Application Bulletin 53/4e
Determination of ammonium or Kjeldahl Nitrogen
Branch
Method 1 – Potentiometric
General analytical chemistry; food, stimulants, beverages,
flavours; water, wastewater, air, environmental protection; determination
fertilizers, base materials, explosives
Instruments
Titrator with SET modus
Keywords 20 mL buret
Kjeldahl; nitrogen determination; ammonium; titration; Kjeldahl digestion and distillation apparatus
photometric titration; potentiometric titration; coulometric
determination; Optrode; Unitrode; separate double Pt-sheet
electrode; branch 1; branch 2; branch 7; branch 11; Electrodes
6.1115.000; 6.0259.100; 6.0309.100 Unitrode with Pt 1000 (head U) 6.0258.600
Summary Reagents
The potentiometric titration of Kjeldahl nitrogen is one of the Sulfuric acid, puriss p.a., 96%
most widely employed analytical methods. Many of the
Sodium hydroxide, puriss p.a., NaOH
standard procedures in the food and animal feed industry, in
Broic acid, puriss p.a., H3BO3
waste water and refuse analysis as well as in agriculture
and the fertilizer industry are based on this method. Hydrochloric acid, c(HCl) = 0.1 mol/L
Extensive test series (interlaboratory tests) have been Catalyst (Kjeldahl tablets, Hg and Se free)
carried out to determine and optimize the recovery rates and
digestion conditions. The knowledge derived from these
tests has been integrated in the corresponding standards. Solutions
Normally, the samples are digested with concentrated Titrant c(HCl) = 0.1 mol/L
sulfuric acid using a catalyst as admixture. The formed If possible this solution should
ammonium sulfate is distilled off as ammonia in alkaline be bought from a supplier.
solution, collected in an absorption solution and then 200 g boric acid is weighed into
c(H3BO3) = 0.1 mol/L
titrated. The first part of this bulletin describes in detail the
a 5 L volumetric flask and
determination of nitrogen after distillation of the digestion dissolved in dist. water. The
solution using either potentiometric or photometric
solution is then filled up to the
indication. The second part indicates the possibilities of the
mark with dist. water.
coulometric titration (without distillation).
w(NaOH) = 40 % 2 kg NaOH is slowly dissolved in
approx. 5 L dist. water.
Sample preparation
Digestion
In a digestion flask an appropriate amount of sample
containing no more than 25 mg N is mixed with 10 – 20 mL
conc. H2SO4 and two Kjeldahl tablets. The digestion flask is
tilted back and forth to make sure that the sample is
completely moistened with H2SO4. Then it is heated up, until
a distinct reaction occurs and continued boiling slightly until
the brown color and all carbon particles have disappeared.
AB 53/4e
Determination of ammonium or Kjeldahl Nitrogen
The solution should now appear clear and greenish. Upon Blank/Sample
completion of the digestion, the mixture is allowed to cool EP1 at pH 4.6
down.
Dynamics 3
Distillation Max. rate 5 mL/min
The Kjeldahl flask containing the digested sample is placed Min. rate 10 µL/min
into the Kjeldahl distillation apparatus and approx. 50 mL
Stop criterion Drift
water and as much w(NaOH) = 40% as needed are added
Stop drift 10 µL/min
to get a blue to brownish solution. The formed ammonia is
then distilled off by steam distillation and retained in the Stop volume 20 mV
form of ammonium in a sample beaker containing 50 mL of EP1 at pH 4.6
w(H3BO3) = 2%.
Calculation
Analysis Titer
Calibration mStd
f=
VEP1 × cHCl × MStd
The electrode is initially calibrated by a two point calibration
with buffer pH 4 and 7.
f: Titer of the selected titrant
Titer mStd: Mass of standard in mg
100 - 150 mg TRIS is weighed into a titration beaker, VEP1: Titrant consumption until the first equivalence
dissolved in approx. 70 mL dist. water and titrated to until point in mL
after the equivalence point. cHCl: Concentration of the selected titrant in mol/L;
here c(HCl) = 0.1 mol/L
Blank
MStd: Molecular weight of the standard (TRIS);
For the blank determination, a digestion and distillation is 121.17 g/mol
performed the same way as described under sample
preparation omitting the sample.
Sample
Sample
mN = (VEP1 - Blank) × cHCl × f × MN
For determining the nitrogen content, the obtained solution
is titrated with c(HCl) = 0.1 mol/L to a pH of 4.6.
mN × 100
wN =
mS
Parameters
m N: Mass of nitrogen in the sample in mg
Calibration VEP1: Titrant consumption until the first equivalence
Mode CAL MEAS pH point in mL
cHCl: Concentration of the selected titrant in mol/L;
Signal drift 2 mV/min
here c(HCl) = 0.1 mol/L
Min. waiting time 10 s f: Titer of the selected titrant
Max. waiting time 110 s MN: Molecular weight of nitrogen in g/mol;
14.007 g/mol
Titer wN: Mass fraction of Nitrogen in %
Mode MET pH 100: Conversion factor
Stirring rate 5 mS: Sample weight in mg
Signal drift 50 mV/min
Min. waiting time 0s
Max. waiting time 26 s
Volume increment 0.1 mL
Stop volume 20 mL
EP criterion 30 mV
EP recognition greatest
Page 2 of 6
AB 53/4e
Determination of ammonium or Kjeldahl Nitrogen
Example determination
Method 2 – Photometric
determination
Instruments
Titrator with MET and/or DET modus
20 mL buret
Kjeldahl digestion and distillation apparatus
Electrodes
Optrode 6.1115.000
Fig. 1: Potentiometric Kjeldahl nitrogen determination in SET
modus Reagents
Sulfuric acid, puriss p.a., 96%
Sodium hydroxide, puriss p.a., NaOH
Boric acid, puriss p.a., H3BO3
Hydrochloric acid, c(HCl) = 0.1 mol/L
Sher indicator
Catalyst (Kjeldahl tablets, Hg and Se free)
Solutions
Titrant c(HCl) = 0.1 mol/L
If possible this solution should
be bought from a supplier.
c(H3BO3) = 0.1 mol/L 200 g boric acid is weighed into
a 5 L volumetric flask and
dissolved in dist. water. The
solution is then filled up to the
mark with dist. water.
w(NaOH) = 40 % 2 kg NaOH is slowly dissolved in
approx. 5 L dist. water.
Sample preparation
Digestion
In a digestion flask, an appropriate amount of sample
containing no more than 25 mg N is mixed with 10–20 mL
conc. H2SO4 and two Kjeldahl tablets. The digestion flask is
tilted back and forth to make sure that the sample is
completely moistened with H2SO4. Then it is heated up, until
a distinct reaction occurs and continued boiling slightly until
the brown color and all carbon particles have disappeared.
The solution should now appear clear and greenish. Upon
completion of the digestion, the mixture is allowed to cool
down.
Page 3 of 6
AB 53/4e
Determination of ammonium or Kjeldahl Nitrogen
Distillation Blank/Sample in MET modus
The Kjeldahl flask containing the digested sample is placed Mode MET pH
into the Kjeldahl distillation apparatus and approx. 50 mL
Stirring rate 5
water and as much w(NaOH) = 40% as needed are added
to get a blue to brownish solution. The formed ammonia is Signal drift 50 mV/min
then distilled off by steam distillation and retained in the Min. waiting time 0s
form of ammonium in a sample beaker containing 50 mL of Max. waiting time 26 s
w(H3BO3) = 2%. Volume increment 0.1 mL
Stop volume 20 mL
Analysis EP criterion 30 mV
EP recognition greatest
Titer
100–150 mg TRIS is weighed into a titration beaker and Blank/Sample in DET modus
dissolved in approx. 70 mL dist. water. Five drops Sher Mode DET pH
indicator are added and the solution is titrated to until after
Stirring rate 5
the equivalence point.
Signal drift 20 mV/min
Blank
Meas. point density 2
For the blank determination, a digestion and distillation is Min. increment 10 µL
performed the same way as described under sample
Max. waiting time 38 s
preparation omitting the sample.
Stop volume 20 mL
Sample EP criterion 5
To the obtained solution, five drops of Sher indicator are EP recognition greatest
added and the solution is titrated until after the first
equivalence point with c(HCl) = 0.1 mol/L. Thereby, the
solution turns from initially greenish over blue to orange. Calculation
Titer
mStd
Parameters f=
VEP1 × cHCl × MStd
Titer
Mode MET pH f: Titer of the selected titrant
mStd: Mass of standard in mg
Stirring rate 5
VEP1: Titrant consumption until the first equivalence
Signal drift 50 mV/min point in mL
Min. waiting time 0s cHCl: Concentration of the selected titrant in mol/L;
Max. waiting time 26 s here c(HCl) = 0.1 mol/L
MStd: Molecular weight of the standard (TRIS);
Volume increment 0.1 mL 121.17 g/mol
Stop volume 20 mL
EP criterion 30 mV
EP recognition greatest
Page 4 of 6
AB 53/4e
Determination of ammonium or Kjeldahl Nitrogen
Sample Method 3 – Coulometric
mN = (VEP1 - Blank) × cHCl × f × MN
determination
mN × 100
wN = Instruments
mS
Titrator with BRC modus
mN: Mass of nitrogen in the sample in mg 20 mL Buret
VEP1: Titrant consumption until the first equivalence Kjeldahl digestion apparatus
point in mL
cHCl: Concentration of the selected titrant in mol/L;
here c(HCl) = 0.1 mol/L Electrodes
f: Titer of the selected titrant
Separate double Pt-sheet electrode 6.0309.100
MN: Molecular weight of nitrogen in g/mol;
14.007 g/mol Generator electrode with diaphragm 6.0344.100
wN: Mass fraction of Nitrogen in %
100: Conversion factor Reagents
mS: Sample weight in mg
Sulfuric acid, puriss p.a., 96%
Potassium bromide, KBr, p.a.
Example determination
Sodium tetraborate decahydrate (Borax), p.a.
Titration in MET modus Hydrochloric acid, HCl, conc, >=37 %
Solutions
Electrolyte 100 g KBr and 60 g borax are
dissolved in approx. 700 mL
dist. water and the pH is
adjusted to 8.6 with conc. HCl
w(NaOH) = 40 % 400 g NaOH is slowly dissolved
in approx. 1 L dist. water.
Sample preparation
Fig. 2: Photometric Kjeldahl nitrogen determination in MET In a digestion flask, an appropriate amount of sample
modus
containing approx. 250 mg N is mixed with 30 – 40 mL conc.
H2SO4 and two Kjeldahl tablets. The digestion flask is tilted
Titration in DET modus back and forth to make sure that the sample is completely
moistened with H2SO4. Then it is heat up, until a distinct
reaction occurs and continued boiling slightly until the brown
color and all carbon particles have disappeared. The
solution should now appear clear and greenish. Upon
completion of the digestion, the mixture is allowed to cool
down.
Approx. 6 g of the digested sample is weight into a 50 mL
beaker and 10 g ice is added. As the pH is adjusted to pH 7
with w(NaOH) = 40%, as much dist. water as needed is
added to the sample solution to dip in the electrode in the
sample solution. After adjusting the pH to pH 7, Cu(OH)2
precipitates, which is removed by filtration with a syringe
filter 0.45 μm. The solution is diluted with dist. water to
Fig. 3: Photometric Kjeldahl nitrogen determination in DET
approx. 60 g. The weight of the digestion flask, of the
modus
Page 5 of 6
AB 53/4e
Determination of ammonium or Kjeldahl Nitrogen
digested sample, of the used aliquot as well as of the end Example determination
weight is noted accurately as they are used for the
calculation of the sample concentration in g/g.
Analysis
100 mL of the electrolyte is placed into the anodic
compartment (coulometric cell) and 5 mL into the cathode
compartment. The coulometer is started and conditioned.
After conditioning 0.2 – 5 g of the sample solution is added.
The sample is titrated by using the BRC mode and the
separated double Pt-sheet electrode for indication.
Parameters Fig. 4: Coulometric nitrogen determination in BRC modus
Mode BRC
Stirring rate 6 Comments
Dynamics 320 mV All weights have to be documented properly as
Max. rate 10’000 μg/g otherwise the sample concentration cannot be
Min rate 100 μg/g calculated.
Stop criterion Drift The parameter dynamics have to be adjusted in each
case individually as the voltage ranges are different for
Stop drift 50 μg/min
different electrodes.
Conditioning On
The pH of the sample is adjusted to pH 7 because
Start drift 50 μg/min
otherwise the pH value of the electrolyte will drop too
Drift correction Off fast.
Stop time Off The digestion with a higher amount of sample takes
about half an hour longer as for lower amounts of
Calculation samples.
mgen. Br2 × 2 × MN
mN =
MBr2 × 3 × 1000 References
Coulometric Titration of Ammonia with Hypobromite,
mN: Mass of nitrogen in the sample in mg
Anal. Chem., 1956, Vol. 28, No. 4
mgen. Br2 : Generated bromine in μg
Direct Coulometric Titrations with Hypobromite Ion,
2: Stoichiometric factor Anal Chem., 1963, Vol. 35, No. 13
MN: Molecular weight of nitrogen in g/mol;
14.007 g/mol Rapid Coulometric Method for the Kjeldahl
MBr2 : Molecular weight of bromine in g/mol/; Determination of Nitrogen, Talanta, 1974, Vol. 21
159.808 g/mol
3: Stoichiometric factor
Author
1000: Conversion of μg to mg
Competence Center Titration
Metrohm International Headquarters
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