Designation: E 291 01

Standard Test Methods for

Chemical Analysis of Caustic Soda and Caustic Potash
(Sodium Hydroxide and Potassium Hydroxide)1
This standard is issued under the fixed designation E 291; 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 (e) 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 E 180 Practice for Determining the Precision of ASTM

1.1 These test methods cover only the analyses usually Methods for Analysis and Testing of Industrial Chemicals4
required on the following commercial products: E 200 Practice for Preparation, Standardization, and Stor-
1.1.1 Caustic soda (sodium hydroxide), 50 and 73 % li- age of Standard and Reagent Solutions for Chemical
quors; anhydrous (solid, flake, ground, or powdered), and Analysis4
1.1.2 Caustic potash (potassium hydroxide), 45 % liquor;
3. Significance and Use
anhydrous (solid, flake, ground, or powdered).
1.2 The analytical procedures appear in the following order: 3.1 Caustic soda and caustic potash are used in a large
Alkalinity (Total), Titrimetric (for 50 to 100 % 8 to 14
number of manufacturing processes. The chemicals are avail-
NaOH and 45 to 100 % KOH) able in several grades depending on their intended use. The test
Carbonate, Gas-Volumetric (0.001 g CO2, min) 15 to 24 methods listed in 1.2 provide procedures for analyzing caustic
Carbonate, Gravimetric (0.001 g CO2, min) 25 to 33
Chloride, Titrimetric, (0.001 g Cl, min) 34 to 40
soda and caustic potash to determine if they are suitable for
Chloride, Potentiometric Titration (0.3 to 1.2 %) 41 to 47 their intended use.
Chloride, Ion Selective Electrode (0.6 to 120 ppm) 48 to 55
Iron, Photometric (0.005 mg Fe, min) 56 to 64 4. Apparatus
Sulfate, Gravimetric, (0.002 g SO3, min) 65 to 71
Keywords 72 4.1 Photometers and Photometric PracticePhotometers
and photometric practice used in these test methods shall
1.3 The values stated in inch-pound units are to be regarded
conform to Practice E 60.
as the standard. The values in parentheses are provided for
information only. 5. Reagents
1.4 Review the current Material Safety Data Sheet (MSDS)
5.1 Purity of ReagentsUnless otherwise indicated, it is
for detailed information concerning toxicity, first-aid proce-
intended that all reagents shall conform to the specifications of
dures, handling, and safety precautions.
the Committee on Analytical Reagents of the American Chemi-
1.5 This standard does not purport to address all of the
cal Society, where such specifications are available.5 Other
safety concerns, if any, associated with its use. It is the
grades may be used, provided it is first ascertained that the
responsibility of the user of this standard to establish appro-
reagent is of sufficiently high purity to permit its use without
priate safety and health practices and determine the applica-
lessening the accuracy of the determination.
bility of regulatory limitations prior to use. Specific hazard
5.2 Purity of WaterUnless otherwise indicated, references
statements are given in Section 6.
to water shall be understood to mean Type II or Type III
2. Referenced Documents reagent water conforming to Specification D 1193.
2.1 ASTM Standards: 6. Hazards
D 1193 Specification for Reagent Water2
6.1 Sodium and potassium hydroxides are caustic alkalies
E 60 Practice for Analysis of Metals, Ores, and Related
which, in their anhydrous or strong solution form, are hazard-
Materials for by Molecular Absorption Spectrometry3
ous materials. In contact with the skin they produce burns

1 4
These test methods are under the jurisdiction of ASTM Committee E15 on Annual Book of ASTM Standards, Vol 15.05.
5
Industrial and Specialty Chemicals and are the direct responsibility of Subcommit- Reagent Chemicals, American Chemical Society Specifications, American
tee E15.01 on General Standards. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Oct. 10, 2001. Published December 2001. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as E 291 65. Last previous edition E 291 96. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
Annual Book of ASTM Standards, Vol 11.01. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
3
Annual Book of ASTM Standards, Vol 03.05. MD.

Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 E 291 01
which may be quite serious unless promptly treated. Their practical metal for a metallic sample container for caustic
action is insidious since they produce no immediate stinging or liquors. For the analysis of 73 % caustic soda, the entire sample
burning sensation and damage may result before their presence should be in the liquid state before removing any portion, and
is realized. such portions must then be used in their entirety to avoid the
6.2 Eyes are particularly vulnerable to severe damage from factor of segregation on freezing. Caustic soda of 73 %
these alkalies. concentration may also be cast into glass or plastic bottles or
6.3 Laboratory workers handling these alkalies should use tubes, or nickel or silver metallic molds. The molds are later
safety goggles or face shields and rubber gloves and avoid removed and the samples chipped or crushed for analysis. If
spillage on clothing. These materials rapidly attack wool and this is done, the factors of segregation on freezing and
leather. atmospheric exposure while crushing must be borne in mind.
6.4 Spilled caustic should be flushed away with water where
7.3 Sampling Devices and Techniques:
possible, or covered with absorbent material (such as sawdust,
vermiculite, or baking soda) and swept up and discarded in 7.3.1 Liquid CausticSimple dipper or tap samples
accordance with all applicable federal, state, and local health from large quantity shipments or tanks of caustic liquor are
and environmental regulations. Last traces may be neutralized inadequate for purchaser and vendor purposes. Numerous
with dilute acetic acid and the area washed with water. specially designed devices are available to procure samples
6.5 Perchloric acid is toxic, corrosive, and a strong oxidizer. from various levels in tanks. A useful type of such samplers for
Laboratory workers handling this acid should use safety small tanks has three or five containers mounted on a single rod
goggles or face shields and rubber gloves. so that when the device is lowered into a tank and the stoppers
are pulled, samples are simultaneously taken at the different
7. Sampling levels. These are then combined to provide a representative
7.1 GeneralThe nature of the caustic alkalies is such as to average sample. Shipments should be sampled at least at the
require special care at all points of sampling and preparation upper, middle, and lower thirds. Samples should never be taken
for analysis. The following information is included in order at the surface of the liquid. If it is not necessary to analyze the
that representative samples may be ensured. Additional pre- liquor before unloading, sampling may be accomplished by a
cautions may be necessary if trace constituents, not covered in continuous drip from a small tap-off with the regulating
these test methods, are to be determined. Instructions for such valve in a vertical section of the unloading line. The drip is
procedures may be obtained from the publications of most so timed as to collect the desired amount of sample uniformly
major producers. Sampling techniques must be such as to limit during the time of unloading.
or prevent atmospheric exposure since sodium and potassium
hydroxides, both as aqueous solutions and as anhydrous 7.3.2 Anhydrous Products:
products, rapidly absorb moisture and carbon dioxide (and 7.3.2.1 Commercial anhydrous caustic soda or caustic pot-
other acid gases) from the atmosphere. The aqueous solutions ash is packaged in drums in solid, flake, ground, or powdered
are corrosive and sampling devices and sample containers must forms. Sampling and handling of these materials must be done
be selected to avoid contamination with any constituent later to with minimum atmospheric exposure.
be determined. Strong aqueous solutions of these alkalies are 7.3.2.2 In the case of flake, ground, or powdered sodium or
available commercially under the names liquid caustic soda potassium hydroxides, the top 3 or 4 in. (75 or 100 mm) of
and liquid caustic potash. Liquid caustic potash at a concen- material in a drum should first be removed and a sample then
tration of 45 % remains liquid at temperatures down to 20F taken from the center part of the drum. The sample should be
(29C), and freezing or crystallization will only be encoun- placed immediately in a suitable wide-mouth container then
tered under severe cold weather. Caustic soda liquors are closed and sealed with taps or wax.
usually shipped in insulated tank cars at elevated temperatures,
7.3.2.3 Solid caustic shall be packaged by filling metal
and minimum temperatures must be maintained if unloading
drums with molten anhydrous product and allowing drums and
and sampling problems are to be avoided. Viscosity increases
contents to cool before sealing air tight. On cooling and
near the freezing point and creates pumping problems. Even
partial freezing changes the composition of the remaining solidifying, impurities present in the caustic tend to segregate
liquor and causes sampling and analysis problems. Be sure and concentrate in the bottom section. To sample such material
contents are completely liquid and well mixed before sam- properly, the metal drum must be opened at the vertical seam
pling. The following minimum temperatures should be main- and removed. The solid cake may then be sampled either by
tained for proper sampling of bulk shipments: drilling at representative levels with a 34 -in. (19-mm) auger bit
50 % NaOH liquor 68F (20C)
(may cause metal contamination) or by splitting the cake in
53 % NaOH liquor 86F (30C) half vertically with hammer and chisel and chiseling off
70 to 73 % NaOH liquor 160F (71C) representative small fragments so that the total sample repre-
7.2 Sample ContainersThe choice of container construc- sents a vertical cross section through the cake. In either case,
tion material is important for caustic liquor samples, especially the sample shall be promptly bottled and sealed in a wide-
for those to be taken or held at elevated temperatures. Glass mouth container. In the laboratory, the lumps shall be reduced
can be used except where silica is to be determined. Polyeth- to convenient size by enclosing in several thicknesses of clean
ylene or polypropylene containers which have high- cloth or kraft paper and pounding with a hammer. The crushed
temperature properties may also be used. Nickel is the best material shall be bottled and thoroughly mixed before analysis.

2
 E 291 01
TOTAL ALKALINITY TABLE 2 Sample Size for Carbonate Analysis
Percent Na2CO3 or Percent
Sample Size, g
8. Scope K2CO3 Expected

8.1 This test method covers the determination of the total 0.01 to 0.10 8 to 10
0.10 to 0.50 5 to 7
alkalinity of 50 and 73 % liquid caustic soda, 45 % liquid 0.50 to 1.00 2 to 4
caustic potash, and anhydrous caustic soda and caustic potash.

9. Summary of Test Method A 3 B 3 0.030990

9.1 Total alkalinity is determined by titration with standard Sodium oxide, wt % 5 W 3 100 (1)
hydrochloric acid solution using methyl orange indicator
solution or modified methyl orange indicator solution. A 3 B 3 0.047102
Potassium oxide, wt % 5 W 3 100 (2)
10. Reagents
10.1 Hydrochloric (or Sulfuric Acid), Special (1.0 N) where:
A = acid required for titration of the sample, mL
Prepare in accordance with Practice E 200.
B = corrected normality of the acid, and
10.2 Methyl Orange Indicator SolutionSee Practice W = weight of sample in the aliquot, g.
E 200.
12.2 Calculate the total alkalinity as the respective hydrox-
10.3 Modified Methyl Orange Indicator SolutionSee
ide as follows:
Practice E 200.
10.4 Water, Distilled, carbon dioxide-free (freshly boiled Sodium hydroxide, wt % 5 1.2907 3 percent Na2O (3)
and cooled). Potassium hydroxide, wt % 5 1.19123 percent K2O (4)
12.3 If actual hydroxide content is desired, the carbonate
11. Procedure content must be determined separately as described in Sections
11.1 Transfer to a tared, covered weighing bottle a sample 15-24 or Sections 25-33. Then:
of such size as determined from Table 1. Sodium hydroxide ~actual!, wt % 5 A 2 ~B 3 0.755! (5)
11.2 Weigh the sample to the nearest 1 mg and transfer it to
a 1-L volumetric flask using several rinses of water to remove
Potassium hydroxide ~actual!, wt % 5 C 2 ~D 3 0.812! (6)
all traces of caustic from the weighing bottle. Dilute the
solution to about 400 mL with water and cool to room where:
temperature. After cooling, dilute to 1 L and mix thoroughly. A = percent NaOH (total alkali),
11.3 With a volumetric pipet, transfer 50 mL (see Note 1) of B = percent Na2CO3,
the prepared solution to a 500-mL Erlenmeyer flask and add 2 C = percent KOH (total alkali), and
to 4 drops of modified methyl orange indicator solution (see D = percent K2CO3.
Note 2). Titrate this solution with standard 1.0 N acid to a gray
end point (see Note 3) and record the volume and temperature 13. Report
of acid used. Correct the acid normality for any difference from 13.1 Report the percentage of sodium oxide or potassium
the standardization temperature by use of the factor DN/ oxide to the nearest 0.01 %.
C = 0.00035 between 20 and 30C adding the correction when
temperature of use is below (subtracting when above) the 14. Precision and Bias
temperature of standardization. (See Practice E 200.) 14.1 The following criteria should be used in judging the
acceptability of results (Note 4):
NOTE 1If a 100-mL buret is to be used for this titration use a 100-mL
aliquot. 14.1.1 Repeatability (Single Analyst)The standard devia-
NOTE 2If desired, methyl orange indicator solution may be used. tion for a single determination has been estimated to be
NOTE 3The analyst should attempt to end the titration at the same 0.057 % absolute at 144 DF. The 95 % limit for the difference
shade of color as was used for the end point in the standardization of the between two such runs is 0.16 % absolute.
acid. 14.1.2 Laboratory Precision (Within-Laboratory, Between-
Days Variability), formerly called RepeatabilityThe standard
12. Calculation
deviation of results (each the average of duplicates), obtained
12.1 Calculate the total alkalinity as percent sodium oxide by the same analyst on different days, has been estimated to be
or potassium oxide as follows: 0.17 % absolute at 72 df. The 95 % limit for the difference
between two such averages is 0.48 % absolute.
TABLE 1 Sample Size for Total Alkalinity 14.1.3 Reproducibility (Multilaboratory)The standard de-
Sample Sample Size, g
viation of results (each the average of duplicates), obtained by
analysts in different laboratories, has been estimated to be
50 % NaOH 65 to 78
73 % NaOH 45 to 52
0.25 % absolute at 10 df. The 95 % limit for the difference
Anhydrous NaOH 32 to 40 between two such averages is 0.70 % absolute.
45 % KOH 100 to 120
Anhydrous KOH 48 to 60 NOTE 4These precision estimates are based on an interlaboratory
study on five samples comprising 45 % KOH, 50 % NaOH, 73 % NaOH,

3
 E 291 01
anhydrous NaOH, and anhydrous KOH. The number of laboratories 16. Summary of Test Method
analyzing each sample ranged from seven to fifteen with one analyst in
each performing duplicate determinations and repeating one day later.6 16.1 Carbon dioxide is evolved by acid decomposition of
Practice E 180 was used in developing these precision estimates. carbonate in the sample. The volume of CO2 is measured and
calculated as sodium carbonate or potassium carbonate.
14.2 BiasThe bias of this test method has not been
determined because of the unavailability of suitable reference
17. Apparatus
materials.
17.1 Carbon Dioxide Evolution, Measurement, and Absorp-
SODIUM CARBONATE OR POTASSIUM tion Device, as illustrated in Fig. 1 and consisting of the
CARBONATE (GAS-VOLUMETRIC TEST METHOD) following special parts:
17.1.1 Aspirator Bottle, J, 500-mL, used for leveling.
15. Scope
17.1.2 Compensator Tube, C, as shown in Fig. 1 and
15.1 This test method describes the gas-volumetric determi- conforming to details shown in Fig. 2.
nation of sodium carbonate or potassium carbonate in caustic 17.1.3 Gas Buret, B, 100-mL, modified as shown in Fig. 3.
soda or caustic potash respectively. The lower limit of deter- 17.1.4 Gas Pipet, K, preferably of the bubbler type.
mination is 0.001 g as carbon dioxide.
17.1.5 Glass Condenser with Jacket, L, 12 in. (305 mm)
long and 114 in. (32 mm) in outside diameter. The condenser
6
Supporting data have been filed at ASTM International headquarters and may
tube shall be of 8-mm outside diameter glass tubing.
be obtained by requesting Research Report No. E15-1040. 17.1.6 Tubing Assembly, D, as illustrated in Fig. 4.

A Water above mercury column of manometer. I Three-way stop cock with TFE-fluorocarbon plug.
B Gas buret, Fig. 3. J Aspirator bottle.
C Compensator tube, Fig. 2. K Absorption pipet for KOH solution.
D Capillary glass tubing with small bubble at D1, Fig. 4. K1 Gas expansion bag.
E Filling funnel. L Glass condenser.
F Heavy rubberor plastic connectors. M Rubber stopper.
G Rubber tubing avout 3 ft (91 cm) long. N Sample receptacles.
H1, H2, H Two way glass stop cock. O Glass water jackets, 212 in. (63.5 mm) in diameter.
FIG. 1 Carbon Dioxide Evolution, Measurement, and Absorption Device

4
 E 291 01

FIG. 2 Compensator Tube NOTE 1Dimensions of tubing diameters are approximate.

FIG. 3 Gas Buret
18. Reagents
18.1 Hydrochloric Acid (sp gr 1.19)Concentrated hydro-
chloric acid (HCl).
18.2 Methyl Orange Indicator Solution (1 g/L)See Prac-
tice E 200.
18.3 Potassium Hydroxide (35 % Solution)Dissolve 350
g of potassium hydroxide (KOH) in 650 mL of water.
18.4 Sodium Carbonate (Na2CO3), anhydrous.
18.5 Water, Distilled, carbon dioxide-free (freshly boiled
and cooled).
19. Preparation of Apparatus
19.1 Assemble the apparatus as shown in Fig. 1 after
preparing the various parts as follows:
19.1.1 Compensator Tube, CWarm the bulb slightly and
place two or three drops of water in the tube. Then add
sufficient mercury so that when the tube is at room temperature
and normal atmospheric pressure the mercury columns are
approximately level and are about 112 to 2 in. (38 to 51 mm)
in length. This is a trial and error operation. Manipulation by
alternately warming and cooling the bulb is helpful in making
this adjustment.
19.1.2 Absorption Pipet, KFill this pipet with sufficient
caustic potash solution to fill the left bulb completely and to
have about 1-in. (25-mm) depth in the right bulb. Protect the
solution from the atmosphere with a gas expansion bag, K2.
FIG. 4 Tubing Assembly
19.1.3 Glass Water Jacket, OBore suitable holes in two
No. 12 rubber stoppers, as shown in Fig. 1, to support the buret
and compensator tube. An additional hole in the top stopper 19.1.4 Use a ring stand about 30 in. (760 mm) high with a
will permit easy filling with water. heavy base to mount the various parts of the apparatus with

5
 E 291 01
suitable clamps. Arrange the parts so that glass tube connec- 21.4 Fill E nearly full with water, heat the contents of N to
tions are as close as possible and held with the rubber or plastic boiling, and continue boiling very gently for at least 2 min.
tubing connectors, F. Remove the burner, open stopcock H2 and lower J (if neces-
19.1.5 Aspirator Bottle, JFill with a 20 % solution of sary) until the water from E fills N and the connecting tube just
sodium chloride (NaCl) or calcium chloride (CaCl2), acidify up to I. Give three-way cock I one-quarter turn to cut off all
slightly, and add a few drops of methyl red indicator solution openings.
to color the solution. Distilled water may be used in place of 21.5 Raise J until its liquid level is approximately the same
the salt solution. as the water in the buret, open H1, and raise or lower J until the
mercury columns in the compensator are level; then close H
20. Calibration of Apparatus (Machine Factor) and H1 and read the buret. Record this buret reading as A.
20.1 The factor may be determined theoretically, but is done 21.6 Holding J slightly above the liquid level in B, open H
more conveniently by a series of actual tests on a sample of and turn I to connect with the absorption pipet K. Raise
known carbon dioxide content. Weigh 2.000 g of anhydrous leveling bottle J to force the gas into potash pipet K until the
Na2CO3, dissolve in 25 mL of water, dilute to 100 mL in a liquid in B reaches a height approximately equivalent to that of
volumetric flask at room temperature, and mix thoroughly. Stopcock I. At this point lower J to return the gas to buret B and
Using 10-mL aliquot portions of this, measured by means of bring the potash level up to the previously marked point. This
volumetric pipet, determine the amount of carbon dioxide procedure should be repeated at least twice more to absorb the
(CO2) it contains by the evolution method as described in carbon dioxide completely. After three passes into K, bring the
Section 21. At least five determinations should be made and the potash liquor level up to the previously marked point and turn
results averaged. The machine factor (F) is calculated as I one-quarter turn. Hold J at the approximate water level of B,
follows: open H1, level the mercury columns as before, and close H and
H1 and read the buret. Record this buret reading as B.
0.2000 3 0.41523
F5 (7) 21.7 The difference (A B), represents the millilitres of
A
CO2 evolved and absorbed. This difference, multiplied by a
where: machine factor, gives the weight of CO2 in the sample.
A = CO2 found, mL.
22. Calculation
21. Procedure 22.1 Calculate the percent solution carbonate or potassium
21.1 Have sample flask N clean and dry. Stopper the flask carbonate present as follows:
with a rubber stopper or cork and weigh to the nearest 0.01 g. ~A 2 B! 3 F 3 2.4083
Transfer the following approximate weight of caustic to the Sodium carbonate, wt % 5 W 3 100 (8)
flask, replace the stopper and reweigh to the nearest 0.01 g.
After weighing, add a small piece of iron wire about the size of ~A 2 B! 3 F 3 3.1405
a pinhead, 1 drop of methyl orange indicator solution, and Potassium carbonate, wt % 5 W 3 100 (9)
water until flask N is about three quarters full. Replace the
stopper. where:
21.2 Before connecting N to the apparatus, make the fol- A = buret reading before KOH addition,
lowing adjustments: B = buret reading after KOH addition,
F = machine factor, and
21.2.1 Check the level of the potash solution in K with
W = sample used, g.
relation to stopcock I. The potash liquor should fill the entrance
tube up to a previously marked point approximately 1 cm
23. Report
below stopcock I. If such is not the case, close H1, open H, turn
I to connect J with K, and lower J to bring the level of the 23.1 Report the percentage of sodium carbonate or potas-
potash up to the previously marked point. Turn three-way sium carbonate to the nearest 0.01 %.
stopcock I one-quarter turn to close all openings.
21.2.2 With stopcock H open, turn stopcock H1 to the open 24. Precision and Bias
position, level the mercury columns by manipulation of level- 24.1 The following criteria should be used for judging the
ing bottle J and close H1. acceptability of results (see Note 5):
21.2.3 Now open stopcock I to connect B with the tube 24.1.1 Repeatability (Single Analyst)The standard devia-
leading to N, fill the buret and tube with the retaining solution tion for a single determination has been estimated to be the
by raising J, and close H when the condenser tube is filled. value given in Table 3 at the indicated degrees of freedom. The
21.2.4 Open stopcock H2 and rinse the funnel E and stopper 95 % limit for the difference between two such runs is also
with water. given in Table 3.
21.3 Connect N to the apparatus and close stopcock H2. Into 24.1.2 Laboratory Precision (Within-Laboratory, Between-
E pour an amount of concentrated HCl slightly more than Days Variability), formerly called RepeatabilityThe standard
enough to neutralize the sample. Now open stopcock H and deviation of results (each the average of duplicates), obtained
then H2 sufficiently to let the acid drop slowly into N until the by the same analyst on different days, has been estimated to be
solution is acid, and close H2. the value given in Table 3 at the indicated degrees of freedom.

6
 E 291 01
TABLE 3 Precision for Carbonate (Gas-Volumetric Method)
Repeatability Laboratory Precision Reproducibility
Standard Degrees of 95 % Range, Standard Degrees of 95 % Range, Standard Degrees of 95 % Range,
Level %
Deviation Freedom Percent Absolute Deviation Freedom Percent Absolute Deviation Freedom Percent Absolute
0.010.02 0.0034 24 0.01 0.0062 13 0.02 0.0093 5 0.03
0.040.08 0.0069 28 0.02 0.0145 14 0.04 0.021 6 0.06
0.120.35 0.017 28 0.05 0.019 14 0.05 0.034 6 0.10

The 95 % limit for the difference between two such averages is hydrate-asbestos absorbent. The increase in weight is a mea-
also given in Table 3. sure of the carbonate present.
24.1.3 Reproducibility (Multilaboratory)The standard de-
viation of results (each the average of duplicates), obtained by 27. Apparatus
analysts in different laboratories, has been estimated to be the 27.1 Fig. 5 illustrates the analytical train required. The
value given in Table 3 at the indicated degrees of freedom. The principal parts are as follows:
95 % limit for the difference between two such averages is also 27.1.1 Separatory Funnel, C, 100-mL capacity.
given in Table 3. 27.1.2 Flask, F, 250-mL extraction.
27.1.3 Condenser, G, 8-in. (203-mm) modified Liebig.
NOTE 5These precision estimates are based on an interlaboratory
27.1.4 Drying Tubes, H and J, Schwartz, glass-stoppered, 6
study on six samples with carbonate contents as follows:
in. (152 mm).
Approximate
Percentage of 27.1.5 Drying Tubes, L, N, O, P, Schwartz, glass-stoppered,
Sample Carbonate 4 in. (101.6 mm).
45 % KOH 0.01 27.1.6 Bubbler Bottle, Q, 4-oz (0.056-L) capacity.
50 % NaOH 0.20, 0.05, 0.13
73 % NaOH 0.08 27.1.7 Siphon-Vacuum Bottle, 1-gal (3.6-L) capacity.
Anhydrous NaOH 0.35
28. Reagents
One analyst in each of fourteen laboratories performed duplicate 28.1 Barium Perchlorate (or Magnesium Perchlorate), an-
determinations and repeated one day later.6 Practice E 180 was used in hydrous, granular.
developing these precision estimates. 28.2 Perchloric Acid (1 + 2)Mix 1 volume of 60 % per-
24.2 BiasThe bias of this test method has not been chloric acid (HClO4) with 2 volumes of water and boil for 10
determined because of the unavailability of suitable reference min in a large Erlenmeyer flask. Cool and bottle.
materials. 28.3 Silver Arsenite in Sulfuric AcidDissolve 2 g of
pulverized arsenious oxide (As2O3) in the least amount of
SODIUM CARBONATE OR POTASSIUM potassium hydroxide (KOH) solution (100 g/L) that will effect
CARBONATE (GRAVIMETRIC TEST METHOD) solution. Dilute to 250 mL and add dilute sulfuric acid (H2SO4,
1 + 9) until neutral to litmus. Add silver nitrate (AgNO3)
25. Scope solution (50 g/L) as long as a yellow precipitate forms, keeping
25.1 This test method covers the gravimetric determination the solution neutral by dropwise addition of KOH (100 g/L)
of carbonate in caustic soda or caustic potash. The lower limit solution when necessary. Stir until coagulated, settle, and wash
of determination is 0.001 g as carbon dioxide. by decantation. Dissolve the precipitate in an excess of
H2SO4(1 + 9), dilute to 150 mL, and filter out any precipitated
26. Summary of Test Method silver chloride (AgCl).
26.1 Carbon dioxide is evolved by acid decomposition of 28.4 Sodium HydrateAsbestos Absorbent, 12 to 20 mesh.
the carbonate in the sample and is absorbed on sodium 28.5 Zinc Metal, clean, mossy.

FIG. 5 Analytical Train

7
 E 291 01
29. Preparation of Apparatus no sample is in place. Tube O shall be used as a precautionary
29.1 The apparatus shall be assembled as shown in Fig. 5 measure. At the indicated gas flow, N will be found to absorb
and should conform to the description given. It shall consist of all the CO2 until its capacity is nearly depleted. Tube O should
a 250-mL extraction flask F in which the CO2 is evolved. Acid always be weighed as a check for any CO2 not absorbed in N.
is admitted through the stopcock D from separatory funnel C
30. Procedure
which should be of at least 80-mL capacity. The acid delivery
tube entering F should be bent upwards at the end to prevent 30.1 Weigh into a tared evolution flask F to the nearest 0.1
the escape of CO2. To the top of C shall be attached a similar g, a sample of size determined from Table 4. Connect the flask
tube B containing sodium hydrate-asbestos absorbent protected F to the analytical train as shown in Fig. 5.
by glass wool, to purify the carrier air which enters at stopcock 30.2 Open all stopcocks and adjust screw clamp U for a
A. The flask shall be heated directly by a bunsen burner and flow of 60 to 80 mL/min corresponding to 3 to 4 bubbles/s
shall be protected from drafts by shield E, either of metal or when the bubbler Q is built as described in 29.4. Close
asbestos. The gases escape from F through an 8-in. (203-mm) stopcock D and pinchcock S. Remove B and add at least 75 mL
water-cooled condenser G. All of this part of the apparatus of the diluted HClO4 into C and replace tube B. Open
shall be conveniently mounted on one large ring stand, pinchcock S and then stopcock D carefully to admit the acid.
facilities being arranged for removing the flask F and guard When all the acid has entered, begin heating with a 1-in.
tube B for each determination. All stoppers and joints must be (25-mm) bunsen flame. When the heating has progressed to the
absolutely airtight. point where the flow of air through the acid delivery tube
29.2 The U-tubes shall be hung individually from hooks by seems to stop and the liquid shows a tendency to back up in the
copper wire loops securely fastened to the necks of the tubes. tube, close D.
H is a 6-in. (152-mm) U-tube containing glass beads and a 30.3 After 5 min of brisk boiling, remove the flame, open
solution of silver arsenite Ag3AsO3 in dilute H2SO4. Its stopcock D, and continue drawing air through the train until the
function is to remove alkali gases, sulfides, chlorides, chlorine, water in bottle R has been siphoned off almost entirely. Close
and other oxidizing gases. I is a plug of glass wool to retain any S, the last stopcock in P, both stopcocks in O and in N, the last
reagent entrained in the gas. J is a 6-in. U-tube containing stopcock in L, and the first stopcock in H.
H2SO4 and glass beads to absorb most of the water from the 30.4 Remove N and O and allow to stand in the balance case
gas. It is also protected by a plug of glass wool I in the outlet for at least 10 min. Open the stopcocks momentarily to attain
tube. K is a bulb containing clean mossy zinc which serves to atmospheric pressure, wipe gently with tissue, and weigh
catch any trace of acid carried over from J. L is a 4-in. accurately to 0.1 mg.
(102-mm) U-tube containing anhydrous barium perchlorate
31. Calculation
(Ba(ClO4)2) or anhydrous magnesium perchlorate (Mg-
(ClO4)2). The tube shall be prepared in three sections separated 31.1 Calculate the percent sodium carbonate or potassium
by glass wool to eliminate channeling by the gases. carbonate as follows:
29.3 N and O are 4-in. U-tubes for the absorption and A 3 2.4083
Sodium carbonate, wt % 5 W 3 100 (10)
weighing of the CO2, each prepared with two sections of
sodium hydrate-asbestos absorbent and one of anhydrous
Ba(ClO4)2 or anhydrous Mg(ClO4)2 separated by glass wool, A 3 3.1405
Potassium carbonate, wt % 5 W 3 100 (11)
the desiccant being nearest the outlet end. These tubes shall be
connected to the system and each other by the short glass tubes
where:
M, and the tubes shall be disconnected and weighed with their
A = total grams increase in the weight of U-tubes O and N,
rubber tubing connections attached.
and
29.4 P is a 4-in. U-tube filled with desiccant to prevent any W = sample used, g.
accidental back draft from containing any weighable moisture.
Q is a bubbler bottle containing concentrated H2SO4. If the 32. Report
bubbler tube is of 6-mm bore and the tip is placed 1.9 cm 32.1 Report the percentage of sodium carbonate or potas-
below the surface of the acid, one bubble per second will sium carbonate to the nearest 0.01 %.
indicate about 20-mL/min gas flow.
29.5 R is a 1-gal (3.6-L) siphon vacuum bottle. It provides 33. Precision and Bias
sufficient vacuum for the flow required, and its capacity is a 33.1 The following criteria should be used for judging the
good measure of the time required for an analysis. The siphon acceptability of results (see Note 6):
can be closed by pinchcock S and the rapidity of emptying
regulated by screw clamp U.
29.6 A freshly prepared train should be conditioned with a TABLE 4 Sample Size for Carbonate Analysis
0.2-g sample of Na2CO3 carried through the analysis to Percent Na2CO3 or Percent Sample
K2CO3 Expected Size, g
saturate the reagents with CO2. Before the train is ready for a
series of determinations, successive weighings of the tube N 0.01 to 0.10 15 to 20
0.10 to 0.50 10 to 15
must agree within 0.0002 g before and after the passage of one 0.50 to 1.00 7 to 10
half of the volume of air represented by the capacity of R, when

8
 E 291 01
33.1.1 Repeatability (Single Analyst)The standard devia- silver nitrate is titrated with standard ammonium thiocyanate
tion for a single determination has been estimated to be the solution using ferric ammonium sulfate indicator.
value given in Table 5 at the indicated degrees of freedom. The
95 % limit for the difference between two such runs is also 36. Reagents
given in Table 5.
33.1.2 Laboratory Precision (Within-Laboratory, Between- 36.1 Ammonium Thiocyanate, Standard Solution (0.1 N)
Days Variability) formerly called RepeatabilityThe standard See Practice E 200.
deviation of results (each the average of duplicates), obtained 36.2 Ferric Ammonium Sulfate Indicator SolutionSee
by the same analyst on different days, has been estimated to be Practice E 200.
the value given in Table 5 at the indicated degrees of freedom. 36.3 Nitric Acid (sp gr 1.42)Concentrated nitric acid
The 95 % limit for the difference between two such averages is (HNO3).
also given in Table 5.
36.4 Silver Nitrate, Standard Solution (0.1 N)See Prac-
33.1.3 Reproducibility (Multilaboratory)The standard de-
tice E 200.
viation of results (each the average of duplicates), obtained by
analysts in different laboratories, has been estimated to be the
value given in Table 5 at the indicated degrees of freedom. The 37. Procedure
95 % limit for the difference between two such averages is also 37.1 If the approximate chloride content of the sample is
given in Table 5. known, take a sample of size as indicated in Table 6.
NOTE 6These precision estimates are based on an interlaboratory 37.2 If the approximate chloride content is unknown, make
study on six samples with carbonate contents as follows: a trial determination with a sample of 10 g. If necessary, repeat
Approximate with a proper size sample for the actual determination.
Percentage of
Sample Carbonate 37.3 Weigh the sample, in a tared and covered weighing
45 % KOH 0.01 bottle, to the nearest 0.001 g for smaller samples (nearest 0.01
50 % NaOH 0.02, 0.05, 0.13
73 % NaOH 0.10 g for larger samples). Transfer the sample quantitatively to a
Anhydrous NaOH 0.41 500-mL Erlenmeyer flask using about 100 mL of water to
effect transfer and solution. Add 1 mL of ferric indicator and
One analyst in each of twelve laboratories performed duplicate deter- (slowly) sufficient HNO3(sp gr 1.42) to dissolve the reddish-
minations and repeated one day later.6 Practice E 180 was used in brown precipitate formed with the ferric indicator. Cool to
developing these precision estimates. room temperature. Add 0.1 N AgNO3 solution (Note 7) in an
33.2 BiasThe bias of this test method has not been excess of 5 to 10 mL over that required to react with the
determined because of the unavailability of suitable reference chloride, agitating continuously while adding. The total
materials. amount added will depend on the average chloride content of
the particular grade of caustic being analyzed.
CHLORIDE, TITRIMETRIC
37.4 Filter off the precipitated silver chloride using semi-
34. Scope quantitative paper and only one 5-mL portion of wash water.
34.1 This test method covers the volumetric determination Leave the filtrate in the receiver flask and back-titrate the
of chloride in caustic soda or caustic potash by the Volhard test excess AgNO3 with 0.1 N NH4CNS solution to the first
method. The lower limit of determination is 0.001 g as reddish-brown color lasting for a minimum of 15 s. Record the
chloride. volumes of titrants used to the nearest 0.02 mL.
NOTE 7It is sometimes preferred to add 0.5 to 1.0 mL of 0.1 N
35. Summary of Test Method
NH4CNS solution before adding AgNO3 which is then added in an amount
35.1 The sample is diluted, acidified, and treated with a 2 to 5 mL in excess of that required to cause the disappearance of the
small excess of standard silver nitrate solution. The precipi- brown color. Any NH4CNS so added must be included in the calculation.
tated silver chloride is removed by filtration and the excess The sample is then back-titrated in accordance with 37.4.

TABLE 5 Precision for Carbonate (Gravimetric Method)

Repeatability Laboratory Precision Reproducibility
Standard Degrees of 95 % Range, Standard Degrees of 95 % Range, Standard Degrees of 95 % Range,
Level, %
Deviation Freedom Percent Absolute Deviation Freedom Percent Absolute Deviation Freedom Percent Absolute
0.010.02 0.0034 20 0.01 0.0025 10 0.01 0.0054 4 0.02
0.040.08 0.0068 20 0.02 0.0058 11 0.02 0.0018 5 0.05
0.120.15 0.0095 10 0.03 0.014 6 0.04 0.031 5 0.09
Apprx. 0.40 0.016 10 0.04 0.025 5 0.07 0.043 4 0.12

9
 E 291 01
TABLE 6 Sample Size for Chloride Analysis potentiometric titration of 0.3 to 1.2 % of chloride in caustic
Percent NaCl or Percent Sample soda and caustic potash. This test method may be applied to
KCl Expected Size, g other concentrations by using equivalent sample weights.
1 to 2 5
0.5 to 0.9 10 42. Summary of Test Method
0.01 to 0.49 20
42.1 Chloride is determined by potentiometric titration with
0.1 N silver nitrate in conjunction with a silver billet combi-
38. Calculation nation electrode. An automatic titrator or a pH meter in the
38.1 Calculate the percentage of chloride as follows: millivolt mode may be used to obtain the potentiometric
titration end point.
@~A 3 N1! 2 ~B 3 N2!# 3 0.035453
Chloride, % 5 W 3 100 (12)
43. Apparatus
where: 43.1 Automatic Titrator or pH Meter, switched to millivolt
A = AgNO3 solution added, mL, mode.
B = NH4CNS solution added, total mL, 43.2 Buret, 20-mL automatic delivery type or 25-mL
N1 = normality of AgNO3 solution used, manual type.
N2 = normality of NH4CNS solution used, and 43.3 Silver Billet, combination electrode.
W = sample used, g. 43.4 Magnetic Stirrer and Stir Bars.
38.2 Calculate the percentage of sodium chloride or potas-
sium chloride, if desired, as follows: 44. Reagents
Sodium chloride, wt % 5 chloride, wt % 3 1.6485 (13) 44.1 Nitric Acid (sp gr 1.42)concentrated nitric acid
(HNO3).
Potassium chloride, wt % 5 chloride, wt % 3 2.1029 (14) 44.2 Phenolphthalein Indicator Solution (10 g/L)
Dissolve 1 g of phenolphthalein in 100 mL of ethanol (95 %)
39. Report as prescribed in Practice E 200.
39.1 Report the percentage of chloride to the nearest 44.3 Silver Nitrate, Standard Solution (0.1 N)Prepare in
0.01 %. accordance with Practice E 200, but standardize using the
potential (end point) break obtained using an automatic titrator
40. Precision and Bias
or pH meter in the millivolt mode.
40.1 The following criteria should be used for judging the
acceptability of results (Note 8): 45. Procedure
40.1.1 Repeatability (Single Analyst)The standard devia- 45.1 For NaOH liquors, NaCl may drop out of solution and
tion for a single determination has been estimated to be must be redissolved prior to analysis. Whether NaCl crystals
0.0071 % absolute at 56 df. The 95 % limit for the difference are visible to the eye or not, place a magnetic stir bar in the
between two such runs is 0.02 % absolute. NaOH sample bottle and place the bottle on a magnetic
40.1.2 Laboratory Precision (Within-Laboratory, Between- stirrer/heater. Loosen, but do not remove the cap on the sample
Days Variability), formerly called RepeatabilityThe standard bottle. Adjust the heater setting to a very low position to allow
deviation of results (each the average of duplicates), obtained heating of the sample to only 25C. Adjust the stirring rate to
by the same analyst on different days, has been estimated to be give a visible vortex. Allow the sample to stir continuously for
0.0036 % absolute at 28 df. The 95 % limit for the difference 1 h. Then tighten the cap and allow the sample to cool to room
between two such averages is 0.01 % absolute. temperature before analysis. After cooling, invert the sample
40.1.3 Reproducibility (Multilaboratory)The standard de- bottle several times immediately before withdrawing the
viation of results (each the average of duplicates), obtained by sample.
analysts in different laboratories, has been estimated to be 45.2 Weigh 10 g of sample to the nearest 0.01 g into a
0.0069 % absolute at 6 df. The 95 % limit for the difference 250-mL beaker containing a stir bar. Carefully dilute to about
between two such averages is 0.02 % absolute 100 mL with water, add 2 drops phenolphthalein, place the
NOTE 8These precision estimates are based on an interlaboratory beaker on the magnetic stirrer, and mix. Neutralize with
study on four samples covering the range from 0.15 to 0.8 % chloride in concentrated nitric acid and add 2 to 10 drops in excess. The
potassium hydroxide and sodium hydroxide. One analyst in each of seven beaker contents must be cooled during the neutralization step
laboratories performed duplicate determinations and repeated one day to prevent violent spattering of the sample. Cover the beaker
later.6 Practice E 180 was used in developing these precision estimates.
with a watchglass and cool the solution to ambient tempera-
40.2 BiasThe bias of this test method has not been ture. Titrate the chloride in the sample with 0.1 N AgNO3 using
determined because of the unavailability of suitable reference a 20-mL buret and following the automatic titrator manufac-
materials. turers instructions for titration and end point determinations.
CHLORIDE, POTENTIOMETRIC TITRATION Perform a blank titration on the same volume of HNO3 used
for acidification of the sample added to the 100 mL of water.
41. Scope 45.3 For manual titrations, in conjunction with a pH meter
41.1 This test method was developed for the analysis of in the millivolt mode, incremental additions of 0.1 N AgNO3
chloride in caustic soda and caustic potash. It covers the are made with corresponding millivolt readings recorded after

10
 E 291 01
each addition. Construct a potentiometric titration curve by 50. Summary of Test Method
plotting millilitres of AgNO3 vs millivolts on linear graph 50.1 The sample is acidified, followed by immersion of a
paper and locate the inflection break point corresponding to the chloride ion selective electrode into the sample solution and
end point volume. measurement of the millivolt response. Comparison of the
46. Calculation response to a standard calibration curve allows interpolation of
chloride amount.
46.1 Calculate the percentage of chloride as follows:
~A 2 B! 3 N 3 0.035453 51. Apparatus
Chloride, wt % 5 W 3 100 (15)
51.1 Expanded Scale pH meter, capable of reading to 0.1
where: mV or equivalent meter.
A = AgNO3 solution required for sample, mL, 51.2 Solid-state Chloride Ion Selective Electrode.
B = AgNO3 solution required for blank, mL, 51.3 Double-junction Reference Electrode.
N = normality of AgNO3 solution used, and
W = sample used, g. 51.4 Magnetic Stirrer and Stir BarsAffix styrofoam, ap-
46.2 Calculate the percentage of sodium chloride, if desired, proximately 12 in. in size, to the stirrer surface to prevent heat
as follows: transfer from the stirrer to the test solution in the beaker.
Electrode readings are somewhat temperature dependent.
Sodium chloride, wt % 5 Chloride, wt % 3 1.6485 (16)

47. Report 52. Reagents

47.1 Report the percentage of chloride or sodium chloride to 52.1 Nitric Acid (5.0 N)Using a graduated cylinder,
the nearest 0.01 %. slowly add 319 mL of concentrated HNO3 to a 1L volumetric
flask which is approximately half-filled with water. Swirl the
48. Precision and Bias contents while adding HNO3. Dilute the contents of the flask to
48.1 The following criteria should be used for judging the the mark with water and mix well.
acceptability of results (Note 9): 52.2 Sodium Chloride, Standard Stock Solution (1000 mg/
48.1.1 Repeatability (Single Analyst)The standard devia- L)Dry NaCl at 105C for 2 h. Weigh 1.000 g of the dried
tion of a single result has been estimated to be 0.00584 % NaCl and transfer to a 1L volumetric flask half-filled with
absolute at 12 df. The 95 % limit for the difference between water. Swirl the contents thoroughly. Then dilute to the mark
two such results is 0.02 % absolute. with water and mix well.
48.1.2 Laboratory Precision (Within-Laboratory, Between- 52.3 Sodium Chloride Standard Solution (20 mg/L)Pipet
Days)Because all data were obtained on a single day, no 20 mL of the 1000-mg/L stock solution (see 52.2) into a 1L
estimate of laboratory precision is possible. volumetric flask and dilute to the mark with water. Mix well.
48.1.3 Reproducibility (Multilaboratory)The standard de- 52.4 Ionic Strength Adjuster (ISA), 5 M Sodium Nitrate
viation of single results obtained by analysts in different Weigh 425 g NaNO3, transfer to a 1L volumetric flask, and
laboratories has been estimated to be 0.0293 % absolute at 5 df. dilute to the mark with water and mix well.
The 95 % limit for the difference between two such results is
0.08 % absolute. 53. Preparation of Calibration Curve
NOTE 9These precision estimates are based on an interlaboratory 53.1 To each of six 100-mL volumetric flasks, pipet 25 mL
study conducted in 19881989 on 50 % sodium hydroxide in which eight of ISA and 10 mL of 5 N HNO3. Swirl contents of each flask.
laboratories ran triplicate determinations on one day on one sample
Then pipet 4, 6, 8, 10, 15, and 20 mL of the 20-mg/L NaCl
containing approximately 1 % sodium chloride. A one-way analysis of
variance was used in developing the precision estimates.6 The terms standard solution successively into the six volumetric flasks.
repeatability, reproducibility, and 95 % limits are used as defined in These six flasks are working standards containing 80, 120, 160,
Practice E 180. The test method is believed applicable to potassium 200, 300, and 400 g NaCl, respectively. Dilute the contents of
hydroxide, but the precision of this application has not been determined. each flask to the mark with water and mix well. Beginning with
48.2 BiasThe bias of this test method has not been the most dilute standard, successively transfer the contents of
determined because of the unavailability of suitable reference each flask to a 150-mL beaker containing a magnetic stir bar.
materials. Place the beaker on a magnetic stirrer.
53.2 Immerse the chloride and reference electrodes. Stir for
CHLORIDE, ION SELECTIVE ELECTRODE 4 min before recording a millivolt reading. After each standard
solution measurement, rinse both electrodes well with water
49. Scope and blot electrodes dry using absorbent paper. Using semilog
49.1 This test method was developed for the analysis of graph paper, plot the millivolt reading for the 4-mL NaCl
chloride in caustic soda and caustic potash. It covers the ion standard on the linear axis versus 80 g NaCl on the log axis.
selective electrode determination of 1 to 120 ppm chloride in Similarly, plot millivolt readings for the other working stan-
caustic soda and caustic potash. This test method may be dards (see 53.1) versus their micrograms of NaCl. For plotting
applied to other concentrations by using equivalent sample the calibration curve, semilog paper having 2 cycles, 10
weights. divisions per inch is recommended.

11
 E 291 01
54. Procedure 57.2 BiasThe bias of this test method has not been
54.1 For NaOH liquors, to ensure a homogeneous sample, determined because of the unavailability of suitable reference
invert the sample bottle several times prior to withdrawing a materials.
portion for analysis. Weigh 10 g of the sample to the nearest
IRON
0.01 g into a 100-mL volumetric flask. Add 40 mL of water
using a graduated cylinder and swirl the contents to mix. 58. Scope
54.2 Pipet 35 mL of 5 N HNO3 into the flask and swirl the 58.1 This test method covers the photometric determination
contents. Allow the contents to come to room temperature of iron in caustic soda or caustic potash. The lower limit of
before dilution to the mark with water and final mixing. determination is 0.1 ppm as iron.
54.3 Transfer the contents of the flask to a 150-mL beaker
containing a magnetic stir bar. Immerse the chloride and 59. Summary of Test Method
reference electrodes and stir for 4 min before recording the 59.1 Iron is reduced to the ferrous condition where it forms
millivolt reading. For replicate analyses, rinse electrodes well an orange-red complex with 1,10-phenanthroline (o-
and blot electrodes dry in between sample measurements. phenanthroline) in an acetate-buffered solution at pH 5. Inten-
54.4 Interpolate the g NaCl value directly from the cali- sity of the color so formed is measured at 510 nm in a
bration curve in accordance with Section 53. photometer calibrated with standard iron solutions. The color
develops within 15 min, is very stable, and follows Beers law.
55. Calculation
55.1 Calculate the ppm chloride as follows: 60. Interferences
C 3 0.60652 60.1 Impurities normally found in caustic soda or caustic
chloride, ppm 5 W (17) potash do not cause any interference. Copper, if present to the
extent of 0.5 mg/100 mL of final solution, changes the hue of
the solution, but interferes only slightly when excess reagent is
where: present. Zinc, cadmium, and nickel form complexes and
C = g NaCl interpolated from calibration curve, and consume reagent but do not interfere when sufficient reagent is
W = sample used, g. present.
55.2 Calculate the ppm sodium chloride, if desired, as
61. Reagents
follows:
61.1 Ammonium Acetate-Acetic Acid SolutionSee Prac-
sodium chloride, ppm 5 chloride, ppm 3 1.6485 (18)
tice E 200.
61.2 Ammonium Hydroxide (1 + 1)Mix equal volumes of
56. Report
concentrated ammonium hydroxide (NH4OH, sp gr 0.90) and
56.1 Report the parts per million of chloride or sodium water.
chloride to the nearest 1 ppm. 61.3 Congo Red Indicator Paper.
61.4 Hydrochloric Acid (sp gr 1.19)Concentrated hydro-
57. Precision and Bias chloric acid (HCl).
57.1 The following criteria should be used in judging the 61.5 Hydroxylamine Hydrochloride Solution (100 g/L)
acceptability of results (Note 10): Dissolve 100 g of hydroxylamine hydrochloride (NH2OHHCl)
57.1.1 Repeatability (Single Analyst)The standard devia- in water and dilute to 1 L.
tion of a single result has been estimated to be 1.02 ppm NaCl 61.6 Iron, Standard Solution (1 mL = 0.010 mg Fe)See
at 18 df. The 95 % limit for the difference between two such Practice E 200.
results is 3 ppm NaCl. 61.7 1,10-Phenanthroline (o-phenanthroline) Solution (3
57.1.2 Laboratory Precision (Within-Laboratory, Between- g/L)See Practice E 200.
Days Variation)Because all the data were obtained on a 62. Preparation of Calibration Curve
single day, no estimate of laboratory precision is available.
57.1.3 Reproducibility (Multilaboratory)The standard de- 62.1 To a series of 100-mL volumetric flasks, pipet 0.5, 1.0,
viation of a single result obtained by analysts in different 2.0, 3.0, and 5.0-mL portions of standard iron solution. To each
laboratories has been estimated to be 5.18 ppm sodium flask add the following reagents in order, mixing after addition
chloride at 8 df. The 95 % limit for the difference between two of each 20 mL of water, 5 mL of hydroxylamine hydrochloride
such results is 15 ppm sodium chloride. solution, and NH4OH (1 + 1) as required to bring the pH to 3.5
to 4.0 (just alkaline to Congo red paper as an external
NOTE 10These precision estimates are based on an interlaboratory indicator). Add 5 mL of ammonium acetate-acetic acid buffer
study conducted in 19881989 on 50 % sodium hydroxide in which nine solution, 5 mL of 1,10-phenanthroline solution, dilute to the
laboratories ran triplicate determinations on the same day on one sample mark with water, mix thoroughly, and allow to stand approxi-
containing approximately 34 ppm sodium chloride. A one-way analysis of
variance was used to estimate the precision of the method.6 The terms
mately 15 min. Prepare a reference solution in another flask
repeatability, reproducibility, and 95 % limits are used as defined in with water and the same reagents as previously indicated.
Practice E 180. This test method is believed applicable to potassium 62.2 Measure the absorbances of the solutions using an
hydroxide, but the precision of this application has not been determined. absorption cell with a 5-cm light path (Note 11) and a

12
 E 291 01
photometer (see 4.1) with a wavelength setting of 510 nm (or tained by analysts in different laboratories, has been estimated
a filter in the range from 500 to 525 nm). Adjust the photometer to be 10.4 % relative at 13 df. The 95 % limit for the difference
to read zero absorbancy on the reagent blank. between two such averages is 29 % relative.
NOTE 11This test method has been written for cells having a 5-cm NOTE 12These precision estimates are based on an interlaboratory
light path. Cells of other dimensions may be used, provided suitable study on four samples covering the range from 4 to 30 ppm iron in
adjustments can be made in the amounts of samples and reagents used. potassium hydroxide and sodium hydroxide. One analyst in each of fifteen
laboratories performed duplicate determinations and repeated one day
62.3 Plot on coordinate paper the absorbances of the cali-
later.6 Practice E 180 was used in developing these precision estimates.
bration solutions versus milligrams of iron present per 100 mL
of solution. 66.2 BiasThe bias of this test method has not been
determined because of the unavailability of suitable reference
63. Procedure materials.
63.1 Into a 400-mL beaker, weigh 40 g of sample to the
nearest 0.1 g. Add 100 mL of water and carefully add HCl (sp SULFATE
gr 1.19) in increments until 50 mL have been added if the 67. Scope
sample is 45 % KOH or 50 % NaOH, 75 mL if the sample is
73 % NaOH, or 100 mL if the sample is anhydrous NaOH or 67.1 This test method covers the gravimetric determination
anhydrous KOH. Cover with a watchglass, heat to boiling, and of sulfate present in caustic soda or caustic potash. The lower
boil for 1 min. (Any red residue of Fe2O3 should disappear limit of determination is 0.002 g as So3.
during the boiling period.) Cool the solution to room tempera-
68. Summary of Test Method
ture, transfer to a 500-mL volumetric flask, dilute to volume
with water, and mix. Pipet an aliquot to contain from 0.005 to 68.1 Sulfate is determined gravimetrically by precipitation
0.050 mg of iron into a 100-mL volumetric flask. Into another as barium sulfate which is filtered off, washed, ignited, and
100-mL volumetric flask put 50 mL of water and 1 mL of HCl weighed.
(sp gr 1.19) for a reference solution.
69. Reagents
63.2 To both sample and reference solutions add reagents as
in 62.1. Dilute to volume, mix thoroughly, and let stand 15 69.1 Barium Chloride Solution (120 g BaCl22H2O/L)See
min. Practice E 200.
63.3 Measure absorbance of the sample solution versus the 69.2 Hydrochloric Acid (sp gr 1.19)Concentrated hydro-
reference solution as in 62.2. chloric acid (HCl).
69.3 Methyl Orange Indicator Solution (1 g/L)See Prac-
64. Calculation tice E 200.
64.1 Convert the photometric reading of the test solution to 69.4 Silver Nitrate Solution (5 g/100 mL)Dissolve 5 g of
milligrams of iron by means of the calibration curve. Calculate silver nitrate (AgNO3) in water and dilute to 100 mL.
the parts per million of iron as follows:
70. Procedure
~A 3 1000!
Iron, ppm 5 B (19) 70.1 Use Table 7 as a guide to the size of sample to be used.
70.2 Weigh the sample in a 600-mL beaker to the nearest 0.1
where: g. Add 300 mL of water and mix. Add 2 to 4 drops of methyl
A = iron found in 100 mL of final solution mg, and, orange indicator solution and acidify carefully with HCl adding
B = sample represented in the aliquot taken, g. 3 mL in excess of that required to neutralize the sample.
Examine the solution at this point. If it contains any insoluble
65. Report
matter, filter off on a retentive filter paper. Return the filtrate to
65.1 Report the concentration of iron to the nearest 0.1 ppm. the beaker and heat to boiling. Add slowly, with constant
66. Precision and Bias stirring, 25 mL of BaCl2 solution. Digest for 30 min on a steam
bath and allow the precipitate to settle overnight at room
66.1 The following criteria should be used for judging the temperature.
acceptability of results (Note 12): 70.3 Filter on ashless, fine quantitative paper and transfer
66.1.1 Repeatability (Single Analyst)The coefficient of the precipitate quantitatively to the paper with a fine stream of
variation for a single determination has been estimated to be hot water from a wash bottle. Wash the precipitate with
5.34 % relative at 98 df. The 95 % limit for the difference successive small portions of hot water until the washings are
between two such runs is 15 % relative. free of chloride on testing with 3 to 4 drops of AgNO3 solution.
66.1.2 Laboratory Precision (Within-Laboratory, Between-
Days Variability), formerly called RepeatabilityThe coeffi-
cient of variation of results (each the average of duplicates), TABLE 7 Sample Size for Sulfate Analysis
obtained by the same analyst on different days, has been Sample Sample Size, g
estimated to be 5.6 % relative at 49 df. The 95 % limit for the 45 % KOH 45 to 55
difference between two such averages is 16 % relative. 50 % NaOH 45 to 55
73 % NaOH 30 to 40
66.1.3 Reproducibility (Multilaboratory)The coefficient Anhydrous KOH and NaOH 20 to 30
of variation of results (each the average of duplicates), ob-

13
 E 291 01
TABLE 8 Precision for Sulfate Determination
Laboratory Precision Reproducibility
Level, % SO3 Coefficient of Degrees of 95 % Range, Coefficient of Degrees of 95 % Range,
Variation Freedom Percent Relative Variation, % Freedom Percent Relative
0.100 6 14 17 11 13 31
0.050 9 13 25 25 12 70
0.010 12 14 39 30 13 84

70.4 Heat a platinum or porcelain crucible to 850 to 900C 73.1.1 Repeatability (Single Analyst)The standard devia-
for 15 min, cool in a desiccator, and weigh to the nearest tion for a single determination has been estimated to be
0.0001 g. Fold the washed filter paper with precipitate and 0.00064 % absolute at 88 df. The 95 % limit for the difference
place in the tared crucible. Dry and char carefully without between two such runs is 0.0018 % absolute.
flaming. Ignite at 850 to 900C for a minimum of 30 min. 73.1.2 Laboratory Precision (Within-Laboratory, Between-
Remove the crucible from the furnace, allow to cool partially, Days Variability), formerly called RepeatabilityThe coeffi-
place in a desiccator, and cool to room temperature. Reweigh cient of variation of results (each the average of duplicates),
to the nearest 0.0001 g. obtained by the same analyst on different days, has been
estimated to be the value given in Table 8 at the indicated
71. Calculation degrees of freedom. The 95 % limit for the difference between
71.1 Calculate the percentage of sulfur trioxide as follows: two such averages is also given in Table 8.
~AB! 3 0.34302 73.1.3 Reproducibility (Multilaboratory)The coefficient
Sulfur trioxide, wt % 5 W 3 100 (20) of variation of results (each the average of duplicates), ob-
tained by analysts in different laboratories, has been estimated
where: to be the value given in Table 8 at the indicated degrees of
A = weight of crucible and precipitate after ignition, freedom. The 95 % limit for the difference between two such
B = weight of empty crucible, and averages is also given in Table 8.
W = weight of sample used, g.
71.2 Calculate the percentage of sodium or potassium sul- NOTE 13These precision estimates are based on an interlaboratory
fate as follows: study on three samples containing approximately 0.01, 0.05, and 0.1 %
sulfur trioxide. The number of laboratories analyzing each sample ranged
Sodium sulfate, wt % 5 percent sulfur trioxide3 1.7741 (21) from twelve to fifteen with one analyst in each performing duplicate
determinations and repeating one day later.6 Practice E 180 was used in
Potassium sulfate, wt % 5 percent sulfur trioxide 3 2.1766 (22) developing these precision estimates.
73.2 BiasThe bias of this test method has not been
72. Report determined because of the unavailability of suitable reference
72.1 Report the percentage of the sulfur trioxide to the materials.
nearest 0.001 %.
74. Keywords
73. Precision and Bias 74.1 caustic soda; caustic potash; chloride; iron; potassium
73.1 The following criteria should be used for judging the carbonate; potassium hydroxide; sodium carbonate; sodium
acceptability of results (Note 13). hydroxide; sulfate; total alkalinity

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