SKALAR METHODS
ANALYSIS: AMMONIA
RANGE: 1 - 500 µg N/liter
SAMPLE: DRINKING, SURFACE, FRESH,
WASTE & SEA WATER
SAN++
Catnr. 156-002w/r issue 011912/MH/99270483
PRINCIPLE
The automated procedure for the determination of Ammonia is based on the modified Berthelot reaction;
ammonia is chlorinated to monochloramine which reacts with phenol. After oxidation and oxidative
coupling a green coloured complex is formed. The reaction is catalysed by nitroprusside, sodium
hypochlorite is used for chlorine donation. The absorption of the formed complex is measured at 630 nm.
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.
PROCEDURE SAMPLE PREPARATION
Water no. 1.1.3
Field of application
Sample preparation for the determination of total alkalinity, aluminium, amino acids, ammonia, anionic
surfactants (MBAS), bromide, calcium, C.O.D., chromium, conductivity, D.O.C., ethanol, hardness,
magnesium, manganese, methanol, nitrate + nitrite, nitrite, nonionics, ortho-phosphate, potassium
permanganate, potassium, total-N (UV digestion), protein, silicate, sodium, volatile acids and urea in water.
Principle
The sample is not preserved and analysed as soon as possible, at least within 24 hours after collection.
Store the sample at 4°C till analysis.
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.
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REAGENTS
A. Buffer solution
Required chemicals: Titriplex III ...................... 50 g. Preparation: Dissolve the Titriplex III in ± 800 ml
C10H14N2Na2O8.2H2O distilled water. Add and dissolve the
Sodium hydroxide ......... 1.2 g. sodium hydroxide. Fill up to 1 liter with
NaOH distilled water, add the Brij 35 and mix.
Distilled water * ....... 1000 ml.
H2O Note: Solution is stable for 1 week. Store at 4°C
Brij 35 (30%)................... 1 ml. when the solution is not used.
B. Phenol solution
Required chemicals: Phenol ............................ 83 g. Preparation: Dissolve the phenol in ± 80 ml distilled
C6H5OH water. Add the sodium hydroxide. Fill up
Sodium hydroxide .......... 40 g. to 1 liter with distilled water and mix.
NaOH
Distilled water * ....... 1000 ml. Note: Solution is stable for 1 week. Store in a
H2O dark coloured bottle.
C. Sodium hypochlorite solution
Required chemicals: Sodium Preparation: Dilute the sodium hypochlorite (13%
hypochlorite............... 200 ml. active chlorine) in ± 700 ml distilled water.
NaClO Fill up to 1 liter with distilled water and
Distilled water * ......... 800 ml. mix.
H2O
Note: When using a different concentrated
sodium hypochlorite solution as 13%,
adjust the amount of added sodium
hypochlorite.
The end concentration of active chlorine
in the chemical cartridge must be 0.3%.
Higher or lower amounts of active
chlorine results in lower sensitivity and
poor linearity. Solution is stable for 1
week.
D. Sodium nitroprusside solution
Required chemicals: Sodium nitroprusside .... 0.5 g. Preparation: Dissolve the sodium nitroprusside in
Na2[Fe(CN)5NO].2H2O ± 800 ml distilled water. Fill up to 1 liter
Distilled water * ....... 1000 ml. with distilled water and mix.
H2O
Note: Store in a dark coloured bottle. Solution is
stable for 1 week. Store at 4°C when the
solution is not used.
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E. Air scrubber solution (2.5M sulfuric acid solution)
Required chemicals: Sulfuric acid ................ 139 ml. Preparation: Dilute carefully the sulfuric acid in
H2SO4 (95-97%) ± 800 ml distilled water. Fill up to 1 liter
Distilled water............ 861 ml. with distilled water and mix.
H2O
F. Rinsing liquid sampler
Required chemicals: Distilled water * Note: Refresh weekly.
H2O
STANDARDS
Stock solution 100 mg N/liter
Required chemicals: Ammonium Preparation: Dissolve the ammonium chloride in ± 800
chloride ................ 381.90 mg. ml distilled water. Fill up to 1 liter with
NH4Cl distilled water and mix.
Distilled water * ....... 1000 ml.
H2O Note: Solution is stable for 1 month. Store at
4°C when the solution is not used.
Stock solution 10 mg N/liter
Dilute 10 ml stock solution 100 mg N/liter to 100 ml with distilled water.*
Note: Prepare the stock solution 10 mg N/liter fresh daily.
Working standards
500 µg N/liter: Dilute 5 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
400 µg N/liter: Dilute 4 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
300 µg N/liter: Dilute 3 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
200 µg N/liter: Dilute 2 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
100 µg N/liter: Dilute 1 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
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 gasses, which must be removed by degassing (degassing procedure see operational
remarks and trouble shooting).
CATALOGUE NUMBERS REQUIRED CHEMICALS
Product Supplier and catnr. Danger classification
Titriplex® III Merck 108421
Sulfuric acid (95-97%) Merck 100731 corrosive
Brij 35 (30%) Skalar SC 13900
Phenol Merck 100206 toxic, corrosive
catnr. 156-002w/r 3 of 6
Sodium hydroxide Merck 106498 corrosive
Sodium hypochlorite solution (13% active chlorine) Acros 21925 corrosive
Sodium nitroprusside dihydrate Merck 106541 toxic
Ammonium chloride Merck 101145 harmful, irritant
RECOMMENDED OPERATIONAL SETTINGS
1. System sample time: 100 sec., wash time: 100 sec., air time: 0 sec.
2. Module sample time: 30 sec., wash time: 30 sec., air time: 0 sec.
3. Calibration type: 1st order ISO 8466-1.
OPERATIONAL REMARKS AND TROUBLE SHOOTING
1. The stabilising time of the system is approximately 20 minutes.
2. The sensitivity of the highest standard 500 µg N/liter is ± 1.100 AU.
3. 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.
4. The connection between the sampler and the sample pump tube is made of SA 5141 tube. When using
a sampler with diluter use SA 5142 tube.
5. If a digital matrix photometer 28505911, is in use, a correction interference filter of 1010 nm ± 10 nm is
advised.
6. If reaction coils with water heating are used, the water bath has to be cooled with tap water when the
environment temperature is above 25°C.
7. 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 other interferences.
8. If solvents or high concentrated acids (> 2M) must be controlled by a rinsing valve, use the solvent/acid
resistant type.
9. Degassing procedures;
10. Cover standards and samples with parafilm to prevent ammonia contamination in the standards and
samples.
11. This analysis is very sensitive for ammonia contamination from the environment. Use clean and closed
bottles and cleaned sample cups.
12. Avoid any turbidity in the reagents, filter if necessary.
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 gasses.
c) Bad: degas the water by ultrasonic waves. This procedure will remove a small part of the dissolved
gasses.
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 with 1% hypochlorite solution for 30 minutes and with
distilled water for another 30 minutes.
3. Monthly; Replace all pump tubing (or shift pump tube one colour bridge on pump).
MODULE CONSUMABLES
silicone tube catnr. SA 3150 sleeves catnr. SA 5406
polyethylene tube catnr. SA 3142 acid flex sleeves catnr. SA 5415
polyethylene tube catnr. SA 5141 pump tube 1.40 ml/min. catnr. SA 3032
polyethylene tube catnr. SA 5142 pump tube 0.23 ml/min. catnr. SA 3026
sleeves catnr. SA 5400 pump tube 1.00 ml/min. catnr. SA 3031
sleeves catnr. SA 5401 pump tube 0.32 ml/min. catnr. SA 3027
MODULE COMPONENTS (for cartridge with electrical heating)
manifold holder catnr. 25200105 reactor catnr. SA 5521
module catnr. SA 5107 clamps small catnr. SA 5111 6x
end block catnr. SA 5109 sinkers catnr. SA 5380
inlet connector catnr. SA 5216 flow cell 50 mm catnr. SA 6275
inlet connector catnr. SA 5246 3x filter 630 nm catnr. SA 6559
glass coil catnr. SA 5326 2x filter 1010 nm catnr. SA 6635
connector catnr. SA 5220 3x air wash bottle catnr. SA 5781
glass coil catnr. SA 5328
REFERENCES
Chemical method (no. 156)
1. Krom, M.,"Spectrophotometric determination of ammonia; a study of modified Berthelot reaction using
salicylate and dichloroisocyanurate", The Analyst, April 1980, Vol. 105, page 305-316.
2. Searle, P.L.,"The Berthelot or indophenol reaction and its use in the analysis chemistry of nitrogen", The
Analyst, Vol. 109, May 1984, page 549-565.
3. ISO 3696:1987, Water for analytical laboratory use. Specification and test methods
4. ASTM, D1193, Standard Specification for Reagent Water.
Sample preparation (water no. 1.1.3)
1. Environmental Protection Agency, methods for chemical analysis of water and wastes, 1983.
2. Standard Methods for the determination of water and waste water, 17th edition, 1989.
3. ASTM, 1990.
4. International Organisation for Standardisation, ISO-5667-3.
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FLOW DIAGRAM
waste
ml/min
Flow cell 50 mm
5521/5300 Filter 630 nm
Cor. Filter 1010 nm
60°C
air
air scrubber
2.5Msulfuric acid
solution
Sodium nitroprusside solution 0.32 5246
5220
Sodium hypochlorite solution 0.23 5246
Phenol solution 0.32 5246
Air *
5326 5326 5328
Sample 1.00 5216
5220 5220
Buffer solution 0.23
1.40
waste
Sampler
* via air wash bottle (containing 2.5Msulfuric acid solution)
Revision: Rev 1 Rev 2 Rev 3 Method:
Date: Analysis: Ammonia
Chemists Range: 1-500 µg N/liter
Authorization Sample: (Sea)water
First issued: 29-07-2010
catnr. 156-002w/r 6 of 6
