SKALAR METHODS

ANALYSIS: TOTAL, FREE & WAD CYANIDE (Part 2)

RANGE: 1 ‐ 100 µg CN/liter /
(50 ‐ 5000 µg CN/liter)
SAMPLE: DRINKING, SURFACE & WASTE WATER
SAN++
Catnr. I296‐311X(+P7 & valve) issue 100113/MH/99283511

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 buffer solution is added to condition the
pH of the sample. The released and free cyanide (as HCN) present in the sample is separated by gas dialysis
into an alkaline recipient stream. The hydrogen cyanide gas diffuses through a hydrophobic membrane
from the acidic donor stream into the alkaline receptor stream. The captured cyanide is measured
amperometrically with a silver working electrode and silver/silver chloride reference electrode.

DEFINITION (free cyanide)

Free cyanide is the sum of HCN and CN‐ and cyanide bound in the metal‐cyanide complexes that are easily
dissociated into free cyanide under test conditions in this method at pH 6 and room temperature.

LABORATORY FACILITIES

1. Maximum power consumption depending on the analyzer 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.

PROCEDURE SAMPLE PREPARATION

According to customer

REAGENTS

A. Digestion reagent (1 liter)

Required chemicals: Sodium dihydrogen Preparation: Dissolve the sodium dihydrogen

phosphate ................... 24.2 g. phosphate in ± 800 ml distilled water. Add
NaH2PO4.H2O the di‐sodium hydrogen phosphate.
di‐Sodium hydrogen Adjust the pH to 6.0 ± 0.1 with 1M sodium
phosphate ..................... 3.5 g. hydroxide solution or 1M hydrochloric
Na2HPO4 acid solution. Fill up to 1 liter with distilled
Distilled water water.
H2O
Note: Solution is stable for 1 week.

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B. Donator reagent (1 liter)

Required chemicals: Sodium dihydrogen Preparation: Dissolve the sodium dihydrogen

phosphate ................... 24.2 g. phosphate in ± 800 ml distilled water. Add
NaH2PO4.H2O the di‐Sodium hydrogen phosphate.
di‐Sodium hydrogen Adjust the pH to 6.0 ± 0.1 with 1M sodium
phosphate ..................... 3.5 g. hydroxide solution or 1M hydrochloric
Na2HPO4 acid solution. Fill up to 1 liter with distilled
Distilled water water, add the Brij and mix
H2O
Brij 35 (30%)............... 5 drops Note: Solution is stable for 1 week.

C. Acceptor solution (1 liter)

Required chemicals: Sodium hydroxide ............ 8 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

D. 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: Solution is stable for 1 week.

E. Rinsing liquid sampler (0.01M) (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

P7. Sodium hydroxide solution (0.01M) (required for predilution step P7) (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

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STANDARDS

Stock solution 100 mg CN/liter (1 liter)

Required chemicals: Potassium Preparation: Dissolve the sodium hydroxide in ± 800

cyanide ................... 250.3 mg. ml distilled water. Add the potassium
KCN cyanide and mix. Fill up to 1 liter with
Sodium hydroxide ..... 400 mg. distilled water and mix.
NaOH
Distilled water Note: Solution is stable for 1 month when
H2O stored in an amber glass bottle at 4C.

Working standards (require predilution step P7)

5000 µg CN/liter: Dilute 5.0 ml stock solution 100 mg CN/liter to 100 ml with rinsing liquid sampler.
2000 µg CN/liter: Dilute 2.0 ml stock solution 100 mg CN/liter to 100 ml with rinsing liquid sampler.
1000 µg CN/liter: Dilute 1.0 ml stock solution 100 mg CN/liter to 100 ml with rinsing liquid sampler.
500 µg CN/liter: Dilute 0.5 ml stock solution 100 mg CN/liter to 100 ml with rinsing liquid sampler.
200 µg CN/liter: Dilute 0.2 ml stock solution 100 mg CN/liter to 100 ml with rinsing liquid sampler.
100 µg CN/liter: Dilute 0.1 ml stock solution 100 mg CN/liter to 100 ml with rinsing liquid sampler.
50 µg CN/liter: Dilute 1.0 ml stock solution 5000 µg CN/liter to 100 ml with rinsing liquid sampler.

Stock standard 10 mg CN/liter

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

Working standards

100 µg CN/liter: Dilute 1.0 ml stock solution 10 mg CN/liter to 100 ml with rinsing liquid sampler.
80 µg CN/liter: Dilute 0.8 ml stock solution 10 mg CN/liter to 100 ml with rinsing liquid sampler.
60 µg CN/liter: Dilute 0.6 ml stock solution 10 mg CN/liter to 100 ml with rinsing liquid sampler.
40 µg CN/liter: Dilute 0.4 ml stock solution 10 mg CN/liter to 100 ml with rinsing liquid sampler.
20 µg CN/liter: Dilute 0.2 ml stock solution 10 mg CN/liter to 100 ml with rinsing liquid sampler.
10 µg CN/liter: Dilute 0.1 ml stock solution 10 mg CN/liter to 100 ml with rinsing liquid sampler.
5 µg CN/liter: Dilute 1.0 ml stock solution 500 µg CN/liter to 100 ml with rinsing liquid sampler.

Notes:
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).

CATALOGUE NUMBERS REQUIRED CHEMICALS

Product Supplier and catnr. Danger classification

Sodium dihydrogen phosphate monohydrate Merck 106346

di‐Sodium hydrogen phosphate Merck 106585
Sodium hydroxide Merck 106498 corrosive
Hydrochloric acid (32%) Merck 100313 corrosive
Potassium cyanide Merck 104967 very toxic, dangerous for the
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 environment
Potassium chloride Merck 104936
Ethanol (abs.) Merck 100983 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: 120 sec., wash time: 120 sec., air: 3 sec.
2. Module sample time (range 1‐100 µg CN/liter): 90 sec., wash time: 90 sec., air: 3 sec.
3. Module sample time (range 50‐5000 µg CN/liter): 120 sec., wash time: 120 sec., air: 3 sec.
4. Calibration type: 1st order ISO 8466‐1. (range 1‐100 µg CN/liter)
5. Calibration type: 2nd order ISO 8466‐2. (range 50‐5000 µg CN/liter)
6. Amperometric detector range: 200 nA. Filter: 0.08Hz
7. To analyze free & WAD cyanide, turn off the power of the UV lamp.

OPERATIONAL REMARKS AND TROUBLE SHOOTING

1. The stabilizing time of the system is approximately 120 minutes with a new electrode and 30 minutes
after 1 day use of electrode. 1 electrode can be used for 1 week. Store electrodes in KCl (3M) while not
in use.
2. The sensitivity of the highest standard 100 µg CN/liter is ± 0.350 AU.
3. The sensitivity of the highest standard 5000 µg CN/liter is ± 1.400 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 5175 tube.
6. Avoid any turbidity in the reagents, filter if necessary.
7. Detergent causes problems in the UV digestion coils. See UV digester maintenance.
8. 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.
9. If solvents or high concentrated acids (> 2M) must be controlled by a rinsing valve, use the solvent/acid
resistant type.
10. 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 or, degas the water by boiling the water for 10 minutes. Cool down
to room temperature before usage. These procedures remove all dissolved air.
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 m/min, a bypass is required to increase the sample
stream to approximately 1.00 ml/min. For 5210 debubbler, when the sample is 1.00 ml/min and higher
use 0.23 ml/min debubble tube.

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START UP AND SHUTDOWN PROCEDURE

Start up

1. Close the pump decks.

2. Make sure that the Cell Mode setting on the BASi detector is in Standby mode (STDBY).
3. Start the chemistry unit with reagents.
4. When the all the lines are filled and the system is running stable turn on the offset box and set the cell
mode setting on the BASi detector in cell mode.
5. Check the next settings by changing display to:
a. APP EV = 0.00
b. offset nA = 10.00
c. check setting filter (Hz) = 0.08
6. When everything is set then change
d. display = Output nA
e. range nA = 200
f. cell mode = Cell
7. Everything is now set for starting the analysis when the baseline is stable.

Shut down

1. When the analysis is finished you must change the cell mode setting on the BASi detector to standby
(STDBY).
2. Turn off the power of the offset box and the BASi detector.
3. Rinse the system for 30 minutes with distilled water.
4. Turn off the chemistry unit and fill the electrodes with potassium chloride (KCl 3M) via the syringe.
5. Open the pump decks.

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 color‐bridge on pump).

ELECTRODE MAINTENANCE

1. The Ag/AgCl reference electrode must be stored daily in 3M potassium chloride solution when not
used.
2. Never store electrode dry.
3. Each electrode is used 1 week and then stored at least 1 week in 3M potassium chloride solution. This
maximizes the lifetime of the electrode.
4. Each week a fresh electrode is taken for the 3M potassium chloride solution storage.
5. Stabilization time (run baseline with reagents) of the instrument in daily routine is 30 minutes if
electrode is already used for 1 day and 120 minutes with a fresh electrode.

More detailed electrode instructions can be found in the BASI A‐1302 manual.

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UV DIGESTER MAINTENANCE

To obtain the best possible results and to maintain a good recovery level of the UV digester the following
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 cartridge 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, 9245 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 cartridge 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, 9245 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.

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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

polyethylene tube catnr. 5141 sleeves catnr. 5406

polyethylene tube catnr. 5142 acid flex sleeves catnr. 5415
acid flex tube catnr. 5180 membrane catnr. 25201302
acid flex tube catnr. 5184 pump tube 0.16 ml/min. catnr. 3025
Teflon tube catnr. 90041448 pump tube 0.42 ml/min. catnr. 3028
glass tube catnr. 5359 pump tube 0.60 ml/min. catnr. 3029
sleeves catnr. 5400 pump tube 1.40 ml/min. catnr. 3033
sleeves catnr. 5401 pump tube 1.60 ml/min. catnr. 3034

MODULE COMPONENTS

manifold holder catnr. 25200105 frame UV dig. catnr. 25550005

module catnr. 5108 lamp holder catnr. 25550006
end block catnr. 5109 housing catnr. 25550007
inlet connector catnr. 5202 2x cover catnr. 25550008
inlet connector catnr. 5247 borosilicate coil catnr. 5561
inlet connector catnr. 5216 debubbler catnr. 5207
inlet connector catnr. 5246 glass coil catnr. 5325 2x
glass coil catnr. 5326 dialyzer catnr. 5274
connector catnr. 5214 debubbler catnr. 5217
glass coil catnr. 5325 connector catnr. 5204
glass coil catnr. 5328 clamps small catnr. 5111 6x
lamp for UV dig. catnr. 5556 sinkers catnr. 5380
power supply catnr. 5549 valve catnr. 5290
reactor catnr. 25500953

MODULE COMPONENTS (predilution step P7)

inlet connector catnr. 5216 clamps small catnr. 5111

glass coil catnr. 5326 sinkers catnr. 5380
debubbler catnr. 5204 pump tube 0.16 ml/min. catnr. 3025
valve catnr. 5290 pump tube 2.50 ml/min. catnr. 3036
splitter catnr. 5260 pump tube 0.80 ml/min. catnr. 3030

REFERENCES

Chemical method (no. 296)

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.

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4. ASTM, D7237‐10, Free Cyanide test method for Free Cyanide Utilizing Gas Diffusion Separation.
5. ASTM D6888 Test Method for available cyanide with ligand replacement.
6. ASTM D2036 Test method for cyanides in water.

FLOW DIAGRAM
free cyanide ml/min
range 1-100 µg CN/liter 3M potassium
chloride solution
0.42 waste X
free waste free waste
5325
***
amperometric detector
** 5217
** silver working electrode
5290 Ag/AgCl reference electrode

**
Acceptor solution 1.60 5247
5274
*
5325
Resample 5207 1.20 5202
waste
Donator reagent 0.42
waste
****
Air 25500953 5590
****
5326 5214 5328
1.00 5216

Digestion reagent 0.42 ambient UV digestion

(turned off)
Digestion reagent 0.23 5246

Sodium hydroxide 1.60 to all waste lines

solution (1M) in waste vessel cyanide

* Teflon membrane catnr. 25201302

** Teflon tube 90041448
5204
waste *** polyethylene tube 5142
Air **** glass tube 5359
2.50 5216 5326
Sodium hydroxide (0.01M)
5260

Sample 0.16 Predilution P7

5290 built up in glass
0.80 waste

Sampler

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 FLOW DIAGRAM
free cyanide ml/min
range 50-5000 µg CN/liter 3M potassium
chloride solution
0.42 waste X
free waste free waste
5325
***
amperometric detector
** 5217
** silver working electrode
5290 Ag/AgCl reference electrode

**
Acceptor solution 1.60 5247 5274
*
5325
Resample 5207 1.20 5202
waste
Donator reagent 0.42
waste
****
Air 25500953 5590
****
5326 5214 5328
1.00 5216

Digestion reagent 0.42 ambient UV digestion

(turned off)
Digestion reagent 0.23 5246

Sodium hydroxide 1.60 to all waste lines

solution (1M) in waste vessel cyanide

* Teflon membrane catnr. 25201302

** Teflon tube 90041448
5204
waste *** polyethylene tube 5142
Air **** glass tube 5359
2.50 5216 5326
Sodium hydroxide (0.01M)
5260

Sample 0.16 Predilution P7

5290 built up in glass
0.80 waste

Sampler

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