ASTM D3712-91(2000)e1
(Test Method)Standard Test Method of Analysis of Oil-Soluble Petroleum Sulfonates by Liquid Chromatography
Standard Test Method of Analysis of Oil-Soluble Petroleum Sulfonates by Liquid Chromatography
SCOPE
1.1 This test method covers the analysis of refined and crude natural and synthetic oil-soluble sulfonate products. Resins, if present, are recovered with the oil phase and carboxylates are recovered as sulfonates.
1.2 This test method covers the determination of mineral oil, sodium sulfonate, inorganic salts, water, basicity or acidity, average molecular weight, and relative density of sodium sulfonate products.
1.3 This test method covers the determination of mineral oil, sulfonate, water, base number, average molecular weight, and relative density of calcium, barium, magnesium, and ammonium sulfonate products.
1.4 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information purposes only.
1.5 This standard does not purport to address all of the safety problems, 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.
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An American National Standard
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Designation:D3712–91(Reapproved 2000)
Designation: 369/(95)
Standard Test Method of
Analysis of Oil-Soluble Petroleum Sulfonates by Liquid
Chromatography
This standard is issued under the fixed designation D3712; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
This test method was adopted as a joint ASTM-IP standard.
e NOTE—Editorial corrections were made throughout in November 2000.
1. Scope* 3.1.1 Following are definitions of the symbols used in
Section 17, and as noted in the sections in parentheses.
1.1 Thistestmethodcoverstheanalysisofrefinedandcrude
A = grams of sample of calcium, barium, magnesium, or ammonium
natural and synthetic oil-soluble sulfonate products. Resins, if
sulfonate (8.1.1).
present, are recovered with the oil phase and carboxylates are
B = volume of chloroform solution, mL (10.1).
recovered as sulfonates. C = grams of sample of sodium sulfonate (10.1.1).
D = grams of oil recovered (10.4).
1.2 This test method covers the determination of mineral
E = grams of sodium sulfonate recovered (10.5).
oil,sodiumsulfonate,inorganicsalts,water,basicityoracidity,
F = grams of residue from chloroform blank (10.6).
average molecular weight, and relative density of sodium
G = grams of residue from alcohol blank (10.6).
H = grams of sodium sulfonate (11.1).
sulfonate products.
I = grams of sodium sulfate ash from sodium sulfonate (11.2).
1.3 This test method covers the determination of mineral
J = T/KS.
oil, sulfonate, water, base number, average molecular weight, K = valence of cation.
S = average equivalent weight of sodium sulfonate (17.1.4).
and relative density of calcium, barium, magnesium, and
T = average molecular weight of calcium, barium, magnesium, or am-
ammonium sulfonate products.
monium sulfonate (17.1.5).
1.4 The values stated in SI units are to be regarded as U = percentage of sodium sulfonate (17.1.2).
V = percentage of calcium, barium, magnesium, or ammonium sul-
standard. The values given in parentheses are provided for
fonate (17.1.3).
information only.
W = grams of water contained in pycnometer at 25°C (6.9).
c
1.5 This standard does not purport to address all of the W = grams of sample contained in pycnometer at 25°C (15.1).
s
X = grams of sodium sulfonate sample for basicity (12.1).
safety concerns, if any, associated with its use. It is the
Y = volume of standard H SO or NaOH solution used to determine
2 4
responsibility of the user of this standard to establish appro-
basicity or acidity (12.1).
Z = normality of standard H SO or NaOH solution to determine free
priate safety and health practices and determine the applica-
2 4
basicity or acidity (12.1).
bility of regulatory limitations prior to use.
AA = grams of sodium sulfonate product ashed (13.1).
BB = grams of sodium sulfate from inorganic salt determination (13.1).
2. Referenced Documents
CC = percentage of free acidity of sodium sulfonate product as
A
H SO (17.1.6).
2 4
2.1 ASTM Standards:
CC = percentage of free basicity of sodium sulfonate product as NaOH
B
D95 Test Method for Water in Petroleum Products and
(17.1.6).
Bituminous Materials by Distillation DD = percentage of inorganic salts as sodium sulfate (17.1.7).
D2896 Test Method for Base Number of Petroleum Prod-
4. Summary of Test Method
ucts by Potentiometric Perchloric Acid Titration
4.1 The sample, except a sodium sulfonate product, is
3. Terminology dissolved in ethyl ether and converted to sulfonic acid, using
dilute hydrochloric acid. The sulfonic acid after extraction is
3.1 Symbols:
converted to sodium sulfonate and the isolated sodium sul-
fonate and mineral oil are dissolved in chloroform.An aliquot
This test method is under the jurisdiction of ASTM Committee D02 on
of the chloroform solution, or a sample of a sodium sulfonate
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
product, dissolved in chloroform, is placed on a silica gel
D02.04 on Hydrocarbon Analysis.
Current edition approved May 15, 1991. Published August 1991. Originally column. The oil is eluted with chloroform, the sulfonate with
published as D3712–78. Last previous edition D3712–83.
Annual Book of ASTM Standards, Vol 05.01.
*A Summary of Changes section appears at the end of this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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D3712–91 (2000)
ethyl alcohol, and both are determined gravimetrically. Aver- 6.8 Water Bath, capable of being maintained at 25 6 0.2°C
agemolecularweightiscalculatedfromtheaverageequivalent (77 6 0.3°F).
weight of the sodium sulfonate, which is determined by ashing
a portion of the isolated sodium sulfonate.
4.2 WaterisdeterminedbyTestMethodD95.Basenumber
is determined by Test Method D2896. Relative density is
determined by pycnometer.
5. Significance and Use
5.1 This test method provides a means of determining
sulfonate content and of classifying and characterizing natural
and synthetic petroleum sulfonate products by sulfonate con-
tent and average molecular weight. Purity of sodium sulfonate
products is measured by basicity and inorganic salt contents
and the reserve alkalinity of alkaline earth sulfonates by the
total base number.
6. Apparatus
6.1 Chromatographic column, made of glass and consisting
of a reservoir and separator section, and fitted with a TFE-
fluorocarbonstopcockwitha2-mmbore,asshowninFig.1.A
column with a detachable reservoir connected by a standard-
taper joint can be used.
FIG. 2 Pycnometer for Determining Relative Density of
6.2 Steam Bath.
Petroleum Sulfonates
6.3 Vacuum Desiccator, shielded.
6.4 Vacuum Oven, capable of being maintained at 100°C
(212°F) and connected to 559 to 635 mm (22 to 29 in.) Hg
6.9 Pycnometer, as shown in Fig. 2. To calibrate, weigh to
vacuum.
thenearest1mgwithcapinplace;thenfillwithdistilledwater
6.5 Muffle Furnace, capable of operating at 800 to 1000°C
at 15 to 20°C (60 to 68°F) and place in water bath at 25 6
(1500 to 1800°F).
0.2°C(77 60.3°F).After30min,adjustthewatermeniscusat
6.6 Dish, platinum, 100-mL capacity.
the top of the neck so it is exactly level. To obtain a flat
6.7 Distillation Apparatus, as described in Test Method
meniscus, add a minute amount of wetting agent to the water
D95.
surface. Remove the pycnometer from the bath, and dry the
outside.Replacethecapandweightothenearest1mg.Record
the mass of water contained as W .
c
7. Reagents and Materials
7.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society,
where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
7.2 Chloroform (Warning—Flammable, Health Hazard.).
7.3 Ethyl Alcohol (95 %)—Either pure grain or denatured
ethyl alcohol conforming to Formula 3Aof the U.S. Bureau of
Internal Revenue (Warning—Flammable. Denatured alcohol
cannot be made nontoxic.).
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
FIG. 1 Chromatographic Column and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
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D3712–91 (2000)
7.4 Ethyl Ether (Warning—Extremely flammable. Harm- layer in the 250-mL separatory funnel with three 50-mL
ful if inhaled. May cause eye injury. Effects may be delayed. portionsofethylether,usingtheethyletherwashestorinsethe
May form explosive peroxides. Vapors may cause flash fire. Erlenmeyer flask first. Combine all the ethyl ether extracts in
Moderately toxic. Irritating to skin.). the 500-mL separatory funnel and wash with 50 mL of dilute
7.5 Filter Paper, slow-filtering, ashless, gravimetric. HCl (1+3). Combine all the aqueous acid layers and reextract
7.6 Hydrochloric Acid (Concentrated)—(Warning— them with 50 mL of ethyl ether.
Poison. Corrosive. May be fatal if swallowed. Liquid and 8.2 Conversion of Sulfonic Acid to Sodium Sulfonate:
vapor cause severe burns. Harmful if inhaled.). 8.2.1 Collect all of the ether washes in the 500-mL separa-
7.6.1 Hydrochloric Acid, Dilute (1 + 1)—One volume of tory funnel and shake with successive 50-mL portions of
concentrated hydrochloric acid (HCl) is added to 1 volume of Na SO solution containing 2 to 3 drops of methyl orange
2 4
water. indicatoruntilawashingdoesnotappearpink.Discardthesalt
7.6.2 Hydrochloric Acid, Dilute (1 + 3)—One volume of washes.
concentrated hydrochloric acid (HCl) is added to 3 volumes of 8.2.2 Drain off as much of the aqueous layer as possible
water. from the washed ether solution. Lay the separatory funnel on
7.7 Isopropyl Alcohol (99 Mass %)—Water content shall be its side and introduce about 10 g of anhydrous Na SO .
2 4
0.9 mass % maximum. (Warning—Flammable.) Stopperthefunnel,makingsurethatthefunnelmouthisfreeof
7.7.1 Isopropyl Alcohol, Dilute (1 + 1)—One volume of 99 Na SO crystals and shake the mixture vigorously for 3 to 4
2 4
mass % isopropyl alcohol is diluted with 1 volume of water. min, to remove the last traces of water, venting the funnel
7.8 Methyl Orange Indicator Solution—Dissolve 1.0 g of frequently. Place a 250-mL Erlenmeyer flask on a steam bath
methyl orange in water and dilute to 1 L. and filter the ether solution through a small plug of cotton,
7.9 Phenolphthalein Indicator Solution—Dissolve1gof placedinthevortexofafilterfunnel,intotheErlenmeyerflask,
phenolphthalein in 100 mL of 50 mass % ethyl alcohol. keeping approximately 50 mL of solution in the Erlenmeyer
7.10 Silica Gel, 250 to 74 µm (60 to 200-mesh). flaskwhileevaporating.Rinsethefunnelandfilterwith50mL
7.11 Sodium Hydroxide Solution, Standard (0.1 mol/L) of ethyl ether, adding the rinsing to the main ether solution.
(Warning—Corrosive. Can cause severe burns or blindness. Evaporate the ethyl ether until approximately 10 mL of
Evolution of heat produces a violent reaction or eruption upon solution remains.Add 50 mLof 99 mass % isopropyl alcohol,
too rapid mixture with water.)—Prepare and standardize a 0.1 several drops of phenolphthalein indicator solution, and titrate
mol/L aqueous, carbonate-free, NaOH solution. with 0.1 mol/L standard NaOH solution to the red color
7.12 Sodium Sulfate, Anhydrous, Crystalline. change. Place the flask on a steam bath and evaporate to
7.13 Sodium Sulfate Solution—Dissolve 240 g of sodium dryness. Dissolve the sodium sulfonate and oil residue in
sulfate (Na SO ) in water and dilute to 1 L. chloroform; transfer quantitatively into a 100-mL volumetric
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7.14 Sulfuric Acid (relative density 1.84)—Concentrated flask, adjust to volume, and proceed directly with Section 10.
sulfuric acid (H SO ), 36 mol/L. (Warning—Poison. Corro- The solution may turn acidic on standing in the laboratory.
2 4
sive. Strong oxidizer. Contact with organic material may cause Should this occur, add sufficient 0.1 N NaOH solution to the
fire. May be fatal if swallowed. Liquid and vapor cause severe aliquot taken until the solution is pink.
burns. Harmful if inhaled. Contact with water liberates large
9. Preparation of the Column
amounts of heat. Spillage may cause fire.
7.14.1 Sulfuric Acid Solution, Standard (0.1 mol/L)—
9.1 With the stopcock closed, pour 80 to 100 mL of
Prepare and standardize a 0.1 mol/L aqueous sulfuric acid
chloroform into the column, and push a wad of cotton to the
(H SO ).
bottom with a rod (Note 1). Compress the cotton enough to
2 4
hold back the silica gel but not enough to impede the flow of
8. Conversion of Calcium, Barium, Magnesium, or
solvent.
Ammonium Sulfonate to Sodium Sulfonate
NOTE 1—Acoarse-fritteddiskmadeofborosilicateglasscanbeusedin
8.1 Conversion of Calcium, Barium, Magnesium or Ammo-
place of the cotton wad.
nium Sulfonate to Sulfonic Acid:
9.2 Pour 15 6 1 g of silica gel into the column containing
8.1.1 Transferapproximately10gofsample,weighedtothe
the chloroform. The column must be free of air bubbles to
nearest 0.001 g into a 250-mL Erlenmeyer flask, designating
avoid channeling. Start the flow of chloroform by opening the
this weight as A.Add 50 mLof ethyl ether and stir to dissolve
stopcock.When the liquid level is within 13 mm ( ⁄2 in.) of the
thesample.Add100mLofdiluteHCl(1+1)andswirltomix
surface of the gel, close the stopcock. Never allow the liquid
thoroughly until reaction is complete. In analyzing barium
level to fall below the surface of the silica gel.
sulfonate products if barium chloride crystallizes out, add
sufficient water to redissolve.
10. Separation of Mineral Oil and Sodium Sulfonate
8.1.2 Quantitatively transfer the mixture to a 500-mL sepa-
10.1 Adsorption of the Sample—Transfer a sufficient quan-
ratory funnel. Shake well, let settle, and draw the aqueous acid
tityofthechloroformsolutionofsodiumsulfonateandmineral
layerintoa250-mLseparatoryfunnel.Extracttheaqueousacid
oil to provide approximately 1.25 g of Na SO (8.2.2) onto the
2 4
column, being careful to prevent channeling. Designate the
volume as B. Use the following information as a guide in
Silica gel, Grade 62, obtainable from the W.R. Grace and Co., Davison
ChemicalCorp.,Baltimore,MD21203,hasbeenfoundsatisfactoryforthispurpose. selecting the appropriate volume of sample:
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D3712–91 (2000)
mm Hg (22 to 25 in.) for 30 min, remove, and weigh again.
Approximate Sulfonate Content of Product Volume of
Aliquot
Repeat the drying and weighing until two successive weights
20 % 75 mL
areobtainedthatdonotdifferbymorethan0.001g.Designate
30 % 50 mL
the weight of the oil residue as D.
Above 40 % 25 mL
10.4.1 Some special petroleum sulfonate products may
10.1.1 For Sodium Sulfonate Products—Transfer approxi-
containalightdistillateasthediluentinsteadofmineraloil.In
mately2gof sample, weighed to the nearest 0.001 g, into a
such cases, it is not possible to attain constant weight and the
100-mLbeaker,designatingthisweightas C.Add10to25mL
oil content determination must be disregarded.
ofchloroformandstirtodissolvethesample.Pourthesolution
10.5 Determination of Sulfonate—Evaporate the alcohol
ontothecolumn,beingcarefultopreventchanneling
...
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