SKALAR METHODS

ANALYSIS: SILICATE
RANGE: 1 - 250 µg Si/liter
SAMPLE: DRINKING, SURFACE, FRESH,
WASTE & SEA WATER
SAN++
Catnr. 563-051 issue 011912/MH/99270483

PRINCIPLE

The automated procedure for the determination of Silicate is based on the following reaction; the sample is
acidified and mixed with an ammonium heptamolybdate solution forming molybdosilicic acid. This acid is
reduced with L(+)ascorbic acid to a blue dye, which is measured at 810 nm. Oxalic acid is added to avoid
phosphate interference.

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.

catnr. 563-051 1 of 6
REAGENTS

Remark: All reagents and standards must be prepared in polyethylene and stored in polyethylene
bottles.

A. Sulfuric acid solution

Required chemicals: Sulfuric acid ............... 22.5 ml. Preparation: Dilute the sulfuric acid in ± 800 ml
H2SO4 (95-97%) distilled water. Fill up to 1 liter with
Distilled water * ...... 977.5 ml. distilled water and mix.
H2O
Note: Solution is stable for 1 week. Store at
4°C when the solution is not used.

B. Ammonium heptamolybdate solution

Required chemicals: Ammonium Preparation: Dissolve the ammonium heptamolybdate

heptamolybdate ............ 20 g.
(NH4)6Mo7O24.4H2O
Distilled water * ....... 1000 ml.
H2O
in ± 800 ml distilled water. Fill up to 1 liter
with distilled water and mix.
Note: Store in a polyethylene bottle. Solution is
stable for 1 month. Do not use metal
spoons for the ammonium
heptamolybdate.

C. Oxalic acid solution

Required chemicals: Oxalic acid ...................... 44 g. Preparation: Dissolve the oxalic acid in ± 800 ml
C2H2O4.2H2O distilled water. Fill up to 1liter with
Distilled water * ....... 1000 ml. distilled water and mix.
H2O
Note: Store in a polyethylene bottle. Solution is
stable for 1 month. Store at 4°C when the
solution is not used.

D. L(+)Ascorbic acid solution

Required chemicals: L(+)Ascorbic acid ............ 40 g. Preparation: Dissolve the L(+)ascorbic acid in ± 800 ml
C6H8O6 distilled water. Fill up to 1 liter with
Distilled water * ....... 1000 ml. distilled water and mix.
H2O
Note: Solution is stable for 1 week. Store at 4°C
when the solution is not used.

E. Rinsing liquid sampler

Required chemicals: Distilled water * Note: Refresh weekly.

H2O

catnr. 563-051 2 of 6
STANDARDS

Stock solution 100 mg Si/liter

Required chemicals: Sodium Preparation: Dissolve the sodium metasilicate in ± 800

metasilicate ............ 1.0119 g.
Na2SiO3.9H2O
Distilled water * ....... 1000 ml.
H2O
ml distilled water. Fill up to 1 liter with
distilled water and mix.
Note: Solution is stable for 1 month. Store in a
polyethylene bottle.

Stock solution 10 mg Si/liter

Dilute 10 ml stock solution 100 mg Si/liter to 100 ml with distilled water.*

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

Store in a polyethylene bottle.

Working standards

250 µg Si/liter: Dilute 2.5 ml stock solution 10 mg Si/liter to 100 ml with rinsing liquid sampler.
200 µg Si/liter: Dilute 2.0 ml stock solution 10 mg Si/liter to 100 ml with rinsing liquid sampler.
150 µg Si/liter: Dilute 1.5 ml stock solution 10 mg Si/liter to 100 ml with rinsing liquid sampler.
100 µg Si/liter: Dilute 1.0 ml stock solution 10 mg Si/liter to 100 ml with rinsing liquid sampler.
50 µg Si/liter: Dilute 0.5 ml stock solution 10 mg Si/liter to 100 ml with rinsing liquid sampler.

Note:
1. Prepare the working standards fresh daily and store in polyethylene measuring flasks.
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

Sulfuric acid (95-97%) Merck 100731 corrosive

Ammonium heptamolybdate tetrahydrate Merck 101182
Oxalic acid dihydrate Merck 100495 harmful
L(+)Ascorbic acid VWR PRO
20150.231
Sodium metasilicate nonahydrate Sigma S 4392
Sodium hydroxide Merck 106498 corrosive

RECOMMENDED OPERATIONAL SETTINGS

1. System sample time: 100 sec., wash time: 100 sec., air time: 0 sec.
2. Module sample time: 60 sec., wash time: 60 sec., air time: 0 sec.
3. Calibration order: 1st order (acc.ISO8466-1)

catnr. 563-051 3 of 6
OPERATIONAL REMARKS AND TROUBLESHOOTING

1. The stabilising time of the system is approximately 20 minutes.

2. The sensitivity of the highest standard 250 µg Si/liter is ± 0.250 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.
5. If a digital matrix photometer 28505911, is in use, a correction interference filter of 1010 nm ± 10 nm is
advised.
6. Avoid any turbidity in the reagents, filter if necessary.
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. Because the range of this method is very low the sample cups must be pre-rinsed with the sample.
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. This procedure removes all dissolved air, 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.

MAINTENANCE

1. Daily; When daily analysis is finished rinse all reagentlines 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)

MODULE CONSUMABLES

silicone tube catnr. SA 3150 sleeves catnr. SA 5401

polyethylene tube catnr. SA 5141 sleeves catnr. SA 5406
polyethylene tube catnr. SA 5142 pump tube 1.20 ml/min. catnr. SA 3032
glass tube catnr. SA 5360 pump tube 0.16 ml/min. catnr. SA 3025
sleeves catnr. SA 5400 pump tube 1.00 ml/min. catnr. SA 3031

catnr. 563-051 4 of 6
MODULE COMPONENTS

manifold holder catnr. 25200105 connector catnr. SA 5202 3x

module catnr. SA 5107 clamps small catnr. SA 5111 5x
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 810 nm catnr. SA 6595
glass coil catnr. SA 5325 filter 1010 nm catnr. SA 6635
glass coil catnr. SA 5324 2x

REFERENCES

Chemical method (no. 563)

1. ISO-16264: Determination of soluble silicals by CFA and photometric detection.

2. Smits, J.D., Milne, P.J., Analytical Chimica Acta, 123, 1981, page 263-270.
3. Babulak, S.W., Gildenberg, L., “Automated determination of silicate and carbonates in detergents”, J. of
the American oil chemists’ society”, Vol. 50, August 1973, page 296-299.
4. Method is based on Skalar Revision I method d.d. 13-01-2000.
5. ISO 3696:1987, Water for analytical laboratory use. Specification and test methods.
6. 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.

catnr. 563-051 5 of 6
 FLOW DIAGRAM
waste
ml/min
Flowcell 50mm
Filter 810nm
Cor. Filter 1010nm

L(+)Ascorbicacid solution 0.16 5246

Oxalicacid solution 0.16 5246

Ammoniumheptamolybdatesol. 0.16 5246

Air
1.00 5216 5324 5324 5325
Sample
0.16 5202 5202 5202
Sulfuricacid solution

completelybuilt up in glass

1.20 waste

Sampler

Revision: Rev 1 Rev 2 Rev 3 Method:

Date: Analysis: Silicate
Chemists Range: 1-250 µg Si/liter
Authorization Sample: (Sea)water
First issued: 17-06-2011

catnr. 563-051 6 of 6