An American National Standard

Designation: D 3230 – 08

Standard Test Method for

Salts in Crude Oil (Electrometric Method)1
This standard is issued under the fixed designation D 3230; 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 (´) 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* 3. Terminology
1.1 This test method covers the determination of the ap- 3.1 Definitions of Terms Specific to This Standard:
proximate chloride (salts) concentration in crude oil. The range 3.1.1 PTB—lb/1000 bbl.
of concentration covered is 0 to 500 mg/kg or 0 to 150 lb/1000 3.1.2 salts in crude oil—commonly, chlorides of sodium,
bbl as chloride concentration/volume of crude oil. calcium, and magnesium dissolved in crude oil. Other inor-
1.2 This test method measures conductivity in the crude oil ganic chlorides may also be present.
due to the presence of common chlorides, such as sodium,
calcium, and magnesium. Other conductive materials may also 4. Summary of Test Method
be present in the crude oil. 4.1 This test method measures the conductivity of a solution
1.3 The values stated in SI units are to be regarded as of crude oil in a mixed alcohol solvent when subjected to an
standard. No other units of measurement are included in this electrical stress. This test method measures conductivity due to
standard. the presence of inorganic chlorides, and other conductive
1.3.1 Acceptable concentration units are g/m3 or PTB (lb/ material, in the crude oil. A homogenized test specimen is
1000 bbl). dissolved in a mixed alcohol solvent and placed in a test cell
1.4 This standard does not purport to address all of the consisting of a beaker and a set of electrodes. A voltage is
safety concerns, if any, associated with its use. It is the impressed on the electrodes, and the resulting current flow is
responsibility of the user of this standard to establish appro- measured. The chloride (salt) content is obtained by reference
priate safety and health practices and determine the applica- to a calibration curve of current versus chloride concentration
bility of regulatory limitations prior to use. For specific of known mixtures. Calibration curves are based on standards
warning statements, see 7.3, 7.4, and 7.11. prepared to approximate the type and concentration of chlo-
rides in the crude oils being tested.
2. Referenced Documents
2.1 ASTM Standards: 2 5. Significance and Use
D 381 Test Method for Gum Content in Fuels by Jet 5.1 This test method is used to determine the approximate
Evaporation chloride content of crude oils, a knowledge of which is
D 1193 Specification for Reagent Water important in deciding whether or not the crude oil needs
D 4928 Test Methods for Water in Crude Oils by Coulom- desalting. The efficiency of the process desalter can also be
etric Karl Fischer Titration evaluated.
D 5002 Test Method for Density and Relative Density of 5.2 Excessive chloride left in the crude oil frequently results
Crude Oils by Digital Density Analyzer in higher corrosion rates in refining units and also has
detrimental effects on catalysts used in these units.
5.3 This test method provides a rapid and convenient means
1
of determining the approximate content of chlorides in crude
This test method is under the jurisdiction of ASTM Committee D02 on oil and is useful to crude oil processors.
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.03 on Elemental Analysis.
Current edition approved May 1, 2008. Published May 2008. Originally
6. Apparatus
approved in 1973. Last previous edition approved in 2006 as D 3230–06.
2
6.1 The apparatus (see Annex A1) shall consist of a control
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
unit capable of producing and displaying several voltage levels
Standards volume information, refer to the standard’s Document Summary page on for applying stress to a set of electrodes suspended in a test
the ASTM website. beaker containing a test solution. The apparatus shall be

*A Summary of Changes section appears at the end of this standard.

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capable of measuring and displaying the current (mA) con- 7.7 Sodium Chloride (NaCl) Solution (10 g/L)—Transfer
ducted through the test solution between the electrodes at each 1.00 6 0.01 g of NaCl into a 100-mL volumetric flask and
voltage level. dissolve in 25 mL of water. Dilute to the mark with mixed
alcohol solvent.
NOTE 1—Some apparatus are capable of measuring voltage and current
internally and, after comparison to internal calibration curves, of display-
7.8 Oil, Refined Neutral—Any refined chloride-free oil of
ing the resultant concentration. approximately 20 mm2/sec (cSt) viscosity at 40°C and free of
additive.
6.2 Test Beaker—See Annex A1. 7.9 Salts, Mixed Solution (Concentrated Solution)—
6.3 Pipet, 10 mL (total delivery)—The type of pipet that is Combine 10.0 mL of the CaCl2 solution, 20.0 mL of the MgCl2
rinsed to ensure the entire volume of the material is contained solution, and 70.0 mL of the NaCl solution, and mix thor-
in the intended volume. oughly.
6.4 Cylinders, 100 mL, stoppered. NOTE 4—The 10:20:70 proportions are representative of the chlorides
6.5 Other volumetric and graduated pipets and volumetric present in a number of common crude oils. When the relative proportions
flasks. of calcium, magnesium, and sodium chlorides are known for a given crude
oil, such proportions should be used for most the accurate results.
7. Reagents and Materials 7.10 Salts, Mixed Solution (Dilute Solution)—Transfer 10
7.1 Purity of Reagents—Reagent grade chemicals shall be mL of the concentrated mixed chlorides solution into a
used in all tests. Unless otherwise indicated, it is intended that 1000-mL volumetric flask, and dilute to the mark with mixed
all reagents shall conform to the specifications of the American alcohol solvent.
Chemical Society, where such specifications are available.3 7.11 Xylene, reagent grade, minimum purity. (Warning—
Other grades may be used, provided it is first ascertained that Flammable. Vapor harmful.)
the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination. 8. Sampling
7.2 Purity of Water—Unless otherwise indicated, references 8.1 Obtain a sample and test specimen in accordance with
to water shall be understood to mean reagent water as defined Test Methods D 4928. Ensure that the sample is completely
by Type II in Specification D 1193. homogenized with a suitable mixer. See Annex A1 of Test
7.3 Mixed Alcohol Solvent—Mix 63 volumes of 1-butanol Methods D 4928 for suitable apparatus and proving.
and 37 volumes of absolute methyl alcohol (anhydrous). To 8.2 Samples of very viscous materials may be warmed until
each litre of this mixture, add 3 mL of water. (Warning— they are reasonably fluid before they are sampled; however, no
Flammable. Liquid causes eye burns. Vapor harmful. May be sample shall be heated more than is necessary to lower the
fatal or cause blindness if swallowed or inhaled.) viscosity to a manageable level.
8.3 Samples of crude oil contain water and sediment and are
NOTE 2—The mixed alcohol solvent is suitable for use if its conduc- inhomogeneous by nature. The presence of water and sediment
tivity is less than 0.25 mA at 125 V ac. High conductivity can be due to will influence the conductivity of the sample. The utmost care
excess water in the solvent and can indicate that the methyl alcohol used
shall be taken in obtaining homogenized representative
is not anhydrous.
samples.
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7.4 Hexanes, Reagent Grade, (Warning—Extremely flam-

mable, harmful if inhaled.) 9. Preparation of Apparatus
NOTE 3—Hexanes solvent is sometimes referred to or sold by other 9.1 Support the apparatus on a level, steady surface, such as
names, such as petroleum naphtha, petroleum ether, ligroine, petroleum a table.
benzin, and industrial naphtha. One should confirm that it meets the 9.2 Prepare the apparatus for operation in accordance with
requirements of 7.4. the manufacturer’s instructions for calibrating, checking, and
7.5 Calcium Chloride (CaCl2) Solution (10 g/L)—Transfer operating the equipment. (Warning—The voltage applied to
1.006 0.01 g of CaCl2, or the equivalent weight of a hydrated the electrodes can be as great as 250 V ac, and hazardous.)
salt, into a 100-mL volumetric flask and dissolve in 25 mL of 9.3 Thoroughly clean and dry all parts of the test beaker, the
water. Dilute to the mark with mixed alcohol solvent. electrodes, and its accessories before starting the test, being
sure to remove any solvent that had been used to clean the
7.6 Magnesium Chloride (MgCl2) Solution (10 g/L)—
apparatus.
Transfer 1.00 6 0.01 g of MgCl2, or the equivalent weight of
a hydrated salt, into 100-mL volumetric flask and dissolve in 10. Calibration
25 mL of water. Dilute to the mark with mixed alcohol solvent.
10.1 The conductivity of solutions is affected by the tem-
perature of the specimen when measurements are made. The
temperature of the test specimen at the time of measurement
3
Reagent Chemicals, American Chemical Society Specifications, American shall be within 3°C of the temperature at which the calibration
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not curves were made.
listed by the American Chemical Society, see Annual Standards for Laboratory
10.2 Establish a blank measurement by following the pro-
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, cedure in 10.3 and 10.4, omitting the mixed salts solution.
MD. When the indicated electrode current is greater than 0.25 mA at

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125 V ac, water or another conductive impurity is present and crude-oil samples by exhaustive extraction of salts with hot water,
its source must be found and eliminated before calibration can followed by titration of the chlorides in the extract.
be completed. Determine a blank measurement each time fresh NOTE 8—In calibrating over a wide range of chloride concentrations, it
may be necessary to apply several voltages to obtain current readings
xylene or mixed solvent is used. within the limit of the apparatus current level display (0 to 10 mA). Higher
10.3 Into a dry, 100-mL graduated, glass-stoppered mixing voltages are applied for low concentrations and lower voltages are applied
cylinder, add 15 mL of xylene. From a pipet (total delivery), for high concentrations.
add 10 mL of neutral oil. Rinse the pipet with xylene until free
of oil. Make up to 50 mL with xylene. Stopper and shake the 11. Procedure
cylinder vigorously for approximately 60 s to effect solution. 11.1 To a dry, 100-mL graduated, glass-stoppered cylinder,
Add a quantity of dilute mixed salts solution, in accordance add 15 mL of xylene and pipet (total delivery) in 10 mL of the
with Table 1, that is appropriate to the range of salt contents to crude oil sample. Rinse the pipet with xylene until free of oil.
be measured. Dilute to 100 mL with mixed alcohol solvent. Make up to 50 mL with xylene. Stopper and shake the cylinder
Again shake the cylinder vigorously for approximately 30 s to vigorously for approximately 60 s. Dilute to 100 mL with
effect solution, and allow the solution to stand approximately 5 mixed alcohol solvent, and again shake vigorously for approxi-
min. Pour the solution into a dry test beaker. mately 30 s. After allowing the solution to stand for approxi-
10.4 Immediately place the electrodes into the solution in mately 5 min, pour it into the dry test beaker.
the beaker, making sure that the upper edge of the electrode 11.2 Follow the procedure in 10.4 to obtain voltage and
plates are below the surface of the solution. Adjust the current readings. Record the indicated electrode current to the
indicated electrode voltage to a series of values, for example nearest 0.01 mA and the nearest voltage.
25, 50, 125, 200, and 250 V ac. At each voltage, note the 11.3 Remove the electrodes from the sample solution, and
current reading and record the voltage displayed and the clean the apparatus.
current to the nearest 0.01 mA. Remove the electrodes from the
solution, rinse with xylene followed by naphtha, and allow 12. Calculation
them to dry. 12.1 Subtract the value obtained for the blank measurement
NOTE 5—With some apparatus, the detailed settings will not be from the value obtained from the specimen measurement to
required since the electronics are built-in for auto-ranging. Determination obtain the net current reading. From the calibration graph, read
of the blank and the calibration standard responses are the same. the indicated salt concentration corresponding to the net
10.5 Repeat the procedure in 10.3, using other volumes of current (mA) reading of the sample.
mixed salts solution (dilute solution) as needed to cover the 12.2 Calculate the concentration in mg/kg by using the
range of chloride contents of interest. appropriate equation given below:
10.6 Subtract the value obtained for the blank measurement 1000X
Salt, mg/kg 5 d (1)
from the indicated current readings of each standard sample,
and plot the chloride content (ordinate) against net current Salt, mg/kg 5 2853 Y/d (2)
(mA) readings (abscissa) for each voltage on 3 by 3 cycle
log-log paper, or other suitable format. where:
X = measured salt concentration in g/m3,
NOTE 6—Some apparatus are capable of internally recording the Y = measured salt concentration in PTB, and
current readings, standard concentration, and blank, and they provide an d = specimen density at 15 C in kg/m3.
output in direct concentration units.
NOTE 7—The apparatus are calibrated against standard solutions of NOTE 9—The density of the specimen can be determined by various
neutral oil and mixed chloride solutions in xylene because of the extreme methods, such as Test Method D 5002 or other density measurement
difficulties in keeping crude oil-brine mixtures homogeneous. The cali- methods.
bration may be confirmed, if desired, by careful replicate analysis of
13. Report
13.1 Report the following information: The concentration in
TABLE 1 Standard Samples
mg/kg as electrometric chloride in crude oil per Test Method
Salt, g/m3 Salt, lb/1000 bbl Mixed Salts Solution D 3230. Alternately, report the concentration directly in g/m3
of Crude Oil of Crude Oil (dilute), mL
or lb/1000 bbl, if so required.
3 1.0 0.3
9 3.0 1.0 NOTE 10—For reporting purposes, the values stated in PTB are the
15 5.0 1.5 preferred units in the United States; in other countries, their common units
30 10.0 3.0
can be used.
45 16.0 4.5
60 21.0 6.0
75 26.0 8.0 14. Precision and Bias 4
90 31.0 9.5 14.1 Precision—The precision of this test method as deter-
115 40.0 12.0
145 51.0 15.0 mined by the statistical examination of the 1997 interlaboratory
190 66.0 20.0 test results is as follows:
215 75.0 22.5
245 86.00 25.5
290 101.0 30.5
4
430 151.0 45.0 Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR: D02-1470.
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14.1.1 Repeatability—The difference between successive NOTE 11—Since all instruments in the 1997 interlaboratory cooperative
results, obtained by the same operator with the same apparatus test program were calibrated in PTB and results reported in PTB, the
under constant operating conditions on identical test material, precision statement was directly obtained in PTB. The resulting precision
data have been mathematically converted into precision in mg/kg,
would in the long run, in the normal and correct operation of
assuming an average density of the crude oil samples of 0.875 kg/L.
the test method, exceed the following values in one case in
twenty. 14.2 Bias—The procedure in Test Method D 3230 has no
0.75
r ~mg/kg! 5 0.3401 X (3) bias since salt content is defined only in terms of this test
0.75
method and certified reference materials are unavailable. How-
r ~lb/1000 bbl! 5 0.2531 Y (4) ever, since the samples from the interlaboratory study were
where: neat desalted crudes, spiked with known quantities of salt (as
X = the average of two test results in mg/kg, and sea water and formation water), bias might be defined as
Y = the average of two test results in lb/1000 bbl (PTB). percent recovery of halide added. Over the range from 5 to 500
14.1.2 Reproducibility—The difference between two single g/m3(1.5 to 150 PTB) salt added, the recovery proved to be
and independent results, obtained by different operators work- approximately constant and averaged 93 %.
ing in different laboratories on identical material, would in the 14.3 The precision statements were derived from a 1997
long run, exceed the following values in only one case in interlaboratory cooperative test program. Participants analyzed
twenty. eight sample sets comprised of crude oils with various concen-
R ~mg/kg! 5 2.7803 X0.75 (5) trations of chlorides. Thirteen laboratories participated with the
0.75
commercial available apparatus.4
R ~lb/1000 bbl! 5 2.069 Y (6)

where: 15. Keywords

X = the average of two test results in mg/kg, and 15.1 chlorides; crude oil; electrometric; halides; petroleum;
Y = the average of two test results in lb/1000 bbl (PTB). salt in crude

ANNEX

(Mandatory Information)

A1. APPARATUS

A1.1 Electrometric Chloride Apparatus (Custom A1.1.1 Milliammeter, 0 to 1 mA dc with 0 to 1 mA ac scale,

Manufacture) (see Fig. A1.1 and Note A1.1) 88 ohm internal resistance.

FIG. A1.1 250 or 540 Volt Transformer

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A1.1.2 Bridge Rectifier, full-wave, 0.75 A capacity at 60
Hz, ambient temperature; minimum of 400 PRV (Peak Reverse
Voltage).
A1.1.3 AC Voltmeter, rectifier type, 2000 ohm/V, 0 to 300 V
range.
A1.1.4 Variable Voltage Autotransformer, input 105 to 117
V, 50/60 Hz, output 0 to 132 V, 1.75 A capacity.
A1.1.5 Transformer, plate supply 240 V, center tap, 50/60
Hz, 250 mA dc capacity.
A1.1.6 Potentiometer, 25 ohm, ten turn.
A1.1.7 Potentiometer, 50 ohm, ten turn.
NOTE A1.1—An equivalent part can be substituted in each case,
provided the electrical characteristics of the entire circuit remain un-
changed and the inductive effects and stray currents are avoided.

A1.2 Test Cell Components (Custom Manufacture) (see

Fig. A1.2)
A1.2.1 Beaker, 100-mL tall form without lip, as described
for use in Test Method D 381.
A1.2.2 Electrode Assembly, as shown in Fig. A1.2 and Fig.
A1.3. The electrodes mounted in parallel position, exactly
opposed and 6.4 6 0.1 mm apart, and electrically separated by FIG. A1.2 Test Cell
a nylon or TFE-fluorocarbon spacer.
calculating and displaying the calibration curves/specimen
A1.3 Electrometric Chloride Apparatus (Commercial measurements, or combination thereof, are not critical to the
Manufacture)4 application as long as each individual component remains
A1.3.1 The apparatus shall consist of a control unit capable specific to the given manufactured apparatus.
of producing and displaying several voltage levels for applying A1.4 Test Cell Components (Commercial Manufacture)
stress to a set of electrodes suspended in a test beaker
A1.4.1 Beaker, 100-mL tall form without lip, as described
containing a test solution. The apparatus shall be capable of
for use in Test Method D 381, is commonly used; however,
measuring and displaying the current (mA) conducted through
minor variations on dimensions are acceptable to accommodate
the test solution between the electrodes at each voltage level.
different manufacturing specifics. The beaker purpose is to
NOTE A1.2—Some apparatus is capable of measuring voltage and provide for containment of the specimen.
current internally and after comparison to internal calibration curves, A1.4.2 Electrode Assembly, shown by example in Fig. A1.2
display the resultant concentration. and Fig. A1.3. The electrode assembly dimensional require-
A1.3.2 The actual construction specifics of the apparatus, ments and means of support in the beaker are not critical to the
such as voltages utilized and means of displaying or recording application as long as each individual component remains
the voltage, displaying or recording the current conduction, or specific to the given manufactured apparatus.

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FIG. A1.3 Electrode Assembly

SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D 3230–06) that may impact the use of this standard.

(1) Deleted reference to Test Method D 91. (3) Added Note 3.

(2) Replaced “ASTM precipitation naphtha” with “hexanes”
in 7.4.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

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