VISCOSITY MEASUREMENT Master Viscometers M. R. CANNON, School of Chemistry and Physics, The Pennsylvania State College, State College, Pa. This paper describes the construction and operation of two types of
Unlike the master viscometer of Figure 1, check runs can be made with the opaque type only by cleaning and reloading. The opaque type has the advantage of no drainage errors and opaque liquids can be tested. I t has the disadvantages of longer time to attain bath temperature (as much as five times as long as the other type), since the oil is stagnant during heating, and a lengthy time for check runs. In general, the normal type shown as Figure 1 is preferable, but if one wishes to study drainage, handle opaque liquids, or increase rates of shear by applied external pressure the opaque type is best. Where external prassures are applied to increase shearing rate, drainage errors would be serious in the normal-type viscometer.
master viscometers designed for accurately calibrating the various types of routine viscometers now in extensive use. The first instrument is calibrated directly with water at POo C. The remaining instruments of larger bore are then calibrated against the first by means of hydrocarbons of suitable viscosity. These calibrated master viscometers are used to establish accurately the viscosity of a whole series of calibrating fluids to be used in calibrating routine viscometers. Since some fluids change in viscosity with age, the master instruments are employed to check the standard fluids two or three times per year. The opaque-type master is useful in handling very dark or opaque liquids and in studying the drainage effect in viscosity measurements.
CALIBRATION PROCEDURE
N TWO previous papers (3,4) simple and accurate routine viscometers were described for the measurement of the viscosities of liquids ranging from one third to more than two thousand times the viscosity of water. A special design ( 4 ) is necessary for the case where the test liquid is so dark or opaque that the operator cannot see through glass that is wet with a thin film of it. Before these routine viscometers are usable it is necessary to cdibrate them accurately. This paper describes suitable master viscometers which were designed and are now used by many laboratories for this special purpose. Obviously, it is not necessary for each laboratory to secure master viscometers, since calibrated routine viscometers are available through scientific supply companies. However, many large laboratories desire to maintain complete calibration facilities and for them master viscometers are recommended. It is unnecessary to use master viscometers in the calibration of the special-type routine viscometer for nonviscous liquids (viscosity range of 0.3 to 2 centipoises) shown as Figure 2 in reference (31,since these can be calibrated directly with water ( 1 ) .
I
The viscosity of water is probably known to a higher degree of accuracy than any other liquid. Its complete stability and general availability make it an excellent reference liquid for all relac tive viscosity measurements. Therefore, a master viscometer of md capillary bore is calibrated by means of distilled water a t 20' C. where the kinematic viscosity of water is 1.007 centi-
n
k-2.54
OPERATION OF MASlER VISCOMETERS
ETCHED LINES
These instruments are used in exactly the same manner as the routine viscometers (a, 4 ) ; in fact, the only major difference is in capillary length and the height of driving liquid head. Most of the errors encountered in viscometry are caused by a loss of driving head and can be reduced in magnitude by having a large driving head. In this respect the master viscometers have four times the head available in the routine type. When made with the dimensions shown they will fit readily mto a constanttemperature bath 60 cm. (24 inches) deep. In order to charge, the instrument is held in an inverted vertical position with the capillary side submerged in the liquid under teat. Suction is then applied to the other arm of the instrument and the meniscus is brought to mark F. The instrument is then revolved to its normal vertical position and placed in the constanttemperature bath. I t may be quick1 aligned to a vertical osition with the aid of a small lumb bo$ made from a piece ofsilk thread and a small piece of Ead wire attached to a small cork to fit into the 1.2-cm. viscometer leg. When the bath temperature is attained suction is applied to raise the meniscus into bulb A , Figure 1. The efflux time is then measured for the liquid to discharge from between the etched marks above and below bulb B. Check runs are made by repeating this procedure. When using the master instrument (Figure 2) it is necessary to close the upper capillary with a short piece of rubber tubing and inchclamp after allowing the fluid to drain from the up r capiltary into A; times are measured for filling bulbs C anB"D after bath temperature is attained. Viscosities calculated by the constants for C and D should agree.
D I M E N S I O N S IN C M
Figure 1.
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h4aster Viscometer, Normal Type
November, 1944
ANALYTICAL EDITION
stokes. This figure may be inaccurate to the extent of *0.5%. However, if all laboratories use this figure relative viscosities can be measured with a higher degree of accuracy, since the measurement of relative viscosities is much simpler than the measurement of absolute viscosities. Fortunately, practically all viscometers in use in this country and abroad have been calibrated using this primary reference viscosity of 1.007 cs. at 20' C., thanks largely to the efforts of the viscosity subcommittee of the American Society of Testing Materials. I n addition, values of 0.689 centistoke for water a t 100' F. (37.78' C.) and 0.518 centistoke at 130" F. (54.44' C.) are recommended by A.S.T.M. When the small-bore master viscometer has been calibrated with water, a more viscous hydrocarbon may be tested in it and this in turn used to calibrate a second master viscometer of larger capillary bore, which could not be calibrated directly with water because of high capillary velocity with resulting low efflux time and a high and inaccurately known kinetic energy correction. A third and fourth master viscometer of successive larger capillary bores may then be calibrated in a similar manner. I n order to avoid cumulative error in this step-up procedure, each may be further checked against the first master viscometer by means of suitable oils. When the fourth is checked against the first it means that the efflux time may be 4 minutes in the fourth and 24 hours in the first. While this procedure is lengthy, it need be done but once each year when master viscometers are checked. When the master viscometers are calibrated, a series of oils or pure hydrocarbons is then tested and their viscosities are accurately established. These standardized fluids are then employed for the daily, weekly, or monthly calibrations of routine viscomters such as the Cannon-Fenske type (8, 4 , the Ubbelohde type (8), the Zeitfuchs type (Q),or any of the other accurate routine viscometers now in extensive use. The calibrating fluids should be carefully selected or prepared. Many lubricating oils increase in viscosity from 0.5 to 1.0% per year by aging at room temperature. I n general, these can be stabilized by desludging with aluminum chloride or by solvent refining followed by the addition of a suitable oxidation inhibitor. Since the oils are stored at room temperature stabilizing is not difficult. A series of high viscosity index stabilized oils in use since 1933 has not changed in viscosity by 0.2% to date. It is preferable to store in glass rather than metal cans and it should be a laboratory rule that when a sample of oil is removed from storage it should be discarded after use. The number of oils to be standardized for use as calibrating fluids will vary with the needs of laboratories. The writer finds a series of 14 such oils ranging in viscosity from 1 to 3000 centistokes by a rough factor of 2 between each adjacent pair (1 w., 2 cs., 4 cs., etc.) to be very convenient. One can operate with fewer oils but calibrations will require a longer time. It is necessary to calibrate a viscometer at only one temperature, since the change of viscometer constant with temperature is very small and can be calculated (3). This variation of constant with temperature amounts to only 0.5% for a change of 43.33' C. (110' F.) in the routine type ( $ 4 ) as proved by experiment. It is much smaller in the master type described here. This change in constant with temperature is due to a change in volume of liquid in the instrument with temperature change since the viscometers are charged a t room temperature, MAGNITUDE AND SOURCE OF ERRORS
Viscosity is usually calculated from efflux times by means of Poiseuille's equation corrected for kinetic energy loss as follows:
This is usually given as :
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SAME SIZES AS UPPER CAPILL
1 1 k?W Figure 2.
DIMENSIONS IN CM.
Master Viscometer, Opaque Type
where KV = kinematic viscosity in stokes w = viscosity in poises p = density in grams per cc. g = gravitational constant in cm. per second per second H = driving fluid head in cm. r = ca illary radius in cm. 1 = e&x time in seconds L = ca illary length in cm. v = e & x volume in cc. m = kinetic energy correction coefficient F
R = -mV 87rL Hundreds of experiments have shown that C is a constant for long capillary viscometers. However, B will be a constant only if m, the kinetic energy correction coefficient, is a constant. From a theoretical standpoint one would not expect m to be a constant and recent extensive measurements indicate that m varies with Reynolds number as well as with the shape of the capillary entrance and exit. If one employs a symmetrical viscometer the value of m will be different for flow to left than for flow to right. Bingham and Geddes (8) and Spooner and &rex (7) have made such measurements and found wide variations in m-for example, ( 2 ) an m of 1.46 for flow to left and an m of 0.74 for flow to right, and ( 7 ) an m of 3.05 for flow to left and an m of 1.52 for flow to right. This indicates the extreme sensitiveness of this loss of driving force at the capillary ends. It is, of course, not surprising to find a different value of m for different flow directions, since the exit end of the capillary contributes more to m than does the entrance end. Consequently, if there are slight differences in the shape of the two ends m will vary with direction of flow. For the master viscometers described here and the routine viscometers previously described, where all capillary ends are
INDUSTRIAL A N D ENGINEERING CHEMISTRY
710
gradually tapered, experiments show that m does not exceed 0.5. However, since it does vary, the safest procedure is so to desi the viscometers that the term B/t is negligible compared to term Ct and the above equation then becomes
tE
KV = Ct If fluids of widely different viscosities leave different quantities of liquid on the walls of the efflux bulb for routine viscometers (3)
and the master viscometer shown as Figure 1, then C will not be a constant, since this drainage will change V. The master viscometer shown aa Figure 2 is free of drainage error, since the liquid is entering clean dry bulbs. On all oils investigated in the two master-type instruments it was found that C is a true constant. This means that the rate of drainage is inversely proportional to the viscosity. Thus, a 3Wcentistoke oil will drain a t only one third the rate of a 100-centistoke oil but the total drainage time will be three times as great for the 3Wcentistoke oil and so in each case the degree of drainage is the same.
The equations and methods for calculating the various corrections in basic calibration work have been presented in detail (3), and are not repeated here. The magnitude of the corrections for the master viscometer shown as Figure 1 is: (a) kinetic energy correction 0.04% for water a t 20" C., less for more viscous fluids; ( b ) surface tension correction when using water and hydrocarbons in the same instrument, 0.09%; (c) change of viscometer con-
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stant with temperature, 0.03% per 30" e. change in temperature. For the master viscometer shown aa Figure 2 the same figures apply, except (c) is 0.1% per 30' C:since the charge is greater. Results are reproducible in these instruments to within 0.1% and consequently relative viscosities can be measured to that degree of precision. Absolute viscosities depend upon the error inherent in the value of 1.007 centistokes taken for water a t 20" C. This is probably in the order of *0.5%. These master viscometers are an improvement over those described earlier (6,6). The capillary diameter required for a given constant C can be calculated from the equations above. LITERATURE CITED
(1) Am. SOC. Testing Materials, "Standards on Petroleum Produotts and Lubricants". Designation D445-39T. (2) Bingham, E. C., and Geddes, J. A., Physics, 4, 203 (1933). (3) Cannon, M. R., and Fenske, M. R., IND. ENO. CHEM.,ANAL. ED.,10, 297 (1938). (4) Ibid., 13, 299 (1941). (5) Cannon, M. R., and Fenske, M. R., Oil and Bas J.,33,52 (1935). (6) Ibid., 34, 45 (1936). (7) Spooner, L. W., and Serex, P., Physics, 6, 162 (1935). (8) Ubbelohde, L., IND.ENG.CHEM.,ANAL.ED.,9, 85 (1937). (9) Zeitfuchs, E. H., Nail. Petroleum News, 29, 68 (1937).
Gum Content of Distillate Diesel Fuels L. W. DICKEY AND R O Y HENRY Standard Oil Company of California, Richmond, Calif. gum content of distillate Diesel fuels is of less significance in their evaluation than is this property of gasolines; there are, however, occasions when it is necessary to compare two Diesel fuels with respect to their tendency to form gum. Furthermore, the advent of increasing quantities of cracked Diesel fuels, complicated by the catalytic action of various metals with which such fuels may come in contact, makes it pertinent to establish a method by which the gum content, preformed and potential, may be determined. The following conditions for the evaporation of the fuel were established as satisfactory, after testing out numerous variations.
the end phase of the evaporation heat the h s k for approximately 15 minutes. Disconnect the flask as previously described, clean the outside thoroughly, and weigh.
APPARATUS
The procedure described constitutes a purely empirical test, as are all similar methods for measuring gum in petroleum products. It is therefore necessary that all details of the test be standardized and followed if results of useful precision are to be obtained. The following variables were investigated in arriving at the selected test conditions. DEGREEOF VACUUM.A vacuum of 50 to 55 cm. (20 to 22 inches) of mercury waa found adequate to volatilize 25 ml. of fuel within an hour, varying the temperature to suit the stock and keeping this to a reasonable maximum. With this degree of vacuum there is little danger of collapsing the flask, and it is easier to avoid trouble from leaks. EVAPOUTION TIME. Polymerization under the conditions existing in the test is a function of both time and temperature. The total period during which the sample is heated is set at about one hour. This period was arbitrarily selected, and further experience with the test, using a wider range of fuels, may show that the heating period can be reduced or that a longer period would be more satisfactory. AMOUNT OF SAMPLE. The amount of sample selected, 25 ml., is sufficient to give a weighable residue with the Diesel fuels available to the authors, and it behaved satisfactorily in the apparatus selected. The residue from smaller samples must be multiplied by a larger factor, and small errors, obviously, would be proportionally magnified.
THE
Erlenmeyer flask, capacity 50 ml. Condenser, Liebig type, water-cooled, with ada ter, preferably sealed on. Filtering flask, capacity 1 liter. 8il bath. Source of inert gas (natural, artificial, nitrogen, carbon dioxide). Vacuum pump. 9
PROCEDURE
Transfer 25 ml. of the Diesel fuel to a tared 50-ml. Erlenmeyer flask. Connect the flask to the condenser and to the source of inert gas by means of a cork stopper fitted with two glass tubes, the ends of which are flush with the bottom of the cork. Attach the filtering h s k to the condenser adapter by means of a rubber stopper, and connect the side arm of the flask to a source of vacuum. Apply a vacuum of 50 to 55 cm. (20 to 22 inches) of mercury to the assembly, and pass gas into the system a t a rate of approximately 250 ml. per minute. Immerse the flask in an oil bath heated to that temperature a t which the sample will be evaporated practically to dryness in 45 * 5 minutes. (This temperature will generally be approximately 150" F. below the 90% point of, the, A.S.T.M. D158 distillation.) At the end of the specified time increase the bath temperature 50" F., and increase the rate of gas flow to approximately 500 ml. per minute. Maintain these conditions for 10 to 15 minutes; then remove the oil bath, shut off the vacuum, and increase the flow of gas until the pressure in the system is approximately atmospheric. Disconnect the tared Erlenmeyer flask, add 25 ml. of a mixture of equal parts of carbon tetrachloride and acetone to the flask, and evaporate to dryness on the steam bath. Connect the flask to the condenser as before, again apply the vacuum, and with the gas flow and temperature as previously established for
Mg of gum per 100 ml. = mg. gain in weight
x
4
Following the procedure outlined samples of Diesel fuels and various distillate fractions of similar boiling range were tested, primarily to establish the repeatability of the method over as wide a range as waa possible with the stocks available. The data are presented in Table I. VARIABLES INVESTIGATED
