ASTM D3712-05(2017)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D3712 − 05 (Reapproved 2017)
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 2. Referenced Documents
1.1 Thistestmethodcoverstheanalysisofrefinedandcrude 2.1 ASTM Standards:
natural and synthetic oil-soluble sulfonate products. Resins, if D95Test Method for Water in Petroleum Products and
present, are recovered with the oil phase and carboxylates are Bituminous Materials by Distillation
recovered as sulfonates. D2896TestMethodforBaseNumberofPetroleumProducts
by Potentiometric Perchloric Acid Titration
1.2 This test method covers the determination of mineral
oil,sodiumsulfonate,inorganicsalts,water,basicityoracidity,
3. Terminology
average molecular weight, and relative density of sodium
3.1 Symbols:
sulfonate products.
3.1.1 Following are definitions of the symbols used in
1.3 This test method covers the determination of mineral
Section 17, and as noted in the sections in parentheses.
oil, sulfonate, water, base number, average molecular weight,
A = grams of sample of calcium, barium, magnesium, or ammonium
and relative density of calcium, barium, magnesium, and
sulfonate (8.1.1).
B = volume of chloroform solution, mL (10.1).
ammonium sulfonate products.
C = grams of sample of sodium sulfonate (10.1.1).
1.4 The values stated in SI units are to be regarded as the
D = grams of oil recovered (10.4).
E = grams of sodium sulfonate recovered (10.5).
standard.
F = grams of residue from chloroform blank (10.6).
1.4.1 Exception—The values given in parentheses are for
G = grams of residue from alcohol blank (10.6).
information only.
H = grams of sodium sulfonate (11.1).
I = grams of sodium sulfate ash from sodium sulfonate (11.2).
1.5 This standard does not purport to address all of the
J = T/KS.
safety concerns, if any, associated with its use. It is the
K = valence of cation.
S = average equivalent weight of sodium sulfonate (17.1.4).
responsibility of the user of this standard to establish appro-
T = average molecular weight of calcium, barium, magnesium, or
priate safety and health practices and determine the applica-
ammonium sulfonate (17.1.5).
bility of regulatory limitations prior to use.
U = percentage of sodium sulfonate (17.1.2).
V = percentage of calcium, barium, magnesium, or ammonium
1.6 This international standard was developed in accor-
sulfonate (17.1.3).
dance with internationally recognized principles on standard-
W = grams of water contained in pycnometer at 25 °C (6.9).
c
ization established in the Decision on Principles for the
W = grams of sample contained in pycnometer at 25 °C (15.1).
s
X = grams of sodium sulfonate sample for basicity (12.1).
Development of International Standards, Guides and Recom-
Y = volume of standard H SO or NaOH solution used to determine
2 4
mendations issued by the World Trade Organization Technical
basicity or acidity (12.1).
Barriers to Trade (TBT) Committee. 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).
BB = grams of sodium sulfate from inorganic salt determination (13.1).
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of
Subcommittee D02.04.0C on Liquid Chromatography.
Current edition approved July 15, 2017. Published July 2017. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1978. Last previous edition approved in 2011 as D3712–05 (2011). contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
DOI: 10.1520/D3712-05R17. Standards volume information, refer to the standard’s Document Summary page on
This test method was adopted as a joint ASTM-IP standard. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3712 − 05 (2017)
CC = percentage of free acidity of sodium sulfonate product as H SO
A 2 4
(17.1.6).
CC = percentage of free basicity of sodium sulfonate product as NaOH
B
(17.1.6).
DD = percentage of inorganic salts as sodium sulfate (17.1.7).
4. Summary of Test Method
4.1 The sample, except a sodium sulfonate product, is
dissolved in ethyl ether and converted to sulfonic acid, using
dilute hydrochloric acid. The sulfonic acid after extraction is
converted to sodium sulfonate and the isolated sodium sul-
fonate and mineral oil are dissolved in chloroform.An aliquot
of the chloroform solution, or a sample of a sodium sulfonate
product, dissolved in chloroform, is placed on a silica gel
column. The oil is eluted with chloroform, the sulfonate with
ethyl alcohol, and both are determined gravimetrically. Aver-
agemolecularweightiscalculatedfromtheaverageequivalent
weightofthesodiumsulfonate,whichisdeterminedbyashing
a portion of the isolated sodium sulfonate.
4.2 Water is determined by Test Method D95. Base number
is determined by Test Method D2896. Relative density is
determined by pycnometer.
FIG. 1 Chromatographic Column
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-
fluorocarbonstopcockwitha2mmbore,asshowninFig.1.A
column with a detachable reservoir connected by a standard-
taper joint can be used.
6.2 Steam Bath.
6.3 Vacuum Desiccator, shielded.
6.4 Vacuum Oven, capable of being maintained at 100°C
(212°F)andconnectedto559mmto635mm(22in.to29in.)
Hg vacuum.
FIG. 2 Pycnometer for Determining Relative Density of
6.5 Muffle Furnace, capable of operating at 800°C to Petroleum Sulfonates
1000°C (1500°F to 1800°F).
6.6 Dish, platinum, 100mL capacity.
obtainaflatmeniscus,addaminuteamountofwettingagentto
6.7 Distillation Apparatus, as described in Test Method
the water surface. Remove the pycnometer from the bath, and
D95.
drytheoutside.Replacethecapandweightothenearest1mg.
6.8 Water Bath, capable of being maintained at 25°C 6
Record the mass of water contained as W .
c
0.2°C (77°F 6 0.3°F).
7. Reagents and Materials
6.9 Pycnometer, as shown in Fig. 2. To calibrate, weigh to
thenearest1mgwithcapinplace;thenfillwithdistilledwater 7.1 Purity of Reagents—Reagent grade chemicals shall be
at 15°C to 20°C (60°F to 68°F) and place in water bath at used in all tests. Unless otherwise indicated, it is intended that
25°C 6 0.2°C (77°F 6 0.3°F). After 30min, adjust the all reagents shall conform to the specifications of the Commit-
water meniscus at the top of the neck so it is exactly level. To tee onAnalytical Reagents of theAmerican Chemical Society,
D3712 − 05 (2017)
where such specifications are available. Other grades may be fire. May be fatal if swallowed. Liquid and vapor cause severe
used, provided it is first ascertained that the reagent is of burns. Harmful if inhaled. Contact with water liberates large
sufficiently high purity to permit its use without lessening the
amounts of heat. Spillage may cause fire.
accuracy of the determination.
7.14.1 Sulfuric Acid Solution, Standard (0.1 mol⁄L)—
Prepare and standardize a 0.1mol⁄L aqueous sulfuric acid
7.2 Chloroform (Warning—Flammable, Health Hazard.).
(H SO ).
2 4
7.3 Ethyl Alcohol (95%) —Either pure grain or denatured
ethyl alcohol conforming to Formula 3Aof the U.S. Bureau of
8. Conversion of Calcium, Barium, Magnesium, or
Internal Revenue (Warning—Flammable. Denatured alcohol
Ammonium Sulfonate to Sodium Sulfonate
cannot be made nontoxic.).
8.1 Conversion of Calcium, Barium, Magnesium or Ammo-
7.4 Ethyl Ether(Warning—Extremelyflammable.Harmful
nium Sulfonate to Sulfonic Acid:
if inhaled. May cause eye injury. Effects may be delayed. May
form explosive peroxides. Vapors may cause flash fire. Mod- 8.1.1 Transferapproximately10gofsample,weighedtothe
erately toxic. Irritating to skin.).
nearest 0.001g into a 250mL Erlenmeyer flask, designating
this weight as A.Add 50mLof ethyl ether and stir to dissolve
7.5 Filter Paper, slow-filtering, ashless, gravimetric.
thesample.Add100mLofdiluteHCl(1+1)andswirltomix
7.6 Hydrochloric Acid (Concentrated)—(Warning—
thoroughly until reaction is complete. In analyzing barium
Poison. Corrosive. May be fatal if swallowed. Liquid and
sulfonate products if barium chloride crystallizes out, add
vapor cause severe burns. Harmful if inhaled.).
sufficient water to redissolve.
7.6.1 Hydrochloric Acid, Dilute (1 + 1) —(See Warning in
8.1.2 Quantitatively transfer the mixture to a 500mL sepa-
7.6.) One volume of concentrated hydrochloric acid (HCl) is
ratory funnel. Shake well, let settle, and draw the aqueous acid
added to 1 volume of water.
layerintoa250mLseparatoryfunnel.Extracttheaqueousacid
7.6.2 Hydrochloric Acid, Dilute (1 + 3) —(See Warning in
layer in the 250mL separatory funnel with three 50mL
7.6.) One volume of concentrated hydrochloric acid (HCl) is
portionsofethylether,usingtheethyletherwashestorinsethe
added to 3 volumes of water.
Erlenmeyer flask first. Combine all the ethyl ether extracts in
7.7 Isopropyl Alcohol (99% by Mass)—Water content shall
the 500mL separatory funnel and wash with 50mL of dilute
be 0.9% by mass maximum. (Warning—Flammable.)
HCl (1+3). Combine all the aqueous acid layers and reextract
7.7.1 Isopropyl Alcohol, Dilute (1+1) —One volume of
them with 50mL of ethyl ether.
99% by mass isopropyl alcohol is diluted with 1 volume of
water. 8.2 Conversion of Sulfonic Acid to Sodium Sulfonate:
8.2.1 Collect all of the ether washes in the 500mL separa-
7.8 Methyl Orange Indicator Solution—Dissolve 1.0g of
tory funnel and shake with successive 50mL portions of
methyl orange in water and dilute to 1L.
Na SO solution containing 2 to 3 drops of methyl orange
2 4
7.9 Phenolphthalein Indicator Solution—Dissolve 1g of
indicatoruntilawashingdoesnotappearpink.Discardthesalt
phenolphthalein in 100mL of 50% by mass ethyl alcohol.
washes.
7.10 Silica Gel, 250µm to 74µm (60mesh to 200mesh).
8.2.2 Drain off as much of the aqueous layer as possible
7.11 Sodium Hydroxide Solution, Standard (0.1mol⁄L) from the washed ether solution. Lay the separatory funnel on
(Warning—Corrosive. Can cause severe burns or blindness.
its side and introduce about 10g of anhydrous Na SO .
2 4
Evolution of heat produces a violent reaction or eruption upon
Stopperthefunnel,makingsurethatthefunnelmouthisfreeof
too rapid mixture with water.)—Prepare and standardize a
Na SO crystals and shake the mixture vigorously for 3min to
2 4
0.1mol⁄L aqueous, carbonate-free, NaOH solution.
4min, to remove the last traces of water, venting the funnel
frequently. Place a 250mL Erlenmeyer flask on a steam bath
7.12 Sodium Sulfate, Anhydrous, Crystalline.
and filter the ether solution through a small plug of cotton,
7.13 Sodium Sulfate Solution—Dissolve 240g of sodium
placedinthevortexofafilterfunnel,intotheErlenmeyerflask,
sulfate (Na SO ) in water and dilute to 1L.
2 4
keeping approximately 50mL of solution in the Erlenmeyer
7.14 Sulfuric Acid (relative density 1.84)—Concentrated
flaskwhileevaporating.Rinsethefunnelandfilterwith50mL
sulfuric acid (H SO ), 36mol⁄L. (Warning—Poison. Corro-
2 4 of ethyl ether, adding the rinsing to the main ether solution.
sive. Strong oxidizer. Contact with organic material may cause
Evaporate the ethyl ether until approximately 10mL of solu-
tion remains. Add 50mL of 99% by mass isopropyl alcohol,
several drops of phenolphthalein indicator solution, and titrate
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not with 0.1mol⁄L standard NaOH solution to the red color
listed by the American Chemical Society, see Annual Standards for Laboratory
change. Place the flask on a steam bath and evaporate to
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
dryness. Dissolve the sodium sulfonate and oil residue in
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
chloroform; transfer quantitatively into a 100mL volumetric
MD.
The sole source of supply of silica gel, Grade 62, known to the committee at
flask, adjust to volume, and proceed directly with Section 10.
this time is W.R. Grace and Co., Davison Chemical Corp., Baltimore, MD 21203.
The solution may turn acidic on standing in the laboratory.
If you are aware of alternative suppliers, please provide this information toASTM
Should this occur, add sufficient 0.1 N NaOH solution to the
International Headquarters. Your comments will receive careful consideration at a
meeting of the responsible technical committee, which you may attend. aliquot taken until the solution is pink.
D3712 − 05 (2017)
9. Preparation of the Column 10.3 Elution of Sulfonate—Tare a second 250mLbeaker to
the nearest 0.0001g and place it under the column. Add
9.1 With the stopcock closed, pour 80mL to 100mL of
230mLofethylalcoholtothereservoir,openthestopcockand
chloroform into the column, and push a wad of cotton to the
adjust the flow rate as described in 10.2.1 (Note 2). When the
bottom with a rod (Note 1). Compress the cotton enough to
receivingbeakerisabouthalffull,removeitandplaceaclean,
hold back the silica gel but not enough to impede the flow of
untared 250mL beaker under the column. Place the tared
solvent.
beakeronthesteambathandevaporategently,blowingfiltered
NOTE1—Acoarse-fritteddiskmadeofborosilicateglasscanbeusedin
airovertheliquidsurface.Whentheliquidlevelinthecolumn
place of the cotton wad.
is within 13mm ( ⁄2in.) of the surface of the gel, close the
9.2 Pour15g 61gofsilicagelintothecolumncontaining
stopcockandquantitativelytransferthecontentsoftheuntared
the chloroform. The column must be free of air bubbles to
beakertothesecondtaredbeakeronthesteambath,bytheuse
avoid channeling. Start the flow of chloroform by opening the
of ethyl alcohol.
stopcock.When the liquid level is within 13mm ( ⁄2in.) of the
NOTE 2—The flow rat
...