Norma ASTM D 2036-09 para Determinación de Cianuro

Designation: D2036 09
Standard Test Methods for

Cyanides in Water
1
This standard is issued under the xed designation D2036; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon () indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope
1.1 These test methods cover the determination of cyanides
in water. The following test methods are included:
Sections
Test Method ATotal Cyanides after
Distillation
12 to 18
Test Method BCyanides Amenable
to Chlorination
2
by Difference
19 to 25
Test Method CWeak Acid
Dissociable Cyanides
26 to 32
Test Method DCyanides Amenable
to Chlorination without Distillation
(Short-Cut Method)
33 to 39
1.2 Cyanogen halides may be determined separately.
NOTE 1Cyanogen chloride is the most common of the cyanogen
halide complexes as it is a reaction product and is usually present when
chlorinating cyanide-containing industrial waste water. For the presence
or absence of CNCl, the spot test method given in Annex A1 can be used.
1.3 These test methods do not distinguish between cyanide
ions and metallocyanide compounds and complexes.
Furthermore, they do not detect the cyanates. Cyanates can be
determined using ion chromatography without digestion.
NOTE 2The cyanate complexes are decomposed when the sample is
acidied in the distillation procedure.
1.4 The cyanide in cyanocomplexes of gold, platinum,
cobalt and some other transition metals is not completely
recovered by these test methods. Refer to Test Method D6994
for the determination of cyanometal complexes.
1.5 Cyanide from only a few organic cyanides are
recovered, and those only to a minor extent.
1.6 Part or all of these test methods have been used
successfully with reagent water and various waste waters. It is
the users responsibility to assure the validity of the test
method for the water matrix being tested.
1.7 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 appro-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. Specic hazard
statements are given in sections 5.1, 8.8, 8.18, 9, 11.3, and
16.1.9.
2. Referenced Documents
2.1 ASTM Standards:
3
D1129 Terminology Relating to Water
D1193 Specication for Reagent Water
D2777 Practice for Determination of Precision and Bias of
Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits
D5788 Guide for Spiking Organics into Aqueous Samples
D5847 Practice for Writing Quality Control Specications
for Standard Test Methods for Water Analysis
D6696 Guide for Understanding Cyanide Species
D6888 Test Method for Available Cyanide with Ligand
Displacement and Flow Injection Analysis (FIA) Utilizing
Gas Diffusion Separation and Amperometric Detection
D6994 Test Method for Determination of Metal Cyanide
Complexes in Wastewater, Surface Water, Groundwater
and Drinking Water Using Anion Exchange Chromatog-
raphy with UV Detection
D7284 Test Method for Total Cyanide in Water by Micro
Distillation followed by Flow Injection Analysis with Gas
Diffusion Separation and Amperometric Detection
D7365 Practice for Sampling, Preservation and Mitigating
Interferences in Water Samples for Analysis of Cyanide
D7511 Test Method for Total Cyanide by Segmented Flow
Injection Analysis, In-Line Ultraviolet Digestion and Am-
perometric Detection
E60 Practice for Analysis of Metals, Ores, and Related
Materials by Spectrophotometry
E275 Practice for Describing and Measuring Performance of
Ultraviolet and Visible Spectrophotometers
1
These test methods are under the jurisdiction of ASTM Committee D19 on
Water and are the direct responsibility of Subcommittee D19.06 on Methods for
Analysis for Organic Substances in Water.
Current edition approved Oct. 1, 2009. Published October 2009. Originally
approved in 1964. Last previous edition approved in 2006 as D2036 06. DOI:
10.1520/D2036-09.
2
For an explanation of the term cyanides amenable to alkaline chlorination, see
Lancy, L. E. and Zabban, W., Analytical Methods and Instrumentation for
Determining Cyanogen Compounds, Papers on Industrial Water and Industrial
Waste Water, ASTM STP 337, 1962, pp. 3245.
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standards Document Summary page on
the ASTM website.
Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

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3. Terminology
3.1 DefenitionsFor denitions of terms used in these test
methods, refer to Terminology D1129 and Guide D6696.
3.2 Acronyms:
3.2.1 HPLC, nhigh performance liquid chromatography
3.2.2 IC, nion chromatography
3.2.3 PAD, npulsed amperometric detection
3.2.4 FIA, now injection analysis
4. Summary of Test Methods
4.1 The cyanide as hydrocyanic acid (HCN) is released
from compounds by means of reux distillation and absorbed
in sodium hydroxide solution. The conditions used for the
distillation distinguish the type of cyanide. The sodium cyanide
in the absorbing solution can be determined colorimetrically,
by ion chromatography, titration, by selective ion electrode, or
as described in Test Method D6888 using ow injection with
amperometric detection.
4.2 Test Method A, Total Cyanides, is based on the decom-
position of nearly all cyanides in the presence of strong acid,
magnesium chloride catalyst, and heat during a 1-h reux
distillation.
4.3 Test Method B, Cyanide Amenable to Chlorination, is
based on chlorinating a portion of the sample under controlled
conditions followed by the determination of total cyanide in
both the original and chlorinated samples. Cyanides amenable
to chlorination are calculated by difference.
4.3.1 This test method can be affected by compounds that
are converted during chlorination to color-producing com-
pounds or react with the reagents used, and cause interference
in the procedure employed to determine cyanide in the absorp-
tion solution.
4.4 Test Method C, Weak Acid Dissociable Cyanides, is
based on the decomposition of cyanides in the presence of
weak acid, zinc acetate and heat during a 1-h reux distillation.
4.5 Test Method D, Cyanide Amenable to Chlorination
without Distillation, is a direct colorimetric procedure.
4.6 In the absence of interference, the minimum concentra-
tion of cyanide in the absorption solution that can be accurately
determined colorimetrically is 0.005 mg/L, ion chromatogra-
phy and Test Method D6888 are 0.002 mg/L, titration is 0.4
mg/L and by selective ion electrode is 0.05 mg/L. Pretreatment
including distillation tends to increase these concentrations to
a degree determined by the amount of manipulation required
and the type of sample.
4.7 Round-robin data indicate the following minimum con-
centrations: colorimetric 0.03 mg/L; titration 1.0 mg/L; and
selective ion electrode 0.03 mg/L. Ion chromatography and
Test Method D6888 have a minimum levels equal to approxi-
mately 0.002 mg/L.
5. Signicance and Use
5.1 Cyanide is highly toxic. Regulations have been estab-
lished to require the monitoring of cyanide in industrial and
domestic wastes and in surface waters (Appendix X1).
5.2 Test Method D is applicable for natural water and clean
metal nishing or heat treatment effluents. It may be used for
process control in wastewater treatment facilities providing its
applicability has been validated by Test Method B or C.
5.3 The spot test outlined in Annex A1 can be used to detect
cyanide and thiocyanate in water or wastewater, and to
approximate its concentration.
6. Interferences
6.1 Common interferences in the analysis for cyanide in-
clude oxidizing agents, suldes, aldehydes, glucose and other
sugars, high concentration of carbonate, fatty acids,
thiocyanate, and other sulfur containing compounds.
6.2 It is beyond the scope of these test methods to describe
procedures for overcoming all of the possible interferences that
may be encountered. Refer to Practice D7365 for potential
interferences for the analysis of cyanide in water.
7. Apparatus
7.1 Distillation ApparatusThe reaction vessel shall be a
1-L round bottom ask, with provision for an inlet tube and a
condenser. The inlet tube shall be a funnel with an 8-mm
diameter stem that extends to within 6 mm of the bottom of the
ask. The condenser, which is recommended, shall be a
reux-type, cold nger, or Allihn. The condenser shall be
connected to a vacuum-type absorber which shall be in turn
connected to a vacuum line which has provision for ne
control. The ask shall be heated with an electric heater.
Examples of the apparatus are shown in Fig. 1. Equivalent
apparatus is acceptable provided cyanide recoveries of 100 6
4 % are documented.
7.1.1 Smaller distillation tubes such as 50-mL MIDI tubes
or 6-mL MicroDist (trademarked) tubes described in Test
FIG. 1 Cyanide Distillation Apparatus
D2036 09
2

Method D7284 can be used if the quality control requirements
in Section 40 are satised. The reagents should be added
proportionately to those specied in this test method for
smaller sample sizes. While the use of smaller distillation tubes
is generally accepted, the interlaboratory study was conducted
with 500-mL samples; therefore, the user is responsible to
determine the actual precision and bias when using a different
type of distillation apparatus.
7.2 Spectrophotometer or Filter Photometer, suitable for
measurement in the region of 578 nm, using 1.0-, 2.0-, 5.0-,
and 10.0-cm absorption cells. Filter photometers and photo-
metric practices used in these test methods shall conform to
Practice E60. Spectrophotometers shall conform to Practice
E275.
7.3 Selective Ion Meter, or a pH meter with expanded
millivolt scale equipped with a cyanide activity electrode and
a reference electrode.
7.4 Mixer, magnetic, with a TFE-uorocarbon-coated stir-
ring bar.
7.5 Buret, Koch, micro, 2- or 5-mL, calibrated in 0.01 mL.
7.6 Ion Chromatograph, high performance ion chromato-
graph equipped with a 10-L sample injection device and
pulsed-amperometric detector.
7.7 Chromatography Column, Dionex IonPac AS7 anion-
exchange, 4 250 mm and matching guard column or equiva-
lent.
8. Reagents and Materials
8.1 Purity of ReagentsReagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specications of the Commit-
tee on Analytical Reagents of the American Chemical Society,
where such specications are available.
4
Other grades may be
used, provided it is rst ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
8.2 Purity of WaterUnless otherwise indicated, references
to water shall be understood to mean reagent water that meets
the purity specications of Type I or Type II water, presented
in D1193.
8.3 Acetic Acid (1 + 9) Mix 1 volume of glacial acetic
acid with 9 volumes of water.
8.4 Acetate BufferDissolve 410 g of sodium acetate trihy-
drate (NaC
2
H
3
O
2
3H
2
O) in 500 mL of water. Add glacial acetic
acid to yield a solution pH of 4.5, approximately 500 mL.
8.5 Barbituric Acid.
8.6 Calcium Hypochlorite Solution (50 g/L)Dissolve 5 g
of calcium hypochlorite (Ca(OCl)
2
) in 100 mL of water. Store
the solution in an amber glass bottle in the dark. Prepare fresh
monthly.
8.7 Chloramine-T Solution (10 g/L)Dissolve 1.0 g of the
white-colored, water-soluble grade powder chloramine-T in
100 mL of water. Prepare fresh weekly.
8.8 Cyanide Solution, Stock (1 mL = 250 g CN
)
Dissolve 0.6258 g of potassium cyanide (KCN) in 40 mL of
sodium hydroxide solution (40 g/L). Dilute to 1 L with water.
Mix thoroughly. Standardize with standard silver nitrate solu-
tion following the titration procedure (see 16.2). (Warning
Because KCN is highly toxic, avoid contact or inhalation (see
9)). Commercial solutions may also be used if certied by the
manufacturer and used within the recommended storage date.
8.8.1 Cyanide I Solution, Standard (1 mL = 25 g CN
)
Dilute a calculated volume (approximately 100 mL) of KCN
stock solution to 1 L with NaOH solution (1.6 g/L).
8.8.2 Cyanide II Solution, Standard (1 mL = 2.5 g CN
)
Dilute exactly 100 mL of KCN standard solution I to 1 L with
NaOH solution (1.6 g/L).
8.8.3 Cyanide III Solution, Standard (1 mL = 0.25 g
CN
) Dilute exactly 100 mL of KCN standard solution II to

1 L with NaOH solution (1.6 g/L). Prepare fresh solution daily
and protect from light.
8.8.4 Cyanide IV Solution, Standard (1 mL = 0.025 g
CN
) Dilute exactly 100 mL of KCN standard solution III to

1 L with NaOH solution (1.6 g/L). Prepare fresh solution daily
and protect from light.
8.9 Hydrogen Peroxide Solution, 3 %Dilute 10 mL of
30 % hydrogen peroxide (H
2
O
2
) to 100 mL. Prepare fresh
weekly.
8.10 Isooctane, Hexane, Chloroform (solvent preference in
the order named).
8.11 Lead Carbonate (PbCO
3
), Lead Acetate
(Pb(C
2
H
3
O
2
)
2
3H
2
O), or Lead Nitrate (Pb(NO
3
)
2
)Lead ac-
etate and lead nitrate can be put in solution with water, if
desired, at a suggested concentration of 50 g/L.
8.12 Lime, hydrate (Ca(OH)
2
), powder.
8.13 Magnesium Chloride SolutionDissolve 510 g of
magnesium chloride (MgCl
2
6H
2
O) in water and dilute to 1 L.
8.14 Potassium Iodide-Starch Test Paper.
8.15 Pyridine-Barbituric Acid ReagentPlace 15 g of bar-
bituric acid in a 250-mL volumetric ask and add just enough
water to wash the sides of the ask and wet the barbituric acid.
Add 75 mL of pyridine and mix. Add 15 mL of hydrochloric
acid (sp gr 1.19), mix, and cool to room temperature. Dilute to
volume with water and mix until all of the barbituric acid is
dissolved. This solution is usable for about 6 months if stored
in a cold dark place. Commercially prepared solutions may be
available; follow the manufacturers expiration date.
8.16 Rhodanine Indicator Solution (0.2 g/L)Dissolve 0.02
g of (p-dimethylaminobenzylidene) in 100 mL of acetone.
8.17 Silver Nitrate Solution, Standard (0.01 N)Dissolve
1.6987 g of silver nitrate (AgNO
3
) in water and dilute to 1 L.
4
Reagent Chemicals, American Chemical Society Specications , American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
D2036 09
3

Mix thoroughly. Commerical solutions that are certied at the
designated normality are suitable if used within the manufac-
turers recommended storage date. Store in a dark container.
8.18 Sodium Arsenite Solution (20 g/L)Dissolve 2 g of
NaAsO
2
in 100 mL of water. WarningThis material has
appeared on lists of suspected and known carcinogens. Avoid
contact with skin.
8.19 Sodium Hydroxide Solution (40 g/L)Dissolve 40 g of
sodium hydroxide (NaOH) in water and dilute to 1 L with
water.
8.20 Sodium Hydroxide Solution (1.6 g/L)Dilute 40 mL of
NaOH solution (40 g/L) to 1 L.
8.21 Sulfamic Acid Solution (133 g/L)Dissolve 133 g of
sulfamic acid in water and dilute to 1 L.
8.22 Sodium Thiosulfate Solution (500 g/L)Dissolve 785
g of sodium thiosulfate (Na
2
S
2
O
3
5H
2
O) in water and dilute to
1 L.
8.23 Sulfuric Acid (1 + 1) Slowly and carefully add 1
volume of sulfuric acid (H
2
SO
4
, sp gr 1.84) to 1 volume of
water, stirring and cooling the solution during the addition.
8.24 Zinc Acetate Solution (100 g/L)Dissolve 120 g of
zinc acetate [Zn(C
2
H
3
O
2
)
2
2H
2
] in 500 mL of water. Dilute to
1 L.
8.25 IC Eluent Solutions, (75 mM sodium hydroxide, 250
mM sodium acetate, and 0.05 % (v/v) ethylenediamine)
8.25.1 Eluent PreparationWeigh 20.50 g of anhydrous
NaOAc and dissolve it in 500600 g of 18 M-cm water. Fill
up to ~980 g with 18 M-cm water. Stir thoroughly and lter
through a 0.2 m Nylon lter. Add 5.97 g (3.9 mL) of 50 %
NaOH and 0.4495 g (0.50 mL ) of ethylendiamine. Fill up to
1015 g (1.0 L) with 18 M-cm water in the bottom container
of the ltration unit. Transfer the solution immediately to the
eluent container, which is connected to nitrogen. Adjust the
ow rate at 0.25 mL/min (for a 2-mm ID column) or 1.00
mL/min (for a 4-mm ID column)
8.26 Ethylene diamine.
8.27 Sodium Hydroxide Solution (50 % W/W). It is essential
to use high quality 50 % (w/w) sodium hydroxide solution for
eluent and diluent preparation for use in ion chromatography.
Sodium hydroxide pellets are coated with sodium carbonate
and, therefore, are not acceptable for this application.
8.28 Sodium Acetate.
9. Hazards
9.1 WarningBecause of the toxicity of cyanide, great
care must be exercised in its handling. Acidication of cyanide
solutions produces toxic hydrocyanic acid (HCN). All manipu-
lations must be done in the hood so that any HCN gas that
might escape is safely vented.
9.2 WarningMany of the reagents used in these test
methods are highly toxic. These reagents and their solutions
must be disposed of properly.
9.3 All reagents and standards should be prepared in vol-
umes consistent with laboratory use to minimize the generation
of waste.
10. Sample and Sample Preservation
10.1 Collect the sample in accordance with Practice D7365.
This standard practice is applicable for the collection and
preservation of water samples for the analysis of cyanide.
Responsibilities of eld sampling personnel and the laboratory
are indicated.
11. Elimination of Interferences
11.1 Refer to Practice D7365 for mitigating interferences
for the analysis of cyanide in water.
11.2 The following treatments are specic for the removal
or reduction of substances that can interfere in the various
methods of this test method. Care must be taken to keep time
of pretreatment at a minimum to avoid loss of cyanide.
11.3 Fatty acids that distill and form soaps in the absorption
solution can be removed by extraction. Acidify the sample with
dilute (1 + 9) acetic acid to a pH 6 to 7 (perform this operation
in the hood and leave the sample there until it is made alkaline
after the extraction). Extract with isooctane, hexane or chloro-
form (preference in order named), with a solvent volume equal
to 20 % of the sample volume. One extraction is usually
sufficient to reduce the fatty acids below the interference level.
Avoid multiple extractions or a long contact time at low pH in
order to keep the loss of HCN to a minimum. When the
extraction is complete, immediately raise the pH of the sample
to 12 to 12.5 with NaOH solution.
11.4 Aldehydes combine with cyanides to form cyanohy-
drins which can hydrolyze to acids under distillation condi-
tions. Glucose and other sugars, if present in the sample, can
also form cyanohydrins with cyanide at the pH of preservation.
Aldehydes can be removed as described in Practice D7365.
11.5 Carbonate in high concentration can affect the distilla-
tion procedure by causing the violent release of carbon dioxide
with excessive foaming when acid is added prior to distillation,
and by lowering the pH of the absorption solution.
11.6 Nitrite and nitrate in the sample can react under
conditions of the distillation with other contaminants present to
form cyanides. The addition of an excess of sulfamic acid to
the sample prior to the addition of sulfuric acid will reduce this
interference. For example, if samples are known or suspected
to contain nitrate or nitrite, add 50 mL of 0.4 N sulfamic acid
solution (40 g/L) per 500 mL sample, then proceed with
distillation after 3 minutes.
11.7 Thiocyanate and other sulfur containing compounds
can decompose during distillation. Sulfur, hydrogen sulde,
sulfur dioxide, etc., formed can be distilled into the absorption
solution. The addition of lead ion to the absorption solution
before distillation followed by ltration of the solution before
the titration or the colorimetric procedure is used will minimize
sulfur and sulde interference. Absorbed sulfur dioxide forms
sodium sulte which reacts with chloramine-T in the colori-
metric determination. Test for the presence of chloramine-T by
D2036 09
4

placing a drop of solution on a strip of potassium iodide test
paper previously moistened with dilute acetic acid. If the test is
negative, add chloramine-T until a positive test is obtained.
11.7.1 Cyanide can be measured in the presence of sulfur
containing compounds by using IC to separate the interferences
from the cyanide (16.5). Samples or distillates containing up to
50 mg/L sulde can be analyzed with sulde abatement
acidication reagent as described in Test Method D6888.
11.7.2 False positive results have been observed for total
cyanide in samples containing thiocyanate in the presence of
ammonia and nitrate. To avoid this interference, use a method
that does not require distillation such as Test Method D6888.
Adding 0.6 g/L ascorbic acid prior to distillation may also
reduce the interference; treated samples should be analyzed
within 24 hours.
11.7.3 Separation of the cyanide from interfering substances
prior to electrochemical determination (see 16.5 for ion chro-
matography procedure) should be conducted when using Test
Method ATotal Cyanides After Distillation, or Test Method
BCyanides Amenable to Chlorination by the Difference
when sulfur, thiocyanate, or other sulfur containing compounds
are present.
11.8 Thiocyanate in the presence of ferric ion is quantita-
tively determined by the colorimetric procedure. Test Method
D outlines a procedure for masking any cyanide amenable to
chlorination in order to determine thiocyanate by difference.
11.9 Substances which contribute color or turbidity interfere
with Test Method D.
TEST METHOD ATOTAL CYANIDES
AFTER DISTILLATION
12. Scope
12.1 This test method covers the determination of cyanides
in water, including the iron cyanide complexes (total cyanide).
12.2 The cyanide in some cyano complexes of transition
metals, for example, cobalt, gold, platinum, etc., is not deter-
mined.
12.3 The cyanide concentration can be determined with
titration, IC-PAD, colorimetric, selective ion electrode
procedure, or ow injection analysis with gas diffusion sepa-
ration and amperometric detection as described in Test Method
D6888.
12.4 This test method has been used successfully on reagent
and surface water and coke plant, renery, and sanitary waste
waters. It is the users responsibility to assure the validity of
the test method for the water matrix being tested.
12.5 Because of the sample preservation, certain suspended
and/or colloidal forms of metal cyanide complexes such as
those from iron and copper will dissolve prior to the distillation
step. The recovery of this cyanide may depend on solution
parameters such as the cyanide concentration in suspended
solids, ionic strength of the sample, sample temperature, acid
digestion times, and so forth.
13. Interferences
13.1 All the chemical compounds listed in Section 6 can
interfere.
13.2 For the removal of these interferences, proceed as
instructed in Sections 10 and 11.
14. Apparatus
14.1 The schematic arrangement of the distillation system is
shown in Fig. 1.
14.2 For the required apparatus, refer to Section 7.
15.1 Refer to Section 8.
16. Procedure
16.1 Distillation Procedure:
16.1.1 Set up the apparatus as shown in Fig. 1.
16.1.2 Add 10.0 mL of 1 M NaOH solution to the absorber.
Dilute with water to obtain an adequate depth of liquid. Do not
use more than 225 mL of total volume in the absorber.
16.1.3 Attach the absorber to the vacuum and connect to the
condenser.
16.1.4 Place 500 mL of the sample in the ask. If cyanide
content is suspected to be more than 10 mg/L, use an aliquot so
that no more than 5 mg of cyanide is in the distilling ask and
dilute to 500 mL with water. Annex A1 describes a procedure
for establishing the approximate cyanide content. Verify a
negative reaction in the spot-plate technique by using 500 mL
of the sample.
16.1.5 Connect the ask to the condenser.
16.1.6 Turn on the vacuum and adjust the air ow to
approximately 1 bubble per second entering the boiling ask
through the air-inlet tube.
16.1.7 Add 20 mL of magnesium chloride solution (8.13)
through the air inlet tube. If the sample contains nitrite or
nitrate, add 15 mL of sulfamic acid solution (8.21).
16.1.8 Rinse the air-inlet tube with a few mL of water and
allow the air ow to mix the content of the ask for
approximately 3 min.
16.1.9 Carefully add 50 mL of H
2
SO
4
solution (1 + 1)
through the air-inlet tube. (Warning Add slowly; heat is
generated and foaming may occur.)
16.1.10 Turn on the condenser cooling water. Heat the
solution to boiling, taking care to prevent the solution from
backing into the air-inlet tube.
16.1.11 Maintain the air ow as in 16.1.6.
16.1.12 Reux for 1 h.
16.1.13 Turn off the heat, but maintain the air ow for at
least an additional 15 min.
16.1.14 For 500-mL macro distillations, quantitatively
transfer the absorption solution into a 250-mL volumetric ask.
Rinse absorber and its connecting tubes sparingly with water
and add to the volumetric ask.
16.1.15 Dilute to volume with water and mix thoroughly.
16.1.16 Determine the concentration of cyanide in the
absorption solution by one of the procedurestitration (Sec-
tion 16.2), colorimetric (16.3), selective ion electrode (16.4),
ion chromatography (16.5), or ow injection with gas diffusion
separation with amperometric detection as described in Test
D2036 09
5

Method D6888 (16.6). See Sections 4.6 and 4.7 for minimum
concentration levels for each procedure prior to choosing a
determinative step.
16.2 Titration Procedure:
16.2.1 Place 100 mL of the absorption solution or an
accurately measured aliquot diluted to 100 mL with NaOH
solution (1.6 g/L) in a ask or beaker.
16.2.2 Add 0.5 mL of rhodanine indicator solution.
16.2.3 Titrate with standard silver nitrate solution (8.17)
using a microburet to the rst change from yellow to salmon
pink.
16.2.4 Titrate a blank of 100 mL of NaOH solution (1.6 g/L)
(8.20).
16.2.5 Record the results of the titration and calculate the
cyanide concentration in the original samples according to Eq
1 (17.1).
16.3 Colorimetric Procedure:
16.3.1 Standardization:
16.3.1.1 Prepare a series of cyanide standards based on the
cell path which is used (Table 1). For this purpose use 50-mL
glass-stoppered volumetric asks or graduated cylinders.
16.3.1.2 Follow 16.3.2.2 through 16.3.2.6 of the procedure.
16.3.1.3 Calculate the absorption factor (17.2.1).
16.3.2 Procedure:
16.3.2.1 Pipet an aliquot of the absorption liquid, such that
the concentration falls within the standardization range, into a
50-mL glass-stoppered volumetric ask or graduated cylinder.
16.3.2.2 If necessary, dilute to 40 mL with the NaOH
solution used in the absorber solution.
16.3.2.3 Place 40 mL of the NaOH solution used in the
absorber solutions in a ask or cylinder for a blank. (Carry out
the following steps of the procedure on the blank also.)
16.3.2.4 Add 1 mL of chloramine-T solution and 1 mL of
acetate buffer, stopper, mix by inversion two or three times, and
allow to stand for exactly 2 min.
16.3.2.5 Add 5 mL of pyridine-barbituric acid reagent,
dilute to volume with water, mix thoroughly, and allow to stand
exactly 8 min for color development.
16.3.2.6 Measure at the absorbance maximum at 578 nm.
Measure absorbance (A) versus water.
16.3.2.7 Calculate the concentration of cyanide (mg CN/L)
in the original sample following equations given in 17.2.
16.4 Selective Ion Electrode Procedure:
16.4.1.1 Place 100-mL aliquots of standard solutions I, II,
III, and IV in 250-mL beakers.
16.4.1.2 Follow 16.4.2.2 and 16.4.2.3.
16.4.1.3 Pipet 10- and 50-mL aliquots of standard solution
IV into 250-mL beakers and dilute to 100 mL with NaOH
solution (1.6 g/L).
16.4.1.4 Follow 16.4.2.2 and 16.4.2.3 of the procedure,
starting with the lowest concentration.
16.4.1.5 Plot concentration values of the standardizing so-
lutions on the logarithmic axis of semilogarithmic graph paper
versus the potentials developed in the standardizing solutions
on the linear axis. Follow manufacturers instructions for
direct-reading ion meters.
16.4.2 Procedure:
16.4.2.1 Place 100 mL of the absorption solution (or an
accurately measured aliquot diluted to 100 mL with NaOH
solution (1.6 g/L)) in a 250-mL beaker.
NOTE 3Check a small portion of the solution for sulde. If it is
present, add either the PbCO
3
or Pb(C
2
H
3
O
2
)
2
immediately before
inserting the electrodes.
16.4.2.2 Place the beaker on a magnetic stirrer, place a
TFE-uorocarbon-coated stirring bar in the solution, stir at a
predetermined constant rate, and maintain constant tempera-
ture.
16.4.2.3 Insert the cyanide specic ion electrode and the
reference electrode in the solution and measure potential or the
cyanide concentration following the manufacturers instruc-
tions.
16.4.2.4 Use values found from the graph or direct-reading
ion meter to calculate the concentration in the original sample
following Eq 5 (17.3).
16.5 Ion Chromatography Procedure:
16.5.1.1 Place 2-mL of standard solutions I, II, III, and IV
into HPLC autosampler vials if using an autosampler, or other
capped glass vial if using a manual injector.
16.5.1.2 Follow 16.5.2.1 through 16.5.2.4 to standardize the
IC detector response by injection of 10 L of each standard
solution.
NOTE 4A 10-L injection was used for the interlaboratory study.
Other levels can be used provided the analyst conrms the precision and
bias is equivalent with that generated using the 10-L injection.
16.5.1.3 Measure the area under the cyanide peak. This is
the detector response.
16.5.1.4 Plot concentration values of the standard solution
versus detector response. Follow manufacturers instruction for
IC systems with computer controlled data stations.
16.5.2 Procedure:
16.5.2.1 Set the ion chromatograph to operate at the follow-
ing conditions or as required for instrument being used:
(a) Flow Rate: 1.0 mL/min.
(b) PAD operated in a dc amperometric mode with a
silver-working-electrode set at 0.05 V in relation to a standard
TABLE 1 Guide for Selection of Appropriate Cell Paths
Standard
Solution
No.
Millitres of
Standard
Solution
Final
Concen-
tration, g
CN/mL
Cell Length,
cm
50 mL 1.0 5.0 10.0
IV 5.0 0.0025 X
IV 10.0 0.0050 X X
IV 15.0 0.0075 X X
IV 20.0 0.0100 X X
IV 25.0 0.0125 X X
IV 30.0 0.0150 X X
IV 40.0 0.0200 X
III 5.0 0.0250 X X
III 10.0 0.0500 X
III 15.0 0.0750 X
III 20.0 0.1000 X
III 25.0 0.1250 X
III 30.0 0.1500 X
0.0 (blank) X X X
D2036 09
6

Ag/AgCl-reference electrode or an equivalent detector. Other
working electrodes such as platinum or boron-doped diamond
electrodes have also been shown to be effective. Optimize the
waveform based on the electrode used.
(c) Column, Dionex IonPac AS 7 anion-exchange,
4 250 mm and matching guard column or equivalent.
(d) Temperature: Ambient.
(e) Sample size: 10 L.
16.5.2.2 Prime the IC pump and ensure that the ow rate is
1.0 mL/min. Allow the detector to warm up for 30-60 min to
stabilize the baseline.
16.5.2.3 Inject 10-L of sample solution into the IC system.
Apply the waveform from Table 2. A10-L injection of 50 ppb
standard of cyanide should result in a well-dened peak with
an area >1.0 nC min and with asymmetry in the range of 0.9 to
2.0 for 2-mm ID column set. With a 4-mm ID column set a
50-L injection of the same standard should generate a peak
area >0.8 nC min in the same range of asymmetry values.
16.5.2.4 Use values found from the graph or data station to
calculate the concentration in the original sample following Eq
5 (17.3).
16.6 Flow Injection Analysis with Gas Diffusion Separation
and Amperometric Detection Procedure:
16.6.1 For total cyanide, test the sample distillates with Test
Method D6888.
17. Calculation
17.1 Titration ProcedureCalculate the concentration in
milligrams of CN per litre in the original sample using Eq 1:
mg CN/L 5 @~A 2 B! 3N AgNO
3
30.052/mL original sample#
3~250/mL aliquot used! 310
6
(1)
where:
A = AgNO
3
solution to titrate sample, mL, and
B = AgNO
3
solution to titrate blank, mL.
17.2 Colorimetric ProcedureCalculate the concentration
in milligrams of CN per litre as follows:
17.2.1 Slope and Intercept of Standard CurveCalculate
the slope on the standard curve, m, and the intercept on c-axis,
b, using Eq 2 and Eq 3, respectively:
m 5
n
(
ca 2
(
c
(
a
n
(
a
2
2 ~
(
a!
2
(2)
b 5
(
a
2
(
c 2
(
a
(
ac
n
(
a
2
2 ~
(
a!
2
(3)
where:
a = absorbance of standard solution,
c = concentration of CN
in standard, mg/L, and

n = number of standard solutions.
17.2.1.1 the blank concentration, 0.0 mg CN
/L, and the

absorbance of the blank must be included in the calculation of
slope and intercept.
17.2.2 ConcentrationCalculate the concentration of cya-
nides using Eq 4:
CN, mg/L 5 ~ma
1
1b! X
40
X
X
250
Y
(4)
where:
a
1
= absorbance of sample solution,
X = aliquot of absorbance solution, mL, and
Y = original sample, mL.
17.3 Selective-Ion Electrode and Ion Chromatography
ProceduresCalculate the concentration in milligrams of CN
per litre using Eq 5:
CN, mg/L 5 CN mg/L from graph or meter (5)
3~100/aliquot! 3~250/mL original sample!
18. Precision and Bias
5
18.1 Precision: All methods have met the requirements for
Practice D2777 for Determination of Precision and Bias of
Applicable Test Methods of Committee D19 on Water.
18.1.1 ColorimetricBased on the results of nine operators
in nine laboratories, the overall and single-operator precision
of this test method within its designated range may be
expressed as follows:
Reagent Water S
T
= 0.06x + 0.003
S
o
= 0.11x + 0.010
Selected Water Matrices S
T
= 0.04x + 0.018
S
o
= 0.04x + 0.008
18.1.2 ElectrodeBased on the results of six operators in
ve laboratories, the overall and single-operator precision of
this test method within its designated range may be expressed
as follows:
Reagent Water S
T
= 0.06x + 0.003
S
o
= 0.03x + 0.008
T
= 0.05x + 0.008
S
o
= 0.03x + 0.012
18.1.3 TitrimetricBased on the results of six operators in
three laboratories, the overall and single-operator precision of
as follows:
Reagent Water S
T
= 0.04x + 0.038
S
o
= 0.01x + 0.018
T
= 0.06x + 0.711
S
o
= 0.04x + 0.027
18.1.4 Ion Chromatography ProcedureThe precision was
determined in accordance with Practice D2777. Based on the
results of eight operators in eight laboratories, the overall and
single-operator precision of this test method within its desig-
nated range may be expressed as follows:
5
Supporting data have been led at ASTM International Headquarters and may
be obtained by requesting RR:D19-1131.
TABLE 2 Waveform for Analysis of Cyanide by Ion
Chromatography
Time (sec)
Potential (V) vs.
Ag/AgCl, 3 M KCl
Integration
0.00 0.10 -
0.20 0.10 Start
0.90 0.10 End
0.91 1.00 -
0.93 0.30 -
1.00 0.30 -
D2036 09
7

xbar 5 1.04x10.35
S
T
5 0.057x13.19
S
o
5 0.020x13.90
18.1.5 A weighted linear regression was used since the
absolute error increased with concentration. More weight was
given to the smaller (lower error) concentrations than to the
larger (higher error) ones. The weighting factor used was
1/s.d.
2
for each of the concentration levels (1).
6
where:
S
T
= overall precision,
S
o
= single operator precision, and
X = cyanide concentration, mg/L.
18.1.6 The precision and bias for Test Method D6888 was
determined in accordance with Practice D2777. Based on the
results of 10 operators in 10 laboratories, the overall and single
operator precision and method bias data are shown in Table 2
of Test Method D6888. The precision and bias were deter-
mined for available cyanide using a synthetic wastewater
matrix.
18.2 Bias:
18.2.1 Recoveries of known amounts of cyanide from
Reagent Water Type II and selected water matrices are shown
in Table 3 and Table 4.
18.2.2 Bias was determined in alkaline reagent water (0.25
M NaOH) for ion chromatography as the determinative step
during an interlaboratory study
7
in accordance with Practice
D2777. The statistical summary for ion chromatography as the
determinative step is shown in Table 5.
18.3 The bias for Test Method D6888 was determined for
available cyanide in a synthetic wastewater in accordance with
Practice D2777. This test method can also be used as a
determinative step for total cyanide after distillation.
18.4 The precision and bias information given in this
section may not apply to waters of untested matrices.
TEST METHOD BCYANIDES AMENABLE TO
CHLORINATION (CATC) BY THE DIFFERENCE
19. Scope
19.1 This test method covers the determination of cyanides
amenable to chlorination in water.
19.2 Iron cyanides are the most commonly encountered
compounds not amenable to chlorination.
19.3 This test method has been used on reagent, surface, and
industrial waste waters. It is the users responsibility to assure
the validity of the test method for the water matrix being tested.
20. Interferences
interfere. See Practice D7365 for further discussion on inter-
ferences. Alternatively, analyze the samples for available
cyanide as described in Test Method D6888, which is less
susceptible to interference than this method.
instructed in Practice D7365 and Sections 10 and 11.
20.3 This test method can be affected by compounds that are
converted during chlorination to volatile compounds which are
collected in the absorption solution and can interfere in the
nal determination.
20.4 If the calculated result is signicantly negative, inter-
ferences are present. In this case, Test Method D6888 can be
used to determine available cyanide.
21. Apparatus
shown in Fig. 1.
21.2 For the required apparatus, refer to Section 7.
23. Procedure
23.1 Sample PreparationDivide the sample into two equal
portions of 500 mL or less. Determine the total cyanide in one
portion as indicated in 23.2. Place the other portion in a 1-L
beaker and chlorinate as outlined in the following steps.
6
The boldface numbers in parentheses refer to the list of references at the end of
this standard.
7
TABLE 3 Reagent Water (Test Method A)
Technique
Amount Added,
mg/L
Amount Found,
mg/L
n S
t
Bias %Bias
Statistical
Signicance,
95 % CL
Colorimetric 0.060 0.060 26 0.0101 0.000 0 No
0.500 0.480 23 0.0258 0.020 4 No
0.900 0.996 27 0.0669 0.096 11 Yes
Electrode 0.060 0.059 18 0.0086 0.001 2 No
0.500 0.459 18 0.0281 0.041 8 Yes
0.900 0.911 18 0.0552 0.011 1 No
5.00 5.07 18 0.297 0.07 1 No
Titrimetric 2.00 2.10 18 0.1267 0.10 5 Yes
5.00 4.65 18 0.2199 0.35 7 Yes
5.00 5.18 18 0.2612 0.18 4 Yes
D2036 09
8

NOTE 5Protect the solution in the beaker from ultraviolet radiation by
wrapping the beaker with aluminum foil or black paper and cover with a
wrapped watch glass during chlorination.
23.1.1 Place the beaker on a magnetic stirrer, insert a TFE
uorocarbon-coated stirring bar in the beaker, and start stirring.
23.1.2 If necessary, adjust the pH to between 11 and 12 with
NaOH solution (40 g/L).
23.1.3 Add Ca(OCl)
2
solution (50 g/L) 3 drops at a time
until there is an excess of chlorine indicated on a strip of
potassium iodide-starch test paper previously moistened with
acetic acid solution.
23.1.4 Maintain the pH and excess chlorine for 1 h while
stirring. Add Ca(OCl)
2
solution or NaOH solution, or both, 2
drops at a time when necessary.
23.1.5 At the end of the hour remove any residual chlorine
by the dropwise addition of NaAsO
2
solution (2 g/100 mL) or
by adding 8 drops of H
2
O
2
solution (3 %) followed by 4 drops
of Na
2
S
2
O
3
solution (500 g/L). Test with potassium iodide-
starch test paper.
23.2 Follow steps 16.1.1 through 16.1.16 for Test Method
A.
24. Calculation
24.1 Calculate the total cyanide in each portion of the
sample following Eq 1, Eq 4, or Eq 5.
24.2 Calculate the concentration of cyanide amenable to
chlorination using Eq 6:
CN, mg/L 5 G 2 H (6)
where:
G = cyanide, determined in the unchlorinated portion of the
sample, mg/L, and
H = cyanide determined in the chlorinated portion of the
sample, mg/L.
5
25.1 Precision:
25.1.1 ColorimetricBased on the results of eight operators
in seven laboratories, the overall and single-operator precision
Reagent Water S
T
S
o
=
=
0.18x + 0.005
0.06x + 0.003
T
S
o
=
=
0.20x + 0.009
0.05x + 0.005
as follows:
Reagent Water S
T
S
o
=
=
0.01x + 0.439
0.241 0.03x
T
S
o
=
=
0.12x + 0.378
0.209 0.01x
25.1.3 where:
S
T
S
o
= single operator precision, and
x = cyanide concentration, mg/L.
TABLE 4 Selected Water Matrices (Test Method A)
Technique
Amount Added,
mg/L
Amount Found,
mg/L
n S
t
Bias %Bias
Statistical
Signicance,
95 % CL
Colorimetric 0.060 0.060 25 0.0145 0.000 0 No
0.500 0.489 26 0.0501 0.011 3 No
0.900 0.959 24 0.0509 0.059 7 Yes
Electrode 0.060 0.058 14 0.0071 0.002 3 No
0.500 0.468 21 0.0414 0.032 6 No
0.900 0.922 19 0.0532 0.022 2 No
5.00 5.13 20 0.2839 0.13 3 No
Titrimetric 2.00 2.80 18 0.8695 0.80 40 Yes
5.00 5.29 18 1.1160 0.29 6 No
5.00 5.75 18 0.9970 0.75 15 Yes
TABLE 5 Final Statistical Summary for Ion Chromatography as the Determinative Step
Sample A Sample D Sample B Sample E Sample C Sample F A + Sulde D + Sulde
Number of retained values 7 7 7 7 7 7 7 7
True Concentration (C), g/L 251 217 866 736 43.3 34.6 251 217
Mean Recovery (XBAR) 250 222 958 801 44 39 248 221
Percent Recovery 99.5 10.2 111 109 100 110 99.0 102
Overall Standard Deviation,
(st)
17.8 20.1 58.8 41.7 7.3 4.6 18.4 13.2
Overall Relative Standard
Deviation,%
7.10 9.08 6.14 5.21 16 12 7.39 5.95
Number of retained pairs 7 7 7 7 7 7 7 7
Single-Operator Standard
Deviation, (so)
9.35 18.0 4.6 8.54
Analyst Relative Deviation,% 4.01 2.12 11 3.72
Bias 0.46 2.11 10.61 8.83 2.6 13 1.02 2.04
NOTE 1Samples prepared in alkaline reagent water (0.25M NaoH). Samples A+Sulde and D+Suide contain 1 mg/L sulde to test for potential
interference.
D2036 09
9

25.2 BiasRecoveries of known amounts of cyanide ame-
nable to chlorination from reagent water Type II and selected
water matrices were as shown in Table 6 and Table 7.
TEST METHOD CWEAK ACID
DISSOCIABLE CYANIDES
26. Scope
26.1 This test method covers the determination of cyanide
compounds and weak acid dissociable complexes in water.
26.2 The thiocyanate content of a sample usually does not
cause interference.
26.3 Any of the three procedures, titration, colorimetric, or
selective ion electrode, can be used to determine the cyanide
content of the absorption solution. The lower limits of detect-
ability are the same as for Test Method A.
26.4 This test method has been used successfully on reagent
and surface water and coke plant, renery and sanitary waste
waters. It is the users responsibility to assure the validity of
the test method for the water matrix being tested.
27. Interferences
27.2 For the removal of these interferences proceed as
28. Apparatus
shown in Fig. 1.
28.2 The required equipment, instruments, and parts are
listed in Section 7.
29.2 Methyl Red Indicator Solution.
30. Procedure
30.1 Distillation Procedure:
30.1.1 Set up the apparatus as shown in Fig. 1.
30.1.2 Add 10.0 mL of NaOH solution (40 g/L) to the
absorber. Dilute with water to obtain an adequate depth of
liquid. Do not use more than 225 mL of total volume in the
absorber.
30.1.3 Attach the absorber to the vacuum and connect to the
condenser.
30.1.4 Place 500 mL of sample in the ask. If cyanide
content is suspected to be more than 10 mg/L, use an aliquot so
that no more than 5 mg of cyanide are in the ask, and dilute
to 500 mL with water.
30.1.5 Connect the ask to the condenser.
30.1.6 Turn on the vacuum and adjust the air ow to
approximately 1 bubble per second entering the boiling ask
through the air-inlet tube.
30.1.7 Add 20 mL each of the acetate buffer and zinc acetate
solutions through the air-inlet tube. Add 2 or 3 drops of methyl
red indicator solution.
30.1.8 Rinse the air-inlet tube with a few mL of water and
allow the air ow to mix the content of the ask. (If the
solution is not pink, add acetic acid (1 + 9) dropwise through
the air-inlet tube until there is a permanent color change.)
30.1.9 Turn on the condenser cooling water, heat the solu-
tion to boiling, taking care to prevent the solution from backing
into the air inlet tube.
30.1.10 Maintain the air ow as in 30.1.6.
30.1.11 Reux for 1 h.
30.1.12 Turn off the heat, but maintain the air ow for at
least an additional 15 min.
30.1.13 Quantitatively transfer the absorption solution into
a 250-mL volumetric ask. Rinse the absorber and its connect-
ing tubes sparingly with water and add to volumetric ask.
30.1.14 Dilute to volume with water and mix thoroughly.
30.1.15 Determine the concentration of cyanide in the
absorption solution by one of the three procedures desceibed in
16.2, 16.3, or 16.4.
31. Calculation
31.1 Calculate the concentration of weak acid dissociable
cyanide in the sample following Eq 1, Eq 4, or Eq 5.
5
32.1 Precision:
32.1.1 ColorimetricBased on the results of nine operators
in nine laboratories, the overall and single-operator precision
TABLE 6 Reagent Water (Test Method B)
Technique
Amount Added,
mg/L
Amount Found,
mg/L
n
S
t
Bias % Bias
Statistical
Signicance,
95 % CL
0.008 0.009 21 0.0033 0.001 13 No
Colorimetric 0.019 0.023 20 0.0070 0.004 21 Yes
0.080 0.103 20 0.0304 0.018 23 Yes
0.191 0.228 21 0.0428 0.037 19 Yes
1.00 0.73 18 0.350 0.27 27 Yes
Titrimetric 1.00 0.81 18 0.551 0.19 19 No
4.00 3.29 18 0.477 0.71 18 Yes
D2036 09
10

Reagent Water S
T
S
o
=
=
0.09x + 0.010
0.08x + 0.005
T
S
o
=
=
0.08x + 0.012
0.05x + 0.008
32.1.2 ElectrodeBased on the results of six operators in
ve laboratories, the overall and single-operator precision of
as follows:
Reagent Water S
T
S
o
=
=
0.09x + 0.004
0.02x 0.009
T
S
o
=
=
0.08x + 0.005
0.02x + 0.004
as follows:
Reagent Water S
T
S
o
=
=
0.532 0.10x
0.151 0.01x
T
S
o
=
=
0.604 0.06x
0.092 + 0.02 x
32.1.4 where:
S
T
S
o
= single-operator precision,and
32.2 BiasRecoveries of known amounts of cyanide from
reagent water Type II and selected water matrices were as
shown in Table 8 and Table 9.
TEST METHOD DCYANIDES AMENABLE
TO CHLORINATION WITHOUT
DISTILLATION, SHORT-CUT METHOD
33. Scope
33.1 This test method covers the determination of free CN
and CN
complexes that are amenable to chlorination in water.

The procedure does not measure cyanates nor iron cyanide
complexes. It does, however, determine cyanogen chloride and
thiocyanate.
33.2 Modication is outlined for its use in the presence of
thiocyanate.
34. Interferences
34.3 The thiocyanate ion which reacts with chloramine-T
will give a positive error equivalent to its concentration as
cyanide.
34.4 Color and turbidity can interfere.
34.4.1 When color or turbidity producing substances are
present, it is recommended that Test Method B or C be used.
34.4.2 Color and turbidity can be extracted from some
samples with chloroform without reduction of the pH.
34.4.3 It is possible with some samples to compensate for
color and turbidity by determining the absorbance of a second
sample solution to which all reagents except chloramine-T
have been added.
34.5 Reducing compounds such as sultes can interfere by
preferentially reacting with chloramine-T.
34.6 The color intensity and absorption is affected by wide
variations in the total dissolved solids content of the sample.
34.6.1 For samples containing high concentrations of dis-
solved solids, 3000 to 10 000 mg/L, add 6 g of NaCl to each
litre of NaOH solution (1.6 g/L) used to prepare the standards.
For samples containing dissolved solids concentration greater
than 10 000 mg/L, add sufficient NaCl to the NaOH solution to
approximate the dissolved solids content.
35. Apparatus
35.1 Spectrophotometer or Filter Photometer, suitable for
measurements in the region of 578 nm, using 1.0-cm absorp-
tion cells. Filter photometers and photometric practices used in
these test methods shall conform to Practice E60. Spectropho-
tometers shall conform to Practice E275.
35.2 Water Bath, capable of maintaining temperature at 27
6 1C.
36.2 Pyridine-Barbituric Acid ReagentFor the preparation
of this reagent, refer to 8.15; however, for this test method,
prepare a fresh solution weekly. Longer storage affects the
results of the test.
TABLE 7 Selected Water Matrices (Test Method B)
Technique
Amount Added,
mg/L
Amount Found,
mg/L
n
S
t
Bias % Bias
Statistical
Signicance,
95 % CL
Colorimetric 0.008 0.013 17 0.0077 0.005 63 Yes
0.019 0.025 18 0.0121 0.006 32 Yes
0.080 0.100 18 0.0372 0.020 25 Yes
0.191 0.229 18 0.0503 0.038 20 Yes
1.00 1.20 18 0.703 0.20 20 No
Titrimetric 1.00 1.10 18 0.328 0.10 10 No
4.00 3.83 18 0.818 0.17 4 No
D2036 09
11

36.3 EDTA Solution (18.5 g/L)Dissolve 18.5 g of the
disodium salt of ethylenediamine tetraacetic acid dihydrate in
water and dilute to 1 L.
36.4 Formaldehyde Solution (10 %) Dilute 27 mL of
formaldehyde (37 %) to 100 mL.
36.5 Hydrochloric Acid (HCl) (sp gr 1.19) (1 + 9)Slowly
add 1 volume of concentrated HCl (sp gr 1.19) to 9 volumes of
water, stirring during the addition.
36.6 Phosphate Buffer Solution (138 g/L)Dissolve 159 g
of sodium dihydrogen phosphate (NaH
2
PO
4
H
2
O) in water,
dilute to 1 L and refrigerate.
36.7 Sodium Carbonate (Na
2
CO
3
), anhydrous.
36.8 Sodium Chloride (NaCl), crystals.
37. Standardization
37.1 From the cyanide standard solutions, pipet a series of
aliquots containing from 0.5 to 5.0 g of cyanide in volumes
not exceeding 20 mL into 50-mL volumetric asks.
37.2 Dilute each solution to 20 mL with NaOH solution (1.6
g/L). Follow 38.3 through 38.7 of the procedure.
37.3 Calculate the absorption factor (17.2.1).
38. Procedure
38.1 Adjust the pH of a small volume of sample (50 mL) to
between 11.5 and 11.9. If the addition of acid is needed, add a
small amount (0.2 to 0.4 g) of sodium carbonate and stir to
dissolve. Then add dropwise while stirring HCl solution
(1 + 9). For raising the pH, use NaOH solution (40 g/L).
38.2 Pipet 20.0 mL of the sample into a 50-mL volumetric
ask. If the cyanide concentration is greater than 0.3 mg/L, use
a smaller aliquot and dilute to 20 mL with NaOH solution (1.6
g/L). Do not exceed the concentration limit of 0.3 mg/L.
38.3 To ensure uniform color development, both in calibra-
tion and testing, it is necessary to maintain a uniform tempera-
ture. Immerse the asks in a water bath held at 27 6 1C for
10 min before adding the reagent chemicals and keep the
samples in the water bath until all the reagents have been
added.
38.4 Add 4 mL of phosphate buffer and swirl to mix. Add
one drop of EDTA solution, and mix.
38.5 Add 2 mL of chloramine-T solution and swirl to mix.
Place 1 drop of sample on potassium iodide-starch test paper
which has been previously moistened with acetate buffer
solution. Repeat the chloramine-T addition if required. After
exactly 3 min, add 5 mL of pyridine-barbituric acid reagent and
swirl to mix.
38.6 Remove the samples from the water bath, dilute to
volume and mix. Allow 8 min from the addition of the
pyridine-barbituric acid reagent for color development.
38.7 Determine the absorbance at 578 nm in a 1.0-cm cell
versus water.
38.8 Calculate the concentration of cyanide as milligrams
per litre, in the original sample following equations given in
17.2.
38.9 If the presence of thiocyanate is suspected, pipet a
second 20-mL aliquot of pH-adjusted sample solution into a
TABLE 8 Reagent Water (Test Method C)
Technique
Amount Added,
mg/L
Amount Found,
mg/L
n
S
t
Bias % Bias
Statistical
Signicance,
95 % CL
Colorimetric 0.030 0.030 25 0.0089 0.000 0 No
0.100 0.117 27 0.0251 0.017 17 Yes
0.400 0.361 27 0.0400 0.039 10 Yes
Electrode 0.030 0.030 21 0.0059 0.000 0 No
0.100 0.095 21 0.0163 0.005 5 No
0.400 0.365 21 0.0316 0.035 9 No
1.000 0.940 21 0.0903 0.060 6 No
Titrimetric 1.00 1.35 18 0.4348 0.35 35 Yes
1.00 1.38 18 0.3688 0.38 38 Yes
4.00 3.67 18 0.1830 0.33 8 No
TABLE 9 Selected Water Matrices (Test Method C)
Technique
Amount Added,
mg/L
Amount Found,
mg/L
n
S
t
Bias % Bias
Statistical
Signicance,
95 % CL
Colorimetric 0.030 0.029 15 0.0062 0.001 3 No
0.100 0.118 24 0.0312 0.018 18 Yes
0.400 0.381 23 0.0389 0.019 5 Yes
Electrode 0.030 0.029 20 0.0048 0.001 3 No
0.100 0.104 21 0.0125 0.004 4 No
0.400 0.357 21 0.0372 0.043 11 No
1.000 0.935 21 0.0739 0.065 7 No
Titrimetric 1.00 1.55 18 0.5466 0.55 55 Yes
1.00 1.53 18 0.4625 0.53 53 Yes
4.00 3.90 18 0.3513 0.10 3 No
D2036 09
12

50-mL volumetric ask. Add 3 drops of 10 % formaldehyde
solution. Mix and allow to stand 10 min. Place in a water bath
at 27 6 1C for an additional 10 min before the addition of the
reagent chemicals and hold in the bath until all reagents have
been added.
38.10 Continue with 38.4 through 38.7.
38.11 Calculate the concentration of cyanide, in milligrams
per litre, in the original sample following equations given in
17.2.
38.12 In the presence of thiocyanate, cyanide amenable to
chlorination is equal to the difference between the concentra-
tion of cyanide obtained in 38.8 and that obtained in 38.11.
8
39.1 Precision:
39.1.1 Based on the results of 14 operators in nine
laboratories, the overall and single-operator precision of this
test method within its designated range may be expressed as
follows:
Reagent Water S
T
S
o
=
=
0.10x + 0.006
0.07x + 0.005
T
S
o
=
=
0.11x + 0.007
0.02x + 0.005
39.1.2 where:
S
T
S
o
= single-operator precision,and
39.2 BiasRecoveries of known amounts of cyanide from
reagent water Type II, seven creek waters, one diluted sewage
(1 + 20) and one industrial waste water are as shown in Table
10 and Table 11.
39.3 This precision and bias information may not apply to
waters of untested matrices.
40. Quality Assurance/Quality Control
40.1 Verication of Systems for Quantifying Cyanide in the
Distillate:
40.1.1 Titration Procedure:
40.1.1.1 Standardize the silver nitrate solution with Potas-
sium Chloride, NIST, at least every six months.
40.1.1.2 Titrate 100-mL aliquots of Cyanide I Solution
Standard and 100-mL aliquots of Sodium Hydroxide Solution
(1.6 g/L) each time the procedure is used. Duplicate titrations
should check within 0.05 mL.
40.1.2 Colorimetric Procedure:
40.1.2.1 Prepare a series of cyanide standards, including
zero (blank), based on the expected concentration range of the
samples, and follow the standardization each time new re-
agents are prepared or every six months.
40.1.2.2 The slope (m) of the standard curve should check
the theoretical value:
1.0-cm cell, 0.220.24 mg CN/L/a; 5.0-cm cell, 0.0440.048
mg CN/L/a; 10.0-cm cell, 0.0220.024 mg CN/L/a
40.1.2.3 At least one standard solution and one blank should
be checked each time the procedure is used.
40.1.3 Selective Ion Electrode Procedure:
40.1.3.1 Follow the standardization procedure each time
new standard solutions are prepared.
40.1.3.2 The slope of the curve should check within 90 % of
the theoretical value: 59.2 mV/decade.
40.1.3.3 At least two standard solutions and one blank
should be checked each time the procedure is used.
40.1.4 Ion Chromatographic Procedure:
40.1.4.1 At least three standard solutions and one blank
should be checked each time the procedure is used.
40.1.4.2 Calibrate the ion chromatograph each time the
procedure is used or whenever the eluent is changed. If the
response or retention time for cyanide varies from the expected
value by more than 6 10 % a new calibration curve must be
prepared.
40.1.4.3 One midrange standard solution and a blank should
be checked each time the procedure is used or at least every 20
samples. If the response or retention time varies from the
expected value by more than6 10 % repeat the test using fresh
standards.
40.2 Verication of the Distillation Procedure:
40.2.1 Verify the distillation procedure as described in
sections 40.3 to 40.8.
NOTE 6With careful selection of concentration all four quantication
procedures can be performed on the same distillate solution. (See Guide
D5788).
40.3 Initial Demonstration of Laboratory Capability:
40.3.1 If a laboratory has not performed the test before or if
there has been a major change in the measurement system, for
example new analyst, new instrument, and so forth, a precision
and bias study must be performed to demonstrate laboratory
capability.
40.3.2 Analyze seven replicates of a standard solution
prepared from an IRM containing a known concentration of
cyanide in reagent water. Each replicate should be taken
through the entire analytical test (that is, the distillation and
8
TABLE 10 Reagent Water (Test Method D)
Amount Added, mg/L
Amount Found,
mg/L
n
S
t
Bias % Bias
Statistical
Signicance,
95 % CL
CN SCN
0.005 0.007 42 0.0049 0.002 40 Yes
0.027 0.036 41 0.0109 0.009 25 Yes
0.090 0.100 42 0.0167 0.010 11 Yes
0.090 0.080 0.080 39 0.0121 0.010 11 Yes
0.270 0.276 42 0.0320 0.006 2 No
D2036 09
13

determinative step) including preservation and any pretreat-
ment used to remove interferences. The replicates may be
intersected with samples.
40.3.3 Calculate the mean and standard deviation of the
seven values and refer to Test Method D5847 for information
on applying the F test and t test in evaluating the acceptability
of the mean and standard deviation.
40.4 Laboratory Control Sample (LCS):
40.4.1 To ensure that the test method is in control, analyze
an LCS containing cyanide at the appropriate concentration
range for each analytical batch of 10 samples. For batches of
less than 10 samples analyze at least one LCS. The LCS should
be taken through the entire analytical procedure. The LCS is
considered in control if the recovery is 85-115 %. If the LCS
falls outside these limits halt the analysis of samples until the
problem is corrected, upon which the samples should be
reanalyzed if possible. If samples cannot be reanalyzed, qualify
the data that the LCS was not within the performance criteria
of the test method.
40.5 Method Blank:
40.5.1 Analyze a reagent water test blank with each analyti-
cal batch of 10 samples or at least once daily if less than 10
samples are analyzed in a given day. The concentration of
cyanide should be less than the reporting limit for the corre-
sponding method or else sample analyses are halted until the
problem is corrected. Affected samples should be reanalyzed or
qualied.
40.6 Matrix Spike (MS):
40.6.1 To check for interferences in the specic matrix
being tested, perform an MS on at least one sample from each
analytical batch by fortifying a known concentration of cyanide
and taking it through the entire analytical procedure.
40.6.2 The matrix spike must produce a concentration that
is 2 to 5 times the background concentration or 10 to 50 times
the detection limit of the test method, whichever is greater.
Calculate the percent recovery of the spike (P) using the
following formula:
P 5 100
?
A~V
s
1V! 2 BV
s ?
CV
where:
A = concentration found in spiked sample,
B = concentration found in unspiked sample,
C = concentration of analyte in spiking solution,
V
s
= volume of sample use, and
V = volume of spiking solution added.
40.6.3 The percent recovery of the spike shall fall within
70-130 % or else one of the following must be employed: the
matrix interference should be removed, all samples in the batch
must be reanalyzed by a test method not affected by the matrix
interference, or the results must be qualied with an indication
that the matrix spike does not fall within the performance
criteria of the test method.
40.7 Duplicate:
40.7.1 To check the precision of sample analyses, analyze a
sample in duplicate with each analytical batch. If the concen-
tration of cyanide is less than ve times the detection limit for
the method, a matrix spike duplicate (MSD) should be used.
Calculate the standard deviation of the duplicate values and
compare to the single operator precision in the collaborative
study using an F test. Refer to 6.4.4 of Test Method D5847 for
information applying the F test.
40.7.2 If the result exceeds the precision limit, the batch
must be reanalyzed or the results must be qualied with an
indication that they do not fall within the performance criteria
of the test method.
40.8 Independent Reference Material (IRM):
40.8.1 In order to verify the quantitative value obtained in
the method, analyze an IRM, preferably analyzed as a regular
sample at least once a quarter. The observed concentration
should fall within the limits set by the outside source of the
IRM.
41. Keywords
41.1 colorimetric; cyanides amendable to chlorination;
distillation; ion chromatography; ion electrode; titration; total
cyanide; weak acid dissociable cyanides
TABLE 11 Selected Water Matrices (Test Method D)
Amount Added, mg/L
Amount Found,
mg/L
n
S
t
Bias % Bias
Statistical
Signicance,
95 % CL
CN SCN
0.005 0.003 40 0.0042 0.002 40 Yes
0.027 0.026 42 0.0093 0.001 4 No
0.090 0.087 42 0.0202 0.003 3 No
0.090 0.080 0.068 37 0.0146 0.022 24 Yes
0.270 0.245 41 0.0319 0.025 9 Yes
D2036 09
14

ANNEX
(Mandatory Information)
A1. SPOT TEST FOR SAMPLE SCREENING
A1.1 Scope
A1.1.1 The spot test procedure allows a quick screening of
the sample to establish if more than 0.05 mg/L (ppm) of
cyanides amenable to chlorination, cyanogen chloride, or
thiocyanate are present in water, waste water, and saline water.
A1.1.2 The test may also be used to establish the presence
and absence of cyanogen chloride by omitting the addition of
chloramine-T.
A1.1.3 With the addition of formaldehyde to the sample, the
amenable cyanide can be masked and under these conditions,
the test is specic to thiocyanate. It is possible therefore to
distinguish between the presence of cyanide and thiocyanate or
possibly judge the relative levels of concentration for each.
A1.1.4 With practice or dilution, the test can be used to
estimate the approximate concentration range of these
compounds, judging from the color development and compar-
ing it to similarly treated samples of known concentration.
A1.2 Interferences
A1.2.1 All the chemical compounds listed in Section 6, with
the exception of the nitrites, may interfere. For their removal,
refer to Sections 10 and 11.
A1.2.2 The thiocyanate ion reacts in the same manner as the
cyanide. The cyanide can be masked and then the test is
specic for thiocyanate.
A1.2.3 The presence of large amounts of reducing sub-
stances in the sample interferes by consuming the
chloramine-T added. Repeat the chloramine-T addition, if
necessary.
A1.3 Apparatus
A1.3.1 Spot Plate, porcelain with 6 to 12 cavities preferred.
A1.4 Reagents and Materials
A1.4.1 Refer to Sections 8 and 36.
A1.4.2 Formaldehyde, 37 %, pharmaceutical grade.
A1.4.3 Hydrochloric Acid (1 + 9) Mix 1 volume of con-
centrated (HCl (sp gr 1.19) with 9 volumes of water.
A1.4.4 Sodium Carbonate, anhydrous Na
2
CO
3
.
A1.5 Procedure
A1.5.1 If the solution subject to spot tests is alkaline in a pH
range greater than 10, neutralize a 20 to 25-mL portion.
A1.5.1.1 Add 1 drop of phenolphthalein indicator solution.
If the sample remains colorless, proceed to A1.5.2.
A1.5.1.2 If the sample turns red, add approximately 250 mg
of sodium carbonate and mix to dissolve.
A1.5.1.3 Add HCl (1 + 9) dropwise while mixing until
colorless.
A1.5.2 Place 3 drops of sample and 3 drops of reagent water
(for a blank) on a white spot plate.
A1.5.3 To each cavity, add 1 drop of chloramine-T solution
and mix with a clean stirring rod.
A1.5.4 To each cavity add 1 drop of phosphate buffer.
A1.5.5 Add 1 drop of pyridine-barbituric acid solution to
each and again mix with a stirring rod.
A1.5.6 After 1 min, the sample spot will turn pink to red if
0.05 mg/L or more of CN is present. The blank spot will be
faint yellow due to the color of the reagents. Until familiarity
with the spot test is gained, it may be advisable to use, instead
of the reagent water blank, a standard solution containing 0.05
mg/L CN for color comparisons. This standard can be made up
by diluting the KCN standard solution (8.8.3).
A1.5.7 If the presence of thiocyanate is suspected, test a
second sample pretreated as follows: Heat a 20 to 25-mL
sample in a water bath at 50C; add 0.1 mL of formaldehyde
and hold for 10 min. This treatment will mask up to 5 mg
CN/L.
A1.5.8 Repeat the spot test with the treated sample. Color
development indicates the presence of thiocyanate. Comparing
the intensity of the colors in the two spot tests is useful in
judging whether both compounds are present and, if so, the
relative concentration of cyanide and thiocyanate.
D2036 09
15

APPENDIX
(Nonmandatory Information)
X1. CYANIDE
X1.1 Introductory CommentsCyanides are used exten-
sively in metal nishing processes and heat treatment of steel,
and are a signicant constituent of wastes from coke oven and
blast furnace operations. As a toxic contaminant of effluents,
they usually appear in the waste waters from quenching, gas
scrub waters, and rinse water effluent from electroplating
plants. The toxic effects of cyanide are so severe and estab-
lished toxicity levels so low (<0.1 mg/L) that regulatory
concern and waste treatment efforts by industry need depend-
able analytical procedures and a better understanding of the
various cyanide complexes that may be encountered.
X1.2 Molecular Hydrogen Cyanide, Cyanides Amenable to
Chlorination, Iron Cyanides:
X1.2.1 Toxicological investigations by Doudoroff and oth-
ers have indicated that the acute toxicity of polluted water is
caused by the molecular hydrogen cyanide (undissociated
HCN) as opposed to the cyanide ion (CN) that may be equally
present (23). Actually, Milne suggested complexing the mo-
lecular HCN with metal salts as a waste treatment process (4)
.
X1.2.2 A number of analytical methods were proposed to
allow a quantitative distinction for the molecular HCN to
establish the acute toxicity levels of surface waters when
cyanide toxicity is suspected (56). The rst question we have
to raise when evaluating these various analytical procedures is
whether the premise regarding the distinction between molecu-
lar or undissociated HCN hydrogen cyanide on the one hand
and cyanide ions on the other hand is valid or not. The
distinction desired is actually the dissociated CN
as distinct
from the CN
tightly bound in the metal complex. Another

term referred to by the authors in reference is free cyanide.
This term doesnt have any toxicological signicance and is
commonly used in the electroplating industry and refers to the
cyanide ion that can be titrated with silver nitrate (Liebig
Titration), forming an insoluble silver cyanide precipitate when
the free cyanide available for complexing the silver is ex-
hausted.
X1.2.3 Lancy and Zabban have shown (7) that in solutions
containing the various metal cyanide complexes, the difference
in cyanide ion activity is due to the difference in measurable
dissociation constants for each of the metal cyanide complexes
investigated.
X1.2.4 Critical evaluation of the toxicity investigations with
various metal cyanide complexes reveals that these reports
conrm the great differences in dissociation by the various
metal cyanide complexes.
X1.2.5 Both Milne (8) and Doudoroff (9) show that in the
critical concentration of 0.01 to 0.5 mg/L of CN at a pH of 7.5,
HCN formation is favored and will be maintained if depleted
by further dissociation of the cyanide complex. Lowering the
pH (that is, increasing the hydrogen ion concentration by 0.3
pH units) doubles the HCN content.
X1.2.6 Doudoroff has found that the toxicity of zinc-,
cadmium-, and copper-cyanide compounds is probably greater
than equal concentrations of sodium cyanide. The synergistic
toxic effects, when both zinc and copper ions are combined
with cyanide, are known. Additional evidence regarding the
toxicity of copper, silver, and nickel cyanide complexes in low
concentrations was reported (10,9,11). Doudoroff, on the other
hand, shows that the iron cyanides do not dissociate to any
measurable extent and therefore are not toxic to sh (2,10,12).
X1.2.7 Differentiation between toxic and nontoxic cyanide
was designated cyanides amenable to chlorination by Lancy
and Zabban(13). Differentiation is based on the oxidizing effect
of chlorine. Resistance of the iron cyanide compounds to
oxidation is due to lack of dissociation rendering them non-
toxic to sh. Test for Cyanides Amenable to Chlorination
Without Distillation is based on rapid dissociation of cyanide
and complexing with chloramine-T. First, the sample aliquot is
prepared in the very low concentration ranges, aiding disso-
ciation which is accelerated by complexing the cyanide ion
with chloramine-T. The latter frees additional cyanide ion to
reestablish the equilibrium that was disturbed. The pH is
reduced signicantly by adding the pyridine-barbituric acid
reagent (pH 5 to 5.5), and the sample is previously heated to
accelerate the dissociation and complexing with chloramine-T.
The test therefore has the necessary ability to measure certain
undissociated cyanides, which could be converted by dissocia-
tion to toxic cyanides as a result of pH changes or dilution of
the sample.
X1.2.8 All metal cyanide complexes are in equilibrium with
the hydrolyzed HCN molecule, the concentration being depen-
dent on the pH of the water and the dissociation constant of the
particular metal cyanide complex present. The tightest com-
plex is formed with iron. Since there is little dissociation, we
may say that the ferrocyanide and ferricyanide compounds are
themselves nontoxic (14,15). The iron cyanide complex is so
tight that the standard alkaline chlorination procedure will not
affect it. Reported analytical data showing a slight reduction in
ferrocyanide content, either in the chlorination step or recovery
in the colorimetric analysis procedure, is most likely due to
impurity in the reagent or the handling of the sample.
Analytical-grade ferrocyanide when dissolved always contains
some dissociated CN
(HCN). The sample has to be handled

carefully to avoid any photodecomposition which will appear
as an oxidizable portion of the total ferrocyanide present
(1617) . All other metal cyanide compounds will be chlori-
nated at a slower rate due to the slow dissociation of the metal
cyanide complex. The equilibrium of the metal cyanide com-
plex and molecular HCN is continuously upset, and as the
dissociation occurs, the hypochlorite ion will react with the
cyanide ion, leading to further dissociation of the metal
D2036 09
16

cyanide complex and then allowing further oxidation by
chlorination. This implies a time dependence regarding the
chlorination reaction with the cyanide ion that is complexed by
such metals as silver, gold, and nickel. The chlorination of
nickel cyanide at a concentration of 20 mg/L CN, as an
example, may not be complete after 1 h even when hypochlo-
rite was added at a 10 % excess of the stoichiometric amount
(13,18,19). Because iron cyanide complexes are not destroyed
by the practical methods of alkaline chlorination and cyanide
in contact with iron salts causes iron cyanide to be always
present in metal nishing waste, the question of proper waste
treatment, or its lack, was many times raised when analyzing
industrial waste using the standard analytical procedures.
There is important practical value, therefore, that a distinction
be made and analytical procedures be developed for Cyanides
Amenable to Chlorination (7,13). As it has been established
that the ferrocyanide complex is not toxic (2,10,14,15) it might
be assumed that a low-cyanide concentration of 1 to 10 mg/L;
if not amenable to chlorination such as iron cyanides, would
have no toxic effect on the environment. However, this
assumption is based on the following two factors:
X1.3 The Iron Cyanides Undergo Dissociation from
Photodecomposition(15 and 17).
X1.3.1 Under strong sunlight, 10 mg/L iron cyanide, ex-
pressed as CN
, may release 1 mg/L HCN in 1 h (Fig. X1.1).

X1.4 Dilution and Dispersion of the Treated Waste in the
Receiving Waters:
X1.4.1 The kind of dilution, mixing in the diluting stream,
clarity of the receiving waters, and the quantity of HCN release
that may be expected are dependent upon particular environ-
mental conditions, considering that only the top layers of the
receiving waters will be subject to the strong sunlight to cause
decomposition. Oxidation by air and bacterial decomposition
in the receiving waters will be additional factors mitigating
against the development of toxic concentration levels.
X1.4.2 Deliberate complexing of simple cyanides with iron
salts as an economical means of waste treatment naturally
should be unacceptable. Higher concentrations of iron
cyanides, in view of the foregoing, require treatment. Suitable
processes for the oxidative destruction of iron cyanides are
available (20), leading to the complete destruction of the
cyanide and precipitation of iron oxide. Insoluble iron cyanide
precipitates are soluble in alkali. Therefore, their being in-
soluble under normal conditions is not an ensurance that the
environment is protected.
X1.5 Cyanogen Chloride:
X1.5.1 Presently the destruction of cyanide compounds in
waste treatment processes is done by oxidation with hypochlo-
rite (OCl
) because the oxidation reaction is rapid and can be

carried to completion using near stoichiometric equivalent of
the reacting chemical. The chlorination reaction has to be
conducted at an alkaline pH because the rst reaction product
formed is cyanogen chloride, a toxic gas, having very low
solubility. The toxicity of cyanogen chloride may exceed the
toxicity of HCN, both in water and in the atmosphere (<0.1
mg/L) (21,22). Cyanogen chloride hydrolyzes at an alkaline pH
to cyanate (CNO
). The rate of hydrolysis is dependent on the

pH conditions and the available excess chlorine, the higher the
pH or the more chlorine present, the faster will the reaction go
to completion. At a pH of 9, with no excess chlorine present,
cyanogen chloride may persist in the treated water for more
than 24 h (2324). In view of the low solubility of cyanogen
chloride and the time dependence for its hydrolysis, it is
desirable to maintain the alkalinity during chlorination at pH
11 or higher. A pH of 12 to 13 may be required when the
chlorination reaction is carried out on a waste water containing
high concentrations of cyanide (>100 mg/L). The low solubil-
ity of cyanogen chloride is reduced further by the reaction heat
generated upon addition of chlorine. The vapor pressure of the
cyanogen chloride gas is increased. Rapid hydrolysis of the
cyanogen chloride is the only means available to avoid the
FIG. X1.1 Photodecomposition Rates for Fe(CN)
6
4
in Direct Sunlight, 20C, pH 7, in Buffered Distilled Water,
75 mm Solution Layer, 1 h Exposure
D2036 09
17

escape of cyanogen chloride into the atmosphere. When
conducting continuous treatment of an effluent, the pH of the
waste stream is lowered after a few minutes of reaction time
because a neutral effluent has to be discharged. After the pH is
reduced, any cyanogen chloride that has not yet undergone
hydrolysis will escape as the toxic cyanogen chloride in the
effluent. At pH 11 and at 10C, the half-life period of cyanogen
chloride before hydrolysis to CNO

, and in the absence of
excess chlorine, is 12.5 min (2324). It is regrettable that the
importance of this reaction and these conditions are not
appreciated by Regulatory Agencies and waste treatment
engineers. Analysis for cyanogen chloride is not performed,
whereas concern is shown for the possible cyanate content of
a treated waste. An analytical procedure for the distinction
between HCN, ferro- and ferricyanide, respectively was pub-
lished by Kruse and Thibault (6).
X1.6 Cyanate Compounds:
X1.6.1 As discussed in X1.5, the cyanogen chloride that is
formed due to the reaction of OCl
with cyanide ions and HCN

during the chlorination reaction will hydrolyze to cyanate
(CNO
). The reported toxicity of cyanate in water is >100

mg/L. The reversion of cyanate to cyanide was attempted with
photodecomposition and reduction, but could not be accom-
plished (25). Theoretical calculations also indicate that cyanate
cannot be reduced to cyanide.
X1.6.2 Acidication and dilution of the cyanate leads to
hydrolysis of cyanate to the ammonium ion (NH
4
+
). Ammonia
toxicity was reported in the 2 to 2.5 mg/L range in hard water
(14). Doudoroff reports toxic effects at even lower levels (<1
mg/L), (21). It can be assumed therefore that the toxicity of
cyanate is mainly due to the fact that it will yield ammonia.
Since chlorination is conducted at high pH, and the treated
waste normally then neutralized, further pH reduction may
occur due to the lower pH condition of natural waters.
Therefore, we may assume that harmful concentrations of
cyanate will not be easily encountered in a natural environ-
ment. A cyanate determination within ASTM has not yet been
formalized. Recommended analytical procedures are available
from the literature (2526).
X1.7 Thiocyanate Compounds:
X1.7.1 The relatively nontoxic thiocyanate compounds (14)
may become extremely toxic due to conversion to cyanogen
chloride (see X1.5.1) when a waste stream containing the
thiocyanate ion undergoes chlorination for disinfection (21,22).
The probable reaction is: KCNS + 4Cl
2
+ 4H
2
O
CNCl + KCl + H
2
SO
4
+ 6 HCl.
X1.7.2 According to Doudoroff, this reaction will occur
even if the chlorine added to the waste stream is not sufficient
to provide a residual (21). Thiosulfate, a common reducing
chemical used to detoxify chloramines, is not as effective for
cyanogen chloride unless a large excess is used (22).
X1.7.3 The determination for cyanides amenable to chlo-
rination will also include the thiocyanate ion due to the
conversion to cyanogen chloride by chloramine-T. A specic
test for thiocyanates is contemplated.
X1.8 Total Cyanide:
X1.8.1 Cobalt cyanide is not recovered completely during
the distillation. The explanation for this condition was given by
Leschber (27) and referred to by original investigations by
Bassett and Corbet (28). Potassium cobalt cyanide, when
boiled with dilute sulfuric acid, partially breaks down to carbon
monoxide, carbon dioxide, and ammonium sulfate.
X1.8.2 The determination of total cyanide retains its signi-
cance. As discussed earlier in X1.2, iron cyanides will not be
revealed by the Cyanides Amenable to Chlorination analysis
methods. To a lesser extent, some of the nickel cyanide, cobalt
cyanide, silver and gold cyanide will also not be completely
recovered. Neither will the standard alkaline chlorination
practices break down these complexes. It has been noted that
the toxic effects of these compounds are also considerably less
and of a different nature: photodecomposition for iron cya-
nides; slow dissociation for nickel-, cobalt-, silver-, and gold
cyanides. At the same time, there are many waste treatment
installations that are either not designed properly, or not
operated properly; therefore, more cyanide compounds that
could have been treated are discharged in the effluent. There
are also some processes generating excessively large quantities
of these complex cyanides, thereby producing a signicant
pollution hazard.
As examples, we should list:
(a) Heat treating processes;
(b) Coke and blast furnace operations;
(c) Cyanide-type processes used for stripping nickel and
cobalt-nickel alloy deposits;
(d) Rinse waters from silver and gold plating operations;
(e) Accidentally mixed waste coming from nickel plating
solutions and cyanide oor spill;
(f ) Regeneration and backwash waters from ion exchange
type waste treatment processes used for the removal of plating
salts from rinse water waste. The treatment of these wastes
consists usually of mixing, partially deliberately, partially due
to the process, and partially accidentally, nickel and iron salts
with cyanide compounds; and
(g) Some waste treatment processes still recommended the
use of iron sulfate for the neutralization of cyanide salts, etc.
X1.8.3 The total cyanide determination therefore must be
used to ensure good waste treatment practices. The mistaken
belief that the enumerated cyanide compounds are not toxic
must be avoided. The fact is that the toxicity is only of a lesser
magnitude.
X1.9 Cyanide in Solid Waste:
X1.9.1 The waste treatment needs for soluble cyanide
sludges is assumed, for example, sludges from plating solu-
tions; cyanide salts removed from heat treat pots or in frozen
condition as drag-out from heat treatment; or cyanide salts as
residue from the evaporation of processing solutions or rinse
waters. The treatment requirements for these highly toxic
residues is obvious.
X1.9.2 Most of the metal cyanide complexes are insoluble
and are made soluble in water only in the presence of excess
alkali metal cyanides. Milne (4) quotes a few examples which,
D2036 09
18

while not complete, should be sufficient to show the insolubil-
ity of some metallic cyanides.
X1.9.3 During waste treatment, if the process is not con-
ducted carefully, as the breakdown of the alkali metal cyanide
is progressing, the metal cyanide will become insoluble, and
will precipitate as the slightly soluble cyanide compound of the
particular metal originally present. As seen from Table X1.1,
some sludges may contain high levels of relatively insoluble
metallic cyanides having high potential toxicity. Lancy and
Zabban have reported (13) the cyanide content in the precipi-
tates when conducting slow chlorination and with no or
minimal chlorine excesses. The complete treatment and re-
moval of the cyanide concentration in the sludge can be
accomplished only by either signicant chlorine excess in the
waste water, or by rapid chlorination to allow breakdown of the
metal cyanide complex before it is precipitated and buried in
the sludge. Some newer waste treatment processes, such as
treatment with peroxygen compounds, will yield considerably
higher available cyanide concentrations in the sludge.
X1.9.4 Iron cyanide is always present in electroplating
solutions. The concentration is usually in the range from 20 to
25 g/L. Only a small quantity of this iron cyanide will appear
in the rinse water effluent, and as it escapes chlorination, it may
form insoluble iron cyanide compounds with other metals
present, such as copper, zinc, iron, etc. The metal iron cyanide
compounds may be considered insoluble and nontoxic, but can
become soluble in the alkaline range (pH > 9) if the solid waste
is leached with alkaline waste. The resolubilized iron cyanide
can undergo photodecomposition as discussed in X1.2. The
insoluble iron cyanide content of solid waste may be a result of
the best treatment that modern technology can do with regard
to treatment and disposal of particular cyanide compounds.
The usual disposal is burial or landll where acid conditions
are far more common than excessive alkalinity which would
cause the redissolution.
X1.9.5 The insoluble cyanide content of a solid waste can
be determined by placing a 500-mg sample with 500 mL of
distilled water into the distillation ask and following the total
cyanide distillation. The calculations should consider a multi-
plication by 1000 to give the cyanide content of the solid waste
sample in ppm. Insoluble iron cyanides in the solid waste can
be leached out before analysis by stirring a weighed sample for
12 to 16 h in a 10 % caustic soda solution. The leachate and
wash waters of the solid waste will give the iron cyanide
content of the sample using the distillation procedure. A
previous chlorination will have eliminated all cyanide ame-
nable to chlorination from the sample. The sample should not
be exposed to sunlight. A method allowing differentiation
between HCN, ferro- and ferricyanide, as mentioned earlier, is
referenced (6,17).
REFERENCES
(1) Miller, J. C. and Miller, J. N., Statistics for Analytical Chemistry, 3rd
ed., Ellis Horwood PTR Prentice Hall, 1993, pp. 124129.
(2) Doudoroff, P., Some Experiments on the Toxicity of Complex
Cyanides to Fish, Sewage and Industrial Wastes, Vol 28, No. 8,
August 1956, p. 1020.
(3) Wuhrmann, K., and Woker, H., Schweizische Zeitschrift Fuer
Hydrologie, Vol 11, 1948, p. 210.
(4) Milne, D., Disposal of Cyanides by Complexation, Sewage and
Industrial Wastes, Vol 22, No. 9, September 1950, p. 1192.
(5) Schneider, C. R., and Freund, H., Determination of Low Level
Hydrocyanic Acid, Analytical Chemistry, Vol 34, 1962, p. 69.
(6) Kruse, J. M., and Thibault, L. E., Determination of Free Cyanide in
Ferro- and Ferricyanides, Analytical Chemistry, Vol 45, 1973, p.
2260.
(7) Lancy, L., and Zabban, W., Analytical Methods and Instrumentation
for Determining Cyanogen Compounds, ASTM STP 337, ASTM
1962.
(8) Milne, D., Equilibria in Dilute Cyanide Waste Solutions, Sewage
and Industrial Wastes, Vol 22, No. 7, July 1950, p. 904.
(9) Anon, Activities Report, U. S. Department of Health Education
Welfare, July 1, 1963June 30, 1964, p. 13.
(10) Doudoroff, P., Leduc, G., and Schneider, C. R., Acute Toxicity to
Fish of Solutions Containing Complex Metal Cyanides, in Relation
to Concentrations of Molecular Hydrocyanic Acid, Transactions of
American Fisheries Society, Vol 95, January 1966, p. 116.
(11) Backsteeg, W., and Thiele, H., Gas and Wasserfach 98, 1957, p. 909.
(12) Doudoroff, P., Toxicity to Fish of Cyanides and Related
Compounds, (A Review), (EPA-600/3-76-038, 1976 NTIS).
(13) Lancy, L., and Zabban, W., Die Beziehung Zwischen Analyse und
Behandlung von cyanidehaltigem Abwasser, Metalloberache, Vol
13, No. 3, March 1963, p. 65.
(14) Ellis, M. M., Detection and Measurement of Stream Pollution, U.
S. Department of Commerce, Bureau of Fisheries, Bulletin No. 22,
1937, p. 427.
(15) Burdick, G. E., and Lipschuetz, M., Toxicity of Ferro and Ferri-
cyanide Solutions to Fish, Transactions of American Fisheries
Society, Vol 78, 1948, p. 192.
(16) Lancy, L. E., and Fischer, G., Die Bestimmung der durch alkalische
Chlorbehandlung zerstrbaren Cyanide,Galvanotechnick, Vol 59,
No. 3, March 1968, p. 192.
(17) Drew, D. M., Simultaneous Determination of Ferrocyanide and
Ferricyanide in Aqueous Solutions Using Infrared Spectrometry,
Analytical Chemistry , Vol 45, 1973, p. 2423.
(18) Leschber, R., Die Beurteilung der Toxizitat cyanidhaltiger
Abwasser, Galvanotechnik, Vol 60, No. 5, May 1969, p. 368.
(19) Lancy, L. E., Uber die Planung von Anlagen zur kontinuierlichen
TABLE X1.1 Solubility of Metal Cyanide Precipitates
in Water
Precipitate
Solubility in
Water, g/L
Temperature,
C
Silver cyanide 0.000028 18
Zinc cyanide 0.0058 18
Copper cyanide 0.014 20
Nickel cyanide 0.0592 18
Cadmium cyanide 17 15
Mercuric cyanide 93 14
D2036 09
19

alkalischen Chlorierung cyanidhaltiger Abwasser, Galvanotechnik,
Vol 49, No. 1, January 1958, p. 14.
(20) U. S. Patent 2 98 682 and 3 101 320.
(21) Doudoroff, P., and Katz, M., Critical Review of Literature on the
Toxicity of Industrial Wastes and Their Components of Fish,
Sewage and Industrial Wastes, Vol 22, No. 11, November 1950, p.
1432.
(22) Zillich, J. A., Toxicity of Combined Chlorine Residuals to Fresh
Water Fish, Journal of the Water Pollution Control Federation, Vol
44, No. 2, February 1972, p. 212.
(23) Pettet, A. E. J., and Ware, G. C., Disposal of Cyanide Wastes,
Chemistry and Industry, Oct. 1, 1955 , p. 1232.
(24) Bailey, P. L., and Bishop, E., Hydrolysis of Cyanogen Chloride,
Journal Chemical Society, 1973, p. 912.
(25) Resnick, J. D., et al., The Behavior of Cyanates in Polluted Water,
Industrial and Engineering Chemistry, Vol 50, January 1958, p. 71.
(26) Procedures for Analyzing Metal Finishing Wastes, Ohio River
Valley Sanitation Commission, 1954, p. 1520.
(27) Leschber, R., Zur Frage des durch Chlorzerstobaren Cyanids,
Galvanotechnik, Vol 59, No. 10, October 1968, p. 823.
(28) Bassett, H., Jr., and Corbet, A. S., Journal Chemical Society, Vol
125, 1924, p. 1358.
(29) Claeys, R., and Freund, H., Chromatographic Separation of HCN,
Environmental Science & Technology, Vol 2, No. 6, June 1968, p.
458.
(30) Montgomery, H. A. C., et al., Determination of Free Hydrogen
Cyanide in River Water, Analyst, Vol 94, April 1969, p. 284.
(31) Nelson, K. H., and Lysyj, I., Analysis of Water for Molecular
Hydrogen Cyanide, Journal of the Water Pollution Control
Federation, Vol 43, No. 5, May 1971, p. 799.
(32) Schuster, H., and Winkel, P., Cyanid Entgiftung, Galvanotechnik ,
Vol. 59, No. 3, March 1968, p. 189.
(33) Bailey, P. L., and Bishop, E., The Determination of Cyanogen
Chloride, Analyst, Vol 97, September 1972, p. 691.
(34) Dodge, B. F., and Zabban, W., Analytical Methods for the Deter-
mination of Cyanates in Plating Wastes, Plating, Vol 39, No. 4,
April 1952, p. 381.
(35) Gardner, D. C., The Colorimetric Determination of Cyanates in
Effluents, Plating, Vol 43, No. 6, June 1956, p. 743.
(36) Leschber, R., Verfahren zur Bestimmung von Cyaniden,
Galvanotechnik, Vol 58, No. 7, July 1967, p. 462.
(37) Lancy, L. E., Abwasserprobleme, Galvanotechnik, Vol 58, No. 4,
April 1967, p. 244.
(38) Weiner, Von R., and Leiss, Chr., Kritische Untersuchungen zur
Kolorimetrischen Cyanidbestimmung,Metalloberache, Vol 26,
No. 6, June 1971, p. 185.
(39) Leschber, R., and Schlichting, H., Uber die Zersetzlichkeit kom-
plexer Metallcyanide bie der Cyanidbestimmung in Abwasser,
Zeitschrift Analytische Chemie, Vol 245, 1969, p. 300.
(40) Bucksteeg, W., and Dietz, F., Zur Bestimmung und Beurteilung des
Cyanides in Wasser, Wasser Luft und Betrieb, Vol 13, November
1969, p. 417.
(41) Bucksteeg, W., and Dietz, F., Zur Bestimmung und Beurteilung des
Cyanides in Wasser, Wasser Luft und Betrieb, Vol 13, December
1969 , p. 475.
(42) Sawicki, E., et al., The 3-Methyl-2-Benzothiazolone Hydrazone
Test Sensitive New Methods for the Detection, Rapid Estimation,
and Determination of Aliphatic Aldehydes,Analytical Chemistry,
Vol 33, 1961, p. 93.
(43) Hauser, T. R., and Cummins, R. L., Increasing Sensitivity of
3-Methyl-2-Benzothiazolone Hydrazone Test for Analysis of Ali-
phatic Aldehydes in Air, Analytical Chemistry, Vol 36, 1964, p. 679.
(44) Methods of Air Sampling and Analysis, 1st ed. 1972. Inter Society
Committee, Air Pollution Control Association 199204.
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D2036 09
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Norma ASTM D 2036-09 para Determinación de Cianuro

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Standard Test Methods for

) Dilute exactly 100 mL of KCN standard solution II to

) Dilute exactly 100 mL of KCN standard solution III to

in standard, mg/L, and

/L, and the

complexes that are amenable to chlorination in water.

tightly bound in the metal complex. Another

(HCN). The sample has to be handled

, may release 1 mg/L HCN in 1 h (Fig. X1.1).

) because the oxidation reaction is rapid and can be

). The rate of hydrolysis is dependent on the

with cyanide ions and HCN

). The reported toxicity of cyanate in water is >100

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