Designation: D 1747 99

AMERICAN SOCIETY FOR TESTING AND MATERIALS 100 Barr Harbor Dr., West Conshohocken, PA 19428 Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

An American National Standard

Standard Test Method for

Refractive Index of Viscous Materials1

This standard is issued under the xed designation D 1747; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon (e) indicates an editorial change since the last revision or reapproval. This standard has been approved for use by agencies of the Department of Defense.

1. Scope 1.1 This test method covers the measurement of refractive indexes, accurate to two units in the fourth decimal place, of transparent and light-colored viscous hydrocarbon liquids and melted solids which have refractive indexes in the range between 1.33 and 1.60, and at temperatures from 80 to 100C. Temperatures lower than 80C can be used provided that the melting point of the sample is at least 10C below the test temperature. 1.2 This test method is not applicable, within the accuracy stated, to liquids having colors darker than ASTM Color No. 4 ASTM color as determined by Test Method D 1500, to liquids which smoke or vaporize readily at the test temperature, or to solids melting within 10C of the test temperature.
NOTE 1The instrument can be successfully used for refractive indices above 1.60; but since certied liquid standards for ranges above 1.60 are not yet available, the accuracy of measurement under these conditions has not been evaluated.

E 1 Specication for ASTM Thermometers5 3. Terminology 3.1 Denition: 3.1.1 refractive indexthe ratio of the velocity of light (of specied wavelength) in air, to its velocity in the substance under examination. The relative index of refraction is dened as the sine of the angle of incidence divided by the sine of the angle of refraction, as light passes from air into the substance. If absolute refractive index (that is, referred to vacuum) is desired, this value should be multiplied by the factor 1.00027, the absolute refractive index of air. The numerical value of refractive index of liquids varies inversely with both wavelength and temperature. 4. Summary of Test Method 4.1 The refractive index normally is measured by the critical angle method using monochromatic light from a sodium lamp. The instrument is previously adjusted by means of calibration obtained with certied liquid standards. 5. Signicance and Use 5.1 Refractive index is a fundamental physical property that can be used in conjunction with other properties to characterize pure hydrocarbons and their mixtures. 5.2 The use of refractive index in correlative methods for the determination of the gross composition of viscous oils and waxes often requires its measurement at elevated temperatures. 6. Apparatus 6.1 Refractometer, precision Abb-type,6 having a range in refractive index from 1.30 to 1.63. Other instruments reading to at least four decimal places may be used..
NOTE 2When other instruments are used, follow the manufacturers instructions for operation, maintenance, calibration, and analysis. For accepting the instrumentation for use, analysis of a NIST traceable certied material to ensure accuracy should be performed.

1.3 The values stated in SI units are to be regarded as standard. The values stated in inch-pound units are for information only. 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specic hazards, see Note 4, Note 5, and Note 6. 2. Referenced Documents 2.1 ASTM Standards: D 362 Specication for Industrial Grade Toluene2 D 841 Specication for Nitration Grade Toluene3 D 1218 Test Method for Refractive Index and Refractive Dispersion of Hydrocarbon Liquids4 D 1500 Test Method for ASTM Color of Petroleum Products (ASTM Color Scale)4
This test method is under the jurisdiction of ASTM Committee D-2 on Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee D02.04.0Don Physical Methods. Current edition approved April 10, 1999. Published May 1999. Originally published as D 1747 60 T. Last previous edition D 1747 94. 2 DiscontinuedSee 1988 Annual Book of ASTM Standards, Vol 06.03. 3 Annual Book of ASTM Standards, Vol 06.04. 4 Annual Book of ASTM Standards, Vol 05.01.
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6.2 Thermostat and Circulating Pump, capable of maintaining the indicated prism temperature constant within 0.02C.

Annual Book of ASTM Standards, Vol 14.03. The Abb-type precision refractometer is no longer available but may be obtainable from instrument exchanges or used equipment suppliers. Other precision refractometers may be suitable, but they have not as yet been tested cooperatively.
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D 1747
The circulating uid consists of ethylene glycol or a mixture of 30 to 40 volume % of glycerin in water owing through the prisms at a xed rate of at least 2.5 L/min. For work at 100C, properly controlled wet steam is also suitable.
NOTE 3The constancy of the prism temperature can be seriously affected by variations in ambient conditions such as air drafts or changes in room temperature. Reasonable precautions should be taken to minimize these factors. Insulation placed on the thermostat, circulating uid lines, and refractometer also may prove to be helpful.

sodium D line certied at 20, 25, 30, 80, and 100C can be obtained from API Standard Reference Office, CarnegieMellon University, Pittsburgh, PA 15213. 8.2 Working StandardsFor working standard hydrocarbons, reasonably well puried samples of n-hexadecane, transdecahydronaphthalene, and 1-methylnaphthalene may be used. Their exact values are determined by comparison with standard samples of the same hydrocarbons having certied values of refractive index.
NOTE 8Caution: Both primary and working standards are combustible.

6.3 Thermometers, conforming to Thermometer 21C for determinations at 80C or Thermometer 22C for determinations at 100C as given in Specication E 1 are recommended. The temperature measuring device, suitably calibrated, shall be positioned to measure the temperature of the prism (see Note 4) within an appropriate holder. The holder shall provide for adeuate immersion of the temperature measuring device and for free ow of the circulating uid. The temperature measuring device holder assembly shall be insulated with a suitable material, such as cork..
NOTE 4In the precision Abb type refractometer, the thermostating liquid should pass the thermometer on leaving, not on entering, the prism assembly.

9. Sample 9.1 A sample of at least 0.5 mL is required. The sample shall be free of suspended solids, water, or other materials that tend to scatter light. Water can be removed from hydrocarbons by treatment with calcium chloride followed by ltering or centrifuging to remove the desiccant. The possibility of changing the composition of a sample by action of the drying agent, by selective adsorption on the lter, or by fractional evaporation, shall be considered. 10. Preparation of Apparatus 10.1 The refractometer shall be kept scrupulously clean at all times. Dust and oil, if allowed to accumulate on any part of the instrument, will nd its way into the moving parts, causing wear and eventual misalignment. If permitted to collect on the prism, dust will dull the polish, resulting in hazy lines. 10.2 Thoroughly clean the prism faces with fresh clean lens tissue or surgical grade absorbent cotton saturated with a suitable solvent. Pass the swab very lightly over the surface until it shows no tendency to streak. Repeat the procedure with a fresh swab and solvent until both the glass and adjacent polished metal surfaces are clean. Do not dry the prism faces by rubbing with dry cotton. 10.3 Adjust the thermostat so that the temperature as indicated by the thermocouple inserted between the prism faces and wet with oil is within 0.2C of the desired test temperature. This temperature is to be held constant to within 0.02C during the test. Observe and record the thermometer reading corresponding to the test temperature. Turn on the sodium arc lamp and allow it to warm up 30 min. 11. Standardization with Reference Liquids 11.1 Introduce a sample of the API Standard transdecahydronaphthalene to the prism which is adjusted to the chosen test temperature of 80 or 100C, turn the telescope adjustment screw until a refractive index scale reading corresponding to the certied refractive index for trans decahydronaphthalene is observed, and adjust the instrument according to the instructions given by the manufacturer until the sharp boundary between the light and dark portions of the eld passes through the intersection of the cross hairs of the telescope. 11.2 Check the accuracy of this setting by loading a fresh sample of trans-decahydronaphthalene and measure its refractive index at the test temperature following the procedure described in Section 12. If the value for the refractive index differs from the certied value by 0.0001 or more units, then
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6.4 Thermocouple, 7 copper-constantan foil type, 0.0005 in. (0.013 mm) thickness, and precision potentiometer. The thermocouple is calibrated by immersing to a depth of 1 in. (25 mm) in a circulating liquid thermostat and comparing with a thermometer of known accuracy. 6.5 Light Source, Sodium Arc LampThe light source shall be a sodium arc lamp, which shall be used only after the removal of Amici compensating prisms, if there are any present in the instrument.
NOTE 5If the eld division as observed in 12.2 shifts when the Amici prism is rotated, the prism should be removed to avoid incorrect readings.

7. Solvents 7.1 Cleaning Solvent,, any suitable solvent capable of cleaning the apparatus as described in Section 10. 1,1,1, Trichloroethane has been found suitable to use.
NOTE 6Warning: Harmful if inhaled. High concentration can cause unconsciousness or death. Contact can cause skin irritation and dermatitis.

7.2 Toluene, conforming to Specication D 362 or Specication D 841.

NOTE 7Warning: Flammable. Vapor harmful.

8. Reference Standards 8.1 Primary Liquid StandardsThe organic liquids listed in Table 1, with the values of their refractive indexes for the
7 A suitable thermocouple is available from RdF Corp., 23 Elm Avenue, Hudson, NH 03051. Part number 20014 should be specied.

TABLE 1 Primary Liquid Standards

Certied Standard Approximate Refractive Index, nD 1.41 1.44 1.59

n-Hexadecane trans-Decahydronaphthalene 1-Methylnaphthalene

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repeat the procedure given in 11.1 until a satisfactory check is obtained. 11.3 Measure the refractive index of API Standard n-hexadecane and 1-methylnaphthalene at the test temperature following the procedure described in Section 12. 11.4 Construct a calibration curve for use at the chosen test temperature. Plot the difference between the observed refractive index for n-hexadecane and its certied value along the ordinate against the refractive index level along the abscissa. Also plot the difference between the observed and certied refractive indices for 1-methylnaphthalene in the same manner. Draw a straight line from the point representing the deviation found for n-hexadecane to zero at the certied refractive index of trans-decahydronaphthalene. Likewise, draw a straight line from this same zero point to the deviation found for 1-methylnaphthalene. 11.5 If it is desired to measure the refractive index of samples at a temperature other than 80 or 100C, obtain calibration data by repeating 11.1-11.4 at this desired temperature. Determine the refractive indices for the API Standard compounds, n-hexadecane, trans-decahydronaphthalene, and 1-methylnaphthalene at the desired temperature by plotting the certied refractive indices at 20, 25, 30, 80, 100C against temperature and drawing a smooth curve between the points. 11.6 Precautions In using pure liquids for calibration or checking of calibration of an Abb-type refractometer, the following precautions should be observed: 11.6.1 Before inserting the hydrocarbon calibrating liquids, the prisms should be ushed with solvents and cleaned as described in 8.2. It is advisable to preheat the solvent before use to minimize thermal shock to the prism. This should be followed by several such ushings with the test liquid and wiping with lens paper. After such cleaning a reading with the test liquid should be taken as described in Section 11. This should be followed by another ushing with the test liquid before taking another reading of the test liquid in the prescribed manner. The prisms cannot be considered free from contaminating substances until two such determinations on the test liquid agree within the limits given in 11.6.2. 11.6.2 In setting the edge of the eld on the cross hairs, readings should be taken in pairs, approaching the alidade setting from one direction only as recommended by the manufacturer. Several such sets will probably be necessary before satisfactory agreement is obtained. Satisfactory agreement is 0.00005 to 0.0001. 11.6.3 For results of highest accuracy, the calibration with hydrocarbons of known properties should be made immediately before the determination on the sample. 11.6.4 Fluctuations in ambient temperatures should be minimized as much as possible during the test. 12. Procedure 12.1 Thoroughly clean the prism faces as described in 10.2. Adjust the thermostat so that the temperature indicated by the thermocouple placed between the faces of the closed prism (loaded with oil) is within 0.2C of the desired value. The thermocouple is used for establishing the correct temperature level and may be removed during measurements of refractive index. The observed reading of the thermometer at this
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temperature must be held constant to 0.02C in the measurements to follow. 12.2 Close the prism box and let it stand for 3 to 5 min to ensure temperature equilibrium between the prisms and the circulating bath liquid. Melt samples which are normally solid in a small container and charge as a liquid to the prism. Charge the sample from a small pipet or medicine dropper through the refractometer opening or onto the prisms open just enough to admit the sample. About 0.2 to 0.5 mL of the sample should be allowed to ush through before completely closing the prisms. Samples of low volatility or high viscosity may be placed directly onto the prism surface by means of a stirring rod, being careful not to touch the prism surface with the rod. If not enough sample has been used to ll the space between the prisms completely or evaporation causes the eld division in the telescope to become uneven, clean the prisms thoroughly before employing a new portion of the sample. 12.3 Set the light source to pass rays into the illuminating prism. Move the telescope by means of the adjustment screw until the eld division is visible in the telescope. 12.4 Adjust the angle of incidence until the eld consists of a light and a dark portion separated by a sharp boundary which may be brought into focus by sliding the telescope eyepiece. In the case of colloidal or suspended matter in the sample, the boundary line may appear diffused or hazy, even though the telescope is perfectly focused. Filtration of the sample will sometimes correct this condition. Water in the sample may also give this hazy effect. 12.5 Turn the adjustment screw so that the eld division passes through the intersection of the crossed lines in the telescope. With the exception of extremely volatile samples, an interval of 2 to 3 min should be allowed before taking readings to permit the sample to come to the same temperature as the refractometer. In setting the edge of the eld on the cross hairs, at least two determinations should be obtained which agree within 0.00005 to 0.0001 for precision work. The nal reading is best obtained by approaching this setting successively from both light and dark sides of the eld. Read the scale through the microscope provided. Focus by sliding the eyepiece in or out. Measure and record the refractive index using at least two separate loadings of sample.
NOTE 9For more reliable results with a sample which shows a diffused or hazy boundary line even after ltration, there are two possible remedies: (1) back window reection if the refractometer is so equipped, or (2) dilution with a suitable solvent. (1) Back window reection also permits measurements of samples too dark for normal operation. The sample is charged in the normal manner. Remove the cover plate on the back of the prism housing and position the light source so that it shines directly into the opening. Bring the boundary line into view. The elds will be reversed and considerably reduced in contrast. Read the refractive index as described above. Care should be exercised during the measurement since the sharp boundary line is faint and difficult to distinguish. (2) The dilution procedure is generally unsatisfactory and should only be used if it is impossible to obtain consistent readings in any other way. The sample is diluted with an equal volume of high boiling solvent whose density and refractive index are known and an appropriate correction applied to the results. Highly aromatic or olenic samples in the gas oil range can be measured by this procedure. The possibility of volume change on mixing should be considered. A check on the density of the

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mixture will show if this occurs.

13. Calculation and Reporting 13.1 Correct the observed refractive index by the amount shown in the calibration curve. Report the value of refractive index as:
nDt 5 . . . (1)

14.1.2 ReproducibilityThe difference between two single and independent results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed 0.0006 units of refractive index only in one case in twenty.
NOTE 10The precision for this test method was not obtained in accordance with RR:D02-1007.8

14. Precision and Bias 14.1 The precision of the test method as obtained by statistical examination of interlaboratory test results is as follows: 14.1.1 RepeatabilityThe difference between successive test results obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed 0.00007 units of refractive index only in one case in twenty.

14.2 The bias for this test method has not been determined. Subcommittee D02.04.0D plans to cooperatively test modern refractometers and determine the bias. 15. Keywords 15.1 oils; purity; refractive index; refractometer; wax

Annual Book of ASTM Standards, Vol 05.03.

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