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Designation: E945 − 12

Standard Test Method for

Determination of Zinc in Zinc Ores and Concentrates by
EDTA Complexometric Titrimetry1
This standard is issued under the fixed designation E945; 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.

1. Scope erations for Chemical Analysis of Metals, Ores, and

1.1 This test method covers the determination of zinc in Related Materials
ores, concentrates, and related materials having chemical E135 Terminology Relating to Analytical Chemistry for
composition within the following limits: Metals, Ores, and Related Materials
E173 Practice for Conducting Interlaboratory Studies of
Element Application Range, %
Methods for Chemical Analysis of Metals (Withdrawn
Zinc 5.0 to 70.0 1998)3
Lead 0.5 to 50.0 E663 Practice for Flame Atomic Absorption Analysis (With-
Copper 0.1 to 3.0
Iron 0.5 to 16.0 drawn 1997)3
Sulfur 4.0 to 30.0 E882 Guide for Accountability and Quality Control in the
Calcium 0.1 to 20.0 Chemical Analysis Laboratory
Magnesium 0.1 to 10.0
Cadmium 0.1 to 8.0 E1601 Practice for Conducting an Interlaboratory Study to
Arsenic 0.01 to 1.0 Evaluate the Performance of an Analytical Method
Antimony 0.01 to 0.005
Bismuth 0.001 to 0.1
Cobalt 0.1 to 0.5 3. Terminology
Nickel 0.3 to 3.0
Silver 0.00 to 150 oz/ton
3.1 Definitions—For definitions of terms used in this test
Gold 0.00 to 1.0 oz/ton method, refer to Terminology E135.
NOTE 1—As used in this test method, percent or “%” refers to a mass
fraction. 4. Summary of Test Method
1.2 This standard does not purport to address all of the 4.1 The sample, after appropriate acid decomposition, is
safety concerns, if any, associated with its use. It is the evaporated to near dryness. The salts are dissolved in acid,
responsibility of the user of this standard to establish appro- interfering elements are removed, and the zinc is extracted as
priate safety and health practices and determine the applica- thiocyanate complex into MIBK. Zinc is determined in the
bility of regulatory limitations prior to use. extract by titrating with EDTA, using an internal indicator.

2. Referenced Documents 5. Significance and Use

2
2.1 ASTM Standards: 5.1 This test method is primarily intended to test materials
D1193 Specification for Reagent Water for compliance with compositional specifications. It is assumed
E29 Practice for Using Significant Digits in Test Data to that all who use this test method will be trained analysts
Determine Conformance with Specifications working in properly equipped laboratories.
E50 Practices for Apparatus, Reagents, and Safety Consid- 5.2 Appropriate quality control practices shall be followed
such as those described in Guide E882.
1
This test method is under the jurisdiction of ASTM Committee E01 on
Analytical Chemistry for Metals, Ores, and Related Materials and is the direct
6. Interferences
responsibility of Subcommittee E01.02 on Ores, Concentrates, and Related Metal- 6.1 With the exception of cadmium and cobalt, elements do
lurgical Materials.
Current edition approved June 1, 2012. Published July 2012. Originally approved
not interfere if their compositional ranges are under the
in 1983. Last previous edition approved in 2007 as E945 – 07. DOI: 10.1520/ maximum limits shown in 1.1.
E0945-12.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on The last approved version of this historical standard is referenced on
the ASTM website. www.astm.org.

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

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 E945 − 12
6.2 When the cadmium content is above 5.0 % in the NOTE 2—The use of varying concentrations of EDTA solution allows
material to be analyzed, some of the cadmium is extracted and the volume of the titrant to be between 30 mL and 50 mL.
will titrate as zinc. The addition of potassium iodide before the Amount of
EDTA · 2H2O EDTA Standard Zinc
titration serves to prevent the interference of cadmium. The If the expected Mass, g/L Concentration Solution to
amount of potassium iodide solution to add in order to prevent zinc is: Use
the interference of cadmium is listed in 13.10.3. 5 % to 20 % 6.642 6 g/L 10 mL
20 % to 40 % 13.29 12 g/L 30 mL
6.3 Cobalt is extracted and titrated with the zinc. If the 40 % to 56 % 17.71 16 g/L 40 mL
56 % to 70 % 22.14 20 g/L 50 mL
cobalt content of the material to be analyzed is less than
0.05 %, the interference is negligible. For cobalt contents 8.8.2 Standardize the EDTA solution by pipetting the sug-
greater than 0.05 %, the cobalt must be extracted as outlined in gested amount of standard zinc solution into a 250-mL
13.9.5. separatory funnel. Add 10 drops of ferric chloride solution, add
distilled water to adjust volume to 50 mL, mix, and proceed as
7. Apparatus directed in 13.9.2. It is recommended that replicate standard-
7.1 Magnetic Stirrer, with TFE-fluorocarbon covered mag- izations be made to ensure better accuracy.
netic stirring bar. A magnetic stirrer provided with illumination 8.8.3 Calculate the zinc equivalent of the EDTA solution as
is preferred. follows:
A
8. Reagents and Materials Zinc Equivalent ~ mg/mL! 5 (1)
B
8.1 Purity of Reagents—Reagent grade chemicals shall be
where:
used in all tests. Unless otherwise indicated, it is intended that
all reagents conform to the specifications of the Committee on A = zinc in the chosen aliquot, mg and
Analytical Reagents of the American Chemical Society where B = EDTA solution (8.8) used, mL
such specifications are available.4 Other grades may be used, 8.9 Ethanol (CH3CH2OH)—Certain denatured ethanols in-
provided it is first ascertained that the reagent is of sufficient terfere with the color of the indicator during the titration. Pure
high purity to permit its use without lessening the accuracy of ethanol is recommended for this reason.
the determination. 8.10 Ferric Chloride Solution (140 g/L)—Dissolve 14 g of
8.2 Purity of Water—Unless otherwise indicated, references ferric chloride (FeCl3·6H2O) in water and dilute to 100 mL.
to water shall be understood to mean reagent water as defined 8.11 4-Methyl-2-Pentanone (MIBK) —CH3COCH2CH
by Type I or II of Specification D1193. Type III or IV may be (CH3)2.
used if they effect no measurable change in the blank or sample
8.12 2-Nitroso-1-Naphthol Solution (10 g/L)—Dissolve 0.5
8.3 Ammonium Fluoride Solution (250 g/L)—Dissolve 250 g of 2-nitroso-1-naphthol (NOC10H6OH) in 50 mL of acetic
g of ammonium fluoride (NH4F) in water and dilute to 1 L. acid. Prepare fresh as needed.
Store in a polyethylene bottle.
8.13 Potassium Iodide (1000 g/L)—Dissolve 100 g of po-
8.4 Ammonium Chloride Solution (250 g/L)—Dissolve 250 tassium iodide (KI) in distilled water and dilute to 100 mL.
g of ammonium chloride (NH4Cl) in water and dilute to 1 L.
8.14 Sodium Fluoride Solution (20 g/L)—Dissolve 10 g of
8.5 Ammonium Thiocyanate (500 g/L)—Dissolve 500 g of sodium fluoride (NaF) in water and dilute to 500 mL. Store in
ammonium thiocyanate (NH4SCN) in distilled water and dilute a polyethylene bottle.
to 1 L.
8.15 Thiourea Solution (100 g/L)—Dissolve 50 g of thio-
8.6 Buffer Solution (pH 5.5)—Dissolve 250 g of hexameth- urea (NH2CSNH2) in water and dilute to 500 mL.
ylenetetramine (C6H12N4) in 750 mL of water. Add 57 mL of
acetic acid, dilute to 1 L, and mix. 8.16 Xylenol Orange Tetrasodium Salt Indicator Solution (2
g/L)—Dissolve 100 mg of xylenol orange tetrasodium salt in
8.7 Chloroform (CHCl3). water and dilute to 50 mL.
8.8 Disodium Ethylenedinitrilo Tetraacetate Dihydrate 8.17 Zinc, Standard Solution (1 mL–3.50 mg)—Dissolve
(EDTA) Standard Solution—Prepare a solution as follows: 3.50 g of zinc (minimum purity 99.99 %) in 10 mL of HNO3
8.8.1 Preparation—Dissolve disodium ethylenedinitrilo tet- and 25 mL of water. Heat gently; when dissolution is complete,
raacetate (EDTA) dihydrate in water, transfer to a 1–L volu- boil. Cool. Transfer to a 1-L flask. Dilute to the mark and mix
metric flask, dilute to volume, and mix. The solution is stable thoroughly.
for several months when stored in plastic or borosilicate glass
bottles. 9. Hazards
Use the following table as a guide for the specific weight of
EDTA · 2H2O to use. 9.1 For precautions to be observed in the use of certain
reagents in this test method, refer to Practices E50.
4
Reagent Chemicals, American Chemical Society Specifications, American 10. Sampling and Sample Preparation
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see the United States Pharmacopeia and 10.1 The gross sample shall be collected and prepared so as
National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD. to be representative of the material to be analyzed.

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 E945 − 12
10.2 Pulverize the laboratory sample to pass a No. 100 13.8 Transfer the solution obtained in 13.6 to a 500-mL
(150-µm) sieve. The repeatability, R1, of Practice E173 corre- volumetric flask. Dilute to volume and mix. Allow any
sponds to the repeatability index, r, of Practice E1601. remaining residue to settle.
11. Rounding Calculated Values 13.9 Extraction:
11.1 Calculated values shall be rounded to the desired 13.9.1 Pipet 50 mL of the clear solution obtained in 13.7.3
number of places as directed in the Rounding-Off Procedure or 13.8 into a 250-mL separatory funnel. Add 10 drops of ferric
section of Practice E29. chloride solution (8.10) and mix.
NOTE 3—Ferric chloride is added to aid the analyst in setting the pH of
12. Interlaboratory Studies the solution. If iron is present in the sample already, the addition of the
12.1 This test method has been evaluated in accordance ferric chloride solution can be eliminated.
with Practice E173. For those methods tested according to 13.9.2 Add 20 mL of NH4Cl solution (8.4) and mix.
Practice E173, the reproducibility, R2, of Practice E173 corre- 13.9.3 Add NH4OH, dropwise, until a slight turbidity de-
sponds to the reproducibility index, R, of Practice E1601. velops. Then add 5 mL of HCl (1 + 4) and mix.
13. Procedure 13.9.4 Add 20 mL of NH4F solution and mix.
13.9.4.1 If the cobalt content of the sample is known to be
13.1 Weigh approximately 2.5 g of sample into a weighing
less than 0.05 %, proceed as directed in 13.9.6. When the
bottle. Dry the bottle and contents at least 1 h at 105 °C, but not
cobalt content is higher than 0.05 %, the cobalt must be
more than 3 h. Cap the bottle and cool to room temperature in
removed. Proceed as directed in 13.9.5.
a desiccator.
13.1.1 Momentarily release the cap to equalize the pressure 13.9.5 Adjust the pH using pH paper to between 3 and 4 by
and weigh the capped bottle and sample to the nearest 0.1 mg. the dropwise additions of HCl (1 + 1) or NH4OH (1 + 1)
13.1.2 Transfer all of the sample into a 250-mL to 300-mL solution. Add 5 drops of H2O2 (30 %) and 2 mL of 2-nitroso-
Erlenmeyer flask or Phillips beaker. Reweigh the capped bottle 1-napthol solution (8.12). Allow to stand 30 min with occa-
to the nearest 0.1 mg. The difference between the mass sional stirring.
recorded in 13.1.1 and the mass recorded in 13.1.2 is the mass 13.9.5.1 Add 20 mL of CHCl3, shake for 30 s, and allow the
of the sample. phases to separate. Discard the lower phase.
13.9.5.2 Add another 20 mL of CHCl3 (8.7) and repeat the
13.2 Moisten the sample in the Erlenmeyer flask with
extraction again discarding the lower phase.
approximately 5 mL of water and add 2 mL to 3 mL bromine.
13.9.5.3 Extract a third time using 10 mL of CHCl3 (8.7)
Allow to stand for 15 min with occasional stirring.
and discard the lower phase. Proceed as directed in 13.9.6.
13.3 Add 10 mL of HNO3 cautiously and allow to stand for 13.9.6 Add 5 mL of thiourea (8.15) solution and 25 mL
5 min with occasional stirring. NH4SCN solution (8.5), mixing after each addition.
13.4 Cautiously add 15 mL of H2SO4 (1 + 1), mix, and heat 13.9.7 Add 80 mL of MIBK (8.11) and shake vigorously for
gently to remove the brown bromine and nitric oxide fumes. 1 min. Allow the phases to separate, and then draw off the
Do not boil. lower aqueous phase into a second separatory funnel. Retain
13.5 Remove from the heat, add 3 drops to 5 drops of HF, the upper organic phase.
5 mL of HClO4, replace on the hotplate, and evaporate the 13.9.8 Add 20 mL of MIBK (8.11) to the second separatory
solution until the volume is reduced to approximately 5 mL. funnel and shake for 1 min. Allow the phases to separate and
discard the lower aqueous phase. Retain the upper organic
13.6 Remove from the heat, wash down the sides with phase.
water, add 5 mL of H2SO4 (1 + 1), add 1 mL of HCl (1 + 4),
13.9.9 Transfer the portions from both separatory funnels to
and dilute to 40 mL. Mix and bring to a boil.
a 400-mL beaker. To each separatory funnel add 1 mL of HCl
13.6.1 For samples containing more than 10 % SiO2, pro-
(1 + 4) and 50 mL of ethanol and shake for 5 s. Transfer both
ceed as directed in 13.7. For samples containing less than 10 %
of these solutions to the 400-mL beaker. Cover the beaker until
SiO2, proceed as directed in 13.8.
the titration is to begin.
13.7 Filter the solution into a 500-mL volumetric flask,
using a Whatman #1 or equivalent paper. Wash the residue 13.10 Titration:
thoroughly to remove soluble precipitate. 13.10.1 Place a stirring bar into the solution in the 400-mL
13.7.1 Transfer the paper plus residue into a platinum beaker and place the beaker on a magnetic stirrer. Begin to stir
crucible. Char the paper at a low temperature and then ignite in at a moderate rate.
a muffle furnace at 800 °C. Remove from the furnace and cool. 13.10.2 While stirring, add 10 mL of NaF solution (8.14),
13.7.2 Add 5 mL of HF, add 5 mL of HClO4, mix, and heat 10 mL of thiourea solution (8.15), and 20 mL of buffer solution
until dense fumes are being given off. Remove from the heat (8.6).
and cool. 13.10.3 If the cadmium content of the original sample is
13.7.3 Dilute with water and transfer to the 500-mL volu- believed to be from 5 % to 10 % add 10 mL of KI solution
metric flask, which contains the filtrate from 13.7. Dilute to (8.13).
volume and mix. Allow any remaining residue to settle. 13.10.4 Add 10 drops of xylenol orange indicator solution
Proceed to 13.9. (8.16) and 0.25 g to 0.30 g ascorbic acid, and continue to stir.

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 E945 − 12
TABLE 1 Statistical Summary
Repeat- Reproduc- Number of Number of
Test
Mean ability ibility Determ- Participating
Sample
(R1, E173) (R2, E173) inations Laboratories
1 11.76 0.177 0.244 20 5
2 15.94 0.124 0.224 19 5
3 44.78 0.591 0.543 19 5
4 54.26 0.683 0.803 20 5

Titrate with the appropriate EDTA solution (8.8) chosen as D = zinc equivalent, (mg/mL) EDTA solution,
prescribed in 8.8 to a yellow end point. E = sample in aliquot extracted, g and
NOTE 4—The reaction between EDTA and zinc is slowed down in the
F = zinc added, mL (Note 5).
presence of organic solvents. On approaching the equivalence point, it is
necessary to work more slowly than usual. Wait 10 s after each addition 15. Precision and Bias5
of EDTA. Should a phase separation occur or the sample become cloudy, 15.1 Precision—The precision of this test method, calcu-
add 20 mL of ethanol and proceed with the titration. lated according to Practice E173, appears in Table 1.
NOTE 5—If the end-point is inadvertently passed, add 1.00 mL of zinc
standard solution (8.17) by means of a microburet. Complete the titration 15.2 Bias—No information on the accuracy of this test
as usual. Correct the final result for the quantity of zinc added. method is available. However, the accuracy may be judged by
14. Calculation comparing accepted reference values with the corresponding
arithmetic averages obtained by interlaboratory testing.
14.1 Calculate the percentage of zinc as follows:
~C 3 D! 2 F 16. Keywords
Zinc, % 5 (2)
E 3 10 16.1 concentrates; EDTA titration; extraction; zinc ores
where:
5
Supporting data have been filed at ASTM International Headquarters and may
C = EDTA used, mL,
be obtained by requesting Research Report RR: RR:E16-1007.

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