067
.8558
.8815
00074
.8629
00068
8460
.9082
00070
.8908
00070
.8734
.9162
00067
.8995
00067
8828
.9193
00069
.9021
00068
.8850
.9232
00068
.9062
00066
.8897
.9361
00071
.9183
00068
9012
0.
D
Do
Do
Do
D40
3o
g/ml
Texas
TABLE
25-50
.8309
0.
Texas
0-25
30-40
g/ml
.9180
00071
.9109
.9194
00066
.9128
.9296
00067
.9229
.9396
.00068
.9328
.9564
00066
.9498
Nature
of oil
25
g/ml
8620
25-50
D50
g/ml
D
50-75
75
g/ml
75-95
0.
00063
8462
0.
00064
8303
0.
00063
Fuel
.8641
00068
.8472
00067
8304
00068
Autocylinder
.8651
00064
.8492
00063
,8335
00063
Fuel
.8713
00067
.8546
00066
8380
00068
Gas engine
.8809
00063
.8652
00062
8496
00062
Locomotive
.9003
00068
.8833
00062
8678
Noncondensing cylinder
.9010
00069
.8838
00061
8686
Locomotive
.9140
00068
.8971
00063
8814
Marine engine
.9171
00065
.9009
00064
8848
Gas engine
.9202
00064
.9043
00064
Do
Autocylinder
0.
0.
0.
95
g/ml
0.
8177
8168
.8209
a
8144
8373
00062
8555
00062
.8563
00064
.8687
00064
.8720
8884
00064
.8757
.9204
00064
.9044
00064
8885
00064
.8758
Stationary engine
.9285
.00064
.9126
00063
8968
00063
.8842
Marine engine
.9386
00064
.9225
00064
9065
00064
Fuel
.9526
00065
.9363
00066
9199
00066
.9537
00065
.9374
00065
9212
00055
Do
a Calculated
a1
is
the change
of
.8936
a
9066
.9082
PLOT OF
XII.
AND
17
AGAINST DENSITY AT
/3
25 C
u>
-^ 5*-^
3D
^_i ^^O
>^o
o~
90
O
80
<
73
^^ -S.
"7 ^T
61
o
u
17
fr
-,
t B
W<5
.80
Density, at 25 C.
Fig.
4.
Plot of a and
j3
against density
when transformed
6o/6o
F were used in
at
XIII.
TABULATED VALUES OF D
TABLE
25 ,
(Fig 4)
(8
-0. 0000004
0.
0000000
0000003
0000000
0000003
0000000
0000003
0000000
00092
0000003
0000000
00091
0000003
0000000
-0. 00099
0.62,
AND
10
25
a,
0.63
00097
0.64
00095
0.65
00094
0.66
0.67.
0.68.
00090
0000002
0.69.
00088
0000002
0000001
0.70.
00087
0000002
0000001
+. 0000001
0.71.
00086
0000002
0000001
0.72.
00084
0000002
0000002
0.73.
00083
0000001
0000002
0.74.
00081
0000001
0000002
0.75.
00080
0000001
0000002
0.76.
00078
0000001
0000002
0.77.
00077
0000001
0000002
0.78.
00075
0000000
0000003
XIV.
Measurements
made on
of
petroleum
the basis of 6o
oils in
and
to water at 6o
Baume
is
ordinarily
I5?56C).
becomes
Specific
gravity
t/i 5
?56
= specific
gravity
i5?56/i5?56 + at0f
2
15.56) +ft (*-i5-56)
in which,
at
aT
at
= a T + 2/3(2 T) and
,
/3 t
= &T
19
For the purpose of calculating the volume of oil at any temperature from the volume at 6o F (15^56 C), the equation is put
in the form:
^t
in
+B
a-15.56)
which
t
j
ft
and
B=Aa - >.
A = -^~
r>
>.
25
of different specific
gravities are
TABLE
Specific gravity
15956
15956
11
'
Specific gravity
15956
15956
**
0.630
0.00156
0.0000030
0.800
0.00091
0.
0000009
0.640
.00150
.0000028
0.810
.00089
0000008
0.650
.00145
.0000026
0.820
.00087
0000007
0.660
.00140
.0000024
0.830
.00084
0000007
0.670
.00136
.0000023
0.840
.00082
0000006
0.680
.00132
.0000022
0.850
.00081
0000006
0.690
.00128
.0000020
0.860
.00079
0000005
0.700
.00125
.0000019
0.870
.00077
.0000005
0.710
.00121
.0000018
0.880
.00076
.0000004
0.720
.00118
.0000016
0.890
.00075
.0000004
0.730
.00114
.0000015
0.900
.00074
0000004
0.740
.00111
.0000014
0.910
.00073
0000003
0.750
.00107
.0000013
0.920
.00072
.0000003
0.760
.00104
.0000012
0.930
.00071
0000002
0.770
.00100
.0000011
0.940
.00070
0000002
0.780
.00097
0000010
0.950
.00069
.0000002
0.790
.00094
.0000009
0.960
.00069
0000002
XV. APPLICABILITY
The expansion
20
oils
having a
unlikely that
cific
any sample
of
2S
gravity of 0.8000 at -%-
is
0.00072,
American petroleum
will
have a rate
of
oil
and
it is very
having a spe-
change
less
than
commercial
It
is
oil
tables
beyond that
point.
may,
21
for example,
for Pennsylvania
1.
The
SOURCES OF ERROR
made by
the
(a)
methods described in
errors in weighing
(6)
this
The density determinations were usually made over a temperaand it is therefore apparent that the result-
ture interval of io C,
22
XVI.
The Bureau has several times been requested to furnish information in regard to the rate of change of density and volume of
petroleum oils at high temperatures, especially in connection
with the calculation of volume of fuel oil at the standard temperature of 60 F, from its volume measured at relatively high
temperatures when fresh from the topping plant. The information is also desired for use in the stillroom, where specific-gravity
determinations of the different cuts must be made with as little
delay as possible. It was therefore thought advisable to make
density determinations on certain of the oil samples at temperatures considerably higher than 50 C, the upper temperature limit
Accordingly, determina-
tions were
From
made on
9, it will
is
up
to 95 C.
be seen that on
practically the
cer-
same
all
The arrangement
and the
solid
change
of density again
measured.
TABLE
The
results are
19 to 25
0.
oil
sample
then a
rate of
shown below:
12
Change
Same
rate of
00063
.00072
of
25 to 50
0.
00063
.00063
50 to 75
75 to 95
00063
0.00063
.00064
.00063
0.
23
'
temperatures a
still
would have been found, but conditions were such that at that
time the measurements could not conveniently be carried lower.
The sample was, however, placed in a glass tube and packed in
an ice bath and its appearance noted as its temperature was
lowered. At temperatures above 25 C the oil was as clear as
before the paraffin was added; at about 20 C it became somewhat cloudy; and at 15 C it was very cloudy or opaque, with
a characteristic flaky appearance. At still lower temperatures it
became practically a solid vaseline-like mass with very pronounced irregular fractures and transverse fissures.
The behavior of the above sample was very similar to that of
certain other samples previously examined, in which abnormally
was
also
solid at
XVII.
The
comparison can
be made, are in substantial agreement with those given by D.
Holde in his book entitled ''Examination of hydrocarbon oils,"
and that of other experimenters; for example, Hans Hofer and
Augustus H. Gill.
Since the direct object of this investigation was to obtain data
from which to calculate expansion tables for petroleum oils, the
work itself can perhaps best be judged by a consideration of these
A comparison of the tables (Circular No 57, this Bureau)
tables.
with those published by the Kaiserlichen Normal Eichungs Kommission (Germany) in 1892 and republished in 1906 shows that
when reduced to the same basis they are in excellent agreement
throughout their entire range. Only in rare instances do the
reduced specific gravities differ by more than one unit in the third
decimal place. In most cases the two tables are in perfect agreement or differ by not more than five units in the fourth decimal
place.
24
is
30
and 40 Baume
Baume
TABLE
[A= Data
in this
two
of
tables give
at 60 F.
13
Manual
Observed values,
20 Be.
Degrees
Observed temperature, F
Baume at
60
Observed values,
30 Be.
Degrees
Baume
60
at
Observed values,
40 Be.
Degrees
Baume at
60
30
21.7
21.8
32.0
32.2
42.4
42.5
40..
21.2
21.1
31.4
31.4
41.6
41.6
50
20.6
20.5
30.7
30.7
40.8
40.8
60
20.0
20.0
30.0
30.0
40.0
40.0
70
19.4
19.4
29.3
29.3
39.2
39.2
80
18.9
18.9
28.7
28.6
38.5
38.4
90
18.3
18.4
28.0
28.0
37.7
37.6
100
17.8
17.8
27.4
27.3
37.0
36.8
17.2
a 17.3
26.8
a 26.7
36.3
a 36.1
no
For the