ASTM D1326-94(2000)

Standard Test Methods for Chemical Analysis of Ammoniacal Copper Arsenate and Ammoniacal Copper Zinc Arsenate (Withdrawn 2006)

SCOPE
1.1 These test methods cover the determination of the chemical analysis of commercial solutions of ammoniacal copper arsenate.  
1.1.1 Test Method D38 covers the sampling of wood preservatives prior to testing.  
1.2 The analytical procedures appear in the following order:  Sections Ammonia (calculated as anhydrous ammonia) 5 to 7 Arsenic (calculated as As2O5) 8 to 9 Copper (calculated as CuO) 10 to 11
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
WITHDRAWN RATIONALE
These test methods cover the determination of the chemical analysis of commercial solutions of ammoniacal copper arsenate.
Formerly under the jurisdiction of Committee D07 on Wood, these test methods were withdrawn without replacement in July 2006.

General Information

• Status: Withdrawn
• Publication Date: 09-Jan-2000
• Withdrawal Date: 12-Jul-2006
• ICS: 71.060.50 - Salts
• Technical Committee: D07 - Wood
• Drafting Committee: D07.06 - Treatments for Wood Products

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:D1326–94 (Reapproved 2000)
Standard Test Methods for
Chemical Analysis of Ammoniacal Copper Arsenate and
,
1 2
Ammoniacal Copper ZincArsenate
This standard is issued under the fixed designation D 1326; 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.
1. Scope 2.2 AWPA Standard:
AWPA A2 Standard Methods for Analysis of Waterborne
1.1 These test methods cover the determination of the
Preservatives and Fire-Retardant Formulations
chemical analysis of commercial solutions of ammoniacal
copper arsenate.
3. Summary of Test Methods
1.1.1 Test Method D38 covers the sampling of wood
3.1 Ammonia—Ammonia is freed from a caustic solution of
preservatives prior to testing.
thesamplebydistillationandabsorbedinameasuredexcessof
1.2 The analytical procedures appear in the following order:
sulfuric acid solution. The unreacted sulfuric acid solution is
Sections
titrated with standardized NaOH solution to determine the
Ammonium bicarbonate (calculated as carbonate) 20 to 22
Ammonia (calculated as anhydrous ammonia) 6 to 9
ammonia reacted with sulfuric acid.
Arsenic (calculated as arsenic pentoxide) 10 to 11
3.2 Arsenic—A diluted sample is acidified with hydrochlo-
Copper (calculated as copper oxide) 13 to 16
ric and hypophosphorous acid to precipitate the arsenic. The
Zinc (calculated as zinc oxide) 17 to 19
arsenicisvolatilizedbyheatinginthepresenceofsulfuricacid,
1.3 This standard does not purport to address all of the
which is then diluted with water and titrated with a standard
safety concerns, if any, associated with its use. It is the
solution of potassium bromate.Arsenic is calculated asAs O .
2 5
responsibility of the user of this standard to establish appro-
3.3 Copper—Ameasured sample is dissolved in hydrochlo-
priate safety and health practices and determine the applica-
ric acid and reacted with potassium iodide to complex the
bility of regulatory limitations prior to use.
copper ion. The solution is then titrated with a standard
solution of sodium thiosulfate. The copper is calculated as
2. Referenced Documents
CuO.
2.1 ASTM Standards:
3.4 Zinc—A diluted and chemically treated sample is
D38 Test Methods for Sampling Wood Preservatives Prior
treated with a standard solution of potassium ferrocyanide in
to Testing
the presence of an oxidation-reduction indicator (dipheny-
D 1193 Specification for Reagent Water
lamine). The zinc is calculated as ZnO.
D 1325 Specification for Ammoniacal Copper Zinc Arsen-
ate
4. Significance and Use
D 3873 Test Method for Valency State of the Arsenic
4.1 Ammoniacal copper arsenate and ammoniacal copper
Component of Ammoniacal Copper Arsenate Solutions
zinc arsenate for use in the preservative treatment of wood
must conform with Specification D 1325.
These test methods are under the jurisdiction of ASTM Committee D-7 on
5. Purity of Reagents
Wood and are the direct responsibility of Subcommittee D07.06 on Treatments for
Wood Products.
5.1 Purity of Reagents—Reagent grade chemicals shall be
Current edition approved July 15, 1994. Published September 1994. Originally
used in all tests. Unless otherwise indicated, all reagents shall
published as D 1326 – 54 T. Last previous edition D 1326 – 87.
conform to the specifications of the Committee on Analytical
The analytical methods and sampling procedures are essentially the same as
those given in theAmericanWood-Preservers’Assn. Standard Methods forAnalysis
Reagents of the American Chemical Society, where such
of Water-Borne Preservatives and Fire-Retardant Formulations (A2-91). Acknowl-
edgmentismadetotheAmericanWood-Preservers’Associationforitsdevelopment
of the subject matter covered in this test.
3 5
Annual Book of ASTM Standards, Vol 04.10. Available fromAmerican Wood-Preservers’Association, P.O. Box 286, Wood-
Annual Book of ASTM Standards, Vol 11.01. stock, MD 21163-0286.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D1326–94 (2000)
freshly boiled water and 2 drops of phenolphthalein indicator
solution to each flask. Titrate with the NaOH solution to the
appearance of a faint, persistent pink color. The titrations
should agree within 0.1 mL; record the average. Calculate the
normality of the NaOH solution as follows:
Normality of NaOH solution 5 3.920/V (1)
where V = mL of NaOH solution required.
7.4 Sulfuric Acid, Standard (0.1 N)—To 100 mLof water in
a1000-mLvolumetricflask,add3.3mLofH SO (spgr1.84);
2 4
mix and cool to 20°C. Dilute to the mark with water.
Standardizeasfollows:Pipet25mLoftheH SO solutioninto
2 4
a 500-mL Erlenmeyer flask, and add 100 mL of water and 2
dropsofphenolphthaleinindicatorsolution.Titratewiththe0.1
N NaOH solution to the appearance of a faint, persistent pink
color. Calculate the normality of the H SO as follows:
2 4
Normality of H SO 5 VN/25 (2)
2 4
A—Round-bottom flask, 500-mL
B—Distillation trap.
C—Condenser.
where:
D—Delivery tube.
E—Erlenmeyer flask, 500-mL.
V = NaOH solution required, mL, and
FIG. 1 Distillation Apparatus for Determination of Ammonia in
N = normality of the NaOH solution.
Ammoniacal Copper Arsenate and Ammoniacal Copper Zinc
7.5 Sodium Hydroxide Solution (100 g/L)—Dissolve 100 g
Arsenate
of NaOH in water and dilute to 1 L.
specifications are available. Other grades shall only be used
8. Procedure
when it is first ascertained that the reagent is of sufficiently
8.1 Transfer a portion of the sample containing not more
high purity to permit its use without lessening the accuracy of
than 0.15 g of NH (Note 1) to the 500-mL distillation flask.
the determination.
Dilute with water to a volume of about 200 mL. Add a few
5.2 Unless otherwise indicated, references to water shall be
glass beads to prevent bumping.Add 20 mLof NaOH solution
understood to mean reagent water conforming to Specification
(100 g NaOH/L) and immediately close the flask with a rubber
D 1193.
stopperthroughwhichaspraytraphasbeeninserted.Thespray
trap shall previously have been connected to a vertical con-
AMMONIA
denser. Place 100 mL of 0.1 N H SO in a 400-mL beaker.
2 4
Adjust the tip of the condenser so that it just dips into the H
6. Apparatus
SO .Add 4 to 5 drops of methyl purple or methyl red indicator
6.1 A typical apparatus for the distillation of ammonia is
solution to the H SO .
2 4
shown in Fig. 1.
NOTE 1—If this procedure is used for testing a solution of treating
7. Reagents
strength, use an accurately measured volume of the filtered solution
equivalent to the appropriate amount of the element to be determined.
7.1 Methyl Purple or Methyl Red Indicator Solution—
Suitable prepared solutions of methyl purple can be purchased.
8.2 After making sure all the connections are airtight,
To prepare the methyl red indicator solution, dissolve 0.1 g of
commence heating the mixture of sample and NaOH solution.
methyl red in 50 mL of alcohol (90 %), dilute to 100 mL with
Distill slowly at first, and finally boil rather vigorously. Distill
water, and filter if necessary.
off about 150 mL of solution. Adjust the height of the beaker
7.2 Phenolphthalein Indicator Solution— Dissolve1gof
throughout the distillation so that the tip of the condenser is
phenolphthalein in 100 mL of alcohol.
always near the surface of the liquid in the receiving vessel. If
7.3 Sodium Hydroxide Standard Solution (0.1 N)—Dissolve
the indicator starts to turn color, add a measured amount of
4 g of NaOH in CO -free water and dilute to 1 Lwith CO -free
2 2
additional0.1NH SO .Whendistillationiscomplete,turnout
2 4
water. Standardize as follows: Place 2 0.8000-g portions of
the flame and lower the receiving vessel. Wash down the
potassium acid phthalate (National Bureau of Standards stan-
condenser tube and its tip into the receiver.
dard sample No. 84) in volumetric flasks, and add 100 mL of
8.3 Titrate the excess acid with 0.1 N NaOH solution.
9. Calculation
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 9.1 Calculate the percentage of ammonia as NH ,as
listed by the American Chemical Society, see Analar Standards for Laboratory
follows:
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
NH,% 5 [~AB 2 CD! 3 1.703]/E (3)
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
MD.
D1326–94 (2000)
13.2 Potassium Chlorate-NitricAcid Mixture—Dissolve 5 g
where:
of KClO in 100 mL of HNO (sp gr 1.42). Prepare this
A =H SO added to the receiving vessel, mL,
3 3
2 4
B = normality of the H SO , solution just before use and do not save any surplus for use
2 4
C = NaOHsolutionusedfortitrationoftheexcessH SO ,
later.
2 4
mL,
13.3 Potassium Iodide Solution (200 g/L)—Dissolve 200 g
D = normality of the NaOH solution, and
of KI in water and dilute to 1 L.
E = sample used, g.
13.4 Sodium Hydroxide Solution (100 g/L)—Dissolve 100 g
of NaOH in water and dilute to 1 L.
ARSENIC
13.5 Sodium Thiosulfate, Standard Solution (0.0500 N)—
10. Reagents
Dissolve 12.4103 g of Na S O ·5H O in water and dilute to
2 2 3 2
1 L in a volumetric flask.
10.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
chloric acid (HCl).
13.6 Starch Indicator Solution—Make a paste of1gof
10.2 Hypophosphorous Acid (50 %).
soluble starch in about 5 mL of water, add 100 mL of water,
10.3 Methyl Orange Indicator Solution— Dissolve 0.1 g of
and boil for 1 min while stirring. Cool and add 1 drop of
methyl orange in water and dilute to 100 mL.
chloroform.Thissolutionissubjecttodecompositionandfresh
10.4 Potassium Bromate, Standard Solution (0.1000 N)—
solution shall be prepared if a dark-blue color is not produced
Dissolve 2.784 g of KBrO in water and dilute to 1 L in a
withadropoftinctureofiodinein100mLofwateronaddition
volumetric flask.
of a drop of the starch indicator solution.
10.5 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
(H SO ).
2 4
14. Procedure for New Solutions
14.1 Transfer a portion of the sample containing the equiva-
11. Procedure
lent of about 0.11 g CuO to a 300-mL Erlenmeyer flask, and
11.1 Transfer a portion of the sample containing arsenic
add 10 mLof water and 10 mLof HCl (sp gr 1.19).Wash down
equivalent to about 0.17 g As O (see Note 1) to a 250-mL,
2 5
the side of the flask with water, boil for 1 min, and neutralize
wide-mouthErlenmeyerflaskanddilutewithwatertoabout50
with NaOH solution until a permanent precipitate just forms.
mL.Add 50 mLof HCl and 20 mLof H PO , mix thoroughly,
3 2
Add HCl (sp gr 1.19) dropwise until the precipitate just
andwarmthesolutiononasteambathuntilaprecipitateforms.
dissolves. Cool to below 20°C. The solution volume should be
Boil gently for about 15 min. With the aid of suction, filter the
20 to 30 mL.
hot solution through a 10-mLGooch crucible containing a mat
14.2 Add 10 mL of KI solution and mix thoroughly by
of medium fiber, acid-washed asbestos, washing the flask and
precipitate thoroughly with water. rotating the flask. Titrate with 0.05 N Na S O solution,
2 2 3
11.2 Place the crucible containing the precipitate in the flask adding 2 mL of starch solution just before the brownish color
in which the precipitation was carried out. Discard the filtrate. of the iodine disappears. Stop the titration when the color
Pour 10 mL of H SO into the flask and while agitating, heat changes from dark blue to cream color.
2 4
over an open flame in a hood until dense white fumes are
14.3 If poor end points or checks are obtained in the
evolved.Allow the flask and contents to cool, and then add 100
titrations (12.2), repeat the determination following the proce-
mLof water very slowly and carefully, especially at first, since
dure described in Section 13.
heat is generated during this addition. Next, add 5 mL of HCl
and 2 drops of methyl orange indicator and titrate immediately
15. Procedure for Used Solutions Contaminated with
withKBrO solution.Whenthesolutionbecomescolorless,the
Organic Matter
end point has been reached.
15.1 In used solutions, the accumulation of organic matter
mayinterferewiththecopperanalysis,resultingininconsistent
12. Calculation
titrations in the determination of copper. In such cases, the
12.1 Calculate the percentage of arsenic as As O,as
2 5
organic matter may be destroyed as follows: Place the sample
follows:
in a 300-mLErlenmeyer flask, add 10 mLof the KClO -HNO
3 3
As O,% 5 0.5746 A/B (4)
2 5
mixture, and boil to dryness, with constant agitation ion.When
dry, bake the residue over an open flame for about 1 min. Cool,
where: then add 20 mL water and 10 mL of HCl (sp gr 1.19). Warm,
A = KBrO solution required for titration of the sample, if necessary, to effect complete solution.
mL, and
15.2 Cool the solution and proceed in accordance with
B = sample used, g.
Section 14, starting with the second sentence of 15.1.
COPPER
16. Calculation
13. Reagents
16.1 Calculate the percentage of copper as CuO, as follows:
13.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
CuO, % 5 ~AB/C! 3 7.96 (5)
chloric acid (HCl).
D1326–94 (2000)
direction. Match up the burette reading with the last drop in
where:
which the brown color is plainly visible.
A = standard thiosulfate solution required for titration of
18.5 Subtract the mL of ZnCl solution used to back titrate,
the sample, mL,
B = normality of sodium thiosulfate solution, and from the mLof K Fe(CN) and this will give the net mLof K
4 6 2
C = sample used, g. Fe(CN) required by the zinc in the sample.
ZINC
19. Calculations
19.1 Calculate the percentage of active ingredient as fol-
17. Reagents
lows:
17.1 Hydrochloric Acid, concentrated.
mL titration 3 normality of K Fe~CN! 3 factor
4 6
17.2 Hydrochloric Acid 1.20—Add one volume concen-
Percentage 5
sample, g
trated acid to 20 volumes water.
(6)
17.3 Alcohol, ethyl or isopropyl.
17.4 Hydrogen Sulfide Gas.
Active Ingredi- Factor
17.5 Ammonium Hydroxide, concentrated.
ents
17.6 UranylAcetate, ⁄10N,4.3gdissolvedin100mLwater. ZnO 4.068
ZnCl 6.814
17.7 Potassium Ferrocyanide Solution , 0.15 N—Weigh
ZnSO 14.373
accurately 21.12 g of pure K Fe(CN) ·3H O, and dissolve it
4 6 2
NOTE 2—The procedure is based on the assumption that both the
in distilled water. Add 0.2 g sodium carbonate to stabilize the
potassium ferrocyanide and zinc chloride solutions are made up to exactly
solution and make the volume up to 1.000 L.The solution shall
0.15 N. If some different weight (g) of zinc metal is used, calculate the
be kept in a dark bo
...