NYKB ENL (so 12185 European Committe for Standardization ‘Com&é Européen de Normalisation Europtisches Komitee lr Normung Central Secretariat: rue de Stassart 38, 8-1050 Brussels (© 1996 Copyright reserved to CEN members Pet. No, ENISO 12185:1996 EDENSITY OSCILLATING U-TUBE, 1P 385 Foreword ‘The textof the Intemational Standard ISO 12185:1996 has been prepared by Technical Committee ISOVTC 28 “Petroleum products and hibreans” in collaboration with Technical Commitee CEN/TC 19 "Petroleum products ubicants and related product’, the Secretariat of wich is held by NN ‘This European Standard shat be given the status of a national standard, ether by publication of an identical text ox by “endorsement atthe latest by December 1996, and enacting national standards shallbe witidrawn athe latest by December 1996, In accordance with tho CENICENELEC Inlemal Regulations, the folowing countries are bound to Implement this European ‘Standard: Ateba, Belgium, Danmark, Fintand, France, Germany, Greece, Iceland, \elan, aly, Luxembourg, Netherands, Norway, Peeugal, Spain, Sweden, Switzerland and United Kingdom, Endorsement notice ‘The text of the Intemational Standard ISO 12185:1996 was approved by CEN as a European Standard without any ‘madiicaion,INTERNATIONAL STANDARD © ISO ISO 12185:1996(E) Crude petroleum and petroleum products — Determination of density — Oscillating U-tube method [wanes esas are Sats en ben ei pms amr — hae le ner! Sane a a a ea Sagomreneg, ace do re cata ey an | ERE SEES Si et mater et 1 Scope This International Standard specifies a method for the determination, using an oseilating U-tube density meter, of the density of crude petroleum and related products within the range 600 kaim® to 1.100 kgim* Which can be handled as single-phase liquids at the test temperature and pressure, ‘This International Standard is applicable to liquids of any vapour pressure as long as suitable precautions. are taken to ensure that they remain in single phase with ne loss of light ends and subsequent changes in composition and density during both the semple ‘ranging and the density determination, NOTE 1 ifthe determined donsity is to be converted to {8 density ot somo reference tomperature using petroleum ‘measurement tables, the determination should be eariad ‘ut at @ temperature as dose as possible to the reference temperate in order to minimize uncertainties due to the use of generalized tebes. This method is not intended for use in calibrating on- line density meters. 2. Normative references The following standards contain provisions which, ‘through reference in this text, constitute provisions of this Intemational Standard. At the time of pubi- cation, the editions indicated were valid. Al standards ‘are subject to revision, and parties to agreements 1653 based on this International Standard are encouraged to investigate the possibilty of applying the most re cent editions of the standards indicated belon, ‘Members of IEC and SO maintain registers of cue ‘ently valid Intemational Standards. 1S0.91-1:1992, Petroleum measurement tables — Part 1: Tables based on reference temperatures of 15°C and 60 degrees F. ISO 91-2:1991, Petroleum measurement tables — Part 2: Tables based on a reference temperature of 20°C. 1s0 3015:1992, Petroleum products ~ Determination of cloud point. 180 9016:1994, Petroleum products — Determination of pour point Iso 3170-1988, sampling. Potroloum —tiquids ‘Manual 180 3171:1988, Petroleum liquids — Automatic pipe fine sampling. 180 3696:1987, Water for anaiytical laboratory use — ‘Specification and test mothods. 180 2898:1983, Crude petroieum and liquid or solid petroleum products — Determination of density or ‘lative density — Capillarystoppered pyknometer and graduated bicapilary pyknameter methods.DENSITY OSCILLATING U-TUBI IP» 389/93, Determination of wax appearance tem perature of middle distilate fusts by cferential ther- ‘mal analysis or differential scanning calorimetry. IP 1998, Standard methods for analysis and testing of petroleum and related products, Appendix G Den: sity of water; Appendix H Density of ambient air, BIPMa Tables, Density of water and Density of ambi- tent aif, to replace, when published, the corresponding IP tables, 3. Definitions For the purposes of this Intermational Standard, the following definitions apply. 3.1. dansity: Mass of the substance, expressed in kilograms, divides by its volume, expressed in cubic metres, 32 reference temperature: Temperature at which the sample density s to be reported. NoTe 2 20°C. This temperature should be either 15°C of 4 Principle ‘A smait (typically fess than 1m portion of the test sample is introduced into 3 tomporature-controlled sample cell, The oscilation frequency is noted, and the density of the test sample calculated using call ‘constants previously determined by measuring the osciltion frequencies when the cell is filed with calibration fluids of known density. 5 Apparatus 5.1 Density meter, capable, once calibrated, of de termining density with a resolution of + 0,1 kai? or better ores 3 Meters commonly dspley two forms of digital result, tether @ density vlue othe period of oscitation from which esty can be calculated. 4 Research has shown that the density meter may show a bias of up to I Kolm? due to viscosity effects. Users should ascertain whether a viscosity correction is required by checking tho result using @ pyknometer method such a3 ‘mat gen in ISO SESH. Alternatively, viscosity effects can 1) Institute of Petroleum, 61 New Cavendish Str 19365 be minimized by using ceritied caltation standards of chemical charecterstics and viscosity simiae to thet of the sample under test (3), ‘5 Problems have been experienced with certain density ‘meters due to condensation gathering on the eel sensors ‘and electonics when te cel tmperatuse is held below the dow-point ofthe ambient iH hove i ck ofthis cccuting, the surrounding ai should bo kept dry 52 Circulating constant-temperature bath, if 1 ‘ured (see 9.1.2), capable of maintaining the porature of the ciculating liquid to within 4 0,05 °C ‘of the required temperature. 53 Calibrated temperature sensor, capeble of ‘measuring the temperature of the cel to an accuracy of atleast + 0,10°C. The rate of energy transfer across the call is low and therefore care should be taken to use sensors with very fine leads in order to minimize heat transfer in oF out of the cell along the leads. 5.4 Homogenizer, suitable for the sample and sample container, and capable of producing hom- ‘geneous subsamples for test (see clause 8); a high Speed shear or static mixer, or other type as appro- rate, 6 Reagents Unless otherwise stated, use only reagents of recog: nized analytical grade 6.1 Flushing solvent. NOTES Any solvent may be ueed provided that it is capable of producing 9 clean cry col 6.2 Ammonium peroxydisulfate, solution In con. centrated suluric acid, 8 of WARNING — Ammonium peroxydisullate is strong oxidizing agent. 63 Calibration fluids A minimum of two calibration fluids are needed to Calibrate the cell. They shall be chosen so that their Gensities bracket the density of the sample under test. The density of the calitvation fds shall be traceable to recognized national standards or based Con internationally accepted values. London WIM BAR, UK. 2) Bureau Internatonal des Poids et Mesures, Pavillon de Bretoul, F-82312 Séwres Cadex. France, 3456DENSITY OSCILLATING U-TUBE, 1P 385 When water andjor ar are used, the requirements of 62.1 and 6.3.2 shall be met 63.1 Water, conforming to 1SO 3696 grade 2 or better. Prior to use, pass the water through a 0,45 um filter, ‘and remove dissolved air by first boiling and then cooling. Once de-aired, handle the water carefully 50 6 to minimize the amount of air redissolved. ‘Obtain the water donsity from the table given in Ap- pendix G of IP “Stendard methods for analysis and testing of petroleum and related products”. On publ- cation of the BIPM tables (see clause 2), the values for density of water gven therein shall be used. NOTE 7 The density of water at varous temperatures ‘iven in Appendix G has been prepared by the Insitute of Petroloum, in order to prove a seurce forthe density of ‘water based on the International Terparature Scale 1990, ‘whist the work to produce new water-densiy tables, based ‘on now water data is cariod out by BIPM, 632 Air, Use the values of the density of air given in Appendix H of IP "Standard methods for analysis and testing of petroleum and related products". On publ- cation of the BIPM tables (see cause 2), the values for density of ambient ar given therein shal be used. NOTE 8 Tho donsiy of ambient air at various tempers tutes given in Appendix H has been prepated by the Int lute of Petrcloum, In order to provide a source for the density of ambiont air based on the international Tempera: ture Seale 1880, whilst work to produce new density of ambient ar tables is cared out by BIPM. 6.4 Water, conforming to ISO 3696 Grade 3. 7 Sampling Unless otherwise specified in a commodity specifi cation, samples shall be taken as. described in 180 3170 or ISO 3171, andjor in accordance with the requirements of national standards or regulations. ‘Special care should be taken to prevent any loss of volatile components from the sample, Wherever Possible samples should bo drawn, transported and stored in the same container The sampling of volatile liquids using automatic tech- riques is not recommended unless a variable-olume sample receiver is used to collect and transport the sample to the laboratory. The use of a fixed-volume receiver (whether itis pressurized or not) could result in lightend loss from the material being sampled, thereby affecting the density measurement When drawing samples using variable-volume re- ceivers, the sampling pressure and temperature of the sample source should be noted on the receiver, label It is essential that the portion of the sample to be ‘ested is representative of the bulk sample, and sam pple mixing is sometimes necessary to ensure ‘homogenization prior to subsampling. 8 Sample preparation 8.1 General ‘Samples shall be handled in such a manner that 2) lightend loss is minirnized; Dy the temperature of the sample does not drop be- low: 1) its cloud point, when determined in accorc ance with ISO 3015; 2) oF its wax appearance temperature (WAT), when determined in accordance with IP sagy93, 3} or 20°C above its pour point, when deter- ‘mined in accordance with ISO 3016, NOTE 9 It should be recognized that 1ss of ight ends ‘during homogenization of heating, necessary when Sediment, water or undissolved wax are present in srmples (of volatile crude petroleum or petioleum prodvets, can ‘aus8 ares in tho determined density value 82 Petroleum products which are free of water and/or sediments and which are sufficiently mobile ‘Mix by gentie shaking, &3 Crude petroleum and petroleum products containing water andjor sediments Mix the sample in the original container, taking all precautions to minimize ight and loss. NOTE 10. Mixing volatie crude petroleum and petioteurn products in an open container wil lead to loss of light com nents and is thorefore nat recommencedDENSITY OSCILLATING U-TUBE, 8.4 Waxy crude petroleum Watm the sample to 3 °C above the WAT or 20°C. above the pour point of the crude petroleum prior to mixing in the original container, taking all precautions 10 minimize lightend loss. 85 Waxy distillates Warm the sample to 3°C above the cloud point prior to mixing 86 Fuel oils Heat the sample until itis fluid prior to mixing 9 Apparatus preparation 9.1 Test temperature 9.1.1 Sample density shall, wherever possible, be eterminad at the reference temperature, IF this is not possible, a temperature shall be chosen which is 3°C above the cloud point or wax appear ‘ance temperature oF 20 °C above the pour point and. below the temperature at which gas appears in the semple. 9.4.2. If the density-meter cell is fited with an inte {gral thermostat, set the cell temperature according to the manufactures instructions. Otherwise, connect 11 to the constanttemperature bath (6.2). Allow the ‘temperature to stabiize, ‘The manufacturer's specified working temperature ‘and pressure ranges for the density-meter cell shel rot be exceeded. When temperature-controlied baths are used, ensure ‘that the circulating liquid remains clean, 92 Cell cleaning Clean and dry the cell using the flushing solvent (6.1) ‘and if necessary water (6.4) followed by @ water miscible solvent (6.1) and blow dry with clean dry ai, Alter testing crude oils containing dissolved salts, clean the cell with water (6.4) after frst washing with the flushing solvent (6.1) 1f the cell shows signs of organic deposits, clean the cell by injecting ammonium peroxydisulfate solution (6.2) imo the call. After removal of the ammonium peroxydisulfate solution, flush the cell with water 305.6 385 (64) followed by a water-miscible solvent (6.1) and blow dry with lean ary ai 10 Apparatus calibration 10.1. Density motors shall be calibrated when fist installed, and whenever the test temperature is changed or when maintenance has been cartied out fr the system disturbed in any other way. ‘The density-meter collation shall be verified within 2 period of not more than seven days prio to use, 10.2 Record the density reading or oscillating period ‘with the clean col filed with ambient air. If air is one of the calibrating fluids, omit 10.3. 10.3 Introduce the frst calibration thid (6.3) nto the cell and allow the cell end its contents to reach term perature equilibrium. Record the oscillation period oF the density reading and the temperature of the col Clean the collin accordance with the procedure given nga, 10.4 Inroduce the second callsration fluid into the cell and allow the cell and its contents to reach ter perature equilibrium. Record the oscillation period or the density reading and the ternperature of the cell 10.5 Caloulate the coll constants in accordance with the manufacturer's instructions, 10.6 Alter calioration, clean and dry the callin ac ‘cordance with the procedure givan in 9.2. 11. Test procedure 111 Check that the density-meter reading when the col is filed with ambient air is within 1 of the least significant digit compared to the reference value ‘achieved during calibration (10.2). If itis not, reclean ‘and dry the cell and repeat the check. If the reading stil differs recalibrate the density meter. 11.2 Introduce the test portion of the sample into the cell using @ suitable syringe or autosampler, filing the coll according to the manufacturer's instructions. ‘When testing waxy distilates or waxy crude oils or residual fuels oils, warm the syringe or autosampler 10.2 temperature 3 °C above the cloud point or WAT, fr 20°C above the pour point of the material being tested.DENSITY OSCILLATING U-TUBE. 1° 385 11.3 When using an autosampler, either eun sam- ples in duplicate or introduce check samples, in order that errors due to bubble formation may be detected and the system performance monitored. 11.4. Do not apply suction to samples prone to light-ond toss at any stage. Either the sample shall bo ‘poured into the sytinge and then injected into the cell, fr the autosampler shall be one which uses vial pressure to force the samplo into the instrument, 11.5 When making a manual injection, switch on the collilurination before injecting, chock the cell for ‘bubbles and fil in accordance with the manufacturer's instructions. If bubbles are detected, empty and refi ‘the call and recheck for bubbles. Turn off the ilumination immediately after exam- ination of the call, as heat generated by the light af fects cell temperature, 11.6 When the density, meter displays 9 reeding steady to within 0,1 kgym® for density, orto five sige nificant figures for the oscilation period, note and re- ‘cord the indicated figure and the coll tomperature to the nearest 0,1 °C. NOTE 11 A consistent ait in tho oscitation period or donsity reading normaly indicates that the cell has not Feachod equilbium tomporature, Random variations in readings normaly indicate that air oF (2s bubbles are present in the cell. In this ease. the cell Should be recharged with fresh sample. Ifthe vatatons In reacing are due to bubbles, may B0 necessary to com duct the test at lower temperature to ensuie that the ‘sample romains in a single phase. It tage water droplets aro present inthe sample due to ie feffidont mixing prior to sample introduction, the indicated donsty or esciating poiod wal tend to be ora 11.7 When measuring the density of viscous lie uids, itis sometimes possible to obtain a stable reac- ing even whan gas or air bubbles are present. With these liquids, a slight overpressure shall be applied to ‘the cell once the first density has been read, and the density rodetermined. If the liquid is in single phase, the shift in density due to the adkstional pressure wil bbe minimal Hf, on the other hand, gas or air bubbles are present, 9 much larger shift in density wil be ob- served as they are compressed. In such cases the cell sholl be emptied and refilled with afresh sample. 11.8 If the sample contains finely suspended water droplets, the density shall be observed as soon as ‘thermal equilbrium has been reached. 308.7 NOTE 12 If samplas containing finaly suspended water ‘ropots are ltt inthe coll for a lengthy pecod, the water roplots wil slowsy coalesce and migrate to the col ant rades, giving an apparent change in density. 11.9 Clean and dry the cell in accordance with the procedure given in 9.2 12 Calculation 12.1 If the density meter displays en oscillation pe- ‘od, calculate sample density from the observed cell ‘scilation period in accordance with the manufac: turer's instructions, 12.2 ff the density is required at a reference tem perature other than that st which it was determined, convert the density to the density at roferenco tem. perature using either [SO 91-1 for 18 °C or 150 91-2 for 20°C, after making an adjustment for the hhydrometer correction (see annex AD. NOTE 19 ISO.91-1 and 180 91-2 cefer the User to the IPIASTMIAPI Petroleum Measirement Tables and the IP Petroloum Measurement Paper Nos. 2 and 3. 13. Expression of results Express the density to the nearest 0,1 kal’, at the ‘ference temperature. 14 Precision 14.1 Repeatability, ‘The difference between two test results obtained by the seme operator with the same apparatus under Constant operating conditions on identical test mar ‘eta, in the normal and correct operation of this test ‘method, would exceed the values given below only in ‘one case in 20. ‘Transparent middle distilates: r= 0,2 kay? Crude oils | and other petroleum products: r= 0.4 kgm? 142 Reproducibility, R The difference between two single and independent results obtained by different operators working in di ferort laboratories on identical test material, in the normal and correct operation of this test method, ‘would exceed the values given only in one case mn 20, Transparent middle dstilates: R = 0,5 Koy?DENSITY OSCILLATING U-TUBE. 17365 Crude ols and other petroleum products: R= 18 kal? NOTE 14 The precision was developed in sconrdence with 150 4289, 15. Test report ‘The test report shall contain at least the following in- formation: 2) @ reference to {SO 12185-1998); thio International Standerd ) the type and identification of the product under test; 3558 a @ 2 ® o the sampling procedures used (see clause 7); the test temperature: NOTE 18 When the tost tomparature is significant diferent fom the reference temperature, st is 120: ‘ommended that the observed density is also reported. the result ofthe test (see clause 13} ‘any deviation, by agreement or otherwise, from the procedure specified; the date of the testDENSITY OSCILLATING U-TUBE. 1P 385 Annex A (normative) Hydrometer corrections to observed density A. Background Corrections to observed density are necessary when ‘measured by methods other than by a soda-ime glass hhydrometer or pykrometer calibrated at 16 °C before ‘entry into 1200, ASTM 1250, API 2640, tables 53A, 638 or 530. The ISO 91-1 and ISO 91-2 standard implementation procedures include an option switch) to alow for two types of density determination: those made using in- struments with or without sodalime glass, if partios ‘mutually agree to use the printed tables instead of the. standard, it shall be recognized that these tables aro based on sodedime glass instruments, If the printed tables 53A, 538 and 53D are entered with @ density determined by any other method, it is necessary 10 first apply a correction to the observed value, If itis agreed to use the printed tables, iis important {o ensure that these are amended in accordance with the information provided in the IP document, Pet- roloum Measurement Paper No. 2 A2_ Determination by a borosilicate glass hydrometer or pyknometer the density is determined by @ hydrometer or yknometer made of borosiicate glass, the observed value shall be adjusted for the differenca between the ‘expansion characteristics ofthe two types of glass as specified in 180 3838, A.3. Determination by a glass hydrometer calibrated at a temperature different from 15 °C If density is determined by a glass {sode-ime or borosilicate) hydrometer or pyknometer calibrated at 4 temperature other than 15 "C, the observed value must be corrected as specie’ in 1SO 38381983, subclause 10.3.4.5. 388.9 A4 Determination by a device oth than a glass hydrometer or pyknometer f density is determined by e different type of device, ‘not subject to the expansion of glass, an adjustment shall be made, before entering the printed tables 534, 598 or 63D, cancelling the hydrometer correction in corporated in the table. AAA The corrections included in tables 53, 538, ‘and 83D were made by multipying the observed density by the following factor: 1 ~ 0,000 023(+ ~ 18) ~ 0,000 000 02(+ ~ 15)? ‘where ris the temperature, in degrees Colsius. ‘To cancel this correction, the observed density is frst rmulipled by the reciprocal ofthis factor. A.42 Example of correction cancelation applied to ‘rude oil Observed density bydrometer! 875.5 kg/m? (aot by glass Observed temperature = 50 * To obtain the crude oil density at 15 °C: 2) calculate the glass correction factor as in &.8.1; 1) correct the density by multiplying the observed density by the reciprocal of the glass correction factor: £875,5 x 1,000 83 78,23 (rounded) (©) enter the table with the corrected observed den- sity at 50°C and read offjcalculate the density st 18°C,DENSITY OSCILLATING U-TUBE. 1P 365 A.A3- Uso of API subroutines When using API computer subroutines, oF any other ‘one that exactly follows the appropriate implemen: 36520 tation procedure, the need to make the correction cancellation described in A.4.1 may be eliminated by setting the hydrometor switch (HYDRO) to 1 before caling the subroutine.DENSITY OSCILLATING U-TUBE, IP 365 Annex B (informative) Bibliography (11 ISO 3007—%, Potrofoum products — Determi {3} FITZGERALD, H. and D. An ss sessment of labore- nation of vapour pressure — Reid metod. tary density meters. IPP Rev, November, 1992, pp. 544.549, £2] 180 4259-1992, Petroleum products —~ Deter- mination and application of precision date in r2- lation to methods of test. 3) Tobe published, (Revision of 1SO 30071886) 365.11