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Total cyanide: the sum of the organically bound cyanide, free cyanide ions, complex compounds and
cyanide bound in simple metal cyanides, with the exception of the cyanide bound in cobalt complexes.
Thiocyanate is not included in this term.
Free cyanide (or alternatively: easily liberatible cyanide): the sum of cyanide ions and the cyanide bound in
simple metal cyanides which is determined in the method described in this flow sheet. Organic cyanides are
not determined.
The automated procedure for the determination of Total Cyanide is based on the following reaction;
complex bound cyanide is decomposed in a continuously flowing stream at a pH of 4.0 by the effect of UV
light. A UV-B lamp (312 nm) and a decomposition spiral of borosilicate glass is used to filter out UV light
with a wavelength of less than 290 nm thus preventing the conversion of thiocyanate into cyanide. The
hydrogen cyanide present at a pH of 4.0 is separated by in-line distillation at 125C under vacuum. The
hydrogen cyanide is then determined photometrically. The photometric determination is based on the
reaction of cyanide with chloramine-T under the formation of cyanogen chloride. This reacts with 4-
pyridine carboxylic acid and 1,3-dimethylbarbituric acid to give a purple colour. This colour is measured at
600 nm. (Method according to ISO 14403)
The automated procedure for the determination of Free Cyanide is based on the following reaction; the UV
lamp is switched off when determining the free cyanide content. A zinc sulfate solution is added to the
sample flow so any iron cyanides present are precipitated as the zinc cyanoferrate complex. The hydrogen
cyanide present at a pH of 4.0 is separated by in-line distillation at 125C under vacuum. The hydrogen
cyanide is then determined photometrically. The photometric determination is based on the reaction of
cyanide with chloramine-T under the formation of cyanogen chloride. This reacts with 4-pyridine carboxylic
acid and 1,3-dimethylbarbituric acid to give a purple colour. This colour is measured at 600 nm. (Method
according to ISO 14403)
LABORATORY FACILITIES
1. Maximum power consumption depending on the analyser configuration, 2000 VA. Check voltage at the
back of the instrument before installation.
2. Facilities for chemical wastes. Check environmental regulations for proper disposal of waste.
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PROCEDURE SAMPLE PREPARATION
Immediately after sampling and filtration, water samples are brought to pH 12 with sodium hydroxide
solution such that the quantity of added alkaline yields a negligible dilution of the sample.
- Test for interferences and treat if necessary. In the case of oxidising agents treat the sample
immediately after sampling.
- Analyse the sample, using the method for total and / or free cyanide, as soon as possible after taking
the sample, but at the latest within three days. Store the sample in the dark.
Soil extract
The soil sample is extracted with 2.5M sodium hydroxide solution. The extract is diluted 100 times, after
which analysis of total and/or easily released cyanide is performed.
Note : The sample preparation in this method is only meant to be an example procedure. It requires
validation on its correct procedure for all types of samples to be analyzed, which is the responsibility of the
user.
REAGENTS
Required chemicals: Citric acid........................ 20 g. Preparation: Dissolve the citric acid in 700 ml
C6H8O7.H2O distilled water. Add the sodium hydroxide
Sodium hydroxide ...... 100 ml. solution (0.4M) and if necessary bring the
NaOH (0.4M) solution to pH 3.8 with hydrochloric acid
Hydrochloric acid ......... 25 ml. solution (1M) or sodium hydroxide
HCl (1M) solution (1M). Add the 25 ml hydrochloric
Distilled water acid (1M). Fill up to 1 liter with distilled
H2O water and mix.
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B2. Zinc sulfate solution (for free cyanide) (1 liter)
Required chemicals: Zinc sulfate ..................... 10 g. Preparation: Dissolve the zinc sulfate in 700 ml
ZnSO4.7H2O distilled water. Fill up to 1 liter with
Distilled water distilled water and mix.
H2O
Required chemicals: Sodium hydroxide ......... 2.3 g. Preparation: Dissolve the sodium hydroxide in 500 ml
NaOH distilled water. Add the potassium
Potassium hydrogen hydrogen phthalate and dilute to
phthalate .................... 20.5 g. approximately 975 ml with distilled water.
C8H5KO4 If necessary bring the solution to pH 5.2
Distilled water with hydrochloric acid solution (1M) or
H2O sodium hydroxide solution (1M). Fill up to
Brij 35 (30%)................... 1 ml. 1 liter with distilled water, add the Brij 35
and mix.
Required chemicals: Sodium hydroxide ......... 7.0 g. Preparation: Dissolve the sodium hydroxide in 500 ml
NaOH distilled water. Add the 1,3-dimethyl
1,3-Dimethyl barbituric acid and the 4-pyridine-
barbituric acid ............. 16.8 g. carboxylic acid and dilute with distilled
C6H8O3N2 water to approximately 975 ml. If
4-Pyridinecarboxylic necessary bring the solution to pH 5.2
acid ............................. 13.6 g. with hydrochloric acid solution (1M) or
C6H5NO2 sodium hydroxide solution (1M). Fill up to
Distilled water 1 liter with distilled water. Mix the
H2O solution intensively (e.g. by using a
magnetic stirrer) for 1 hour at 30C and
then filter over a pleated filter.
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F. Sodium hydroxide solution (0.1M) (1 liter)
Required chemicals: Sodium hydroxide ............ 4 g. Preparation: Dissolve the sodium hydroxide in 800
NaOH ml distilled water. Fill up to 1 liter with
Distilled water distilled water and mix.
H2O
Note: Refresh weekly.
Required chemicals: Sodium hydroxide ..... 400 mg. Preparation: Dissolve the sodium hydroxide in 800
NaOH ml distilled water. Fill up to 1 liter with
Distilled water distilled water and mix.
H2O
Note: Refresh weekly.
Required chemicals: Sodium hydroxide .......... 40 g. Preparation: Dissolve the sodium hydroxide in 800
NaOH ml distilled water. Fill up to 1 liter with
Distilled water distilled water and mix.
H2O
Note: Refresh weekly.
STANDARDS
Required chemicals: Potassium cyanide . 250.3 mg. Preparation: Dissolve the sodium hydroxide in 800
KCN ml distilled water. Add the potassium
Sodium hydroxide ..... 400 mg. cyanide and mix. Fill up to 1 liter with
NaOH distilled water and mix.
Distilled water
H2O Note: Solution is stable for 1 month. Store at
4C when the solution is not used.
Dilute 10 ml stock solution 100 mg CN/liter to 100 ml with 0.01M sodium hydroxide solution.
100 g CN/liter: Dilute 1.0 ml stock solution 10 mg CN/liter to 100 ml with 0.01M sodium hydroxide sol.
80 g CN/liter: Dilute 0.8 ml stock solution 10 mg CN/liter to 100 ml with 0.01M sodium hydroxide sol.
60 g CN/liter: Dilute 0.6 ml stock solution 10 mg CN/liter to 100 ml with 0.01M sodium hydroxide sol.
40 g CN/liter: Dilute 0.4 ml stock solution 10 mg CN/liter to 100 ml with 0.01M sodium hydroxide sol.
20 g CN/liter: Dilute 0.2 ml stock solution 10 mg CN/liter to 100 ml with 0.01M sodium hydroxide sol.
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Working standards (soil extract)
100 g CN/liter: Dilute 1.0 ml stock solution 10 mg CN/liter to 100 ml with 0.025 M sodium hydroxide sol.
80 g CN/liter: Dilute 0.8 ml stock solution 10 mg CN/liter to 100 ml with 0.025 M sodium hydroxide sol.
60 g CN/liter: Dilute 0.6 ml stock solution 10 mg CN/liter to 100 ml with 0.025 M sodium hydroxide sol.
40 g CN/liter: Dilute 0.4 ml stock solution 10 mg CN/liter to 100 ml with 0.025 M sodium hydroxide sol.
20 g CN/liter: Dilute 0.2 ml stock solution 10 mg CN/liter to 100 ml with 0.025 M sodium hydroxide sol.
Note:
1. Prepare the working standards fresh daily.
2. The water used for the reagents and standards must be degassed properly before making up the
reagents and standards. Especially water produced by reverse osmosis or ion exchange equipment
contains a lot of air, which must be removed by degassing (degassing procedure see operational
remarks and trouble shooting).
START UP PROCEDURE
1. All reagent lines are put on distilled water (rinse the system for 10 minutes according daily procedure).
2. Turn off the power of the heaters and rinse for 30 minutes.
3. Turn off the power of the UV lamp.
4. Turn off the power of the vacuum pump
5. Turn off the power of the pump on the module holder.
6. Open the pump deck.
Procedure
To check if the cyanide system is suitable for measurement the recovery rates of potassium
hexacyanoferrate(III) and potassium thiocyanate are measured from fresh standards. For this procedure
the ISO14403 norm is followed. The results are compared to the potassium cyanide result from the
calibration curve (highest standard).
First the system is calibrated with potassium cyanide standards, immediately hereafter the recovery
standards are analysed as samples (in duplo).
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Recoverys rates
The recovery rates are calculated from the measured result of the highest potassium cyanide standard from
calibration curve (1) and the measured results of potassium hexacyanoferrate (2), and potassium
thiocyanate (3).
Prepare a K3[Fe(CN)6] standard with the same cyanide concentration as the highest cyanide standard.
Make up with 0.01 M NaOH and store in a dark coloured bottle in a dark place.
Prepare a KSCN standard with the cyanide concentration 10 times higher as the highest cyanide standard
(6).
Make up with 0.01 M NaOH and store in a dark coloured bottle in a dark place.
Note: All standards are light sensitive and will yield free CN as soon as the solutions are in contact with
light. Always prepare fresh and analyse them within 1 hour and protect from light.
Do not store the solid chemicals longer as 1 year and buy small amounts.
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Potassium hexacyanoferrate(III) Merck 104973
Potassium thiocyanate Merck 105125 harmful
Sodium hypochlorite solution (13% active chlorine) Acros 21925 corrosive
Ethanol (abs.) Merck 100986 highly flammable
Chromosulfuric acid for cleaning glass vessels LAB Merck 102499 carcinogenic, oxidizing,
corrosive, sensitizing,
dangerous for the
environment
GENERAL REMARKS
1. In most analyses, the first peak coming from the baseline is lower than it should be. The first peak
coming from the baseline is rejected and will not be included in the calculation of the CV-value.
2. If the sample take up volume is less than 1.00 ml/min, a bypass is required to increase the sample
stream to approximately 1.00 ml/min. For SA 5210 debubbler, when the sample is 1.00 ml/min and
higher use 0.23 ml/min debubble tube.
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MAINTENANCE
1. Daily; when daily analysis is finished rinse all reagent lines with distilled water for 30 minutes.
2. Weekly; to decontaminate the system, rinse 30 minutes with 0.5M sodium hydroxide solution and
another 30 minutes with distilled water.
3. Monthly; replace all pump tubing (or shift pump tube one colour bridge on pump).
UV DIGESTER MAINTENANCE
To obtain the best possible results and to maintain a good recovery level of the UV digester the following
weekly cleaning procedure must be followed for cleaning the digester coil.
Syringe of 25 ml
10% chromic acid solution**
** If due to waste disposal regulations it is not allowed to use chromic acid please use the alternative
cleaning method mentioned below.
1. The chemical module must first be rinsed with clean water by pumping clean water through all reagent
lines for at least 20 minutes.
2. Stop the peristaltic pump and keep the pump deck on peristaltic pump closed.
3. Switch off all reactors.
4. Disconnect (pull off) the silicon air injection tube at manifold (5216, 5245 or other) which is connected
to the digester coil .Put directly a piece of disposal paper on the needle to absorb any out coming
liquid.
5. Connect the syringe at the manifold position where silicon tube was removed.
6. Flush 20 ml of 10% chromic acid through the digester coil via manifold, and wait for 15 minutes.
7. Flush 50 ml of clean water via manifold and continue directly with next step.
8. Disconnect the syringe and connect the silicon air injection tube again.
9. Switch on peristaltic pump or switch off complete system and open pump decks.
Syringe of 25 ml
2M hydrochloric acid solution (HCl)
2M sodium hydroxide solution (NaOH)
Ethanol (purity 96% or higher)
Clean water (distilled, reverse osmosis)
1. The chemical module must first be rinsed with clean water by pumping clean water through all reagent
lines for at least 20 minutes.
2. Stop the peristaltic pump and keep the pump deck on peristaltic pump closed.
3. Switch off all reactors.
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4. Disconnect (pull off) the silicon air injection tube at manifold (5216, 5245 or other) which is connected
to the digester coil. Put directly a piece of disposal paper on the needle to absorb any out coming
liquid.
5. Connect the syringe at the manifold position where silicon tube was removed.
6. Flush 20 ml of 2M hydrochloric acid solution through digester coil via manifold, and wait for 5
minutes.
7. Flush 20 ml of clean water via manifold and continue directly with next step.
8. Flush 20 ml of 2M sodium hydroxide solution through digester coil via manifold and wait for 5
minutes.
9. Flush 20 ml of clean water via manifold and continue directly with next step.
10. Flush 20 ml of ethanol through digester coil via manifold and wait for 5 minutes.
11. Flush 20 ml of clean water via manifold and continue directly with next step.
12. Disconnect the syringe and connect the silicon air injection tube again.
13. Switch on peristaltic pump or switch off complete system and open pump decks.
MODULE CONSUMABLES
MODULE COMPONENTS
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REFERENCES
1. Water quality - Determination of total cyanide and free cyanide by continuous flow analysis, ISO
14403:2002(E), First edition 2002-03-01.
2. ISO 3696:1987, Water for analytical laboratory use. Specification and test methods.
3. ASTM, D1193, Standard Specification for Reagent Water.
Sample preparation (water according to ISO 14403)
1. Water quality - Determination of total cyanide and free cyanide by continuous flow analysis, ISO
14403:2002(E), First edition 2002-03-01.
2. ISO 5667-3:2003, Water quality - Sampling - part 3: Guidance on the preservation and handling on
water samples.
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FLOW DIAGRAM
waste
ml/min
Flow cell 50 mm
Colour reagent 0.42 5246 Filter 600 nm
air built up
in glass
vacuum sleeved
## pump with
3142 9031 acidflex
condensor
5371
1.60
waste
5376
2.50 5142
waste
5142
5202 *
0.10 5246 5130 5304 cooling 5362
Sodium hydroxide solution (0.1M)
2.50
waste
5304 cooling
Air
5590 # 5521
Sample 1.00 5326 5214 5328
5216
** 5201
Distillation reagent 0.42 UV digestion 125C
Distilled water (B1)/ 1.00 5246
Zinc sulfate sol. (B2)
Sodium hydroxide 1.60 to all waste lines
solution (1M) in waste vessel cyanide
1.20
waste
Sampler
* distillation unit is situated at the back panel of the module support holder
**glass tubing 5359 (2.0mmI.D., 4.0mmO.D.)
#
air linlet via 50 cm 5133 tube with restrictor (3 cm 5142 tube)
## air restrictor 110 cm 3142 tube
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