*Trademark of The Dow Chemical Company

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Copyright 2002 The Dow Chemical Company
ANALYTICAL METHOD
Effective: 08 April 96 DOWM 100896-TE96A
Supersedes: DOWM 100896-TE91A
VERSENE 100 Chelating Agent
1. Scope
This method is applicable to the determination of chelation value, active ingredient, pH,
specific gravity, and APHA color in VERSENE* 100 chelating agent over the ranges
given in the table below (Note 13.1).
Test Item Applicable Range
Chelation Value 90 - 110 mg CaCO
3
/g chelating agent
Active Ingredient 35.0 - 40.0 weight % as Na
4
EDTA
pH (1% solution) 10 - 12
Specific Gravity 1.250 - 1.320
APHA Color 0 - 500
2. Principle
2.1 Chelation value: An aliquot of a sample of VERSENE 100 chelating agent is
dissolved in water and sodium hydroxide (NaOH) is added to a pH of 11 to 12.
Ammonium oxalate is added and the resulting mixture is titrated with calcium
chloride solution to the first permanent turbidity.
2.2 Active ingredient: A calculated value is determined based on the chelation value.
2.3 pH: A 1% aqueous solution of VERSENE 100 chelating agent is prepared. The
pH of the solution is measured at 25C with a pH meter with glass and reference
electrodes. This procedure is based on ASTM E 70 (Section 14.1).
2.4 Specific gravity: The specific gravity in air is determined by means of a
hydrometer at 25C. This procedure is based on ASTM D 891 (Section 14.2).
08 April 96 2 of 10 pages DOWM 100896-TE96A
2.5 APHA Color: The transmittance of monochromatic light through the sample is
related to its color by comparison with APHA standards. This procedure is based
on ASTM D 1209 (Section 14.3).
3. Safety
3.1 Each analyst should be acquainted with the potential hazards of the equipment,
reagents, products, solvents, and procedures before beginning laboratory work.
SOURCES OF INFORMATION INCLUDE: OPERATION MANUALS,
MATERIAL SAFETY DATA SHEETS, LITERATURE AND OTHER
RELATED DATA. Safety information for non-Dow products should be
requested from the supplier. Disposal of waste materials, reagents, reactants, and
solvents must be in compliance with laws and regulations from all applicable
governmental agencies.
3.2 Sodium hydroxide pellets and 50% caustic soda solution are highly corrosive
materials which can cause serious burns to the skin and eyes. Eye contact of only
a few seconds can cause permanent damage, even blindness. Consult the Material
Safety Data sheets (Section 3.1) for these materials prior to use. Wear
appropriate personal protective equipment.
4. Interferences
No direct interferences have been observed in the use of this method. If results are
suspect based on the analytical history of the product, the data should be confirmed by an
alternate method.
5. Apparatus
5.1 Analytical balance: capable of weighing to 0.0001 g, available from Mettler-
Toledo Inc., PO Box 71, Hightstown, NJ 08520, or equivalent.
5.2 Indicating pH paper: for range 11 to 12, Alkacid Range 5 paper, available from
Fisher Scientific, 711 Forbes Avenue, Pittsburgh, PA 15219, or equivalent.
5.3 Magnetic stirrer: with black top or black cover, Fisher Economy Stirrer, available
from Fisher Scientific, or equivalent.
08 April 96 3 of 10 pages DOWM 100896-TE96A
5.4 pH Meter: with glass and reference electrodes, Corning model 130 pH meter,
equipped with a Corning No. 476022 glass electrode and a Corning No. 476002
reference electrode, available from Corning Inc., Science Products Div., HP-AB-
03, Corning, NY 14831, or equivalent.
5.5 Water bath: capable of equilibrating at 25.0 0.1C, Haake Refrigerating
Circulator C1-K20, available from Fisher Scientific, or equivalent.
5.6 Hydrometer: with a range of 1.20 to 1.40, available from Fisher Scientific, or
equivalent.
5.7 Colorimeter: Manostat model (used to be called Klett-Summerson), with a No.
42 blue filter and a 4-cm cell, available from Curtin Matheson Scientific, PO Box
1546, Houston, TX 77251, or equivalent.
5.8 Volumetric flask: 100-mL volume, available from Fisher Scientific, or
equivalent.
6. Reagents
6.1 Ammonium oxalate: monohydrate, calcium free, ACS reagent grade, available
from Mallinckrodt, Inc., 675 Brown Road., St. Louis, MO 63134, or equivalent.
6.2 Ethylenediaminetetraacetic acid (EDTA): 99.99% purity or greater, Ultrapure
reagent material such as Ultrex EDTA, available from J. T. Baker Inc., 222 Red
School Lane, Phillipsburg, NJ 08865, or equivalent.
6.3 Calcium chloride dihydrate: ACS reagent grade, available from Mallinckrodt,
Inc., or equivalent.
6.4 Sodium hydroxide pellets: ACS reagent grade, available from J. T. Baker Inc., or
equivalent.
6.5 Deionized water: available from any reliable laboratory water purification
system, or from Fisher Scientific, or equivalent.
6.6 Platinum-cobalt color standard: 500 APHA, available from Aldrich Chemical
Co., Inc., 1001 W. St. Paul Avenue, PO Box 355, Milwaukee, WI 53201, or
equivalent.
08 April 96 4 of 10 pages DOWM 100896-TE96A
7. Reagent Solutions
7.1 Ammonium oxalate, 3% solution: Dissolve approximately 30 g of ammonium
oxalate (Section 6.1) in one liter of deionized water (Section 6.5) and mix
thoroughly.
7.2 Calcium chloride, 0.5 M: Dissolve approximately 73.5 g of calcium chloride
dihydrate (Section 6.3) in one liter of deionized water (Section 6.5). This solution
must be standardized against standard EDTA as outlined in Section 8 prior to use.
7.3 50% Sodium hydroxide solution: Slowly dissolve approximately 500 g of sodium
hydroxide pellets (Section 6.4) in 500 mL of deionized water (Section 6.5).
WARNING: This procedure is extremely exothermic and the solution will
become quite hot. The pellets and solution are extremely corrosive. Wear
the proper protective equipment. Mix the resulting solution thoroughly and
store in a polyethylene bottle.
7.4 APHA color standards: Prepare standards having colors of 100, 200, 300 and 400
by pipetting the volume of 500 APHA standard (Section 6.6) listed in the table
below into separate 100-mL volumetric flasks. Dilute each flask to volume with
deionized water (Section 6.5) and mix well.
APHA Standard to Prepare Volume of APHA 500 Standard to Add
(mL)
100 20
200 40
300 60
400 80
8. Standardization
Standardize the calcium chloride solution (Section 7.2) prior to use as follows:
8.1 Standardization solution:
8.1.1 Weigh (and record to the nearest 0.001 g) 2.5 to 3.0 g of Ultrapure EDTA
(Section 6.2) into a 200-mL beaker.
8.1.2 Add 80 mL of deionized water (Section 6.5) and sufficient 50% sodium
hydroxide solution (Section 7.3) to the beaker in Section 8.1.1 to raise the
pH to 11 to 12 (measure the pH with pH paper). Add 20 mL of 3%
ammonium oxalate solution (Section 7.1) to the beaker.
08 April 96 5 of 10 pages DOWM 100896-TE96A
8.1.3 Place the beaker on a magnetic stirrer which has a black top or cover and
stir the resulting solution in Section 8.1.2 gently. Locate and utilize a
light source so that the beaker is illuminated from behind.
8.2 Titrate the resulting standardization solution (Section 8.1.3) with the calcium
chloride solution (Section 7.2) until the first permanent turbidity is noted.
Perform the titration slowly, especially when nearing the endpoint. Measure the
pH of the mixture with pH paper. The pH at this endpoint must be 11 or higher.
If the pH is below 11, add enough 50% sodium hydroxide solution (Section 7.3) to
bring the pH to above 11. If the turbidity disappears, continue the titration with
calcium chloride to the first permanent turbidity. Record the volume (mL) of
titrant required to reach the endpoint.
8.3 Calculate the molarity of the standardized calcium chloride as follows:
A
B
C


=
3422 .
where:
A = molarity (moles/L) of the calcium chloride solution
B = weight (g) of the EDTA sample titrated (Section 8.1.1)
C = volume (mL) of the calcium chloride titrant used to reach the end point
of the standardization titration (Section 8.2)
3.422 =
1000
292 2


mL L
g mole
/
. /
292.2 = molecular weight (g/mole) of H
4
EDTA
9. Calibration
Calibrate the spectrophotometer prior to use as follows:
9.1 Zero spectrophotometer with deionized water (Section 6.5).
9.2 Analyze deionized water (Section 6.5) and each APHA standard solution (100 -
500 APHA units; Sections 6.6 and 7.4) as follows: Pour each solution into a
clean cell and insert the cell into the spectrophotometer so that the path length is 4
cm. Record the reading.
9.3 Prepare a standard curve either by manually plotting the data (APHA units vs.
reading) or by entering the data into a spreadsheet such as Excel and having the
software calculate the slope and intercept for the data.
08 April 96 6 of 10 pages DOWM 100896-TE96A
10. Procedure
10.1 Determine the chelation value of the sample as follows:
10.1.1 Weigh (and record to the nearest 0.001 g) 8.0 + 0.3 g of the sample to be
analyzed into a clean 200-mL beaker.
10.1.2 Add 80 mL of deionized water (Section 6.5) and 20 mL of 3% ammonium
oxalate solution (Section 7.1) to the beaker in Section 10.1.1. Add
sufficient 50% sodium hydroxide solution (Section 7.3) to the beaker to
raise the pH to 11 to 12 (measure the pH with pH paper).
10.1.3 Place the beaker on a magnetic stirrer which has a black top or cover and
stir the resulting solution in Section 10.1.2 gently. Locate and utilize a
light source so that the beaker is illuminated from behind.
10.1.4 Titrate the resulting standardization solution (Section 10.1.3) with the
standardized calcium chloride solution (Section 7.2) until the first
permanent turbidity is noted. Perform the titration slowly, especially
when nearing the endpoint. Measure the pH of the mixture with pH paper.
The pH at this endpoint must be 11 or higher. If the pH is below 11, add
enough 50% sodium hydroxide solution (Section 7.3) to bring the pH to
above 11. If the turbidity disappears, continue the titration with calcium
chloride to the first permanent turbidity. Record the volume (mL) of
titrant required to reach the endpoint.
10.1.5 Calculate the chelation value for the sample as follows:
D
E A
F

=
100
where:
D = the chelation value for the sample (mg CaCO
3
per g of chelating
agent)
E = volume (mL) of calcium chloride titrant used to reach the end
point of the sample titration (Section 10.1.4)
A = molarity (moles/L) of the calcium chloride solution (Section 8.3)
F = weight (g) of sample titrated (Section 10.1.1)
100 = molecular weight (g/mole) of CaCO
3
08 April 96 7 of 10 pages DOWM 100896-TE96A
10.2 Determine the concentration (weight %) of active ingredient in the sample as
follows:
G
E A
F


=
38
where:
G = concentration (weight %) of active ingredient (as Na
4
EDTA) in the
sample
E = volume (mL) of calcium chloride titrant used to reach the end point
of the sample titration (Section 10.1.4)
F = weight (g) of sample titrated (Section 10.1.1)
38 = molecular weight (g/mole) of Na
4
EDTA divided by 10
10.3 Determine the pH of the sample as follows:
10.3.1 Weigh 1.00 + 0.05 g of sample into a tared 250-mL beaker. Add 99.0 +
0.1 g of deionized water (Section 6.5) to the beaker (the total weight
should be 100.0 0.1 g.) and mix well.
Follow the manufacturer's instructions for the operation and calibration of the pH meter.
Refer to ASTM E 70 for additional information on the subject (Section 14.1).
10.3.2 Equilibrate the temperature of the resulting solution in Section 10.3.1 to
25C using a water bath. Measure the pH of the solution at 25C and
report the pH meter reading as the pH of the sample.
10.4 Determine the specific gravity of the sample at 25C according to Method A of
ASTM D 891 (Section 14.2).
Note: Method B of ASTM D 891 (Section 14.2) is an acceptable alternative but requires
additional equipment.
10.5 Determine the APHA color of the sample as follows (Section 14.3):
10.5.1 Pour the sample into a clean cell. Insert the cell into the
spectrophotometer so that the path length is 4 cm. Record the reading.
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10.5.2 Either manually read the APHA color from a manually plotted graph
(Section 9.3) or determine the APHA color value as follows:
APHA Color Value

=
R I
S
where:
R = reading recorded for the sample (Section 10.5.1)
I = y-intercept of the standard curve (Section 9.3)
S = slope of the standard curve (Section 9.3)
11. Precision (Note 13.2)
11.1 Chelation Value and Active Ingredient: Data obtained from multiple analyses
[n
(val)
= 10] of a single sample on two separate days indicate a standard deviation
[s
(val)
] of 0.060 weight % determined at an average concentration of 37.5 weight %
Na
4
EDTA in VERSENE 100 chelating agent. The actual 95% confidence
interval for the mean of the validation data [t
s
n
( n - 1)
( val )
( val )
where t
(n-1)
= 2.262] was
determined to be 0.043 weight %. Assuming a normal distribution of results
and equal variability between laboratories, the 95% confidence interval for a
single value [1.96
s
n
(val)
(analysis)
where n
(analysis)
= 1] is estimated to be 0.12 weight %.
11.2 Determination of pH: The procedure for pH measurement is essentially
equivalent to ASTM E 70 (Section 14.1), with the exception of sample
preparation. The precision of the method should be equivalent to that reported in
the ASTM standard.
11.3 Determination of specific gravity: The procedure for specific gravity
measurement is equivalent to ASTM D 891 (Section 14.2). The precision of the
method should be equivalent to that reported in the ASTM standard.
11.4 Determination of APHA color: The procedure for APHA color measurement is
equivalent to ASTM D 1209 (Section 14.3). The precision of the method should
be equivalent to that reported in the ASTM standard.
12. Accuracy (Note 13.2)
12.1 Chelation Value and Active Ingredient: Analysis of four mixtures containing 40
to 100 weight % chelating agent gave recoveries that averaged 100.0% with a
range of 99.6 to 100.2% and a standard deviation of 0.16%.
08 April 96 9 of 10 pages DOWM 100896-TE96A
12.2 Determination of pH: The procedure for pH measurement is essentially
equivalent to ASTM E 70 (Section 14.1), with the exception of sample
preparation. The accuracy of the method should be equivalent to that reported in
the ASTM standard.
12.3 Determination of specific gravity: The procedure for pH measurement is
equivalent to ASTM D 891 (Section 14.2). The accuracy of the method should be
equivalent to that reported in the ASTM standard.
12.4 Determination of APHA color: The procedure for APHA color measurement is
equivalent to ASTM D 1209 (Section 14.3). The accuracy of the method should
be equivalent to that reported in the ASTM standard.
13. Notes
13.1 The applicable ranges listed in Section 1 are estimates based on technical
experience with the product and instrumentation. These estimates were made
because the ranges studied during the method validation were limited. If results
are suspect based on the analytical history of the product, the data should be
confirmed by an alternate method.
13.2 In accordance with good laboratory practices, it is strongly suggested that the
precision and accuracy of the method be re-determined if another set of
equipment is to be used or the method is to be used in another laboratory.
14. References
14.1 ASTM E 70-90 (or most current version), "Test Method for pH of Aqueous
Solutions with the Glass Electrode", available from American Society for Testing
and Materials (ASTM), 100 Barr Harbor Drive, West Conshohocken, PA 19428.
14.2 ASTM D 891-95 (or most current version), "Standard Test Methods for Specific
Gravity, Apparent, of Liquid Industrial Chemicals", available from American
Society for Testing and Materials (ASTM).
08 April 96 10 of 10 pages DOWM 100896-TE96A
14.3 ASTM D 1209-93 (or most current version), "Standard Test Methods for Color of
Clear Liquids (Platinum-Cobalt Scale)", available from American Society for
Testing and Materials (ASTM).
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