Viscosity Blending Relationships of Heavy Petroleum Oils
VERLE H. RAHMES, Stanolind Oil and Gas Co., Tulsa, Okla., AND
W. L. NELSON, University of Tulsa, Tulsa, Okla.
A total of 30 petroleum oil systems, using 17 different
oils, was investigated. Each system was investi-
gated at three or more compositions. The results
were compared with viscosities predicted by a num-
ber of methods that have been proposed in the litera-
ture. The Wright method, a new way of using the
A.S.T.M. chart for predicting blend viscosities, was
found to give the best results in most cases. Many
of the systems investigated were rather extreme, in
HEX oils of different viscosities are miued, the resulting
blend usually has a lower viscosity than would be com-
puted by assuming that viscosities are additive.
In 1887, Arrhenius ( 3 ) proposed a miuture rule in which log
viscosity was taken to be additive. Later, Bingham (5) proposed
reciprocal viscosities or fluidities, and in 1917 Kendall and Monroe
(11) proposed cube root of viscosity as the additive function.
Expressed as equations, these rules are:
1ogv1,t = xvl log 91 + x,, logqr Arrhenius (1)
1/11,2 = X&I + xS/w Bingham (2)
q1,t = xlill +
52 7 2 / * Kendall and Monroe (3)
where q is viscosity in absolute units, xe is volume fraction, and
xis mole fraction. These three rules were all designed for “ideal”
solutions and are generally not very accurate for use in predicting
viscosities of petroleum oil blends, although (1) and (3) may
have some application (8, 10).
The several methods that have been proposed and used for
predicting viscosities of petroleum oil blends are all empirical.
Wilson (16) found that the viscosity of the blend depended not
only on the amounts and viscosities of the oils being blended
but also on the base or nature of the oil. His work led to three
blending charts, one for blending oils of the same base, one for
use when the higher viscosity oil is of paraffin base, and one for
use when the higher viscosity oil is of naphthene base.
In 1932, the American Society for Testing Materials published
a viscosity-temperature chart (1) which may also be used as a
blending chart. This is the most widely used blending chart,
but Wilson’s charts are also used and have been reprinted in
several standard books on petroleum refining (4, 13).
At about the same time that the A.S.T.M. chart was first
published, Cragoe (6) presented a comparable method. His
viscosity function, L’, is approximately additive for mixtures and
so can be used in predicting the viscosities of blends.
In 1946, Wright (17‘) proposed a new method of using the A S . -
T.AI. chart for blending. The procedure is to plot the viscosity-
temperature lines of the oils and then to “blend” by linear
proportioning along the In T axis. Thus, blending is done a t
“constant viscosity” rather than a t constant temperature as in
the conventional use of the chart. Figure 1 illustrates the use of
Wright’s method of predicting blend viscosities. This figure is
included because Wright’s paper has not yet appeared in any
readily available publication.
In addition, several methods involving the use of correction
factors have been proposed. Lederer (12) proposed the equation
Xu1
Xe1
+ 55~02
= log111,2 - log 12
1% 1 1 - log 1 2 (4)
where xwis weight fraction and s is a constant, for any one system,
which is evaluated by examining one blend experimentally.
912
that the component oils varied considerably in
chemical nature. Two of these systems were found
to exhibit definite viscosity minima. I t was con-
cluded that the use of viscosity-temperature char-
acteristics of the component oils, as in the Wright
method, is a definite improvement in viscosity pre-
diction methods. However, sometimes differences
in oils are not indicated by these relationships, but
do affect blend viscosities to a considerable extent.
Cragoe (6) in presenting his method also introduced an equa-
tion involving a correction factor:
L’1,2 = ZWl L’, + XWZL’2 +xu1 xr2 c (5)
where L‘ is Cragoe’s viscosity function and C is a constant for
any one system, again evaluated from the results of one blend.
Such methods yield results that are usually of about the same
order of accuracy as the experimental work.
EXPERIMENTAL WORK AND DISCUSSION OF RESULTS
In the experimental work, 30 binary petroleum oil system
using 17 different oils were investigated. Viscosities were deter-
mined a t three or more compositions in each system. One pur-
pose was to compare the different prediction methods as to
applicability, and as a result many of the systems represent
unusual or extreme cases. Modified Ostwald viscometers were
used and viscosities were determined in accordance with A.S.T.M.
standards (‘3). All blending Tas done volumetrically, and the
over-all error of blending and viscosity determination is believed
to be not more than 0.5%. Properties and the source of the 17
oils are given in Table I.
Systems of Large Viscosity Ratio. The first 13 systems
exhibit a relatively large range of viscosity ratios (3 to 40) and
2 5000
2
0
ul 1000
\\
I
45
40 100
\
PI0
I
300
TEMPERATURE, F.
Figure 1. Use of Wright Method
Draw viscosity-temperature lines of oils A and B
To make blend having 400 seconds at 100’ F. use r
39.0 % oil B
MO
-
.N
.
0.64
-.- -
PR
Locate point R so that = and draw viscosity-temperature
line of blend through pointm 0 and R
V O L U M E 20, NO. 10, O C T O B E R 1 9 4 8 913

were made on a volumetric rather than weight basis. In the

Table I. Properties and Sources of Oils Used in Blends case of the Cragoe method, the results obtained by the use of
Kinematic Viscosity A.P.!. volume per cent are different from those obtained by the use of
Oil At looo F. At 210° F. V.I. Gravity Description weight per cent, but both involve relatively large errors in many
A 45.12 5.303 22.2 22.2 Refined naphthenic cases and the over-all results are about the same. Actually, a
oil
B 221.2 18.08 97.2 28 .O Solvent refined oil comparison based on the &st eight systems shows that there ip
C 30.09 4.914 92.0 30.9 Solventrefined oil
D 21.45 3.583 13.6 23.0 Raw distillate from somewhat better average accuracy when volume per cent is used.
naphthenic crude In the case of the Lederer method, results are almost exactly
E 392.1 16.31 -5.0 18.9 Raw distillate from
naphthenic crude the same for weight and volume per cent; the use of volume per
31.92 4.419 6.8 22.8 Raw distillate from
naphthenic crude cent merely results in a different numerical value of the constant.
488.7 19.87 18.9 20.2 Raw distillate from In the above comparison, the A.S.T.M. chart and Cragoe's
naphthenio crude
187.9 9.086 -83.7 12.3 Solvent extract method gave similar results. The principal difference between
34.21 5.612 112.7 31.8 Solvent refined oil
516.9 16.50 -62.5 15.4 Solvent extract the two methods is that the A.S.T.M. chart tended to give higher
100.3 10.86 100.3 28.3 Acid treated Daraf- viscosities than the experimental ones, whereas the Cragoe
fin base oil
iM 93.81 9.691 87.5 28.3 From. mixed base method usually gave lover ones. These results are averages that
crude
N 116.7 9.639 52.6 19.8 Acid treated naph- include a number of somewhat extreme blends-that is, blend9
thenic base oil There the viscosity index difference is large-and therefore are
0 312.1 19.80 77.5 24.8 Not known
P 90.52 7.312 3.9 17.1 Solvent e x t r a c t not representative of the results that would be expected in normal
Q 13.45 2.719 12.7 23.5 lubricating oil blending. In fact, in the case of the A.S.T.M.
crude
chart, a considerable part of the average error can be attributed
R 32.21 5.190 98.9 31.1 Technical white oil to the very large errors encountered in System JE, which has the
very high viscosity index difference of 118. This error and the
large errors in some less extreme systems emphasize the limita-
both large and small differences between viscosity indexes of the tions of the A.S.T.M. chart.
components. Viscosity ratio is defined as the ratio of the vis-
cosity of the high viscosity oil in a system to the viscosity of the
low viscosity oil, and viscosity index difference, as used in this Table 11. Comparison of Prediction Methods
paper, is the viscosity index of the low viscosity oil minus the Cragoe, Lederero,
Prediction method A.S.T.M. Wilson Wright Val. % Vol. %
viscosity index of the high viscosity oil. Table I1 gives per-
Av. error 5.4 2.9 1.8 5.0 0.5
centage errors in the viscosities predicted by the various methods Max. error 25.7 10.6 10.1 13.4 1.4
for the first 13 systems. -.
9% blends less than 2%
in error '" 23 62 72 21 100
Cragoe's and Lederer's methods are modifications of the Requires one experimental blend.
methods as they were proposed by these authors-i.e., blends

Table 111. Viscosities of Blends

Kinematic Viscosity viscosity V.I. Kinematic Viscosity Viscosity v.1.
System Composition At looo F.At 210° F. Ratio Difference System Composition At 100' F. At 210' F. Ratio Ditierencr
1. F E 25 F 75 E 179.7 11.15 12.4 11.8 14. QC 25 Q 75 C 24.32 4.257 2.25 -79.3
50 F 50 E 94.06 7.985 50 Q 50 C 20.11 3.653
75 F 25 E 52.86 5.829 75 Q 25 C 16.38 3.131
2. J E 25 J 75 E 164.9 11.57 11.5 117.7 15. Q F 25 Q 75 F 25.29 3.892 2.36 5.9
50 J 50 E 85.13 8.598 50 Q 50 F 20.41 3.462
75 J 25 E 51.79 6.875 75 Q 25 F 16.49 3.059
3. FB 25 F 75 B 133.5 12.68 7.0 -90.4 16. QD 25 Q 75 D 19.11 3.362 1.59 -0.9
50 F 50 B 82.31 8.791 50 Q 50 D 16.92 3.127
75 F 25 B 50.74 6.250 75 Q 25 D 15.14 2.915
4. JB 25 J 75 B 130.9 13.28 6.5 15.5
50 J 50 B 80 I90 9.735 17. QJ 25 Q 75 J 27.22 4.773 2.54 -100.0
75 J 25 B 52.09 7.362 50 Q 50 J 21.44 3.978
75 Q 25 J 17.02 3.249
5. D L 25 D 75 L 68.63 8.070 4.7 -86.7
50 D 50 L 46.20 6.237 18. OB 25 0 75 B 238.6 18.53 . 1.41 19.7
75 D 25 L 31.44 4.635 50 0 50 B 260.7 18.93
75 0 25 B 285.6 19.19
5. CL 25 C 75 L 73.66 8.911 3.3 -8.3
50 C 50 L 53.97 7.206 19. OE 25 0 75 E 350.9 17.17 1.26 82.5
75 C 25 L 40.08 5.911 50 0 50 E 334.7 17.81
75 0 25 E 321.7 18.77
7. DN 25 D 75 N 74.76 7.397 5.5 -39.0
50 D 50 N 48.59 5.744 ;20. OG 25 0 75 G 420.8 19.78 1.56 58.6
75 D 25 N 31.82 4,513 50 0 50 G 363.0 19.92
6. CN 25 C 75 N 78.89 7.966 3.9
75 0 25 G 334.9 19.70
39.4
50 C 50 N 54.99 6.715 21. OK 25 0 75 K 427.8 17.18 1.66 140.0
75 C 25 N 39.86 5.690 50 0 50 K 371.4 17.73
D. DK 25 D 75 K 24.1
75 0 25 K 333.9 18.81
183.6 10.31 76.1
50 D 50 K 78.63 6.845 22. B R (See Table IV and discussion)
75 D 25 K 38.97 4.871
'10. QK 25 Q 75 K 152.2 9.408 38.4 75.2 23. M P 25 M 75 P
50 M 50 P
88.62
88.56
....
.... 1.038 -83.6
50 Q 50 K
75 Q 25 K
58.63
26.03
5.854
3.888 75 M 25 P 90.56 ....
11. RO 25 R 75 0 159.7 13.54 9.7 21.4 24. LP 25
50
L
L
75 P
50 P
90.52
92.09
....
.... 1.055 -96.4
50 R 50 0
75 R 25 0
89.09
52.22
9.596
6.928 75 L 25 P 95.17 ....
12. co 25 C 75 0 158.2 13.46 10.4 14.5 25. F C 25
50
F
F
75
50
C
C
30.14
30.46
....
.... 1.059 85.2
50 C 50 0 86.41 9.465
75 c 25 0 49.68 6.755 75 F 25 C 30.94 ....
13. QL 25 Q 75 L 60.27 7.630 7.5 -87.6 26. JF 25 J 75 F 31.93 ....
.... 1.079 -105.9
50 Q 50 L 36.39 5,421 50 J 50 F 32.29
75 Q 25 L 22.00 3.825 75 J 25 F 33.23 ....
914 ANALYTICAL CHEMISTRY
The Wright method, which inherently takes into account the
difference in viscosity index of the blending stocks, gives con-
siderably better results in this comparison. The Wilson charts,
or equations, give results that are better than those from the
A.S.T.M. chart but not so good as those obtained when the
Wright method is used. The Wright method should generally
give better results than Wilson's, because the Kright method
involves a quantitative measure of the difference in the oils
being blended, whereas Wilson's method uses only a qualitative
evaluation of the difference. Both the Wright and Wilson
methods give somewhat high maximum errors, and in the case of
the Wright method this seems to be an indication that there are
important differences in oils which are not disclosed completely
by differences in viscosity index, or more properly, by differences
in viscosity-temperature slope.
The Lederer method shows an accuracy that is approximately
the same as the over-all experimental accuracy. Cragoe's
equation with the correction factor (Equation 5 ) was also employed
on Systems 1 through 8 and R as found to give results very similar
to the Lederer method. In most cases where great accuracy is
required, either Lederer's or Cragoe's correction method can be I

I I 1
pmployed. 20 40 60 80 100
Experimental viscosities of each blend are given in Table VOLUME PER CENT 8
111. Viscosities predicted by the various methods and per Figure 2, Viscosity of BH Blends at 100' F.
cent errors on each blend are not included, but are available in
the original work (15). Four other systems were studied ( f b ) , siderably more than the over-all experimental error. Investi-
but are not included because the accuracy of the work was not gation showed, in the case of these four systems, that the con-
comparable with the results presented here. stant, s, in Lederer's equation did not remain essentially constant
All the viscosities so far mentioned were determined a t 100' F. with composition. Again, in these systems, there was some
Viscosities a t 210" F. were also determined and various indication that Wright's method failed to evaluate completel!
prediction methods were again examined. A comparison for the blending characteristics of certain of the oils, as it gave
the first eight systems showed that errors from most of the results that were only slightly better than the conventional use of
methods were about one third as large as the errors found with the A.S.T.M. chart.
viscosities a t 100" F. The difference apparently can be ac- Minimum Viscosity Systems. System 22 (BH) is the most ex-
counted for by the decrease in viscosity ratio a t 210" F., as the treme of all the systems investigated. The viscosity index
viscosity index difference remains the same. The decrease in the difference is very large (181) and the viscosity ratio is small
error by most of the methods is very nearly proportional to the (1.18). This system gave results that are unusual for petroleum
decrease in viscosity ratio. oil systems because it exhibited a minimum viscosity. Blende
were made a t each 10% composition increment in order to obtain
a complete viscosity-composition curve. Figure 2 is a plot of
viscosities at 100' F. against composition and Table IV is a tabu-
Table IV. System BH
lation of viscosities a t 100' and 210" F. for System BH. The
Centistokes
Composition A t looo F. At 210' F. V.I.
minimum viscosity occurs a t about 30% B, a t which point the
H 187.9 -83.7
viscosity is 4.6% below that of oil H.
9.086
10B 90H 181.3 The phenomenon of minimum viscosity is well known in mix-
20B 80H 179.8 10.27 -12.3
30B 70H 179.3 tures of certain organic compounds such as acetone-carbon di-
40B 60H 181 .O 11.71 32.4 sulfide (9),and is also found in the addition of certain salts to
50B 50H 183 .O
60B 40H 187 .O 13.45 63.6 water (fd), but has apparently not been very nidely observed
70B 30H 193.0 in petroleum oil systems. Only one literature reference (7
SOB 20H 200.3 15.63 84.5
90B 10H 210.9 was found which reported similar blending characteristics-
B 221.2 18.08 97.2
in blends of paraffin wax with transformer oil.
At 210" F., system BH shows no minimum point (see Table
IV). I t has been observed in some of the classical examples of
Systems of Small Viscosity Ratio. The discussion-thus far minimum viscosity systems that the minimum point shifts,
applies to systems of large viscosity ratio (1to 13). In addition, a with increase in temperature, toward the low viscosity component
number of systems in which the viscosity ratio was small were and finally disappears (9).
investigated. It was hoped that, in such systems, the effect For minimum viscosity to be exhibited by a system, it is gener-
of viscosity ratio on blend viscosity would be minimized and that ally considered that the components must be of considerably
any errors resulting from the application of the various pre- different chemical nature. It is evident, from their properties
diction methods would be almost entirely due to viscosity index and sources, that B and H are different types of oils. That is
difference or, a t least, to some difference in the chemical nature true, even if both oils are considered to consist essentially of
of the oils being blended. hydrocarbons. There is, further, the possibility that oil H
Systems 14 through 17 are of small viscosity ratio and are in may contain a considerable portion of heterocyclic ring com-
the low-viscosity range, whereas systems 18 through 21, also of pounds.
small viscosity ratio, are in a higher viscosity range. The errors Further investigation was conducted in an attempt to dis-
from systems 14 though 17 are comparatively small by all the cover additional systems exhibiting viscosity minima. Systems
prediction methods investigated but the errors from systems 18 23 through 26 were chosen as among the most likely to exhibit
through 21 are rather large. Even Lederer's method gives an minima, because it appeared that if minima are to occur, vis-
werage error of 0.9% for systems 18 through 21, which is con- cosity index difference should be large and viscosity ratio small
V O L U M E 20, NO. 10, O C T O B E R 1 9 4 8
Of these four systems, only 23 (MP) showed a definite minimum,
although the three other systems tended to exhibit a constant
viscosity over certain ranges of composition.
Prediction of viscosities in systems exhibiting minima should
De expected to be difficult. In general, the prediction methods
discussed give viscosities that are intermediate to those of the
-wo components. The two methods involving correction factors
iwm be made to predict viscosity minima but only the Cragoe
method gives reliable results. The Lederer method, when ap-
died to system BH, gave very erratic results, as it showed a
maximum toward B as well as the desired minimum point near H
I t one point, the viscosity predicted by the Lederer equation was
in error by 98y0. If a prediction method is to be used on such
systems, the Cragoe equation (Equation 5), or one having a similar
mathematical form in which the correction factor i s added
)r subtracted, should be used.
CONCLU sIon s
rhe Wright method, a modification of the conventional uae of
the A.S.T.M. chart, gave the best results of any of the prediction
methods not requiring blend data. This conclusion is based on
results from 13 systems or a total of 39 blends investigated a t
100” F. and is substantiated by 12 other systems investigated
at 100”F., and 8 systems investigated a t 210” F. The advantage
of the Wright method is probably greater in this comparison than
would normally be found, because many of the systems reported
here were extreme cases.
The correction methods of Lederer and Cragoe generally
g w e very good accuracy. Perhaps the Cragoe equation or an
pquation of similar form has wider application, as this type of
-quation was found to be fairly good even for systems having a
viscosity minimum.
Certain extreme petroleum oil systems evhibit viscosity
~niiiima. For minima to occur, the oils should vary conqiderably
In chemical nature (or viscosity index difference) and the vis-
Ivosity ratio should be relatively small. There may also be
,Ither necessary conditions.
There are indications in several cases that the viscosity-
temperature slope, whirh is used bv the I17right method t o
Rapid Determination of Sulfides, Thiosulfates, and
Sulfites
In ReJinery Spent Caustic Solutions
J. H. KARCHMER AND J . W.DUNAHOE, Humble Oil and ReJining Company, Baytown, Tex.
I ?J ORDER t o avoid pollution of natural waters by alkali sul-
fides from refinery effluents, a close control of the sulfide con-
tent of plant spent caustic must be maintained. Rapid methods
of determination are necessary, so that the air-bloLYing treatment
Lhat is carried out to oxidize the sulfides t o thiosulfates and sul-
fates, which are not regarded as harmful to marine life, can be
rerininated at the earliest possible time. Although the sulfide
content is the prime interest in plant control, it is also desirable to
have a procedure that can be used to determine thiosulfates and
sulfites rapidly and with a reasonable degree of accuracy.
The determination of those sulfur compounds likely to be
present in caustic solution spent in oil refinery operations is de-
scribed in reference texts and literature articles. The methods
which are applicable to the determination of one, two, or three
constituents in the mixture are usually based upon iodometric or
915
evaluate the “degree of nonideality” of a system, does not
always properly predict blending characteristics.
ACKNOWLEDGMENTS
The authors express their appreciation to the Ethyl Corpora-
tion for financial aid through the Ethyl Fellowship a t the Univer-
sity of Tulsa. They are also indebted to F. T. Gardner of the
University of Tulsa and J. C. Geniesse of the American Society
for Testing Materials, for advice and information. Samples
were furnished by the Atlantic Refining Company, The Texas
Company, Mid-Continent Petroleum Corporation, Sinclair
Refining Company, and the General Petroleum Corporation.
LITERATURE CITED
drn. Soc. Testing Materials, Philadelphia, Pa., D341-39
Ibid., D445-42T.
Arrhenius. S.,2. p h y s i k . Chem., 1, 285 (1887).
Bell, H. S.,“Anierican Petroleum Refining,” 3rd ed., p. 422,
New York. D. Van Nostrand Co.. 1945.
Bingham, E. C., Am. Chem. J., 34, 481 (1905); J . Rheol., 3,
95 (1932).
Cragoe, C. S.,Proc. World Petroleum Congr. (London), Vol. 11,
529 (1933).
Dean, E. TV., and Cooke, M. B., J . Ind. Ens. Chem., 14. 410
(1922).
Epperson, E. R., and Dunlap, H. L., Ibid., 24, 1369 (1932).
Hatschek, E., “Viscosity of Liquids,” p. 141, New York, D. Van
Nostrand Co., 1928.
Herschel, W. H.. U. S. Bur. Standards, Tech. Paper 164 (June
18, 1920).
Kendall, J., and Monroe, K. P., J . Am. Chem. Soc., 39, 1787
(1917).
Lederer, E. L., Proc. World Petroleum Congr. (London), Vol. 11.
526 (1933).
Nelson, W.L., “Petroleum Refinery Engineering,” 2nd ed., p.
120, New York, McGraw-Hill Book Co., 1941.
Rabinovitch, A. I., J . Am. Chem. SOC.,44.954 (1922).
Rahmes, M. H., master’s thesis, University of Tulsa, May 1947.
Wilson, 0. G., Jr., A‘utl. Petroleum N e w , p. 87 (May 23, 1929).
Wright, TV. A., Division Petroleum Chemistry, 109th meeting.
A.C.S., Gen. Papers, p. 71, Atlantic City, N. J.
RECEIVED December 18, 1947. Presented before the Oklahoma Section of
the American Institute of Chemical Engineers, Bartlesville, Okla.. October
11, 1947.
acidimetric methods, and in the case of mercaptans (thiols), po-
tentiometric ( 1 1 ) and amperometric (6) methols are given.
Sulfides may be determined by direct titration with zinc reagent
( 4 ) , by direct iodometric titration ( 1 2 ) , and by iodometric titra-
tion following precipitation from the sample with ammoniacal
zinc chloride (10) Sulfides and thiosulfate may be determined in
a mixture by removal of the sulfides with cadmium carbonate
followed by iodometric determinations on both the precipitate
and the filtrate (29). Treadwell and Hall (16) give methods for
the determination of sodium sulfide, sodium bisulfide, and hydro-
gen sulfide by a combination acidimetric and iodometric method,
while Scott gives a method for determining sulfides, thiosulfates,
sulfites, and polysulfides in commercial sodium sulfide (9)
Mercaptides in presence of sulfides may be determined by a
potentiometric titration with silver nitrate solution (11).
Of these methods and numerous others, the method of Bal-
deschwieler (1)was the only one directly applicable to the analysis