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SKALAR METHODS

ANALYSIS: TOTAL & FREE CYANIDE


RANGE: 1 - 100 g CN/liter
SAMPLE: DRINKING, SURFACE & WASTE WATER /
SOIL EXTRACT
SAN++
Catnr. I295-004w/r issue 121412/MH/99276285

TERMS AND DEFINITIONS

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.

PRINCIPLE (total cyanide)

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)

PRINCIPLE (free cyanide)

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

2.5M sodium hydroxide solution 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

A. Distillation reagent (1 liter)

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.

Note: This solution can be kept for 3 months in a


refrigerator (2 to 5C). Due to the addition
of the hydrochloric acid the pH of this
buffer solution is about 3.4. After mixing
with the sample a pH of 3.8 is achieved.

B1. Distilled water (for total cyanide)

Required chemicals: Distilled water Note: Refresh weekly.


H2O

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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

C. Buffer solution pH 5.2 (1 liter)

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.

Note: This solution can be kept for 3 months


provided it is stored in the dark and
refrigerated (2 to 5C).

D. Chloramine-T solution (1 liter)

Required chemicals: Chloramine-T................. 2.0 g. Preparation: Dissolve the chloramine-T in 800 ml


C7H7ClNNaO2S.3H2O distilled water. Fill up to 1 liter with
Distilled water distilled water and mix.
H2O
Note: This solution can be stored for 3 months
provided it is stored in the dark and
refrigerated (2 to 5C).

E. Colour reagent (1 liter)

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.

Note: This solution can be kept for 3 months


provided it is stored in the dark and
refrigerated (2 to 5C).

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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.

G. Rinsing liquid sampler (1 liter)

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.

H. Sodium hydroxide solution (1M) (1 liter)

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

Stock solution 100 mg CN/liter (1 liter)

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.

Stock solution 10 mg CN/liter

Dilute 10 ml stock solution 100 mg CN/liter to 100 ml with 0.01M sodium hydroxide solution.

Note: Prepare the stock solution 10 mg CN/liter fresh weekly.

Working standards (water)

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. Prepare all reagents and standards.


2. Check if the pump deck requires grease (catnr. SA 2010).
3. Close the pump deck.
4. Put all the reagent lines in the appropriate reagent canisters.
5. Turn on the power of the vacuum pump.
6. Turn on the cooling water.
7. Turn on the power of the UV lamp (for total cyanide only).
8. Turn on the power of the heater (reactor/water bath).
9. Turn on the power of the pump on the module holder to start pumping reagents.
10. Let the system stabilize for 30-40 minutes.

SHUT DOWN 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.

UV DIGESTER RECOVERY CHECK

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).

Recovery rates to be achieved

Total Cyanide Recovery rate Calculation


(2) K3[Fe(CN)6] 90% (2) / (1) * 100 (%)
(3) KSCN < 1% (3) / (6) * 100 (%)

Free Cyanide Recovery rate Calculation


(4) K3[Fe(CN)6] < 5% (4) / (1) * 100 (%)
(5) KSCN < 1% (5) / (6) * 100 (%)

Recovery Stock standards

100 mg CN/liter from K3[Fe(CN)6]


210.9 mg/l: make up in 0.01M NaOH solution, store in dark coloured bottle and in a dark place.

100mg CN/liter from KSCN


373.5 mg/l: make up in 0.01M NaOH solution, store in dark coloured bottle and in a dark place.

Recovery working standards

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.

CATALOGUE NUMBERS REQUIRED CHEMICALS

Product Supplier and catnr. Danger classification

Citric acid monohydrate Merck 100244 irritant


Sodium hydroxide Merck 106498 corrosive
Hydrochloric acid (32%) Merck 100313 corrosive
Zinc sulfate heptahydrate Merck 108883 irritant, dangerous for
environment
Potassium hydrogen phthalate Merck 104874
Brij 35 (30%) Skalar 13900
Chloramine-T trihydrate Merck 102426 harmful, corrosive,
sensitising
1,3-dimethyl barbituric acid Fluka 39565
4-Pyridinecarboxylic acid Merck 800736 irritant
Potassium cyanide Merck 104967 very toxic, dangerous for the
environment

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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

RECOMMENDED OPERATIONAL SETTINGS

1. System sample time: 80 sec., wash time: 80 sec., air: 0 sec.


2. Module sample time: 80 sec., wash time: 80 sec., air: 0 sec.
3. Calibration type: 1st order ISO 8466-1.

OPERATIONAL REMARKS AND TROUBLE SHOOTING

1. The stabilising time of the system is approximately 30 minutes.


2. The sensitivity of the highest standard 100 g CN/liter (total cyanide) is 0.350 AU.
3. The sensitivity of the highest standard 100 g CN/liter (free cyanide) is 0.360 AU.
4. Persons using this Skalar method should be familiar with normal laboratory practice. This Skalar
method does not purport to address all of the safety problems, if any, associated with its use. It is the
responsibility of the user to establish appropriate safety and health practices and to ensure compliance
with any national regulatory conditions.
5. The connection between the sampler and the sample pump tube is made of 5141 tube.
6. If a digital matrix photometer 28505901, is in use, a correction interference filter of 650 nm 10 nm is
advised.
7. Avoid any turbidity in the reagents, filter if necessary.
8. Detergent causes problems in the UV digestion coils. See UV digester maintenance.
9. If reaction coils with water heating are used, the water bath has to be cooled with tap water when the
environment temperature is above 25C.
10. The reagent bottles must be rinsed thoroughly with distilled water before refilling with fresh reagents.
This is done to remove precipitation of micro organism and interferences.
11. If solvents or high concentrated acids (> 2M) must be controlled by a rinsing valve, use the solvent/acid
resistant type.
12. Degassing procedures;
a) Good: degas the water with a helium gas flow of approximately 20 liter/hour with aid of a sparger.
Degas 5 liter water for 15 minutes. This procedure removes all dissolved air or, degas the water by
boiling the water for 10 minutes. Cool down to room temperature before usage.
b) Medium: degas the water with a nitrogen gas flow of approximately 20 liter/hour with aid of sparger.
Degas 5 liter water for 15 minutes. This procedure will remove most of the dissolved air.
c) Bad: degas the water by ultrasonic waves. This procedure will remove a small part of the dissolved air.

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.

Required reagents and hardware

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.

Cleaning procedure UV digester

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.

Alternative cleaning method

Required reagents and hardware

Syringe of 25 ml
2M hydrochloric acid solution (HCl)
2M sodium hydroxide solution (NaOH)
Ethanol (purity 96% or higher)
Clean water (distilled, reverse osmosis)

Cleaning procedure UV digester

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

silicon tube catnr. 3150 sleeves catnr. 5401


polyethylene tube catnr. 3142 sleeves catnr. 5406
polyethylene tube catnr. 5141 acid flex sleeves catnr. 5414
polyethylene tube catnr. 5142 acid flex sleeves catnr. 2CA14321
glass tube catnr. 5359 pump tube 1.20 ml/min. catnr. 3032
pvc tube catnr. 5155 pump tube 1.00 ml/min. catnr. 3031
silicon tube catnr: 5150 pump tube 0.42 ml/min. catnr. 3028
tygon tube catnr. 5130 pump tube 2.50 ml/min. catnr. 3036
tygon tube catnr. 5133 pump tube 0.10 ml/min. catnr. 3024
sleeves catnr. 5400 pump tube 1.60 ml/min. catnr. 3034

MODULE COMPONENTS

manifold holder catnr. 25200105 connector catnr. 5201


module catnr. 5107 distillation unit catnr. 5362
module catnr. 5115 heat exchanger catnr. 5304 2x
end block catnr. 5109 reactor catnr. 5521 2x
inlet connector catnr. 5216 connector catnr. 5202
inlet connector catnr. 9245 air/liquid separator catnr. 5376
inlet connector catnr. 5246 4x glass condenser catnr. 5371
glass coil catnr. 5326 vacuum pump catnr. 9031
lamp for UV dig. catnr. 5556 connector catnr. 9220 2x
power supply catnr. 5549 glass coil catnr. 5325
frame UV dig. catnr. 25550005 clamps large catnr. 5110 2x
lampholder catnr. 25550006 clamps small catnr. 5111 4x
housing catnr. 25550007 clamps 12 mm catnr. 90035653
cover catnr. 25550008 clamps 50 mm catnr. 5113
borosilicate coil catnr. 5561 sinkers catnr. 5380
connector catnr. 5214 flow cell 50 mm catnr. 6425
glass coil catnr. 5328 filter 600 nm catnr. 6553

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REFERENCES

Chemical method (no. I295)

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

Chloramine-T solution 0.42 5246


Air
5325 5521/5300
Buffer solution 0.42 9245
9220 9220
Resample 0.42 37C

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

Revision: Rev 2 Rev 3 Rev 4 Rev. 5 Method:


Date: 06-10-2004 18-11-2004 29-08-2007 21-11-2012 Analysis: Total & Free Cyanide
Chemists A.V. J.H. M.P. J.H. Range: 1-100 g CN/liter
Authorisation C.B. C.B. A.v.D. P.D. Sample: Water
First issued: 07-09-2004

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