APPLICATION VAPODEST PAGE 1 OF 3

AMMONIUM IN SOLID SAMPLES

1. Principle
The ammonium nitrogen of the sample is stripped off as ammonia from a buffer solution, received in boric
acid and determined volumetrically.

2. Area of Usage
Type of Sample Amount of Sample g Content or Recovery mg N
soils 1-2 from 0.1 to 100
sewage sludge
compost
substrates
sediments
ash

3. Chemicals
3.1. Phosphate-buffer solution:
14.3 g Potassium dihydrogenphosphate and 68.8 g dipotassium hydrogenphosphate, anhydrous,
are diluted in 1 L distilled water

Alternative buffer solution:

Solution A: 6.2 g H3BO4 + 7.46 g KCl, distilled water added to 1 L
Solution B: NaOH c = 0.1 mol/l
Preparation: 500 ml Solution A + 210 ml Solution B, distilled water to be added to 1 L

3.2. Boric acid H3BO3, w = 2 %

3.3. Colour indicator M 5 or mixing indicator acc. to Sher or similar
3.4. Sulphuric acid H2SO4, c = 0.005 mol/l or hydrochloric acid HCl, c = 0.01 mol/l
3.5. Distilled water

4. Instruments
VAPODEST 10/s – 50s
Digestion tubes:
Cat. no. Name
12-0301 KJELDATHERM digestion tube KTG, macro 250ml, L 300mm x AD 42mm
12-0310 Jumbo digestion tube KDD 400, 400ml, for direct distillation, L 300mm x AD 54mm
12-0311 Jumbo digestion tube KDD800, 800ml, for direct distillation, L 300mm x AD 70mm
12-0312 Kjeldahl flask KD250, 250ml, with enlarged neck for VAPODEST
12-0313 Kjeldahl flask KD500, 500ml, with enlarged neck for VAPODEST
12-0314 Kjeldahl flask KD750, 750ml, with enlarged neck for VAPODEST
12-0308 KJELDATHERM digestion tube BS400, 400ml, diminished

5. Analysis
5.1. Sample Preparation
The required sample size depends on the expected content:

Amount of Sample g Concentration of N ppm Percentage by Mass N

10 30 to 300 0.003 to 0.03
5 300 to 600 0.03 to 0.06
2 600 to 1400 0.06 to 0.14
1 1400 to 2800 0.14 to 0.28

In case of lower contents it is advisable to lower the concentration of the titration solution, in case of higher
contents vice versa.

The dry content of the sample must be known for the calculation of the ammonium content.

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AMMONIUM IN SOLID SAMPLES

The homogenized sample is weighed into the digestion tube with a precision of 1 mg using weighing paper.
Any sample material on the tube wall has to be prevented! Then, the sample is slurred with 50 ml distilled
water.

Prior to distillation, 20 ml of the buffer solution are added to the sample using a pipette or a dispenser and the
ammonia is stripped off from this weak alkaline solution without delay, received in boric acid and determined
titrimetrically.

5.2. Distillation and Programming of VAPODEST

Depending on the model, VAPODEST takes over these steps with different automation levels.
The dosing of the chemicals is achieved by a volume flow. In 1 second, 10 ml of a solution with the density of
water are transported. A solution of higher density needs more time (caustic soda 30 %: approx. 8 ml/s)

Use the VAPODEST following the Instruction Manual. Start with a blank distillation in order to warm up the
instrument as well as to clean it. Check whether all chemicals are present in required quantity!

The sample tube containing the sample and buffer solution is inserted into the VAPODEST.
An Erlenmeyer flask (with enlarged neck) containing 50 ml boric acid is positioned under the outlet tubing for
the distillate (VAP 10s to VAP 30s, not necessary with VAP 45s and VAP 50s). The outlet tubing must be
immerged in the boric acid solution.
Then the program is started. The amount of distillate should be around 100 ml.

The following table shows the program parameters to be set with different VAPODEST models.
Manual dosing have to be done with utmost care and under consideration of the chemicals' harmfulness.
For bigger samples the amount of chemicals and distillation time must be adapted.

VAP 10/s VAP 20s VAP 30s VAP 45s VAP 50s
H2O Addition 0 ml 0 ml 0 ml 0 ml 0 ml
NaOH Addition 0 ml 0 ml 0 ml 0 ml 0 ml
Reaction Time - 0s 0s 0s 0s
Distillation Time 3 min 30 s 3 min 30 s 3 min 30 s 3 min 30 s 3 min 30 s
Steam Power 100 % 100 % 100 % 100 % 100 %
H3BO3 Addition ~ 70 ml ~ 70 ml ~ 70 ml ~ 70 ml ~ 70 ml
Suction Sample manual* manual* 0 s* 0 s* 0 s*
Suction Receiver manual manual manual 30 s 30 s
1
Titration manual manual manual automatic automatic
Calculation manual manual manual manual automatic

* suction of sample is not recommended, since this may block the suction tubings
1
if equipped with external titrator
All activities to be done manually are written in italics.

5.3.Titration
A titration to the end point is performed. At pH 5, the mixture indicator M 5 changes its colour from green to
grey. Other indicators can be used. However, the titration point should be within the pH range of the boric
acid (if 2 % - pH approx. 4.3).
If an electrode is used for titration, the pH-value of the undiluted boric acid is measured first, then it is back-
titrated to this value and the amount of consumed titration solution is noted down (VAP 10s to VAP 30s).
Hydrochloric acid c = 0.01 mol/l or sulphuric acid c = 0.005 mol/l is recommended.
Depending on the ammonium content of the sample a higher concentrated titration solution may be required.

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AMMONIUM IN SOLID SAMPLES

5.4. Determination of the Blank Value

For determination of the blank value, a sample tube without sample but with all chemicals is run through the
whole analysis course. The consumption of titration solution is determined. This consumption is deducted
from the consumption of the sample. This procedure is needed in order to detect contaminations of the
chemicals and instruments as well as to take into account the dilution factor of the boric acid.
The consumption with a 0.01 mol/l titration solution should be around 0.5 to 0.6 ml.

5.5. Quality Assurance

If electrodes are used for the end point determination (VAP 50s), these electrodes must be calibrated at least
once a week.
A 1 mg NH4-N standard has to be measured at least 3 times every day and the results are noted down in a
chart. Samples measured prior to this procedure must have nearly the same titration volume. Otherwise, the
first standard value must be rejected.

5.6. Preparation of a Standard Solution

4.717 g (NH4)2SO4 (dried at 105 °C) are weighed into a 1 L measuring flask, dissolved and then filled up with
distilled water to receive 1 L. This corresponds to a content of 1 mg N per ml.
Then, 20 ml of this parent solution are pipetted into a 1 L volumetric flask and distilled water is added up to
1 L. From this solution, 50 ml are used for the determination (corresponds to 1 mg absolute N).

6. Evaluation
The content of ammonium in percentage NH4 % is calculated as follows:

NH4 % = ( c (VSample - VBL) M 100 ) / E

+
c = H ion concentration of the titration solution mmol/ml
VSample = Consumption of titration solution for the sample ml
VBL = Consumption of titration solution for the blank sample ml
M = Molar mass of ammonium mg/mmol
E = Initial sample weight corrected with the dry content mg

For calculation of other contents (e.g. nitrogen) the corresponding molar mass is used in this equation.

C.2.1. Ammonium in Solid Samples.doc

20.09.2010 mkr-rbr