ASTM D3712-05(2011)
(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
SIGNIFICANCE AND USE
This test method provides a means of determining sulfonate content and of classifying and characterizing natural and synthetic petroleum sulfonate products by sulfonate content 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.
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 the standard. The values given in parentheses are for information only.
1.5 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.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D3712 − 05 (Reapproved 2011)
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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope 3. Terminology
1.1 Thistestmethodcoverstheanalysisofrefinedandcrude
3.1 Symbols:
natural and synthetic oil-soluble sulfonate products. Resins, if
3.1.1 Following are definitions of the symbols used in
present, are recovered with the oil phase and carboxylates are
Section 17, and as noted in the sections in parentheses.
recovered as sulfonates.
A = grams of sample of calcium, barium, magnesium, or ammonium
sulfonate (8.1.1).
1.2 This test method covers the determination of mineral
B = volume of chloroform solution, mL (10.1).
oil,sodiumsulfonate,inorganicsalts,water,basicityoracidity,
C = grams of sample of sodium sulfonate (10.1.1).
average molecular weight, and relative density of sodium D = grams of oil recovered (10.4).
E = grams of sodium sulfonate recovered (10.5).
sulfonate products.
F = grams of residue from chloroform blank (10.6).
G = grams of residue from alcohol blank (10.6).
1.3 This test method covers the determination of mineral
H = grams of sodium sulfonate (11.1).
oil, sulfonate, water, base number, average molecular weight,
I = grams of sodium sulfate ash from sodium sulfonate (11.2).
and relative density of calcium, barium, magnesium, and
J = T/KS.
K = valence of cation.
ammonium sulfonate products.
S = average equivalent weight of sodium sulfonate (17.1.4).
1.4 The values stated in SI units are to be regarded as the T = average molecular weight of calcium, barium, magnesium, or
ammonium sulfonate (17.1.5).
standard. The values given in parentheses are for information
U = percentage of sodium sulfonate (17.1.2).
only.
V = percentage of calcium, barium, magnesium, or ammonium
sulfonate (17.1.3).
1.5 This standard does not purport to address all of the
W = grams of water contained in pycnometer at 25°C (6.9).
c
safety concerns, if any, associated with its use. It is the
W = grams of sample contained in pycnometer at 25°C (15.1).
s
responsibility of the user of this standard to establish appro- X = grams of sodium sulfonate sample for basicity (12.1).
Y = volume of standard H SO or NaOH solution used to determine
2 4
priate safety and health practices and determine the applica-
basicity or acidity (12.1).
bility of regulatory limitations prior to use.
Z = normality of standard H SO or NaOH solution to determine free
2 4
basicity or acidity (12.1).
AA = grams of sodium sulfonate product ashed (13.1).
2. Referenced Documents
BB = grams of sodium sulfate from inorganic salt determination (13.1).
CC = percentage of free acidity of sodium sulfonate product as H SO
A 2 4
2.1 ASTM Standards:
(17.1.6).
D95Test Method for Water in Petroleum Products and
CC = percentage of free basicity of sodium sulfonate product as NaOH
B
Bituminous Materials by Distillation (17.1.6).
DD = percentage of inorganic salts as sodium sulfate (17.1.7).
D2896TestMethodforBaseNumberofPetroleumProducts
by Potentiometric Perchloric Acid Titration
4. Summary of Test Method
4.1 The sample, except a sodium sulfonate product, is
1 dissolved in ethyl ether and converted to sulfonic acid, using
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of
dilute hydrochloric acid. The sulfonic acid after extraction is
Subcommittee D02.04.0C on Liquid Chromatography.
converted to sodium sulfonate and the isolated sodium sul-
Current edition approved Jan. 1, 2011. Published February 2011. Originally
fonate and mineral oil are dissolved in chloroform.An aliquot
approved in 1978. Last previous edition approved in 2005 as D3712–05. DOI:
of the chloroform solution, or a sample of a sodium sulfonate
10.1520/D3712-05R11.
This test method was adopted as a joint ASTM-IP standard.
product, dissolved in chloroform, is placed on a silica gel
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
column. The oil is eluted with chloroform, the sulfonate with
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
ethyl alcohol, and both are determined gravimetrically. Aver-
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. agemolecularweightiscalculatedfromtheaverageequivalent
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3712 − 05 (2011)
weightofthesodiumsulfonate,whichisdeterminedbyashing 6.8 Water Bath, capable of being maintained at 25 6 0.2°C
a portion of the isolated sodium sulfonate. (77 6 0.3°F).
4.2 Water is determined by Test Method D95. Base number
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.
6.2 Steam Bath.
FIG. 2 Pycnometer for Determining Relative Density of
6.3 Vacuum Desiccator, shielded.
Petroleum Sulfonates
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
vacuum.
6.9 Pycnometer, as shown in Fig. 2. To calibrate, weigh to
6.5 Muffle Furnace, capable of operating at 800 to 1000°C thenearest1mgwithcapinplace;thenfillwithdistilledwater
(1500 to 1800°F). at 15 to 20°C (60 to 68°F) and place in water bath at 25 6
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 Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
FIG. 1 Chromatographic Column MD.
D3712 − 05 (2011)
7.4 Ethyl Ether(Warning—Extremelyflammable.Harmful thoroughly until reaction is complete. In analyzing barium
if inhaled. May cause eye injury. Effects may be delayed. May sulfonate products if barium chloride crystallizes out, add
form explosive peroxides. Vapors may cause flash fire. Mod- sufficient water to redissolve.
erately toxic. Irritating to skin.).
8.1.2 Quantitatively transfer the mixture to a 500-mL sepa-
ratory funnel. Shake well, let settle, and draw the aqueous acid
7.5 Filter Paper, slow-filtering, ashless, gravimetric.
layerintoa250-mLseparatoryfunnel.Extracttheaqueousacid
7.6 Hydrochloric Acid (Concentrated)—(Warning—
layer in the 250-mL separatory funnel with three 50-mL
Poison. Corrosive. May be fatal if swallowed. Liquid and
portionsofethylether,usingtheethyletherwashestorinsethe
vapor cause severe burns. Harmful if inhaled.).
Erlenmeyer flask first. Combine all the ethyl ether extracts in
7.6.1 Hydrochloric Acid, Dilute (1 + 1) —(See Warning in
the 500-mL separatory funnel and wash with 50 mL of dilute
7.6.) One volume of concentrated hydrochloric acid (HCl) is
HCl (1+3). Combine all the aqueous acid layers and reextract
added to 1 volume of water.
them with 50 mL of ethyl ether.
7.6.2 Hydrochloric Acid, Dilute (1 + 3) —(See Warning in
7.6.) One volume of concentrated hydrochloric acid (HCl) is
8.2 Conversion of Sulfonic Acid to Sodium Sulfonate:
added to 3 volumes of water.
8.2.1 Collect all of the ether washes in the 500-mL separa-
tory funnel and shake with successive 50-mL portions of
7.7 Isopropyl Alcohol (99 Mass %)—Water content shall be
0.9 mass % maximum. (Warning—Flammable.) Na SO solution containing 2 to 3 drops of methyl orange
2 4
indicatoruntilawashingdoesnotappearpink.Discardthesalt
7.7.1 Isopropyl Alcohol, Dilute(1+1) —One volume of 99
mass % isopropyl alcohol is diluted with 1 volume of water. washes.
8.2.2 Drain off as much of the aqueous layer as possible
7.8 Methyl Orange Indicator Solution—Dissolve 1.0 g of
from the washed ether solution. Lay the separatory funnel on
methyl orange in water and dilute to 1 L.
its side and introduce about 10 g of anhydrous Na SO .
2 4
7.9 Phenolphthalein Indicator Solution—Dissolve1gof
Stopperthefunnel,makingsurethatthefunnelmouthisfreeof
phenolphthalein in 100 mL of 50 mass % ethyl alcohol.
Na SO crystals and shake the mixture vigorously for 3 to 4
2 4
7.10 Silica Gel, 250 to 74 µm (60 to 200-mesh).
min, to remove the last traces of water, venting the funnel
frequently. Place a 250-mL Erlenmeyer flask on a steam bath
7.11 Sodium Hydroxide Solution, Standard (0.1 mol/L)
and filter the ether solution through a small plug of cotton,
(Warning—Corrosive. Can cause severe burns or blindness.
placedinthevortexofafilterfunnel,intotheErlenmeyerflask,
Evolution of heat produces a violent reaction or eruption upon
keeping approximately 50 mL of solution in the Erlenmeyer
too rapid mixture with water.)—Prepare and standardize a 0.1
flaskwhileevaporating.Rinsethefunnelandfilterwith50mL
mol/L aqueous, carbonate-free, NaOH solution.
of ethyl ether, adding the rinsing to the main ether solution.
7.12 Sodium Sulfate, Anhydrous, Crystalline.
Evaporate the ethyl ether until approximately 10 mL of
7.13 Sodium Sulfate Solution—Dissolve 240 g of sodium
solution remains.Add 50 mLof 99 mass % isopropyl alcohol,
sulfate (Na SO ) in water and dilute to 1 L.
2 4 several drops of phenolphthalein indicator solution, and titrate
with 0.1 mol/L standard NaOH solution to the red color
7.14 Sulfuric Acid (relative density 1.84)—Concentrated
change. Place the flask on a steam bath and evaporate to
sulfuric acid (H SO ), 36 mol/L. (Warning—Poison. Corro-
2 4
dryness. Dissolve the sodium sulfonate and oil residue in
sive. Strong oxidizer. Contact with organic material may cause
chloroform; transfer quantitatively into a 100-mL volumetric
fire. May be fatal if swallowed. Liquid and vapor cause severe
flask, adjust to volume, and proceed directly with Section 10.
burns. Harmful if inhaled. Contact with water liberates large
The solution may turn acidic on standing in the laboratory.
amounts of heat. Spillage may cause fire.
Should this occur, add sufficient 0.1 N NaOH solution to the
7.14.1 Sulfuric Acid Solution, Standard (0.1 mol/L)—
aliquot taken until the solution is pink.
Prepare and standardize a 0.1 mol/L aqueous sulfuric acid
(H SO ).
2 4
9. Preparation of the Column
8. Conversion of Calcium, Barium, Magnesium, or
9.1 With the stopcock closed, pour 80 to 100 mL of
Ammonium Sulfonate to Sodium Sulfonate
chloroform into the column, and push a wad of cotton to the
8.1 Conversion of Calcium, Barium, Magnesium or Ammo-
bottom with a rod (Note 1). Compress the cotton enough to
nium Sulfonate to Sulfonic Acid:
hold back the silica gel but not enough to impede the flow of
8.1.1 Transferapproximately10gofsample,weighedtothe
solvent.
nearest 0.001 g into a 250-mL Erlenmeyer flask, designating
NOTE1—Acoarse-fritteddiskmadeofborosilicateglasscanbeusedin
this weight as A.Add 50 mLof ethyl ether and stir to dissolve
place of the cotton wad.
thesample.Add100mLofdiluteHCl(1+1)andswirltomix
9.2 Pour 15 6 1 g of silica gel into the column containing
the chloroform. The column must be free of air bubbles to
The sole source of supply of silica gel, Grade 62, known to the committee at
avoid channeling. Start the flow of chloroform by opening the
this time is W.R. Grace and Co., Davison Chemical Corp., Baltimore, MD 21203.
stopcock.Whentheliquidleveliswithin13mm( ⁄2in.)ofthe
If you are aware of alternative suppliers, please provide this information toASTM
surface of the gel, close the stopcock. Never allow the liquid
International Headquarters. Your comments will receive careful consideration at a
meeting of the responsible technical committee, which you may attend. level to fall below the surface of the silica gel.
D3712 − 05 (2011)
10. Separation of Mineral Oil and Sodium Sulfonate 10.4 Determination of Oil—Evaporate the chloroform solu-
tion from 10.2.2 until all but a few millilitres of chloroform
10.1 Adsorption of the Sample—Transfer a sufficient quan-
havebeenevaporated.Removethebeakerfromthesteambath
tityofthechloroformsolutionofsodiumsulfonateandmineral
and cool to room temperature. Place the beaker in a vacuum
oiltoprovideapproximately1.25gofNa SO (8.2.2)ontothe
2 4
desiccator with a vacuum of 559 to 635 mm (22 to 25 in.) of
column, being careful to prevent channeling. Designate the
mercuryatroomtemperature.Whenthechloroformappearsto
volume as B. Use the following information as a guide in
have evaporated, remove the beaker and weigh. Return the
selecting the appropriate volume of sample:
beaker to the vacuum desiccator with a vacuum of 550 to 635
Approximate Sulfonate Content of Product Volume o
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