APPLICATION VAPODEST PAGE 1 OF 3

AMMONIUM IN AQUEOUS SAMPLES

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

2. Areas of Usage

Type of Sample Amount of Sample Content or Recovery

water 1 - 500 ml 0.1 mg N to 100 mg N
sewage
eluates
extracts

3. Chemicals
3.1. Phosphate-buffer solution:
14.3 g Potassium dihydrogen phosphate and 68.8 g dipotassium hydrogen phosphate, anhydric, are
diluted in 1 l distilled water.

Alternative buffer solution:

Solution A: 6.2 g H3BO4 + 7.46 g KCl, then add H2Odest. to 1 l
Solution B: NaOH c = 0.1 mol/l
Preparation: 500 ml Solution A + 210 ml Solution B, then fill up to 1 l

3.2. Boric acid w = 2 %

3.3. Indicator for proportion of ingredients M 5 or indicator for proportion of ingredients acc. to Sher or similar
3.4. Sulphuric acid c = 0.005 mol/l or hydrochloric acid c = 0.01 mol/l

4. Instruments
4.1. VAPODEST 10 – 50s
4.2. The following digestion tubes from C. Gerhardt can be used:

Article No. Form Type Size

6100 Kjeldatherm digestion tube KTG 250 ml
6106 Special tube VAP 6 KTG/K 250 ml
6460 Tube KDD 400 400 ml
6461 Tube KDD 800 800 ml
6462 Kjeldahl flask KD 250 250 ml
6465 Kjeldahl flask KD 500 500 ml
6467 Kjeldahl flask KD 750 750 ml
6108 Kjeldatherm digestion tube with taper BS 400 400 ml

5. Analysis
5.1. Sample Preparation
The amount of sample depends on the expected content of nitrogen:

Amount of Sample in ml Concentration of Nitrogen in mg/l

100 0.1 to approx. 35
50 20 to approx. 70
20 50 to approx. 175
10 100 to approx. 350
5 300 to approx. 700

Samples with higher concentration must be diluted with distilled water.

Samples with an acid pH-value must be neutralized!

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AMMONIUM IN AQUEOUS SAMPLES

Each digestion tube is rinsed with distilled water. 100 ml of the sample or a part of the sample completed up to
100 ml are pipetted into the digestion tubes. 20 ml of the buffer solution are added with help of a pipette or a
dispenser and immediately after this the sample is distilled 4 minutes.

5.2. Distillation and Programming of VAPODEST

From this weak alkaline solution the ammonia is expulsed, received in boric acid and determined titrimetrically.
Vapodest does these various steps in different variations of automation. The dosing of the chemicals is
achieved by a volume flow. In 1 second, 10 ml of a solution with the density of water is transported. Whenever
higher density is reached then less is transported. (caustic soda 30 %: approx. 8 ml/s)

The following table shows the programs to use for the different Vapodest models. The manual dosing has to
be done with utmost care and under consideration of the danger of the used chemicals.

VAP 10 VAP 20 VAP 30 VAP 40 VAP 50s

H2O Addition - - 0s 0s 0 ml
NaOH Addition 0 ml 0s 0s 0s 0 ml
Reaction Time 0s 0s 0s 0s 0s
Distillation Time 240 s 240 s 240 s 240 s 240 s
Steam Power 100 % 100 % 100 % 100 % 100 %
Suction Sample manual manual 30 s 30 s 30 s
H3BO3 Addition manual manual manual 5s 50 ml
Suction Receiver manual manual manual manual 30 s
Titration manual manual manual manual automatic
Calculation manual manual manual manual automatic

For samples bigger than 100 ml the amount of chemicals and distillation time must be adapted accordingly.

Start use of the VAPODEST according to the Instruction Manual and with a blank distillation in order to warm
up and clean the instrument. Check that all chemicals are present in the needed quantity.

Distillation
The sample flask is inserted in the VAPODEST after addition of the buffer solution. An Erlenmeyer flask with a
wide opening, filled with 50 ml boric acid has to be put directly under the outlet tubing for the distillate. (VAP 10,
VAP 20 and VAP 30, VAP 40 empty, none when using VAP 50s). The outlet tubing for the distillate must be
immerged in the boric acid. Then the program is started and the distillation gets running. The amount of
distillate should be around 100 ml. After termination of the distillation the receiving solution is taken away and
the outlet tubing is cleaned with some distilled water.

5.3.Titration
A titration to the end point is used. The indicator for the proportion of ingredients M 5 changes at pH 5 from
green to grey. Of course, other indicators can be chosen. However, the titration point should be within the pH
range of the boric acid (when using a 2 % acid about 4.3). If titration is done with an electrode the pH value of
the undiluted boric acid must be measured first. This value has to be reached again by titration; the amount of
consumed titration solution is noted down (VAP 10 – VAP 40).
We recommend a hydrochloric acid c = 0.01 mol/l or a sulphuric acid c = 0.005 mol/l. Depending on the
ammonium content of the sample a higher concentrated titration solution may be necessary.

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AMMONIUM IN AQUEOUS SAMPLES

5.4. Determination of the Blank Value

This is done by running the complete analysis with a sample tube without sample but with all chemicals for the
analysis. 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. It should be about 0.5 to 0.6 ml
of a 0.01 mol/l titration solution.

5.5. Quality Assurance

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

5.6. Preparation of a Standard Solution

4.717 g (NH4)2SO4 (dried at 105 °C) are weighed in, diluted in a 1 l measuring flask and then filled up to 1 l
with distilled water. This corresponds to a content of 1 mg N per ml.
Then, 20 ml of this parent solution are pipetted into a measuring tube. Again, 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 mass per unit volume of ammonium ß(NH4+) in mg/l is calculated with the following formula:

ß(NH4+) = ( c (V - VBL) M) 1000 / VSample

+
c = H ion concentration of the titration solution in mmol/ml
V = Consumption of titration solution of the sample in ml
VBL = Consumption of titration solution of the blank value in ml
M = Molar mass ammonium in mg/mmol
VSample = Volume of the sample in ml

For calculation of other contents (e.g. nitrogen) the corresponding molar masses must be used in this formula.

C.2.2. Ammonium in Aqueous Samples GB.doc

20.9.2010 mkr-rbr