Analytical Methods

Stamicarbon bv
P.O. Box 53 - 6160 AB Geleen, The Netherlands
rev. by description checked date scanned
- LPO First Issue MEE Jan 2008
This Volume is the property of Stamicarbon bv and, except where otherwise agreed in writing, it is put at the receiver's
A4-00000-A
disposal without consideration other then the receiver's agreement that it shall not be reproduced, copied, lent or disposed of
directly or indirectly nor used for any purpose other than that for which it is specifically furnished, and that it is to be
returned to Stamicarbon bv on demand together with any copies made.
prepared by date pertaining drawings project

LPO Jan 2008 ZURE
checked by date
MEE Jan 2008 UREA PLANT
seen by date
ANALYTICAL METHODS UREA
size
revision -
A4 00000
STAMICARBON CONFIDENTIAL INFORMATION Sheet 1 of 165
Stamicarbon bv, Mauritslaan 49, Urmond P.O. Box 53, 6160 AB Geleen, The Netherlands
Number Version Date Title
305 1 September 2003 Determination of formaldehyde in water

(HPLC method)
400 2 August 2003 Sampling by the bladder method
401 2 September 2002 Sampling of product from the urea plant

(bladder method)
402 1 May 2000 Determination of biuret in urea

(spectrophotometric method)
403 1 September 2001 Determination of carbon dioxide in

products from the urea plant
(formaldehyde method)
404 1 May 2000 Determination of urea in urea solutions

(gravimetric method)
405 1 September 2001 Determination of urea

(spectrophotometric diacetyl monoxime
method)
406 2 July 2004 Determination of water in urea
407 1 February 2004 Determination of water in liquid ammonia
408 3 July 2004 Determination of formaldehyde in urea

410 3 August 2004 Determination of free ammonia in urea

(Titrimetric with use of an indicator)
411 2 January 2003 Determination of ammonia in water

412 1 February 2004 Determination of ammonia in gas
415 1 October 2002 Determination of the crushing strength or

the deformation strength of (fertilizer)
granules/prills
416 1 October 2002 Determination of the particle size

distribution of (fertilizer) granules/prills
417 1 March 2004 Determination of total nitrogen in urea

(Titrimetric, after digestion)
project ZURE
A4-00000-A
Analytical Methods Urea drawing nr A4-00000

revision -
Stamicarbon bv, Mauritslaan 49, Urmond P.O. Box 53, 6160 AB Geleen, The Netherlands
Number Version Date Title
418 1 March 2004 Determination of impact (shock) of final

product
419 1 March 2004 Determination of oil in liquid ammonia

(infrared spectrophotometric method)
420 1 July 2002 Determination of urea in water

(gravimetric xanthydrol method)
421 1 May 2004 Determination of urea in off gas prilling

tower (Isokinetic Particulate sampling, In-
stack, Gravimetric method)
422 1 December 2003 Determination of chloride in steam

condensate (spectrophotometric method)
424 1 November 2002 Determination of the bulk density of

(fertilizer) granules/prills (Loose and
Tapped)
425 2 August 2004 Determination of total ammonia in urea.

(titrimetric with use of an indicator)
427 3 August 2004 Determination of free and total ammonia

in urea (Titrimetric, potentiometric)
429 1 April 2003 Determination of formic acid in water

(ionchromatographic)
430 1 November 2002 Determination of the rolling tendency of

(fertilizers) granules/prills
431 1 January 2004 Determination of pH, Buffervalue and

ammonium salts of urea
432 1 March 2004 Determination of the friability of
(fertilizer) granules (Ball mill technique)
project ZURE
A4-00000-A
Analytical Methods Urea drawing nr A4-00000

revision -
DSM Melamine
Skill Centre
Analytical method 305, version 1 Date: 30 September 2003
DETERMINATION OF FORMALDEHYDE IN WATER

(HPLC method)
Authorisation :
(signature)
Jan Jaap Nusselder, Manager PAR Melamine Skill Centre
Keywords: Formaldehyde, HPLC, fluorescence detection
1. Scope
Determination of the formaldehyde concentration in water by means of a HPLC

analysis using post-column derivatization reaction and fluorescence detection.
2. Safety
Chemicals to be used:
Acetic acid
Acetonitril
Acetylacetone
Ammonium acetate
Formaldehyde
Phosphoric acid
Sodium hydroxide
2-Propanol
Work safely, especially with hazardous chemicals, as in this method
formaldehyde (suspected carcinogen) with a MAC value of 1 ppm (1.5 mg/m3)
MAC TGG-15 min.of 2 ppm (3 mg/m3). Never use hydrochloric acid in the
neighbourhood of formaldehyde, because formaldehyde reacts with
hydrochloric acid giving off very toxic “bis(chloromethyl)ether”, which can
cause lung cancer.
Use the guidelines of e.g. Safety Data Sheets (SDS) or a local equivalent.
A HPLC apparatus operates under high pressure (100 - 400 bar). In spite of the
use of small volumes, always wear safety glasses when working with HPLC.
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Aanmaakdatum: 12 augustus, 1997
Dokument filename: j:\quality\formul\fscm042.doc
Method 305v1 page 1 of 9

DSM Melamine
Skill Centre
3. Principle
Dissolution of the sample in buffer solution.

HPLC determination of the formaldehyde concentration using post-column
derivatization reaction in which formaldehyde reacts at 90°C with acetylacetone and
ammonium acetate to yield diacetyldihydrolutidine which can be determined by
fluorescence detection.
4. Apparatus
4.1. HPLC system complete, containing:

4.1.1 HPLC pump, e.g. HP 1050, set at 1.0 ml/min.
4.1.2 HPLC pump e.g. 2150 LKB Bromma, set at 1.0 ml/min
4.1.3 Autosampler injector set at 20°C
4.1.4 Sample loop 20 µL
4.1.5 Analytical column Inertsil ODS-3, dp 5 µm, dimensions: 250 mm * 4.6 mm,
including guard column (e.g. Chrompack)
4.1.6 Column heater module, e.g. Waters, set at 30.0°C
4.1.7 Column oven e.g. 2155 HPLC from LKM Bromma, set at 90°C
4.1.8 Fluorescence Detector e.g. F1050 Hitachi set at an excitation wavelength of
410 nm and an emission wavelength of 510 nm
4.1.9 Chromatography integration system e.g. Waters Empowered computer
system.
4.2. Eluent filtration apparatus e.g. Waters complete.
Sartorius cellulose acetate filter, pore size of 0.45 µm for aqueous and non-
aggressive organic solvents.
4.3 Ultra sonic bath e.g. Cole Parmer type 8893, temperature set at 20°C
4.4 pH meter provided with a combined glass pH electrode, e.g. Knick type 766
Calimatic.
5. Chemicals
5.1. Phosphoric acid 85% e.g. Baker Chemicals

5.2. Sodium hydroxide > 99%, e.g. Merck z.a. art. nr. 106498.
5.3. Formaldehyde solution 37.0 – 38.0 wt% stabilized with about 10% methanol
e.g. Merck; known composition
5.4. Helium, free of organic impurities.
5.5. Water, HPLC quality, e.g. Milli-Q water.
5.6. Sodium hydroxide solution 1 mol/L: dissolve 40 gram sodium hydroxide (5.2)
into 1 L water (5.5).
5.7. Acetonitril HPLC grade, e.g. Baker Chemicals
5.8. Ammoniumacetate, CH3COONH4 > 96.0% e.g. Merck
5.9. Acetylacetone, C5H8O2 > 99.5 % e.g. Merck
5.10. Acetic acid 99 – 100% e.g. Riedel-de Haën
5.11. 2-propanol > 99.5 %, e.g. Merck
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5.12. Eluent solutions

The HPLC apparatus uses 5 solutions:
- Solution A: 100% buffer solution (6.1)
- Solution B: 100 % acetonitril (5.7)
- Solution C: 20 v/v% acetonitril (5.7) in buffer solution A (6.1)
- Solution D: 1v/v % acetonitril (5.7) in water (5.5) used for priming the
autosampler
- Hantz reagent (6.2)
6. Procedure
6.1 Preparation of the buffer solution A (see 8.1)

- Add into a 1L measuring flask approximate 970 ml of water (5.5).
- Add 1.0 gram of Phosphoric acid (5.1).
- Add 10 g sodium hydroxide solution (5.6).
- Mix.
- Fill up to 990 ml with water (5.5) and mix again.
- Adjust the pH to 6.80 using a pH meter (4.4) with 1 M NaOH (5.6).
- Fill up to the mark with water (5.5).
- Filter the eluent through a 0.45 µm filter (4.2).
- Degas the eluent for 30 minutes with He gas: flow approx. 100 ml/min. (5.4).
- Connect the eluent to the HPLC apparatus (4.1).
6.2 Preparation of the Hantz reagent

- Add into a 1L measuring flask 150 g ammoniumacetate (5.8)
- Add approximately 900 ml water (5.5) and mix.
- Add 3 ml acetylacetone (5.9) and mix
- Add 2 ml acetic acid (5.10) and mix
- Fill up to the mark with water (5.5).
- Mix this reagent for at least 30 minutes (see 8.2)
6.3 Preparation of the standard formaldehyde solution

Use only freshly prepared standard solutions
- Prepare a calibration standard of formaldehyde by dissolving ca. 0.1 g
formaldehyde solution (5.3) in 100 ml buffer solution (6.1) (= solution I).
- Prepare a second calibration standard of formaldehyde by dissolving ca. 0.2 g
formaldehyde solution (5.3) in 200 ml buffer solution (6.1) (= solution J).
- Dilute subsequently 0.05 g, 0.10 g and 0.15 g of solution I in 50ml buffer solution
(6.1) and 0.20 g, 0.25 g and 0.30 g of solution J in 50 ml buffer solution (6.1)
6.4 HPLC start-up

- Switch on the He degassing.
- Turn seal wash on (see 8.4). The water bottle for the seal wash is situated on top
of the lab table. The flow (ca. 1 drop of water per second) can be adjusted. If the
bottle is empty, the seal wash flow can be readjusted by draining with a syringe.
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- Clean the sparge filter (see 8.3) of the buffer solution A (6.1) once a week.
- Before starting the HPLC (4.1), the eluent solutions must be degassed for 30
minutes with He gas: flow approx. 100 ml/min. This is especially important for
acetonitril.
- Purge if necessary solutions (A), (B), (C) and the Hantz reagent. Perform a purge
when changing the eluent solutions by means of opening the purge valve on the
HPLC pump. Close this purge valve firmly. Purge with 5 ml/min.
- Switch on the autosampler (4.1.3) and adjust temperature to 20°C
- Switch on the fluorescence detector (4.1.8).
- Switch on the Waters column heater module (4.1.6). Press ‘menu/enter’ button
and select with the arrow key up ‘ON’. Press ‘menu’ again. The oven heats up till
30°C.
- Switch on the LKB Bromma oven (4.1.7). Gradually increase the temperature to
90°C.
- The reversed phase HPLC column (4.1.5) needs to be activated when storing
overnight at 100% buffer solution or storing for a prolonged time at 50%
acetonitril/50% buffer. This is done by running a gradient till 80 % acetonitril and
returning till 100% buffer solution. Activate the column by running a wash gradient
method 1 or method 2, depending on the stop conditions of the former analysis.
Press METHOD’, ‘1’ and ‘ENTER’ (See attachment 11.1 for further details).
- Increase flow from 0.2 ml/min till 1.0 ml/min in steps of 0.2 ml/min by pressing
‘FLOW’ followed by 0.2 till 1.0 and ‘ENTER’.
- After 30 minutes this wash gradient can be stopped by pressing ‘STOP’ and
‘ENTER’ key.
- Load method 4 by pressing ‘METHOD’ , ‘4’ and ‘ENTER’. The system is now
running isocratic at 1.0 ml/min with 100 % buffer solution A.
- Start the pump of the Hantz reagent with a flow of 1.0 ml/min.
- Allow the system to stabilize for at least 30 minutes.
6.5 Shutting down

When storing the column for more than 2 days run a gradient till 50% acetonitril
and store the column in 50% acetonitril and 50% buffer.
- Press ‘METHOD’ ‘5’ ‘ENTER’
- Increase flow from 0.2 ml/min till 1.0 ml/min in steps of 0.2 ml/min by pressing
‘FLOW’ followed by 0.2 till 1.0 and ‘ENTER’
- Press ‘START’ ‘Enter’.
- After minimal 30 minutes press ‘PUMP ON/OFF’ ‘ENTER’.
- Turn off the helium purge, seal wash, autosampler, detector and column ovens.
6.6 Analysis of formaldehyde in water

- If necessary dilute a g of sample with buffer solution (6.1) to a mass of b g.
- Inject 20 ml of this buffer solution onto the column.
- Determine the peak surface of the component (Fs).
- Calculate the formaldehyde content of the sample according to 7.2
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DSM Melamine
Skill Centre
7
7. Calculation
7.1 Calculate, the calibration factor of formaldehyde using the formula:
Cm
fm = -----------
Am
Where: fm: calibration factor for formaldehyde

Cm: concentration of formaldehyde in mg/kg
Am: peak surface area of formaldehyde
Calculate the average factor, or use linear regression calculation.
7.2 Calculate the formaldehyde concentration of the sample in mg/kg resin, using the
formula:
Cs = f * As * b / a
Where: Cs: the concentration of formaldehyde in the sample in mg/kg

f: calibration factor for formaldehyde
As: sample peak surface area from formaldehyde
a: the amount of sample solution, in g.
b: the amount of sample and buffer solution, in g
Accuracy of the analysis method is determined by analysing 1 sample 10 times

(including sample preparation). The relative standard deviation is about 2 %.
8. Remarks
8.1 Prepare a fresh buffer solution(6.1) as often as possible and discard the old
buffer solution because of the possibility of bacterial growth in this buffer
solution.The buffer solution remains stable for approximately 1 week.
8.2 Mix the Hantz reagent carefully for at least 30 minutes. This is necessary
because the miscibility especially of the acetylaceton is difficult. The Hantz
reagent is stable for maximum 1 week.
8.3 Clean sparge filters every week. The filter is situated in bottle A at the end of the
tubing from the bottle A to the gradient mixer. There must be a free flow from
buffer solution to the gradient mixer when disconnecting line A from the gradient
mixer. Remove the filter from the tubing and place with 2-propanol (5.11) for 5
minutes into a ultrasonic bath (4.3). Rinse with water (5.5), also for 5 minutes in
an ultrasonic bath (4.3).
8.4 Replace the seals once every year.
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DSM Melamine
Skill Centre
9. References
G:\skill centre\organization\analytical methods\doc\305v1.doc

RC 96 13120
10. Reason for revision

New method
11. Attachments
11.1 Gradient compositions

11.2 Chromatogram of a standard formaldehyde solution
11.3 Chromatogram of a sample solution
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DSM Melamine
Skill Centre
Attachment 11.1 Gradient compositions
Three methods are used to run the methylol analysis. Method 1 and 2 are used to
activate the column and method 3 is used to run the real methylol analysis.
Method 1 is used when starting at 100% buffer and ending at 100% buffer, while
method 2 is used when starting at 50% buffer and ending at 100% buffer.
So depending on the stop conditions of the former analysis (the last eluent
composition can be seen by pressing ‘%’ key on the HPLC pump), method 1 or 2
should be used. The gradients used in method 1, 2 and 3 are summarised in table 1.
Increase the flow over the column gradually, start with a flow of 0.2 ml/min and
increase with steps of 0.2 ml/min till 1.0 ml/min. Avoid sudden pressure pulses and
abrupt changes in eluent compositions.
Note: Method 2 stops with another eluent composition than it starts. Be sure to
stop the run before the end of this run. The initial ‘%’ must be manually reset
to 0% (B).
Table 1: Gradient composition of method 1,2 and 3.
Method 1 Method 2 Method 3

Time Composition Time Composition Time Composition
* * *
0 0% (B) 0 50% (B) 0 0% (B)
10 80% (B) 10 80% (B) 30 30% (C)
15 80% (B) 15 80% (B) 38 70% (C)
20 50% (B) 20 50% (B) 40 100% (C)
30 0% (B) 30 0% (B) ** 40.01 20% (B)
42.5 80% (B)
45 20% (B)
45.01 100% (C)
50 0% (B)
* Rest is (A)
** This method stops with another eluent composition than it starts. Do not stop the
gradient run before initial ‘%’ is reset to 0% (B).
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DSM Melamine
Skill Centre
Attachment 11.2 Chromatogram of a standard formaldehyde solution
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DSM Melamine
Skill Centre
Attachment 11.3 Chromatogram of a sample solution
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DSM Melamine
Skill Centre Melamine
Sampling method 400, version 2 Date: 22 August, 2003
SAMPLING BY THE BLADDER METHOD
Authorisation :
(signature)
Jan Jaap Nusselder, Manager PAR Skill Centre Melamine.
Keywords: Urea, Sampling, Bladder
1. Scope and Field of Application
Sampling of products by means of a rubber bladder and preliminary treatment of the

sample for analysis.
The method is particularly intended for use:
· Under those circumstances where the usual method of sampling (for instance
draining ) may lead to losses or to changes in the composition of the product.
· With products flowing through a line at elevated temperature and under a
pressure which is at least slightly above atmospheric.
· With products composed of a more or less concentrated liquid-phase and a
gas-phase.
2. Safety
- Use the required personal protective devices during sampling (extra long rubber
gloves and face shield).
- Sampling should be done by two persons.
- Take into account the temperature and pressure in the line.
- Always follow local safety regulations.
Work safely, especially with hazardous chemicals. Use the guidelines of e.g. Safety
Data Sheets (SDS) or a local equivalent.
3. Principle
Collecting of the sample in a bladder partly filled with water.

Calculation of the amount of water and the amount of sample from the differences
between the mass of the empty bladder and the mass of the bladder before and after
sampling.
Introducing of the contents of the bladder to a measuring flask or use as such.
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Method 400V2 page 1 of 5

DSM Melamine
4. Apparatus
4.1 Natural rubber bladder ( diameter about 35 cm), provided with a PTFE adapter,
with PTFE -stopcock for example BOLA-stopcock-hose connector, ( Cat.No. E
650-12, connector outer ø 11.0 mm, stopcock bore 6.0 mm) and thick-walled
transparent silicon tubing ( length approx. 15 cm), usable specially at high
temperatures ( above 75 °C ), see figure 1
4.2 Natural rubber bladder ( diameter about 35 cm), provided with a PVC adapter,
with PVC-stopcock for example COMER-stopcock, (D.20, PN16, DN15-½"PVC,
stopcock bore 14 mm) and thick-walled transparent silicon tubing ( length
approx. 15 cm), usable until a maximum temperature of 75 °C, see figure 1
4.3 Bladders e.g. Glassworks: A.J.Janssen, Geleen, The Netherlands
4.4 Balance e.g. Mettler Toledo PG-2002.
4.5 Faceshield, e.g. type Perfo B from MS Safety Shop Schippers Bladel BV
4.6 Rubber gloves extra long, e.g. Emperor 108 from MS Safety Shop Schippers
Bladel BV
4.7 Hose clambs, 10-14 mm
5. Chemicals
5.1 Demi-water
5.2 Hydrochloric acid (2 mol/L), e.g. titrisol Merck
6. Procedure
6.1 Preparation of the bladder:

In case of a new bladder:
- Rinse with hydrochloric acid (5.2) to remove the talcum powder.
- Rinse the bladder with water until pH is neutral.
6.1.1 Method a:
- Inspect the bladder by inflating with N2 and immersing in a bin filled with water.
- Wash the inside of the bladder with water (5.1) to remove any impurities.
- Remove the water thoroughly as possible and weigh the dry empty bladder
(m 0).
- After that, transfer 750 ml of water (5.1) into the bladder and shake for 1 min.
- Fill a 250 ml flask with water from the bladder and close the flask (= solution to
be used in the determination of the blank).
- Remove the air from the bladder and weigh (m 1).
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DSM Melamine
6.1.2 Method b:
- Remove the water thoroughly as possible and weigh the dry empty bladder
(m 0).
- Transfer approx. 500 ml of water (5.1) into the bladder, remove the air from
the bladder and weigh (m 1).
6.2 Sampling:
- Use the required protective devices: rubber gloves (4.6) and face shield (4.5).
- If the sampling valve is clogged, heat it gently, taking care not to overheat one
point of the valve.
- After that, carefully open the sampling valve and purge the sampling line for a
few moments to the chemical sewer or in the open air.
- Close the valve and, if necessary, clean the sampling point properly.
- Connect the bladder to the sampling point and open the bladder cock.
- Proceed as follow:
- One person holds the connection between the bladder and the sampling point
with one hand (with glove (4.6)) and handles the sampling valve with the other
hand. The other person shakes the bladder in the mean time.
- Open carefully the sampling valve and introduce a smooth constant stream of
the product into the bladder (check flow visual through the silicon tube). Stop
sampling as soon as the required amount of the product has been collected in
the bladder.
- First close the sampling valve and then the bladder cock and immediately
remove the bladder from the sampling point.
- Allow the bladder to cool and weigh (m 2).
6.3 Preliminary treatment of the sample for analysis:
6.3.1 Method a:
- Transfer the content of the bladder into a 2-litre measuring flask.
- Rinse the bladder several times with water (5.1).
- Discharge the water into the measuring flask.
- Fill up to 2000.0 ml with water (5.1) and mix (= solution A).
- For calculation of the dilution factor see 7.
6.3.2 Method b:
- Transfer the content of the bladder into a flask and mix.
- Depending on the amount of the sample and the probably composition, take
aliquot portions of the resulting solution for use in the determinations specified.
- For calculation of the dilution factor see 7.
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DSM Melamine
7. Calculation
The dilution factor (f) is calculated with the formula:
For method a:
2000
f= ---------------
( m2- m 1)
for method b:
( m2- m 0 )
f= ---------------
( m2- m 1)
Where:
f : dilution factor
m2 : weight bladder + water + sample in g
m1 : weight bladder + water in g
m0 : weight bladder in g
(weigh accuracy 0.01 g)
8. Reference
G:\methods\doc\400v2.doc
DSM method M 0003-E
CHEMLAB 1921 MN
9. Reason for Revision
Upgrade and addition of calculation formula
10. Attachments
Figure of apparatus for sampling by the bladder method
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DSM Melamine
Attachment 1:
Figure 1: Apparatus for sampling by the bladder method
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DSM Melamine UCONTROLLED COPY
Sampling method 401, version 2 Date: 24 September, 2002

SAMPLING OF PRODUCTS FROM THE UREA PLANT
( bladder method)
Authorisation :
(signature)
Keywords: Urea, Sampling, Bladder
1. Scope and Field of Application
Sampling:
a. the urea solution of the outlet of the reactor
b. the urea solution of the outlet of the stripper before the expansion valve
c. the urea melt from the evaporation unit
d. the urea solution of the outlet recirculation separator
e. the carbamate solution from the low pressure carbamate condensor
f. the liquid to the desorber
g. the reflux condensor level tank
h. the urea solution from the buffertank
i. The liquid from the desorber to the sewer
This method is to be used in combination with sampling method SCM-400.
2. Safety
- Use the required personal protective devices during sampling (extra long rubber
gloves and face shield).
- Sampling should be done by two persons.
- Take into account the temperature and pressure in the line.
- Always follow local safety regulations.
Work safely, especially with hazardous chemicals. Use the guidelines of e.g. Safety Data
Sheets (SDS) or a local equivalent.
3. Chemicals
3.1 Demi-water
3.2 Hydrochloric acid (2mol/L) e.g. titrisol Merck
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DSM Melamine UCONTROLLED COPY
4. Procedure
4.1 Preparation of the bladder:

For the products as described above under 1.c. - 1.i. follow method a.
For the products as described above under 1.a. and 1.b., proceed as follows:
- wash the bladder twice with warm (± 50 °C) hydrochloric acid (3.2), each time use
about 200 ml
- after that, wash with water until pH is neutral.
If pH is neutral proceed with method a.
4.1.1 Method a:
- Remove the water thoroughly as possible and weigh the dry empty bladder (m 0 ).
- Transfer approx. 500 ml of water (3.1) into the bladder, remove the air from the
bladder and weigh (m 1 ).
4.2. Sampling:
Follow procedure a (see sampling method SCM-400 under 6.2) for the products as
described above under 1.a. - 1.e. and 1.g.
Follow procedure b (see sampling method SCM-400 under 6.2) for the products as
described above under 1.f., 1.h. and 1.i.
In this way usually collect about 400 g of the products in the bladder.
4.3. Preliminary treatment of the sample for analysis:

Follow method a (see sampling method SCM-400 under 6.3).
5. Reference
DSM method M 0003 31-E
Upgrade.
Point i of the sampling in paragraph 1, Scope and Field of Application, was missed in
paragraph 4.1., preparation of the bladder and in paragraph 4.2., sampling.
7. Attachments
No attachments.
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DSM Melamine UNCONTROLLED COPY
Analytical method 402, version 1 Date: 10 May, 2000
DETERMINATION OF BIURET IN UREA

Authorisation :
(signature)
Jan Jaap Nusselder, manager PAR Skill Centre Melamine
Keywords: Biuret, Urea, Spectrophotometric
1. Scope
Determination of the biuret content of urea.

The method is also applicable to products formed in the preparation of urea.
Cyanuric acid does not interfere if the amount of sample for analysis contains less than
25 mg of cyanuric acid.
Ammonia bound as carbonate, hydrogen carbonate or carbamate, does not interfere if
the solution to be measured with the spectrophotometer contains less than 1.5 mg of
NH3. If more than 1.5 mg of NH3 is present, see 9.1.
Water-insoluble substances that can’t be removed by filtration do not interfere
(see 9.2).
The determination can also be performed by means of filter photometry.
2. Safety
Copper(II) sulphate pentahydrate
Potassium sodium tartrate tetrahydrate
Potassium hydroxide
Biuret
Methanol
Ammonium hydroxide
Acetone.
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3. Principle
In an alkaline medium biuret reacts with copper(II) sulphate to form a violet complex
compound. Excess of copper is kept in solution by means of potassium sodium tartrate.
The extinction of the coloured solution is measured at a wavelength of 550 nm.
4. Apparatus
4.1 Ultra sonic bath e.g. Cole Parmer type 8893, set at 20°C
4.2 Drying oven, temperature set at 105°C e.g. Hereaus type VT 6130M
4.3 Spectrophotometer or filterphotometer e.g. Hitachi. In case of a filterphotometer it
should have a filter with a maximum transmission at app. 550 nm.
4.4 Steam bath e.g. Type LT 6 from Labo Tech
4.5 Magnetic stirrer e.g. IKA combi mag. RCT
4.6 1G3 filter crucible
4.7 Diaphragm vacuum pump, e.g. Vacuubrand type MZ-2C
4.8 Rotavapor, e.g. Büchi type R-124
4.9 Pressure gauge, e.g. Vacuubrand type DVR-1
4.10 Round bottom boiling glask, e.g. Duran, 100 ml with joint 24/29
5. Chemicals
5.1 Demi water, free from carbon dioxide: boil demi water under reflux for 15 minutes,
cool down to 20°C. Cover this water with a nitrogen gas blanket.
5.2 Copper (II) sulphate pentahydrate (CuSO4.5H2O) cryst. extra pure e.g. Merck
5.3 Copper (II) sulphate solution: dissolve in demi water (5.1) in a 1L measuring flask
6.00 g of copper(II)sulphate pentahydrate (5.2). Fill up to 1000.0 mL with demi
water (5.1) and mix (see 9.3).
5.4 Potassium hydroxide (KOH) pellets 85% p.a. e.g. Merck
5.5 Potassium sodium tartrate tetrahydrate (KNaC4H4O6.4H2O) cryst. extra pure e.g.
Merck.
5.6 Potassium sodium tartrate solution: dissolve in demi water (5.1) in a 1L measuring
flask 32.0 g of potassium hydroxide (5.4) and 20.0 g of potassium sodium tartrate
(5.5). Fill up to 1000.0 mL with demi water (5.1) and mix. Allow this solution to stand
for 2 days before using it or place the solution for 10 minutes in an ultra sonic bath
(4.1) at 20°C.
5.7 Biuret (C2H5N3O2 ) ± 99% e.g. Fluka, dried for 3 hours at 105°C in a drying oven
(4.2) (see 9.5).
5.8 Methanol 99% e.g. Merck.
5.9 Ammonium hydroxide, 28% NH3 in water e.g. Sigma
5.10 Ammonium hydroxide 10 wt%, dilute 35.71 g of ammonium hydroxide (5.9) in
64.29 g demi water in a 200 ml measuring flask and mix.
5.11 Acetone, 99% e.g. Merck
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6. Calibration
– Dissolve in demi water in a 1L measuring flask, 4.000 g of biuret (5.7), fill up with
demi water and mix (= solution I).
– Dissolve in demi water in a 500 ml measuring flask, 2.000 g of biuret (5.7), fill up with
demi water and mix (= solution II).
– Pipette 100.00 ml of solution I into a 500 ml measuring flask, fill up with demi water
and mix (= solution G). (1 ml º 0.8 mg biuret)
– Pipette 50.00 ml of solution II into a 250 ml measuring flask, fill up with demi water
and mix (= solution K). (1 ml º 0.8 mg biuret)
– Take two series of eight 50 ml measuring flasks.
– Pipette into the flasks of each series 0, 5.00, 11.00, 17.00 ml of solution G and 2.00,
8.00, 14.00, 20.00 ml of solution K.
– Introduce into the eight flasks of the first series:
10.00 ml potassium sodium tartrate solution (5.6)
10.00 ml copper (II) sulphate solution (5.3)
Fill up with demi water and mix (= standard solutions).
– Introduce into the eight flasks of the second series:
Fill up with demi water and mix (= reference solutions).
– Perform the following measurements at a wavelength of 550 nm and an optical path
length of 4 or 5 cm using a spectrophotometer (4.3).
– Adjust the photometer to 100% transmission relative to each reference solution, and
measure the extinction (E0= extinction of standard solution containing no biuret, Ei=
extinction of standard solution containing biuret) of the corresponding standard
solution.
7. Sample preparation
– Weigh a g (accurate to 1 mg) of sample into a 200 ml measuring flask (see 9.1 and
9.7). Usually ± 10 g of sample is used so that 1 – 15 mg of biuret will be present in
the extinction measurement.
– Fill up with demi water and mix. If necessary, filter through a folded filter (= solution
A).
– Pipette 20.00 ml of solution A into a 50 ml measuring flask and add:
Fill up with demi water and mix (= solution B).
– Pipette 20.00 ml of solution A into a second 50 ml measuring flask and add:
Fill up with demi water and mix (= solution C).
– Add into a third 50 ml measuring flask:
Fill up with demi water and mix (= solution D) (see 9.4).
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– Add into a fourth 50 ml measuring flask:

Fill up with demi water and mix (= solution F).
length of 4 or 5 cm using a spectrophotometer (4.3)
– Adjust the photometer to 100% transmission relative to solution F and determine the
extinction of solution D (=ED) (see 9.4).
– Adjust the photometer to 100% transmission relative to solution C and determine the
extinction of solution B (=EB).
8 Calculation
8.1 Calculation of the biuret calibration curve.
Calculate the calibration factor of each standard solution using formula:
Ci
fi= -----------
Ei – E0
Where: fi= calibration factor for standard solution i

Ci= biuret concentration of standard solution i in mg/50 ml
E0= extinction of standard solution containing no biuret.
Ei= extinction of standard solution containing biuret.
Calculate the average calibration factor, or use linear regression to calculate the
calibration curve (see attachment 1).
8.2 Calculation of the biuret content in wt% using formula:
b * 200 * 100 b
wt% biuret= ---------------------- = ----
1000 * a * 20 a
Where: b= amount of biuret (mg/50 ml) corresponding to the difference

in extinction (EB-ED)
a= amount of sample taken into investigation (g)
Accuracy of the analysis method determined by analysing 1 sample 10 times (including

sample preparation). The relative standard deviation = 2.0% (based on 1 times s).
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9. Remarks
9.1 If the solution to be measured with the spectrophotometer contains more than 1.5
mg of NH3 proceed as follows:
– Transfer a g of sample into a 250 ml beaker.
– Add 5 ml of demi water.
– Add 50 ml of methanol (5.8).
– Add a few boiling chips.
– Heat to boiling temperature on a steam bath (4.4) (fume-cupboard) and evaporate
until 10 ml of liquid is left.
– Cool down to ± 25 °C.
– Transfer the content of the beaker to a 200 ml measuring flask. Fill up with demi
water and mix. If necessary filter through a folded filter (= solution A).
– Proceed as described under chapter 7.
9.2 Water- insoluble, non-filterable substances produce turbidity. This affects the
extinction in such way that too high biuret concentrations may be found. By
measuring with respect to a reference solution this hazard is eliminated.
9.3 Copper(II)sulphate is not stable in solutions containing carbon dioxide. After
a while a precipitate of basic copper carbonate will form.
9.4 To check the condition of the copper(II)sulphate solution, run a blank with this
solution (=D) each time an analysis is performed. The extinction ED should remain
constant. If it does not, adjust the copper(II)sulphate solution to the concentration
prescribed.
9.5 If biuret is contaminated with cyanuric acid and/or urea, it should be purified as
follows:
– Transfer 5 g of biuret into a 100 ml beaker.
– Add 15 ml of ammonium hydroxide 10 wt% (5.10).
– Add a magnetic stirring rod and stir (4.5) for 15 minutes. Cyanuric acid and urea
dissolve while biuret is practically insoluble.
– Pass the solution through a 1G3 filter crucible (4.6) and wash the crucible twice
with 5 ml of demi water followed by three times with 10 ml of acetone (5.11).
– Finally dry (4.2) for 3 hours at 105°C and keep the biuret in a brown, wide-mouth
bottle with ground stopper.
9.6 Urea causes an increase in extinction. Per g of urea in 50 ml of the solution to be
measured with the spectrophotometer the extinction increases with 0.0034, which
corresponds to 0.17 mg of biuret.
9.7 For the determination of biuret in urea solutions prepare the sample as follows:
– Place a round bottom boiling flask (4.10) for 1 hour in a drying oven (4.2) at 105 °C.
Allow the flask to cool in a desiccator.
– Weigh a g (accurate to 0.01 g) of the sample to this flask. Use such an amount of
sample that a residue of 3 – 8 g will be obtained.
– Connect the flask to the rotavapor (4.8).
– Set the water bath of the rotavapor at a temperature of 40 °C (In case of urea
solutions with small amounts of biuret never use temperatures higher than 50°C) and
the stirrer speed to 150 rpm.
– Use a vacuum pump (4.7) to create a vacuum of 50 mbar, read on a pressure gauge
(4.9).
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– Stop evaporating when the content of the flask has solidified, allow the flask to stand
for 25 minutes.
If ammonia and/or ammonium salts are present in the urea solution in amounts
interfering with the determination of biuret (more than 1.5 mg of NH3 in the solution
to be measured with the spectrophotometer) proceed as follows:
After evaporation add 50 ml of methanol (5.8) to the content of the flask.
Again evaporate to dryness
– After that, place the flask for 1 hour in a drying oven (4.2) at 105 °C. Allow the flask to
cool in a desiccator.
– Dissolve the content of the flask in water.
– Transfer the solution into a 200 ml measuring flask, fill up with demi water and mix.
If necessary, filter through a folded filter (= solution A).
– Proceed as described under chapter 7 using this solution as solution A.
10. Reference
G:\Os99\990120020.xls
DSM method 135-E
DSM method 382-E
AGRO method 0042-E
Upgrade.
12. Attachments
An example of a biuret calibration curve.
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Attachment 1: Biuret calibration curve (wavelength 550 nm, optical path length 5 cm)
Calibration curve Biuret

(w avelength: 550 nm, optical path length: 5cm)
0,400
0,350
y = 0,0218x
0,300 R2 = 0,9961
extinction (550 nm)
0,250
0,200
0,150
0,100
0,050
0,000
0,00 2,00 4,00 6,00 8,00 10,00 12,00 14,00 16,00 18,00
concentration biuret m g/50 m l
[Biuret] (mg/50 ml) Extinction

(*)
0,00 0,000
1,60 0,044
4,00 0,097
6,41 0,144
8,81 0,193
11,21 0,244
13,61 0,304
16,02 0,337
(*): Photometer adjusted to 100% transmission relative to the reference solution and
the extinction of the corresponding standard solution was measured.
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Analytical method 403, version 1 Date: 13 September, 2001
DETERMINATION OF CARBON DIOXIDE IN PRODUCTS FROM THE

UREA PLANT
(formaldehyde method)
Authorisation :
(signature)
Keywords: Urea, Carbon dioxide, Titrimetric, Potentiometric, Formaldehyde
1. Scope
Determination of the carbon dioxide content of ammonium containing solutions

obtained in the preparation of urea.
Acid radicals other than carbonate, carbamate or bicarbonate should be absent.
Guanidine interferes with the determination.
The method is applicable to amounts of 20mg/L – 600 mg/L of carbon dioxide (see 8.2)
in the presence of not more than 2 g of ammonia. The ratio of “free“ ammonia to
“carbon-dioxide-bound” ammonia should not exceed 4.
2. Safety
Urea
Hydrochloric acid
Sodium hydroxide
Formaldehyde
Never use concentrated hydrochloric acid in the neighbourhood of formaldehyde

because formaldehyde reacts with hydrochloric acid giving off very toxic
“bis(chloromethyl)ether“, which can cause lung cancer.
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3. Principle
– Binding of carbon dioxide (present as ammonium carbonate, ammonium carbamate

and ammonium bicarbonate) as sodium carbonate by treatment with a known amount
of sodium hydroxide, ammonium hydroxide being formed.
– Conversion of ammonium hydroxide into hexamethylenetetramine and water by
addition of formaldehyde.
– Potentiometric titration with hydrochloric acid of the excess sodium hydroxide and the
sodium carbonate formed, to pH 8.7. The amount of acid consumed is a measure of
the carbon-dioxide content.
4. Apparatus
4.1 Potentiometric titrator, e.g. Mettler DL 25

4.2 Combi pH electrode, e.g. Orion
5. Chemicals
5.1 Hydrochloric acid 0.1 mol/L, e.g. titrisol Merck

5.2 Hydrochloric acid 0.5 mol/L, e.g. titrisol Merck
5.3 Sodium hydroxide 0.2 mol/L, e.g. titrisol Merck
5.4 Sodium hydroxide 1.0 mol/L, e.g. titrisol Merck
5.5 Formaldehyde solution 37 wt% neutralized to pH 8.7, e.g. Merck
5.6 Demi water free from carbon dioxide: boil demi water under reflux for 15 minutes,
cool down to 20°C. Cover this demi water with a nitrogen gas (5.7) blanket.
5.7 Nitrogen, free from carbon dioxide
6. Procedure
– Perform all the operations while passing nitrogen (5.7) over the solution.
– Pipette 15.00 ml of sodium hydroxide into a 250 ml beaker.
Use sodium hydroxide solution (5.3) if 20 – 100 mg/L of carbon dioxide is present.
Use sodium hydroxide solution (5.4) if 100 – 600 mg/L of carbon dioxide is present.
– Add vc ml of sample, accurate to 0.01 ml. Use such an amount of sample that 20 –
600 mg of carbon dioxide will be present in 100 ml (see 8.1).
– Dilute to 150 ml with demi water (5.6).
– Add a magnetic stirring bar.
– Add 25.0 ml of formaldehyde solution (5.5).
– Slowly titrate (4.1, 4.2) to pH 8.7 with hydrochloric acid (5.1) if sodium hydroxide
solution (5.3) has been used.
– Slowly titrate (4.1, 4.2) to pH 8.7 with hydrochloric acid (5.2) if sodium hydroxide
solution (5.4) has been used.
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– Stop the titration if the pH remains 8.7 for 5 seconds. Titrant consumption= v ml.
– Run a blank. Titrant consumption = v0 ml.
7. Calculation
7.1 Calculation of the carbon dioxide content in mg/L using the formula.
(v0 - v) * c * 44 * 1000
--------------------------------
vc
Where: v0 = amount of hydrochloric acid consumed in the blank in ml

v = amount of hydrochloric acid consumed in the determination in ml
c = concentration of hydrochloric acid used in mol/L
vc = amount of sample taken into investigation in ml
44 = molar mass of carbon dioxide in g/mol
8. Remarks
8.1 The method is applicable to the following urea solutions:

a. urea solution outlet reactor (vc = ± 10 ml)
b. urea solution outlet stripper before expansion valve (vc = ± 25 ml)
c. gas from rectifying column to low pressure carbamate condensor
(vc = ± 10 ml)
d. urea solution outlet recirculation separator (vc = ± 100 ml)
e. carbamate solution from low pressure carbamate condensor (vc = ± 5 ml)
f. liquid to desorber (vc = ± 25 ml)
g. reflux condensor level tank (vc = ± 5 ml)
h. urea solution from buffertank (vc = ± 100 ml)
8.2 For solutions with a carbon dioxide concentration < 20 ml/L, a infrared detection
method should be used.
9. Reference
DSM 0648-E
DSM 0648 10-E
SCM 024
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11. Attachments
No attachments
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Analytical method 404, version 1 Date: 29 May, 2000
DETERMINATION OF UREA IN UREA SOLUTIONS

(gravimetric method)
Authorisation :
(signature)
Jan Jaap Nusselder, manager PAR Skill Centre Melamine.
Keywords: Urea, Gravimetric
1. Scope
Determination of the urea content of urea solutions. Compounds, yielding an

evaporation residue (e.g. biuret) by the side of urea, are included in the
determination. The method is not applicable in the case of higher biuret contents.
2. Safety
Work safely. Use the guidelines of e.g. Safety Data Sheets (SDS) or a local
equivalent.
3. Principle
- Removal of water, ammonium- carbonate and carbamate and other volatile

substances by evaporation.
- Determination of the mass of urea as evaporation residue.
4. Apparatus
4.1 Diaphragm vacuum pump, e.g. Vacuubrand type MZ-2C

4.2 Rotavapor, e.g. BÜCHI type R-124
4.3 Pressure gauge, e.g. Vacuubrand type DVR-1
4.4 Drying oven, e.g. Heraeus type T6120
4.5 Round bottom boiling flask, e.g. Duran ,100 ml , with joint 24/29
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5. Chemicals
No chemicals necessary.
6. Procedure
- Place the round bottom boiling flask (4.5) for 1 hour in a drying oven (4.4) at 105
°C. Allow the flask to cool in a desiccator and weigh the flask (m0 g) (accurate to
0.01 g).
- Weigh a g (accurate to 0.01 g) of the sample into this flask. Use such an amount
of sample that a residue of 3 – 8 g will be obtained.
- Connect the flask to the rotavapor (4.2).
- Set the water bath of the rotavapor at a temperature of 40 °C and the stirrer
speed to 150 rpm.
- Use a vacuum pump (4.1) to create a vacuum of 50 mbar, read on a pressure
gauge (4.3).
- Stop evaporating when the content of the flask has solidified (see 8.2), allow the
flask to stand for 25 minutes.
- After that, place the flask for 1 hour in a drying stove at 105 °C. Allow the flask to
cool in a desiccator and weigh the flask (m1 g) (see 8.1).
7. Calculation
Calculate the urea content in g/kg, using the formula:
( m1 - m0 )
-------------- * 1000
a
Where:
m0 = weight of flask, empty and dried, in g
m1 = weight of flask with evaporation residue after drying, in g
a = the sample amount of the original sample in g
(weigh accuracy 0.01 gram)
Accuracy of the analysis method determined by analysing 1 sample 10 times

(including sample preparation). The relative standard deviation = 5 % (based on 1
times s).
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8. Notes
8.1 If more than 40 mg biuret is present in 1 g of evaporation residue, this residue

will not be freed of water in drying for 1 hour at 105 °C. In this case, urea has
to be determined via the determination of total nitrogen.
8.2 Keep the evaporation residue for the determination of biuret, if so desired.
9. Reference
DSM method 0382-E
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11. Attachments
No attachments.
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DETERMINATION OF UREA
(spectrophotometric method, diacetyl monoxime method)
Authorisation :
(signature)
Keywords: Urea, Spectrophotometric, diacetyl monoxime
1. Scope
Determination of the urea content of NP and NPK granules and of water, in

concentrations from 0.5 to 10 mg/kg and mg/L, respectively. If the procedure described
here is followed, hydrazine (< 0.2 mg/L) and ammonia do not interfere.
2. Safety
Urea
Sulphuric acid
Phosphoric acid
Acetic acid
Diacetyl monoxime
Thiosemicarbazide
Iron(III)chloride hexahydrate
Diacetyl monoxime and thiosemicarbazide are very toxic, take the appropriate
precautions (fume-cupboard, gloves and goggels).
3. Principle
Reaction of urea with diacetyl monoxime in a phosphoric acid medium to form a violet-
coloured compound (using iron (III) as a catalyst).
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4. Apparatus
4.1 Spectrophotometer or filterphotometer e.g. Hitachi. In case of a filterphotometer it

4.2 Electric laboratory mill, e.g. Retsch type ZM 100
4.3 Circulatory thermostat e.g. Lauda type M12
4.5 Brown bottle e.g. Duran Schott
4.6 Double fluted filter normal speed, e.g. Schleicher & Schuell type 1506
5. Chemicals
5.1 Sulphuric acid (H2SO4), 18 mol/L (r 1.84 g/ml), e.g. Merck

5.2 Phosphoric acid (H3PO4), 15 mol/L (r 1.71 g/ml), e.g. Merck
5.3 Acetic acid (C2H4O2), 18 mol/L (r 1.06 g/ml), e.g. Merck
5.4 Acetic acid 2 wt% solution, dilute 20 g acetic acid (5.3) in 980 g of demi water and
mix.
5.5 Diacetyl monoxime (C4H7N02) > 99%, e.g. Merck
5.6 Diacetyl monoxime solution 25 g/L: dissolve 25 g of diacetyl monoxime (5.5) in
acetic acid (5.4) in a 1 L measuring flask, make up to the mark with acetic acid
(5.4) and mix.
5.7 Thiosemicarbazide (CH5N3S) > 98%, e.g. Merck
5.8 Thiosemicarbazide solution 5 g/L: dissolve 5 g of thiosemicarbazide (5.7) in demi
water in a 1L measuring flask, make up to the mark with demi water and mix.
5.9 Colour reagent: Pipette 67.0 ml of acetyl monoxime solution (5.6) and 67.0 ml of
thiosemicarbazide solution (5.8) in a 1L measuring flask, make up to the mark
with demi water and mix.
5.10 Iron (III) chloride hexahydrate (FeCl3.6H20) > 99%, e.g. Merck
5.11 Iron (III) chloride solution 15 g/L: dissolve 15 g of iron (III) chloride (5.10) in demi
water in a 1L measuring flask, make up to the mark with demi water and mix.
5.12 Phosphoric acid iron (III) solution: add 25 ml of iron (III) chloride solution (5.11)
and 150 ml of water to 300 ml of phosphoric acid (5.2) and mix.
5.13 Acid reagent: pipette 1.00 ml of phosphoric acid iron(III) solution (5.12) into a 1L
measuring flask, add 700 ml of demi water and mix. While stirring and cooling,
cautiously add 200 ml of sulphuric acid (5.1) and mix. Store the reagent in a
brown bottle (4.5).
5.14 Urea > 99.8 wt%, e.g. Merck
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6. Calibration
– Dissolve in demi water in a 1L measuring flask, 1000 mg of urea (5.14), make up to

the mark with demi water and mix (= solution I).
– Dissolve in demi water in a 500 ml measuring flask, 500 mg of urea (5.14), make up
to the mark with demi water and mix (= solution II).
– Pipette 10.00 ml of solution I into a 1L measuring flask, make up to the mark with
demi water and mix (= solution A, 1 ml º 0.01 mg urea).
– Pipette 5.00 ml of solution II into a 500 ml measuring flask, make up to the mark with
demi water and mix (= solution B, 1 ml º 0.01 mg urea).
In the case of measurements at a path length of 5 cm, proceed as follows:

– Pipette into measuring flasks of 50 ml: 0 (= blank), 2.00 and 4.00 ml of solution A and
1.00 and 3.00 ml of solution B.
– Dilute all flasks to 10 ml with demi water.
– Add 5.0 ml of colour reagent (5.9) and mix.
– Add 20.0 ml of acid reagent (5.13) and mix.
– Place the flasks in the thermostat (4.3) and allow to stand at 90 °C for 1 hour.
– Cool to room temperature.
– Make up to the mark with demi water and mix.
– Determine the absorbance (4.1) at a wavelength of 525 nm and a path length of 5
cm.
In the case of measurements at a path length of 1 cm, proceed as follows:

– Pipette into measuring flasks of 50 ml: 0 (= blank), 1.00, 5.00 and 7.00 ml of solution
A and 3.00 and 9.00 ml of solution B.
– Dilute all flasks to 10 ml with demi water.
– Place the flasks in the thermostat (4.3) and allow to stand at 90 °C for 1 hour.
– Determine the absorbance (4.1) at a wavelength of 525 nm and a path length of 1
cm.
7.1 NP and NPK granules
– Grind the granules (4.2) to a particle size of less than 0.5 mm. This should be done
in a room with a relative humidity of 40-60% and a temperature of 22 ± 2°C.
– Weigh a g (accurate to 1 mg) of sample into a 250 ml measuring flask. Usually ± 10 g
of sample is used.
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– Add a stirring bar to the flask.

– Add 200 ml of demi water.
– Place the flask on a magnetic stirrer (4.4) and stir for 1 hour.
– Remove the stirring bar from the flask, make up to the mark with demi water and mix.
– Filter through a double fluted filter (4.6), discarding the first two 30 ml portions of the
filtrate.
– Pipette v ml of the clear filtrate into a 50 ml measuring flask. Perform the analysis on
max. 10 ml of solution which may contain at most 0.1 mg of urea.
– Dilute to 10 ml if necessary.
– Add to a second 50 ml measuring flask 10 ml of demi water (=blank).
– Place the flasks in the thermostat (4.3) and allow to stand at 90°C for 1 hour.
– Determine the absorbance (4.1) at a wavelength of 525 nm and a path length of 1 or
5 cm.
7.2 Urea solutions
– If the urea solution is turbid, filter through a double fluted filter (4.6).
– Pipette v ml of the clear solution into a 50 ml measuring flask. Perform the analysis
on max. 10 ml of solution which may contain at most 0.1 mg of urea.
– Dilute to 10 ml if necessary.
– Add to a second 50 ml measuring flask 10 ml of demi water (=blank).
– Place the flasks in the thermostat (4.3) and allow to stand at 90°C for 1 hour.
– Determine the absorbance (4.1) at a wavelength of 525 nm and a path length of 1 or
5 cm.
8 Calculation
8.1 Calculation of the urea calibration curve.
Ci
fi = -----------
Ei – E0
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Ci= urea concentration of standard solution i in mg/50 ml
E0= extinction of standard solution containing no urea (=blank)
Ei= extinction of standard solution containing urea
8.2 Calculation of the urea content of the NP and NPK granules in mg/kg using formula:
b * 250 * 1000
mg/kg urea = -----------------------
a*v
Where: b= amount of urea (mg/50 ml) corresponding to the difference in

extinction (Es-E0)
v= amount of clear filtrate in ml
Es= extinction of sample solution
E0= extinction of blank solution containing no urea
8.3 Calculation of the urea content of the urea solution in mg/L using formula:
b * 1000
mg/L urea = ------------------
v
Where: b= amount of urea (mg/50 ml) corresponding to the difference in

extinction (Es-E0)
v= amount of clear urea solution in ml

sample preparation for NP and NPK granules). The relative standard deviation = 1.0%
(based on 1 times s).
9. Remarks
9.1 The use of clean glassware is very important. Therefore it is recommended to wash
the glassware with acid reagent (5.13) and colour reagent (5.9) prior to
measurement.
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10. Reference
DSM-DMG 0209-E
Note ABR 87-10: Determination of trace quantities of urea (1)
Note ABR 88-21: Determination of trace quantities of urea (2)
Upgrade.
12. Attachments
An example of a urea calibration curve.
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Attachment 1: Example of a Urea calibration curve (wavelength 525 nm, optical

path length 1 cm)
Calibration curve Urea

(wavelength: 525 nm, optical path length: 1 cm)
0,45
0,4
0,35
extinction (525 nm)
0,3 y = 4,2749x
2
R = 0,9954
0,25
0,2
0,15
0,1
0,05
0
0 0,02 0,04 0,06 0,08 0,1
concentration urea in mg/50 ml
[Urea] Extinction Es – E0
(mg/50 ml) Es
0,00 0,0187 (= E0) 0
0.0101 0.0606 0.0419
0.0305 0.1624 0.1437
0.0506 0.2282 0.2095
0.0708 0.3347 0.3160
0.0915 0.3990 0.3803
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DETERMINATION OF WATER IN UREA
Authorisation :
(signature)
Keywords: Urea, Urea melt, Water, Hydranal, Biamperometric
1. Scope
Determination of water in urea. This method is also applicable to urea melt and to other
solid intermediate products from the urea plant.
2. Safety
Hydranal Composite 5K
Hydranal Working medium K
Hydranal Water standard
Methanol
Urea
3. Principle
- Dissolution of the urea directly in the Hydranal Working medium K in the titration
vessel. Or dissolution of the urea melt into methanol.
- Titration of water, in the urea or urea melt/methanol solution, with the Hydranal
Composite 5K titrant.
- Biamperometric detection of the titration endpoint, with a Pt/Pt-electrode.
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Method 406V1, page 1 of 5

4. Apparatus
4.1 Karl Fischer titrator, e.g. Mettler DL 18

4.2 Printer, e.g. GA42
4.3 Burette 5 ml, e.g. Mettler DV405.
4.4 PTFE coated bottle 500 ml and screw-cap, heat resistant to a temperature of 140 °C
e.g. Schott
5. Chemicals
5.1 Hydranal Composite 5K titrant (1 ml » 5 mg H20), e.g. Riedel de Haën

5.2 Hydranal Working medium K solvent, e.g. Riedel de Haën
5.3 Methanol, dry (water content <0.01 wt%), e.g. MERCK
5.4 Hydranal Water standard (1 g contains 10.0 ± 0.1 mg H20), e.g. Riedel de Haën.
6. Procedure
6.1 Titre determination of the Hydranal Composite 5K titrant (5.1)

- Determine the water content of the methanol (blank).
- Weigh 10 ml methanol (5.3), accurate to 0.1 mg.
- Transfer the methanol to the titration vessel (4.1) see (9.1).
- Perform the titration and determine the water concentration in wt%.
- Perform the analysis in triple and calculate the average water concentration = b1 wt%.
- Prepare three calibration standards.

- Weigh 20 ml methanol (= a1 g) (5.3) accurate to 0.1 mg to a 50 ml flask.
- Add 0.35 g (= a2 g) demi water accurate to 0.1 mg close the flask and mix properly.
- Weigh 1 g (accurate to 0.1 mg) of each calibration sample.
- Transfer the calibration sample to the titration vessel (4.1) see (9.1).
- Analyse the water concentration = b2 wt%.
- Calculate the titre of the Hydranal Composite 5K titrant in mg H2O/ml using the
formula given in 7.1.
6.2 Determination of water in the Hydranal Water standard (5.4)

- Weigh 1 g (= e g) Hydranal Water standard (5.4) accurate to 0.1 mg.
- Transfer this standard to the titration vessel (4.1) see (9.1).
- Perform the titration.
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- Calculate the water concentration in wt% according to the formula given in 7.2.
- The water concentration must be between the given borders of the Hydranal-Water
standard.
6.3 Determination of water in urea

- Weigh 10 g of urea accurate to 0.1 mg (= w g).
- Transfer the urea directly to the titration vessel (4.1) see (9.1).
- Wait 5 minutes until all the urea is dissolved in the Hydranal Working medium (5.2).
6.4 Determination of water in urea melt

- Weigh a dry bottle including screw cap (dried for 1 hour at 105°C) of 500 ml (4.4)
(= c1 g).
- Add ± 50 ml urea melt and weigh the bottle again (= c2 g).
- Cool down to ambient temperature.
- Add ± 400 ml methanol (5.3) and weigh the bottle again (= c3 g).
- Mix until all the urea is dissolved.
- Weigh ± 10 g (= c4 g) accurate to 0.1 mg of the urea/methanol solution using a
syringe.
- Transfer this solution to the titration vessel (4.1) see (9.1).
- Calculate the water concentration in the original urea melt sample according to the
7. Calculation
7.1 Titre calculation of the Hydranal Composite 5K titrant (in mg H2O/ml)
(b1 * a1 * 0.01) + a2
Tn = -------------------------- * 100 * T0
(a1 + a2) * b2
Where: a1 : weight of methanol for the calibration standard in g

a2 : weight of demi water for the calibration standard in g
b1 : average water concentration in the blank methanol in wt%
b2 : analysed water concentration in the calibration standard in wt%
T0 : old titre of the Hydranal Composite 5K titrant in mg H2O/ml
Tn : new titre of the Hydranal Composite 5K titrant in mg H2O/ml
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7.2 Calculation of the water concentration in the Hydranal Water standard in wt%
v*T
------------- * 100
e * 1000
Where: e : weight of the Hydranal Water standard in g

v : consumed Hydranal composite 5K titrant in ml
T : titre of the Hydranal composite 5K titrant in mg H2O/ml
7.3 Calculation of the water concentration in urea in wt%
v*T
------------- * 100
w * 1000
Where: w : weight of the urea in g

v : consumed Hydranal Composite 5K titrant in ml
T : titre of the Hydranal Composite 5K titrant in mg H2O/ml
Accuracy of the analysis method determined by analysing 1 sample 10 times. The

relative standard deviation = 4 % (based on 1 times s)
7.4 Calculation of the water concentration in the urea melt in wt%
(c3 – c1)
Dilution factor: f = ---------------
(c3 – c2)
f*v*T
wt% H2O in urea melt = -------------- * 100
c4 * 1000
Where: c1 : weight of the dry bottle in g

c2 : weight of the bottle with urea in g
c3 : weight of the bottle with urea and methanol in g
c4 : weight of the urea/methanol solution in g
T : titre of the Hydranal Composite 5K titrant in mg H2O/mL.
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Accuracy of the analysis method, including sample preparation determined by analysing

1 sample 10 times. The relative standard deviation = 4 % (based on 1 times s)
8. Reference
DSM 805-E
DMG 309
DMG 0281-2B-E
9. Remarks
9.1 Always close the titration vessel immediately to prevent moisture contamination.
Upgrade and new titrant and titration medium.

Titration medium Pyridine, which is very harmful, is replaced by hydranal.
11. Attachments
No attachments
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DSM Melamine
Analytical method 406, version 2 Date: 05 July 2004
DETERMINATION OF WATER IN UREA
Authorisation :
(signature)
Keywords: Urea, Urea melt, Water, Hydranal, Biamperometric
1. Scope
Determination of water in urea. This method is also applicable to urea melt and to other
solid intermediate products from the urea plant.
2. Safety
Hydranal Working medium K
Methanol
Urea
3. Principle
- Dissolution of the urea directly in the Hydranal Working medium K in the titration
vessel. Or dissolution of the urea melt into methanol.
- Titration of water, in the urea or urea melt/methanol solution, with the Hydranal
Composite 5K titrant.
- Biamperometric detection of the titration endpoint, with a Pt/Pt-electrode.
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4. Apparatus

4.4 PTFE coated bottle 500 ml and screw-cap, heat resistant to a temperature of 140 °C
e.g. Schott
5. Chemicals

5.2 Hydranal Working medium K solvent, e.g. Riedel de Haën
6. Procedure

- Determine the water content of the methanol (blank).
- Transfer the methanol to the titration vessel (4.1) see (9.1).

- Weigh 20 ml methanol (= a1 g) (5.3) accurate to 0.1 mg to a 50 ml flask.
- Add 0.35 g (= a2 g) demi water accurate to 0.1 mg close the flask and mix properly.
- Transfer the calibration sample to the titration vessel (4.1) see (9.1).

- Transfer this standard to the titration vessel (4.1) see (9.1).
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standard.
6.3 Determination of water in urea

- Fill the titration vessel with Hydranal Working medium K (5.2) and neutralize the water
content.
- Weigh 10 g of urea accurate to 0.1 mg (= w g).
- Transfer the urea directly to the titration vessel (4.1), see (9.1).
- Wait 5 minutes until all the urea is dissolved in the Hydranal Working medium K (5.2).
6.4 Determination of water in urea melt

- Weigh a dry bottle including screw cap (dried for 1 hour at 105°C) of 500 ml (4.4)
(= c1 g).
- Add ± 50 ml urea melt and weigh the bottle again (= c2 g).
- Cool down to ambient temperature.
- Add ± 400 ml methanol (5.3) and weigh the bottle again (= c3 g).
- Mix until all the urea is dissolved.
- Weigh ± 10 g (= c4 g) accurate to 0.1 mg of the urea/methanol solution using a
syringe.
- Transfer this solution to the titration vessel (4.1) see (9.1).
- Calculate the water concentration in the original urea melt sample according to the
7. Calculation
(b1 * a1 * 0.01) + a2
Tn = -------------------------- * 100 * T0
(a1 + a2) * b2

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v*T
------------- * 100
e * 1000

T : titre of the Hydranal composite 5K titrant in mg H2O/ml
7.3 Calculation of the water concentration in urea in wt%
v*T
------------- * 100
w * 1000
Where: w : weight of the urea in g

T : titre of the Hydranal Composite 5K titrant in mg H2O/ml

relative standard deviation = 4 % (based on 1 times s)
7.4 Calculation of the water concentration in the urea melt in wt%
(c3 – c1)
Dilution factor: f = ---------------
(c3 – c2)
f*v*T
wt% H2O in urea melt = -------------- * 100
c4 * 1000
Where: c1 : weight of the dry bottle in g

c2 : weight of the bottle with urea in g
c3 : weight of the bottle with urea and methanol in g
c4 : weight of the urea/methanol solution in g
T : titre of the Hydranal Composite 5K titrant in mg H2O/mL.
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Accuracy of the analysis method, including sample preparation determined by analysing

1 sample 10 times. The relative standard deviation = 4 % (based on 1 times s)
8. Reference
DSM 805-E
DMG 309
DMG 0281-2B-E
9. Remarks
Give more attention for the solvent at paragraph 6.3.
11. Attachments
No attachments
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DSM Melamine
Analytical method 407, version 1 Date: 20 February 2004
DETERMINATION OF WATER IN LIQUID AMMONIA
Authorisation :
(signature)
Jan Jaap Nusselder, Manager PAR Melamine Skill Centre.
Keywords: Liquid Ammonia, Water, Karl Fisher, Hydranal, Biamperometric
1. Scope
Determination of water in liquid ammonia, in concentrations between 0,005 and 1,0 wt%
2. Safety
Methanol
Liquid Ammonia
Ethylene glycol
Acetic acid
Work safely, especially with hazardous chemicals.
Liquid ammonia is highly corrosive and toxic. Liquid ammonia irritates the eyes
and the skin and causes serious chemical burns by frostbite.
Its vapour is strongly irritant to the mucous membrane and eyes, and produces a
suffocating effect on the respiratory tract.
Another person should always accompany a person taking samples.
When sampling, use thick rubber gloves, a facial shield and a helmet.
A gas mask with an ammonia filter should be within reach and ready for use.
Never work solitaire with the liquid ammonia at the laboratory till after the
evaporation of the liquid ammonia.
Never use materials made of polyethylene.
Hydranal Composite 5K contain toxic substances. Avoid inhalation and skin
contact.
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3. Principle
- Sampling of the liquid ammonia in a conical flask containing ethylene glycol

- Evaporation of the ammonia and dissolution of the residue in methanol
- Titration of water, in the methanol solution, with the Karl Fischer reagent (Hydranal
Composite 5K titrant).
- Biamperometric detection of the titration endpoint, with a Pt/Pt-electrode (9.4).
4. Apparatus

4.4 PTFE outside coated conical flask of about 750 ml, provided with a normal-ground-
joint adapter tube and a 500 ml mark, see appendix 11.1. Use clamps to connect
the loose components with the conical flask.
4.5 Rack for at least 2 flasks (see 4.4). A is purge flask, B is sample flask.
4.6 Water bath with circulation-pump thermostat, capable of being set to 30°C.
4.7 Electronic thermometer with a long measuring probe and suitable for measuring
temperatures till –30°C.
4.8 Measuring flask, 50 and 100 mL, glass.
5. Chemicals

5.4 Ethylene glycol water content <0.1 wt%, e.g. GR for analysis, MERCK
5.5 Acetic acid, >99,8 wt%, e.g. GR for analysis, MERCK
5.6 Nitric acid,65%. e.g. MERCK
5.7 Hydrochloric acid, 37%, e.g. MERCK
6. Procedure
6.1 Sampling
- Place two dry conical flasks (4.4) in the rack (4.5), one to purge the sample line and
one to take the sample.
- Introduce 5,00 ml of ethylene glycol (5.4) into the sampling flask (4.4)
- Close the inlet and the outlet of the two flasks (4.4) with rubber stoppers pierced
through with a capillary (e.g. a syringe needle) having a inside diameter of 1 mm (see
9.2). Close all glass connections with clamps.
- Install (when necessary) a sample line with a control valve.
- Remove the capillary-pierced stoppers from the inlet and the outlet of the flasks (4.4).
- Connect the inlet of the purge flask A (4.4) to the sampling point and the outlet to the
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purge line.
- Cautiously open the valve of the liquid-ammonia line so that in about 1 minute 500 ml
of liquid ammonia flows into the purge flask A (4.4).
- (Note: If 500 ml is not sufficient to purge the sample line, adjust the purging procedure
to the operating conditions).
- Close the valve, disconnect the purge flask A (4.4) and now collect the sampling flask
B (4.4) to the sampling point and the purge line.
- At the sampling point, record the pressure or the temperature of the liquid ammonia to
be sampled, in order to be able to determine the evaporation factor during sampling;
see table appendix 11.2.
- Cautiously open the valve and take a sample by allowing 500 ml (=V1 ml) of liquid
ammonia to flow into the sample flask B (4.4) in about 1 minute.
- Close the valve, disconnect the sampling flask B (4.4) and place the capillary-pierced
stoppers on the inlet and outlet of the two flasks A and B (4.4).
6.2 Sample preparation

- In the fume-hood, remove the capillary-pierced stoppers from the conical flasks A and
B (4.4) and place the rack (4.5) with the flasks (4.4) in the water bath (4.6) so that
only the bottom of the flasks is in contact with the water (temperature approx. 30
°C). Place the flasks (4.4) in that way, that eventually spouting liquid ammonia from
the flask (4.4), cannot hit a person.
- Completely evaporate the liquid ammonia (in approx. 30 minutes).
- Remove the rack (4.5) from the water bath (4.6) immediately after the ammonia has
evaporated, dry the sampling flask B (4.4) on the outside and wash the contents into
a dry 100 ml measuring flask (4.8) with the aid of methanol (5.2).

* Determine the water content of the methanol (blank) by:
- Transfer the methanol (5.2) to the titration vessel (4.1).
- Weigh 20 ml methanol (= a1 g) (5.2) accurate to 0.1 mg to a 50 ml flask (4.8).
- Add 0.35 g (= a2 g) demi water accurate to 0.1 mg close the flask (4.8) and mix
properly.
- Transfer the calibration sample to the titration vessel (4.1).
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- Transfer this standard to the titration vessel (4.1) filled with neutralized dry methanol
(5.2).
- Perform the titration, consumption v ml.

standard.
6.5 Determination of water in liquid ammonia

- Add 2,00 ml of acetic acid (5.5) to the contents of the measuring flask (4.8) obtained
according to 6.2, make up to the mark with methanol (5.2) and mix (solution I).
- Immediately after completion of the neutralization, pipette V2 ml of sample solution I
into the titration vessel (4.1) filled with neutralized dry methanol (5.3).
- Perform the titration, consumption va ml.
- Perform a blank solution by introducing 5,00 ml of ethylene glycol (5.4) and 2,00 ml of
acetic acid (5.5) into a dry 100 ml measuring flask (4.8), make up to the mark with
methanol (5.2) and mix (solution II).
- Immediately after titration of solution I, pipette V2 ml of blank solution II (the same
amount as sample solution I) into the titration vessel (4.1), close the vessel and
perform the titration, consumption vb ml.
7. Calculation
(b1 * a1 * 0.01) + a2
Tn = -------------------------- * 100 * T0
(a1 + a2) * b2

v * Tn
------------- * 100
e * 1000
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Tn : titre of the Hydranal composite 5K titrant in mg H2O/ml
7.3 Calculation of the water concentration in liquid ammonia in wt%
(va-vb) * Tn * F * 10
--------------------------
V2 * 0,68 * V1
Where: va : consumed Hydranal Composite 5K titrant in ml in the sample

vb : consumed Hydranal Composite 5K titrant in ml in the blank
Tn : titre of the Hydranal Composite 5K titrant in mg H2O/ml
F : the evaporation factor (see appendix 2), which is a correction factor
for the amount of ammonia which evaporates during sampling.
V2 : the amount of solution I and II respectively, in ml, pipetted into the
titration vessel.
V1 : the amount of liquid ammonia used, in ml, normally 500 mL
0,68 : the density of the liquid ammonia at –33°C and 1 bar.
Accuracy of the analysis method determined by analysing 1 sample 21 times, based on

only the water determination without sample preparation.
The relative standard deviation = 1.0 % (based on 1 times s) and only for the water
determination without sample preparation. The relative standard deviation of the total
analysis with the sample preparation included is not determined, but is much larger then
the mentioned relative standard deviation.
8. Reference
AGRO 0019-E
(ISO 7105)
9. Remarks
9.2 The capillary is necessary because pressure build-up in the flask owing to
evaporation ammonia must be prevented and the release of ammonia vapour during
transportation of the sample from the sampling point to the fume-hood of the
laboratory should be a minimum.
9.3 The methanolic solution of ethylene glycol to which acetic acid has been added
should be processed immediately, since extra water is formed as a result of the
esterification which occurs.
9.4 After some time the endpoint determination may become insensitive. In such a case
clean the platinum electrode by immersing 1 minute in a mixture (1:1) of nitric acid
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(5.6) and hydrochloric acid (5.7) . Rinse the electrode with water. Dry the electrode
with a tissue and rinse the electrode with methanol (5.2).
The translation from an AGRO analytical method to a SCM analytical method
11. Attachments
11.1 Conical flask for sampling liquid ammonia, scale 1:14

11.2 Relation between the pressure, temperature and evaporation factor of liquid
ammonia
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Appendix 11.1: Conical flask for sampling liquid ammonia
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Appendix 11.2: Relation between the pressure, temperature and evaporation factor of
liquid ammonia
Temp Over- Evapor. Temp Over- Evapor.

pressure factor pressure factor
°C kg/cm2 bar F °C kg/cm2 bar F
+35 12.56 12.32 0.769 +02 3.66 3.59 0.880

+34 12.27 12.03 0.772 +01 3.51 3.44 0.883
+33 11.96 11.73 0.775 +00 3.36 3.29 0.886
+32 11.65 11.42 0.779 -01 3.21 3.15 0.890
+31 11.32 11.10 0.782 -02 3.07 3.01 0.893
+30 10.99 10.78 0.785 -03 2.94 2.88 0.897
+29 10.65 10.45 0.789 -04 2.80 2.75 0.900
+28 10.32 10.12 0.792 -05 2.68 2.62 0.903
+27 9.98 9.79 0.796 -06 2.55 2.50 0.907
+26 9.64 9.46 0.799 -07 2.42 2.38 0.910
+25 9.30 9.13 0.802 -08 2.30 2.26 0.913
+24 8.98 8.80 0.806 -09 2.18 2.14 0.917
+23 8.65 8.48 0.809 -10 2.06 2.02 0.920
+22 8.33 8.17 0.812 -11 1.94 1.91 0.924
+21 8.02 7.86 0.816 -12 1.83 1.79 0.927
+20 7.71 7.56 0.819 -13 1.71 1.68 0.930
+19 7.41 7.27 0.822 -14 1.60 1.57 0.934
+18 7.12 6.98 0.826 -15 1.48 1.46 0.937
+17 6.84 6.71 0.829 -16 1.37 1.35 0.940
+16 6.57 6.44 0.833 -17 1.26 1.24 0.944
+15 6.31 6.18 0.836 -18 1.16 1.13 0.947
+14 6.05 5.93 0.839 -19 1.05 1.03 0.950
+13 5.81 5.69 0.843 -20 0.95 0.93 0.954
+12 5.57 5.46 0.846 -21 0.85 0.83 0.957
+11 5.35 5.24 0.849 -22 0.76 0.74 0.961
+10 5.13 5.03 0.853 -23 0.67 0.65 0.964
+9 4.92 4.82 0.856 -24 0.58 0.57 0.967
+8 4.72 4.63 0.860 -25 0.50 0.49 0.971
+7 4.52 4.44 0.863 -26 0.43 0.42 0.974
+6 4.34 4.25 0.866 -27 0.36 0.35 0.977
+5 4.16 4.08 0.870 -28 0.29 0.29 0.981
+4 3.99 3.91 0.873 -29 0.24 0.24 0.984
+3 3.82 3.75 0.876 -30 0.19 0.19 0.988
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Analytical method 408, version 3 Date: 5 July, 2004
DETERMINATION OF FORMALDEHYDE IN UREA

Authorisation :
(signature)
Keywords: Formaldehyde, Urea, Spectrophotometric, Chromotropic acid
1. Scope
Determination of the formaldehyde content of urea.

In the presence of nitrate formaldehyde must be separated by ion-exchange.
Hexamethylenetetramine (HMTA) interferes (see 9.1).
2. Safety
Chromotropic acid
Sulphuric acid
Formaldehyde = suspected carcinogen with a MAC TGG-15 min. value of 3 mg/m3
and a MAC TGG 8h value of 1.5 mg/m3.
Never use Hydrochloric acid in the neighbourhood of formaldehyde, because
formaldehyde reacts with Hydrochloric acid giving off very toxic
“bis(chloromethyl)ether” , which can cause lung cancer.
3. Principle
Reaction of formaldehyde with 4,5-dihydroxy 2,7-naphtalene disulphonic acid sodium

salt (= chromotropic acid) in sulphuric acid medium forming a violet coloured
compound.
Determination of the extinction of the coloured solution at a wavelength of 570 nm.
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4. Apparatus
4.1 Spectrophotometer or filter photometer e.g. Hitachi. In case of a filter photometer it

4.3 Steambath e.g. Type LT 6 from Labo Tech or electric heating equipment.
4.4 Hardened filter e.g. Whatmann
5. Chemicals
5.1 Chromotropic acid disodium salt dihydrate C10H6Na2O8S2.2H20 p.a. e.g. Merck
5.2 Chromotropic acid solution: transfer 2.0 g chromotropic acid (5.1) in a 25 ml flask,
add 20 ml of demi water and stir for 15 minutes with a magnetic stirrer (4.2).
Filter through a hardened filter (4.4). This solution is stable for at least 1 week.
5.3 Sulphuric acid, 96% e.g. Merck
5.4 Formaldehyde solution 37 - 38 wt% e.g. Merck, r = 1.09 kg/L
Determine the formaldehyde content (Cf) according to ISO 2227
6. Calibration
– Transfer 3.6 g (m1) or 3,3 ml formaldehyde solution (5.4) to a 1 liter measuring flask.
Fill up to the mark with demi water and mix (= solution I).
– Transfer 1.8 g (m2) or 1,65 ml formaldehyde solution (5.4) to a 500 ml measuring
flask. Fill up to the mark with demi water and mix (= solution II).
– Pipette 20.00 ml of solution I in a 1 liter measuring flask and weigh the exact
amount (m3). Fill up with demi water and mix (= solution A).
– Pipette 10.00 ml of solution II into a 500 ml measuring flask and weigh the exact
amount (m4). Fill up with demi water and mix (= solution B).
– Pipette into 50 ml measuring flasks respectively: 0 (=blank) , 1.00, 3.00 and 5.00 ml
(Vi) of solution A. If necessary dilute to 5 ml with demi water.
– Pipette into 50 ml measuring flasks respectively: 2.00 and 4.00 ml of solution B (Vi).
If necessary dilute to 5 ml with demi water.
– Divide the solution over the entire bottom of the 50 ml measuring flask.
– Add 1.0 ml chromotropic acid solution (5.2) and mix.
– Carefully add 30 ml sulphuric acid (5.3) and mix.
– Heat for 30 minutes on a closed steam bath (4.3) or electric at a temperature of
125°C.
– Remove from the steam bath and cool down to ambient temperature.
– Carefully transfer the contents of the evaporating dish into a 500 ml measuring flask
containing already 200 ml of demi water.
– Fill up to the mark with demi water and mix.
– Perform the extinction measurements at a wavelength of 570 nm and an optical
path length of 5 cm using a spectrophotometer (4.1).
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– Weigh a g (accurate to 0.01 g) of sample into a 1 liter measuring flask. Usually ± 5 g

of sample is used containing no more than 30 mg of formaldehyde.
– Dissolve the sample in demi water. Fill up with demi water and mix. (= solution M)
– Pipette V ml (at most 5 ml) of solution M into a 50 ml measuring flask. If necessary
dilute to 5 ml with demi water.
– Divide the solution over the entire bottom of the measuring flask
– Add 1.0 ml chromotropic acid solution (5.2) and mix.
– Carefully add 30 ml sulphuric acid (5.3) and mix.
– Heat for 30 minutes on a closed steam bath (4.3) or electric at a temperature of
125°C.
– Remove from the steam bath and cool down to ambient temperature.
– Carefully transfer the contents of the evaporating dish into a 500 ml measuring flask
containing already 200 ml of demi water.
– Fill up to the mark with demi water and mix.
– Perform the extinction measurements at a wavelength of 570 nm and an optical
path length of 5 cm using a spectrophotometer (4.1).
– Also perform a blank (E0)
8 Calculation
8.1 Calculation of the formaldehyde concentration in the standards using formula:
for solution I :
m1 * Cf * m3 * Vi
Ci= -----------------------
100 * 1000
for solution II :
m2 * Cf * m4 * Vi
Ci= -----------------------
100 * 500
Where: m1= amount in g of formaldehyde used for solution I

m2= amount in g of formaldehyde used for solution II
m3= amount in g of formaldehyde used for solution A
m4= amount in g of formaldehyde used for solution B
Ci= formaldehyde concentration of standard solution i in mg/500 ml
Cf= formaldehyde concentration of formaldehyde solution (5.4) in wt-%
Vi= amount in ml taken of standard solution A or B
The density of solution I and II is assumed to be 1.000 kg/L
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8.2 Calculation of the formaldehyde calibration curve.
Ci
fi= -----------
Ei – E0

Ci= formaldehyde concentration of standard solution i in mg/500 ml
E0= extinction of standard solution containing no formaldehyde
Ei= extinction of standard solution containing formaldehyde
8.3 Calculation of the formaldehyde content in wt% using formula:
b * 100
-------------
a*V
Where: b= amount of formaldehyde (mg/500 ml) corresponding to the

difference in extinction (E-E0)
V= amount in ml taken from solution M

sample preparation). The relative standard deviation = 2.2% (based on 1 times s).
9. Remark
9.1 If hexamethylenetetramine is present next to formaldehyde, the formaldehyde

concentration should be analysed using HPLC with fluorescence detection.
10. Reference
SBB 0071-02-E
ISO 2227, Formaldehyde solutions for industrial use, Determination of formaldehyde
content.
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Upgrade.
Change the safety data of formaldehyde.
In paragraph 6, calibration: add weighing of the pipetted amount.
Add electric heating in paragraph 6 and 7, with the temperature.
Change the reference method for the determination of formaldehyde in ISO 2227 (5.4).
12. Attachments
An example of a formaldehyde calibration curve.
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Attachment 1: Example of a formaldehyde calibration curve (wavelength 570 nm,

optical path length 5 cm)
Calibration curve Formaldehyde

(wavelengt h: 570 nm, optical pat h lengt h 5 cm)
0,8
0,7
y = 5,4105x
0,6 R2 = 0,9954
Extinction (570 nm)
0,5
0,4
0,3
0,2
0,1
0
0 0,02 0,04 0,06 0,08 0,1 0,12 0,14 0,16
concentration form aldehyde mg/ 500 m l
[Formaldehyde] Extinction
(mg/500 ml)
0.00 0,000
0.0269 0.151
0.0537 0.300
0.0806 0.464
0.1343 0.705
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DSM Melamine
Analytical method 410, version 2 Date: 21 Jan. 04
DETERMINATION OF FREE AMMONIA IN UREA
Authorisation :
(signature)
Keywords: Urea, Free ammonia, Titrimetric, Indicator, Phenolphthalein
1. Scope
Determination of the free ammonia content (NH3) of urea and other intermediate
products obtained in the production of urea. By the term, ‘free ammonia’ is meant the
ammonia present in the sample. Any other ammonia compounds are not included in
the determination.
2. Safety
Hydrochloric acid
Phenolphthalein
Ethanol
3. Principle
Dissolving of the sample in water.

Titration of the free ammonia with hydrochloric acid.
Indicating the endpoint of the titration with phenolphthalein indicator.
4. Apparatus
4.1 Burette, 5 ml
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5. Chemicals
5.1 Hydrochloric acid, 0.01mol/L e.g. Titrisol from Merck.

5.2 Phenolphthalein indicator pH 8.2 – 9.8, e.g. Merck
5.3 Ethanol 96 % e.g. Merck
5.4 Phenolphthalein indicator solution: dissolve 100 mg phenolphthalein (5.2) in 100 ml
ethanol (5.3).
6. Procedure
- Add into a 400 ml beaker a g, accurate to 0.01 g, of urea (usually ± 15g).

- Add 200 ml of demi water and dissolve the urea (=solution A) (see 8.1).
- Add a few drops of phenolphthalein indicator solution (5.4).
- Titrate with hydrochloric acid 0.01 mol/l (5.1) to disappearance of the pink colour (V
ml)
7. Calculation
Calculate the free ammonia content using formula:
V * T * 17.03 * 1000
ppm free NH3= ----------------------------
a
Where: V= titrated volume of hydrochloric acid in ml

T= concentration of the hydrochloric acid solution in mol/l
a= sample weight in g
17.03= molar weight of NH3 in g/mol

sample preparation). The relative standard deviation = 8 % (based on 1 times s).
8. Remarks
8.1 This method is also applicable for e.g. urea melt. Urea melt is a melt of 95-99 wt%
urea and 1 - 5 wt% water with original temperature of 130°C. Only take care that
solution A, the measuring solution, contains about 15 g urea/200 ml.
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9. Reference
Chemlab 1605-OV-E
Change in definition of a urea melt.
11. Attachments
No attachments.
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DSM Melamine
Analytical method 410, version 3 Date: 30 August 2004
DETERMINATION OF FREE AMMONIA IN UREA

Authorisation :
(signature)
Keywords: Urea, Free ammonia, Titrimetric, Indicator, Phenolphthalein
1. Scope
Determination of the free ammonia content (NH3) of urea and other intermediate
products obtained in the production of urea. By the term, ‘free ammonia’ is meant the
ammonia present in the sample. Any other ammonia compounds are not included in
the determination.
2. Safety
Hydrochloric acid
Phenolphthalein
Ethanol
3. Principle

Titration of the free ammonia with hydrochloric acid.
Indicating the endpoint of the titration with phenolphthalein indicator.
4. Apparatus
4.1 Burette, 5 ml
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5. Chemicals

5.2 Phenolphthalein indicator pH 8.2 – 9.8, e.g. Merck
5.3 Ethanol 96 % e.g. Merck
5.4 Phenolphthalein indicator solution: dissolve 100 mg phenolphthalein (5.2) in 100 ml
ethanol (5.3).
6. Procedure

- Add a few drops of phenolphthalein indicator solution (5.4).
- Titrate with hydrochloric acid 0.01 mol/l (5.1) to disappearance of the pink colour (V
ml)
7. Calculation
Calculate the free ammonia content using formula:
V * T * 17.03 * 1000
ppm free NH3= ----------------------------
a


8. Remarks
8.1 This method is also applicable for e.g. urea melt. Urea melt is a melt of 95-99 wt%
urea and 1 - 5 wt% water with original temperature of 130°C. Only take care that
solution A, the measuring solution, contains about 15 g urea/200 ml.
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9. Reference
Chemlab 1605-OV-E
Change in definition of a urea melt.
11. Attachments
No attachments.
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DSM Melamine
Skill Centre
Analytical method 411, version 2 Date: 09 January 2003
DETERMINATION OF AMMONIA IN WATER

Authorisation :
(signature)
Keywords: Water, Ammonia, Spectrophotometric.
1. Scope
Spectrophotometric determination of 0.01 to 10 ppm ammonia in water.

Some other amines are also determined as ammonia even after distillation.
Distillation is necessary if the water is coloured and/or turbid.
2. Safety
Hydrochloric acid
Salicylic acid sodium salt
Tri-sodium citrate-2-hydrate
Disodiumpentacyanonitrosoferrate(III))
Sodiumhydroxide
Dichloroisocyanuric acid sodium salt dihydrate
Ammoniumchloride
Bromothymolblue
Magnesiumoxide
Work safely, especially with hazardous chemicals. Use the guidelines of e.g. Material
Safety Data Sheets (MSDS) or a local equivalent.
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3. Principle
Reaction of ammonium with hypochlorite ions and salicylate at a pH of approximately

12.6, in the presence of disodiumpentacyanonitrosoferrate (III) as a catalyst, forming
a green/blue coloured complex.
Sodiumcitrate is added to mask possible disturbing cat ions.
4. Apparatus
4.1 Spectrophotometer or filterphotometer e.g LICO. In case of a filterphotometer it

4.2 Rotavapor, e.g. Büchi
4.3 Waterbath, e.g. Lauda
4.5 Drying oven, temperature set at 105°C, e.g. Hereaus type VT 6130M
4.6 pH meter, e.g. Orion, provided with a combined glass pH electrode, e.g. Orion
sure flow.
5. Chemicals
5.1 Milli-Q water

5.3 Hydrochloric acid (0.1 mol/L), e.g. titrisol Merck
5.4 Salicylic acid sodium salt (C7H5NaO3), 99+ % e.g. Aldrich
5.5 Tri-sodium citrate-2-hydrate (C6H5Na3O7.2H2O), 99.5 % e.g. Riedel de Haёn
5.6 Di-sodiumpentacyanonitrosoferrate(III) dihydrate (C5N6OFeNa2.2H2O), 99%.
Riedel de Haёn
5.7 Sodiumhydroxide, p.a., e.g. Merck
5.8 Dichloroisocyanuric acid sodium salt dihydrate (C3N3O3Cl2Na.2H2O), ± 98%
Fluka
5.9 Ammoniumchloride, p.a. e.g. Merck, dried for 3 hours at 105°C in a drying oven
(4.5).
5.10 Magnesium oxide, free of carbonate, 99+ % Aldrich.
Heat the magnesium oxide at 500°C to remove the carbonate.
5.11 Salicilate solution: dissolve 65 g of salycilic acid sodiumsalt (5.4) and 65 g of
tri-sodium citrate-2-hydrate (5.5) in 400 ml water (5.1) in a 500 ml measuring
flask (the pH of the solution need to be ≤ 8, if not, use hydrochloric acid (5.2) to
bring the pH ≤ 8). Add 485 mg of disodiumpentacyanonitrosoferrate(III)
dihydrate (5.6), mix and fill up to the mark with water (5.1).
This solution is stable for at least 2 weeks, if stored in a brown bottle.
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5.12 Dichloroisocyanuric acid sodium salt dihydrate solution: dissolve 16 g of

sodiumhydroxide (5.7) in 300 ml water (5.1) in a 500 ml measuring flask. Cool
the solution until room temperature and add 1 g of dichloroisocyanuric acid
sodium salt dihydrate (5.8), mix and fill up to the mark with water (5.1).
This solution is stable for at least 2 weeks if stored in a refrigerator (+/- 4 °C).
5.13 Sodiumhydroxide, 1 mol/L: e.g. titrisol Merck.
5.14 Bromothymolblue indicator solution: dissolve 0.5 g of bromothymolblue in water
(5.1) in a 1 L measuring flask; fill up to the mark with water (5.1) and mix.
6. Calibration
- Dissolve in water (5.1) in a 1 L measuring flask, 382 mg of ammoniumchloride

(5.9). Use 1 M hydrochloric acid (5.2) to bring the pH at 2.
Fill up to the mark with water (5.1) and mix (=solution I).
- Dissolve in water (5.1) in a 500 ml measuring flask, 191 mg of ammonium
chloride (5.9). Use 1 M hydrochloric acid (5.2) to bring the pH at 2. Fill up to the
mark with water (5.1) and mix (=solution II).
- Pipette 10 ml of solution I into a 1 L measuring flask. Fill up to the mark with
water (5.1) and mix (=solution A). This solution is stable for one day.
- Pipette 5 ml of solution II into a 500 ml measuring flask. Fill up to the mark with
water (5.1) and mix (=solution B). This solution is stable for one day.
- Pipette into measuring flasks of 50 ml: 0 (blank), 1.00, 4.00 and 8.00 ml of
solution A (the solutions may contain at most 10 ug of ammonia).
- Pipette into measuring flasks of 50 ml: 2.00 and 6.00 ml of solution B (the
solutions may contain at most 10 ug of ammonia).
- Add 4.0 ml salycilate solution (5.11) and mix.
- Add 4.0 ml dichloroisocyanurate solution (5.12) and mix.
- The pH of the solutions needs to be 12.6 +/- 0.1.
- Fill up to the mark with water (5.1) and mix.
- Place the flasks in a water bath (4.3) and allow to stand at 25 +/- 1°C for 1 hour.
- Perform the extinction measurements (Ei) at a wavelength of 655 nm and an
optical path length of 5 cm using a spectrophotometer (4.1).
- The solutions should be measured within 3 hours.
- Measure the pH of the sample, if necessary neutralize the sample with

sodiumhydroxide (5.13) or hydrochloric acid (5.2).
- Analyse the sample as soon as possible and store it in a refrigerator.
- Transfer a ml (at most 40 ml) of the sample into a 50 ml measuring flask. This
volume may not contain more than 10 ug of ammonia.
- Add 4.0 ml salycilate solution (5.11) and mix.
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- Add 4.0 ml dichloroisocyanurate solution (5.12) and mix.

- The pH of the solution needs to be 12.6 +/- 0.1.
- Place the flasks in the water bath (4.3) and allow to stand at 25+/-1° C for 1 hour.
- Perform the extinction measurements (Es) at a wavelength of 655 nm and an
optical path length of 5 cm using a spectrophotometer (4.1).
- Also perform a blank (E0).
- The solutions should be measured within 3 hours.
8. Calculation
8.1 Calculation of the ammonia calibration curve.
Fi= Ci
---------
Ei - E0
Where: Fi= calibration factor for standard solution i

Ci= ammonia concentration of standard solution i in ug/50 ml
E0= extinction of standard solution containing no ammonia
Ei= extinction of standard solution containing ammonia
8.2 Calculation of the ammonia content in mg/L using formula:
Cs = b
-----
a
Where: b= amount of ammonia (µg/50ml) corresponding to the difference in

extinction (Es – E0)
a= amount of sample taken into investigation (ml)
Cs= ammonia concentration in the sample in mg/L

(including sample preparation). The relative standard deviation = 1.5 % (based on 1
times s).
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9. Remarks
If the sample is coloured or turbid, or if substances are present which form a

precipitate during the forming of the coloured compound, the ammonia must be
isolated as follows:
- Transfer 30 ml of hydrochloric acid (5.3) to a round bottom boiling flask.
- Transfer 250 ml of the water sample to the round bottom boiling flask.
- Add a few drops of bromothymolblue solution (5.14) to the flask.
- The pH needs to be between pH = 6.0 (indicator yellow) and pH = 7.4 (indicator
blue). Use sodiumhydroxide (5.13) or hydrochloric acid (5.2).
- Add 0.25 g of magnesium oxide (5.10) and a few boiling chips.
- Immediately connect the flask to the rotavapor and mix.
- The speed of the distillation should be about 10 ml/min.
- Distil about 150 ml of the liquid.
- Transfer the distillate to a 250 ml measuring flask.
- Use sodium hydroxide (5.13) to bring the pH at 3 - 4.
- Transfer a suitable amount (at most 40 ml) ug of ammonia) of this distillate to a
50 ml measuring flask, and proceed as described under 7. This volume may not
contain more than 10 µg of ammonia.
- Also run a blank, using the same procedure.
10. Reference
G:\methods\doc.411v1.doc
DSM 0103-E
NEN 6472
11. Reasons for Revision
Measuring range extended from 0.01 - 0.4 mg/kg to 0.01 - 10 mg/kg.
12. Attachments
An example of an ammonia calibration curve.
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DSM Melamine
Skill Centre
Attachment 1: Example of an ammonia calibration curve (wavelength 655 nm,

optical path length 5 cm)
Calibration curve ammonia

(wavelength: 655 nm, optical path length: 5 cm)
0.9
0.8
y = 0.0853x
extinction (655 nm)
0.7 2
R =1
0.6
0.5
0.4
0.3
0.2
0.1
0
0 2 4 6 8 10
concentration ammonia, ug/50 ml
AMMONIA (µG/50 ML) EXTINCTION
0 0
0.975 0.081
2.403 0.205
4.698 0.397
7.242 0.620
9.673 0.825
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DSM Melamine
Analytical method 412, version 1 Date: 20 February 2004
DETERMINATION OF AMMONIA IN GAS OF THE UREA PLANT
Authorisation :
(signature)
Jan Jaap Nusselder, manager PAR Melamine Skill Centre.
Keywords: Ammonia, Gas, Urea plant, Potentiometric Titration
1. Scope
Potentiometric determination of the ammonia content (NH3) of gas (e.g. off gas from
the prilling tower) obtained in the production of urea, by detection of equivalence
points.
2. Safety
Sodium hydroxide
Sulphuric acid
Bromphenol blue
3. Principle
Absorption of ammonia in water containing a known amount of sulphuric acid.

Determination of ammonia in the acid extract by back-titration of the excess sulphuric
acid with sodium hydroxide, using bromphenol blue as indicator, or potentiometric to pH
4,5.
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4. Apparatus
4.1 Apparatus for the determination of ammonia in gas from the prilling tower, see
appendix 1.
4.2 Potentiometric titrator, e.g. Mettler DL 25 or Metrohm Titrino
4.3 Combi pH electrode, e.g. Orion type 81-72 BN.
4.4 Washing bottle, capacity 250 ml, with sintered glass filter
4.5 Manometer, filled with demiwater
4.6 Gasmeter
4.7 Thermometer
4.8 Pressure regulator, filled with demiwater. The water level depends on the
resistance in t the washing bottle and the rate of sample introduction
4.9 Measure flask, 250 mL.
4.10 Vacuumpomp
5. Chemicals
5.1 Sodium hydroxide solution, c(NaOH) = 0,1 mol/L, e.g. Titrisol from MERCK
5.2 Sulphuric acid, c(H2SO4) = 0.05 mol/L e.g. Titrisol from MERCK.
5.3 Bromphenol blue:
5.4 Bromphenol blue solution: triturate 40 mg of bromphenol blue with 1 ml of sodium
hydroxide solution (5.1), dilute to 100 mL and mix.
6. Procedure
6.1 Sampling
- The quantity of air passed through should be such (usually 1 m3) that 2 – 200 mg of
ammonia is absorbed.
- Transfer 50,00 mL of sulphuric acid (5.2) to wash bottle A (4.4) and so much water
that the wash height is 8 cm.
- Set up the apparatus as indicated in the figure; at wash bottle A (4.4), connect it to
the sample point, and at stopcock 2 connect it to the vacuum pump.
- Close stopcock 1, switch on the vacuum pump and open stopcock 2 to such an
extent that a moderate stream of air is aspirated through pressure controlling device
E (4.8).
- Record the readings of the gas meter C (4.6) (= V0 L), the thermometer D (4.7) (=
T1 °C) and the barometer B (4.5) (= B1 mbar).
- Open stopcock 1 and, by adjusting stopcock 2 and controller E (4.8), pass air
through at a rate of 200 litres per hour.
- Record the under pressure indicated by manometer B (4.5) (U1 mbar).
- At the end of the sampling procedure, once more record the under pressure
indicated by manometer B (4.5) (U2 mbar), the temperature indicated by
thermometer D (4.7) (T2 °C) and the barometric pressure (B2 mbar).
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- Close stopcock 1 and record the reading of the gas meter C (4.6) (V1 L)
- Close stopcock 2 and disconnect the apparatus from the sample point and the
vacuum pump.
- Switch off the vacuum pump.
- Transfer the contents of the wash bottle A (4.4) to a 250 ml measuring flask (4.9),
make up to the mark and mix (Solution I).
6.2 Determination
- Calibrate the titrator (4.2) at pH 7.00 and 4.00 according to the instruction manual of
the titrator.
- Pipette 100,00 mL of solution I into a 300 mL conical flask.
- Add three drops of bromphenol blue (5.3) and titrate with sodium hydroxide
solutions (5.1) until the colour changes (consumption v1 ml).
- Or perform an endpoint titration with sodium hydroxide solution (5.1) to pH 4.5.
- Determine the consumption of the sodium hydroxide solution (5.1) at the
equivalence point in mL (v1 mL).
- Run a blank by titrating 50,00 ml of sulphuric acid (5.2) with sodium hydroxide
solution (5.1), (consumption v0 mL).
7. Calculation
7.1 Calculation of the amount of air passed through wash bottle A, normalised to 0 °C,
1013 mbar and dry, using formula:
(V1 – V0) * f * 273 * (B – U – W t)

V = --------------------------------------------
(273 + t) * 1013
Where: V0 = the gas meter reading at the beginning of the sampling procedure,
in L
V1 = the gas meter reading at the end of the sampling procedure, in L
f = the correction factor of the gas meter
B = the average barometric pressure during the sampling procedure, in
mbar (= ½ B1 + ½ B2)
t = the average temperature during the sampling procedure, in °C
(= ½ t1 + ½ t2)
U = the average under-pressure during the sampling procedure, in
mbar (= ½ U1 + ½ U2)
Wt = the water vapour pressure at the average temperature T °C, in
mbar, see table (appendix 2)
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7.2 Calculation of the ammonia content, using formula:
(v0 – 2,5*v1) * T * 17.03 * 1000

3
mg/m NH3= ----------------------------------------
V
Where: v0 = the quantity of sodium hydroxide solution consumed in the blank, in

ml.
v1 = the quantity of sodium hydroxide solution consumed in the
determination, in ml.
T = the concentration of the sodium hydroxide solution, in mol/l.
V = the quantity of air passed through, in litres, see 7.1

8. Remarks
8.1 This method is also applicable for the following samples:

a. Air from the prilling tower of the urea plant.
b. gas outlet 4 bar absorber of the urea plant.
9. Reference
DSM 0465-E
DSM 381-34-E
New analytical method
11. Attachments
11.1 Apparatus for absorption of ammonia

11.2 Table, saturated water vapour pressure above water, in mbar at different
temperatures.
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Attachment 1: Apparatus for absorption of ammonia
A = washing bottle, capacity 250 mL, with sintered glass filter

B = manometer, filled with demiwater
C = gasmeter
D = thermometer
E = pressure regulator, filled with demiwater. The water level depends on the
resistance in the washing bottle and the rate of sample introduction.
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Attachment 2: Table, saturated water vapour pressure above water, in mbar at

different temperatures.
Temp Vapour Temp Vapour Temp Vapour

°C mbar °C mbar °C mbar
0 6.1 14 16.0 28 28.4
1 6.6 15 17.1 29 30.0
2 7.1 16 18.2 30 31.8
3 7.6 17 19.4 31 33.7
4 8.1 18 20.6 32 35.7
5 8.7 19 22.0 33 37.7
6 9.3 20 23.4 34 39.9
7 10.0 21 24.9 35 42.2
8 10.7 22 26.4 36 44.6
9 11.5 23 28.1 37 47.1
10 12.3 24 29.8 38 49.7
11 13.1 25 31.7 39 52.4
12 14.0 26 33.6 40 55.3
13 15.0 27 35.6
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Sampling method 415, version 1 Date: 29 October 2002
DETERMINATION OF THE CRUSHING STRENGTH OR THE

DEFORMATION STRENGTH OF (FERTILIZER) GRANULES/PRILLS
Authorisation :
(signature)
Keywords: Crushing strength, deformation strength
1. Scope
Determination of the crushing strength or deformation strength of (fertilizer)

granules/prills under static compressive load.
2. Safety
Work safely.
3. Principle
The crushing or deformation strength is in this analytical method understood to be

the force required per unit of cross-sectional area of a granule to crush the granule
or, if it is not crushed, to deform it by 0.1 mm.
- Subjection of a granule to a force, which is increased at a constant rate.
- Determination of the force applied at the moment at which the granule is crushed,
or, if it is not crushed, the moment at which it is deformed by 0.1 mm.
4. Apparatus
4.1 Apparatus for determining the crushing or deformation strength of fertilizer

granules e.g. Lloyd Instruments type LRX + Material Testing Systems (see 8.1)
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5. Chemicals
No Chemicals necessary.
6. Procedure
6.1 Sample
At least 10 round granules are required to determine the crushing or deformation
strength. These granules are obtained as follows:
- Of a granulated product analyze the sieve fraction containing granules of average
diameter d (see method SCM 416).
To this end, sieve the “as supplied” product through the woven wire sieve which
has an aperture size that most closely approaches the average diameter of the
product from both sides. Take the roundest granules from the sieve fraction, if
necessary select granules with the apparatus used for determining the rolling
tendency according to method SCM 430.
Assume their diameter d to be the average of the apertures of the two sieves
used.
- Of a prilled product, analyze prills which diameters that come closest to the
average diameter d.
To this end, sieve the “as supplied” product through the woven wire sieve which
aperture size most closely approaches this average diameter.
Use only sound, round prills, which are retained in the meshes when the sieve is
turned upside down.
Their diameter d is the size of the apertures of the sieve used.
6.2. Determination
- With a pair of tweezers, place one granule of sample in the centre of the pressing
table of the crushing tester (4.1)
- Press the start button to raise the pressure and start the recording. If the granule
is crushed, the crushing tester (4.1) will relieve the pressure.
- Remove the remains of the granule with a brush (see 8.3).
- Repeat the above operations with at least nine granules,
7. Calculation
7.1 The granule is crushed (= crushing strength)

- The crushing tester gives the crushing strength in N (Newton)
- Calculate the average crushing strength in N.
7.2 The granule is deformed (deformation strength)

- The crushing tester gives the deformation strength in N (Newton)
- Calculate the average deformation strength in N.
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8. Remarks
8.1 This apparatus is preferably to be set up in an area conditioned at a temperature

of 22 ± 2 °C and a relative humidity between 40 and 45 %.
8.2 The crushing or deformation strength is dependent on, among other factors, the
nature and composition of the product and, within the accuracy op the
determination depends only little on the diameter of the granule.
It is desirable to determine the crushing strength of the individual components of
bulk blends (where possible).
8.3 Keep the surface of the pressing table clean to permit proper contact.
9. Reference
Method SCM 416

Method SCM 430
AGRO 1031-E
Manual of the Lloyd Instruments type LRX + Material Testing Systems
Upgrade and new equipment.
11. Attachment
Information with respect to the crushing tester.
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Attachment 1: Information with respect to the crushing tester
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DSM Melamine
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DSM Melamine
Skill Centre
Analytical method 416, version 1 Date: 29 October, 2002
DETERMINATION OF THE PARTICLE SIZE DISTRIBUTION OF

(FERTILIZER) GRANULES/PRILLS
Authorisation :
(signature)
Jan Jaap Nusselder, manager PAR Melamine Skill Centre
Keywords: Urea, Particle size distribution, Sieve analysis
1. Scope
Determination of the particle size distribution of (fertilizer) granules/prills.

The method is applicable to samples with a mean particle size between 0.18 and 16
mm.
2. Safety

3. Principle
Dividing of the sample into a number of fractions with the help of a sieve shaker and
a set of wired sieves.
Weighing of the amount of sample retained on each sieve and calculation of the
different fractions.
4. Apparatus
4.1 Sieve shaker (see 8.1) giving vertical and horizontal motion to the granules, e.g.
Retsch AS 200 control G
4.2 Stainless steel woven wire test sieves provided with calibration certificates (with
diameters of 20 cm and 5 cm wide vertical rims) and having square apertures
according to ISO-565, e.g. Retsch (see attachment 2).
4.3 Stainless steel bottom pan with a diameter of 20 cm, e.g. Retsch.
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4.4 Sieve cover with a diameter of 20 cm, e.g. Retsch.

4.5 Sample divider, e.g. Retsch type PTZ/PR 40
4.6 Ultra sonic bath, e.g. Cole Parmer type 8893
4.7 Drying oven, e.g. Hereaus type VT 6130 M
5. Chemicals
6. Procedure
- Select a series of test sieves (4.2). If necessary, add one or more sieves from
the list of supplementary sizes for an accurate division of the sample into
fractions of different particle sizes.
- Place the bottom pan (4.3) on the sieve shaker (4.1) and stack the selected
sieves on top in order of increasing aperture size (see 8.2).
- Use the product as received, in an amount such that, after sieving the maximum
permissible volume of sample on each sieve used is not exceeded (see 8.1 and
attachment 2).
Use either the entire sample or a representative portion obtained with a sample
divider (4.5).
- Weigh the sample (see 8.3), accurate to 0.1 g (= m g) and place it on the top
test sieve.
- Place the cover (4.4) on the top sieve, fix the test sieve assembly and start the
sieve shaker (4.1).
- Sieve for 10 minutes (see 8.4).
- Remove the cover.
- Carefully lift the first sieve from the stack and invert it over a collecting bin.
Gently tap the side of the sieve a few times, if necessary remove granules which
are retained in the apertures by cautiously pressing them loose by hand (see
8.5).
- Weigh the sieve residue, accurate to 0.1 g (= m1 g).
- Proceed in the same way with the other sieves and with the bottom pan (= m2,
m3, m4, ..., mz g).
- Check that the maximum amount of residue permitted on each sieve has not
been exceeded (see attachment 2). If it has, the analysis should be repeated
with a smaller amount of sample or with a different set of sieves.
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7. Calculation
7.1 Calculate M, the sum of the weights of the different sieve fractions:
M = m1 + m2 + … + mz
Where: m1: the weight of the sieve fraction on the first sieve, in g
m2: the weight of the sieve fraction on the second sieve, in g
mz: the weight of the sieve fraction on the bottom pan, in g
M: the sum of the sieve fractions, in g.
7.2 Determine the difference between sample weight and sum of sieve fractions:
M–m
This difference should be £ 0.005 g. If this condition is not met, the sieve
analysis must be repeated with a fresh sample portion.
7.3 Calculate F, the magnitude of each sieve fraction in wt %, using the formula:
mi
F= ------- * 100
M
Where: F: the sieve fraction between sieve i and the sieve above that , in wt %
(round off to the nearest 0.1 %).
mi: the weight of the sieve fraction on sieve i, in g
M: the sum of the sieve fractions, in g.
Accuracy of the analysis method determined by analysing 1 sample (urea prill) 10

times gives a relative standard deviation = 4.5 % for sieves with aperture size of 1.40
mm and smaller and a relative standard deviation of 2.0% for sieves with aperture
size of 1.70 mm and larger. (based on 1 times s).
8. Remarks
8.1 The sieve shaker must preferably be installed in a conditioned area with a
temperature of 22 ± 2 °C and a relative humidity between 40 and 45 %. All
operations must be carried out in this area.
8.2 If the sieve assembly is too high for the shaker, longer guide rods or some
‘half-height’ sieves (= 2.5 cm) must be used.
8.3 Depending on the average particle size and the type of fertilizer a set of sieves is
recommended. (see attachment 1)
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8.4 The sieving time depends on the nature of the sample and on the type and
setting (amplitude) of the shaker.
8.5 Never use a hard brush to remove granules that are retained in the apertures.
Regularly clean the sieves by immersion in an ultrasonic bath (4.6) filled with
water followed by drying in an oven (4.7) at a temperature of 100°C.
8.6 Regularly check (at least once a year) the accuracy of the sieving apertures with
a standard sample of glass beads or by means of a duplicate analysis with a
spare set of new sieves with a calibration certificate.
9. Reference
G:\methods\doc\SCM427v1
AGRO 1011
Upgrade.
11. Attachments
Sieves, Aperture sizes and an example for the calculation and presentation of the
analytical results.
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Attachment 1: Sieves
Recommended sieves depending on average particle size and type of fertilizer
Urea Urea Ammonium sulphate

granules prills (AS) crystals
Sample (g) 175 – 225 125 – 175 150 – 200 100 – 150
Mean particle ±3 ±2 ±2 ±1
size (mm)
Set of sieves 4.75 2.8 4.75 2.0
with aperture 4.0 2.36 4.0 1.7
sizes (mm) 3.35 2.0 3.35 1.4
2.8 1.7 2.8 1.0
2.36 1.4 2.36 0.71
2.0 1.0 2.0 0.5
1.4 0.5 1.4
0.5 1.0
In case of urea granules:

the fraction < 2 mm is called: fines
the fraction < 1.4 mm is called: segregating fines
the fraction < 0.5 mm is called: dust
In case of urea prills:
the fraction < 1 mm is called: segregating fines
the fraction < 0.5 mm is called: dust
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Attachment 2 : Aperture sizes
Aperture sizes in mm according to ISO Maximum volume of residue

565 table 2 permitted on the sieve at the
Principal sizes Supplementary sizes R completion of sieving cm3 (*)
R 20/3 (mm) 40/3 (mm)
16.0 16.0 500
13.2
11.2 11.2 400
9.5
8.0 8.0 250
6.7
5.6 5.6 200
4.75
4.00 4.00 150
3.35
2.80 2.80 120
2.36
2.00 2.00 100
1.70
1.40 1.40 80
1.18
1.00 1.00 70
0.85
0.71 0.71 60
0.60
0.50 0.50 50
0.425
0.355 0.355 40
0.300
0.250 0.250 35
0.212
0.180 0.180 30
(*): The mass of the sample is calculated by multiplying the volume given in the table
by the bulk density (g/cm3) of the sample.
The principal sizes are also given in the standards series of DIN-4188, AFNOR X 11-
501, BS-410, ASTM E 11-81 and NEN 2560.
The supplementary sizes are listed in the standard series of ASTM 11-70 and BS-
410 only.
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Attachment 3: Example
Example for the calculation and presentation of the analytical results

Sample: urea prill
100
90 Urea 46% N-5
80 x( Q=10.00 % ) x( Q=50.00 % ) x( Q=90.00 % )

µm µm µm
1422.050 1669.254 2063.244
70
60
Q3(x) / %
50
40
30
20
10
0
400 600 800 1000 2000 4000
Particle Size / µm
particle size Urea 46%N
grain class Q3(x)
mm %
< 0.50000 0.01

0.50000 - 1.00000 0.21
1.00000 - 1.40000 6.43
1.40000 - 1.70000 54.98
1.70000 - 2.00000 88.20
2.00000 - 2.36000 98.45
2.36000 - 2.80000 99.97
2.80000 - 3.15000 99.99
> 3.15000 100.00
Sieving loss [%] 0.02
Return Weight [g] 104.32
x( Q=10.00 % ) [mm] 1.42205
x( Q=50.00 % ) [mm] 1.66925
x( Q=90.00 % ) [mm] 2.06324
xm [mm] 1.70692
Span value 0.384
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Analytical method 417, version 1 Date: 10 March 2004
DETERMINATION OF TOTAL NITROGEN IN UREA

(Titrimetric, after digestion)
Authorisation :
(signature)
Keywords: Urea, Total nitrogen, titrimetric, digestion, distillation
1. Scope
Determination of the total nitrogen content of urea. Nitrogen present as ammonium salts,
biuret, cyanuric acid etc. is included in the determination.
The nitrogen content can also be calculated from the water and formaldehyde content of
urea. For the determination of these two contents use analytical method SCM 406 and
SCM 408.
2. Safety
Sulphuric acid
Sodiumhydroxide
3. Principle
- Conversion of the nitrogen present in urea to ammonia by heating with sulphuric acid.
- Determination of ammonia by the distillation method:
- Releasing of ammonia with sodium hydroxide, distillation and collection of the
released ammonia in a known amount of sulphuric acid.
- Titration of the excess amount of acid with sodium hydroxide, as a measure of the
amount of ammonia nitrogen.
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4. Apparatus
4.1 Digestion flask of 300 mL.

4.2 Distillation apparatus for the determination of ammonia nitrogen, see appendix 1.
4.3 Glass pearls
4.4 Boiling chips
5. Chemicals
5.1 Sulphuric acid, 98 wt%, c(H2SO4) = 18 mol/L, e.g. MERCK, for the determination of
nitrogen.
5.2 Sulphuric acid, c(H2SO4) = 0.5 mol/L, Titrisol e.g. MERCK.
5.3 Sodium hydroxide solution, c(NaOH) = 10 mol/L or min. 32% GR for analysis (for the
determination of nitrogen e.g. MERCK.
5.4 Sodium hydroxide solution, c(NaOH) = 0,5 mol/L, Titrisol e.g. MERCK
5.5 Methyl orange solution 0.1 wt%, e.g. MERCK
6. Procedure
6.1 Determination of the total nitrogen content of urea

- Transfer a g (usually 2,5 g) of the sample to a 300 mL digestion flask (4.1).
- Wash the neck of the flask with 20 mL of demi water and next with 20 ml of sulphuric
acid (5.1).
- Add some glass pearls (4.3)
- Heat the flask and its contents over a small flame until the liquid boils; make sure that
the flame does not touch the flask above the liquid level. Other heating sources are
also permitted.
- Boil until white fumes escape and then heat for another 30-40 minutes.
- Cool, cautiously dilute the contents of the flask with 100- 150 mL of demi water while
swirling, and cool again.
- Transfer the contents of the flask to a 500 mL measuring flask, make up to the mark
and mix (= solution I).
- With a pipette, transfer 15,00 mL of sulphuric acid (5.2) to the receiver and 35 mL
demi water and connect the receiver to the apparatus.
- Pipette 50 mL of solution I into the distilling flask, add three drops of methyl orange
(5.7) and neutralize with sodium hydroxide solution (5.3).
- Dilute to 300 mL, add 15 mL of sodium hydroxide solution (5.3) and a few boiling
stones and immediately connect the flask to the apparatus.
- Distil the liquid until 200 mL has been transferred.
- Remove the receiver from the apparatus and wash the contents of the siphon into the
receiver with demi water.
- Titrate the excess amount of acid with sodium hydroxide solution (5.4) (consumption
V ml)
- Run a blank: titrate with sodium hydroxide solution (5.4) (consumption Vo ml).
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7. Calculation
7.1 Calculation of the total nitrogen content in wt%
(Vo – V) * c * f * 14.01
-----------------------------
10 * a
Where:
Vo : the amount of sodium hydroxide solution (0,5 mol/L), consumed in the blank, in mL
V : the amount of sodium hydroxide solution (0,5 mol/L), consumed in the
determination, in mL.
c : the concentration of the sodium hydroxide solution (0,5 mol/L)
f : the dilutionfactor, in this case = 10.
a : the amount of sample used, in g

relative standard deviation = 0.20% (based on 1 times s)
7.2 Calculation of the total nitrogen content in wt% from the water- and formaldehyde
content (SCM 406 and SCM 408)
(100 – X - Y) * 28
-----------------------
60
Where:
X : the water content determined by SCM 406, in wt-%
Y : the formaldehyde content determined by SCM 408, in wt-%
Accuracy of the analysis method determined from the relative standard deviations of the
two analytical methods. The relative standard deviation = 0.02% (based on 1 times s)
8. Reference
SCM 406
C5-0224/2003, European Parlement, 14-5-2003, Common stand.
DSM 0201-E
DSM 0130-E
9. Remarks
none
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- The translation from a DSM analytical method to a SCM analytical method.

- Change the method conform the common stand of the European Parlement (8).
- Add the calculation method (7.2) from the water- and formaldehyde content.
11. Attachments
11.1 Distillation apparatus for the determination of ammonia nitrogen
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Appendix 11.1: Distillation apparatus for the determination of ammonia nitrogen
A = distilling flask (volume 750 mL)

B = splash head
C = condensor
D = receiver (volume 500 mL)
E = adapter
F = siphon, filled with demi water
® and ¬ is cooling water
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Analytical method 418, version 1 Date: 11 March, 2004
DETERMINATION OF THE SHOCK RESISTANCE OF (FERTILIZER)

PRILLS
Authorisation :
(signature)
Keywords: Urea, prills, shock resistance
1. Scope
Determination of the resistance to shock loading of (fertilizer) prills. The shock

resistance is here understood to mean the percentage of prills that is not crushed
when subjected to a specified shock load.
This method is to be used in combination with:
SCM 430: Determination of the rolling tendency of (fertilizer) granules/prills
SCM 416: Determination of the particle size distribution of (fertilizer) granules/prills
2. Safety
Work safely.
3. Principle
- Determination of the rolling tendency of the sample.

- Shooting of the sample against a metal plate, placed at an angle of 45°, by
means of compressed air.
- Sieving the sample thus treated.
- Determination of the rolling tendency of the sieved sample.
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4. Apparatus
4.1 Equipment for the determination of the shock resistance (see attachment 1)
4.1.1 Metering device
4.1.2 Manometer
4.1.3 Reducing valve
4.1.4 Shooting pipe (glass)
4.1.5 Metal plate
4.1.6 Holder (Perspex) for the metal plate (4.1.5)
4.1.7 Receiver
4.1.8 Plastic stopper with seal (rubber ring)
4.2 Sieve shaker, woven wire sieves and bottom pan according to method SCM 416
4.3 Equipment for the determination of the rolling tendency of fertilizer granules/prills
according to SCM 430
4.4 Dry gas meter, calibrated, with a capacity of 25 m3/hour
4.5 Stopwatch
4.6 Compressed air with a gauge pressure of at least 2 bar (200 kPa)
5. Chemicals
6. Procedure

- Determine the average particle size distribution (d50) of the sample according to
SCM 416.
- If the d50 of the sample is < 2.5 mm, sieve approximately 200 g of the original
sample through two sieves with apertures 3.35 and 1.0 mm.
- If the d50 of the sample is ³ 2.5 mm use two sieves with apertures of 4.0 and 1.4
mm.
- Use a g (approximately 100 g) of the fraction 1.0 mm – 3.35 mm or 1.4 mm – 4.0
mm to determine the shock resistance. Use 50 g to determine the rolling
tendency.
6.2 Determination of the shock resistance

- Determine the rolling tendency (= A%) of 50 g of sieved sample according to
SCM 430.
- Connect the equipment for determining the shock resistance (4.1) to the
compressed air system and use the reducing valve (4.1.3) to set the manometer
(4.1.2) to the pressure determined in chapter 8.
- Close the receiver (4.1.7) with the stopper (4.1.8).
- Start the metering device (4.1.1) and introduce a g of sieved sample into the
funnel of the metering device (4.1.1). Feed the sample at a rate of 20 g/minute
(calibrate beforehand).
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- After all the sample has been shot, close the valve in the compressed air line,
remove the stopper (4.1.8) and, using a brush, transfer the contents of the
receiver (4.1.7) to a sieve with apertures of 1.0 mm or 1.4 mm depending on the
d50 (see 6.1), equipped with a bottom pan (4.2).
- Remove any grit formed by sieving and introduce the sieve fraction into the funnel
of the metering device of the apparatus for determining the rolling tendency (4.3)
- After the entire sample has been fed, weigh the product in the receiver for the
round prills (= b g).
7. Calculation
7.1 Rolling tendency after the shooting test

Calculate the rolling tendency (= B) of the sample after the shooting test, in wt%
using the formula
b
B = --------- * 100
a
Where: a= amount of sieved sample tested in g

b= mass of the round prills in the sieved product in g
7.2 Shock resistance

Calculate the shock resistance S in wt% using the formula
B
S = --------- * 100
A
Where: A= the rolling tendency of the prills in the sieved sample before the test
B= the rolling tendency of the prills in the sieved sample after the test
Accuracy of the analysis method, including sample preparation determined by

analysing 1 sample 10 times. The relative standard deviation = 10% (based on 1
times s)
8. Determination of the pressure of the compressed air at an air velocity of 21

m/s
- Carefully remove the plate holder (4.1.6) from the shooting pipe (4.1.4) and
connect the gas meter (4.4) to this end of the shooting pipe (4.1.4) by means of a
flexible tube with a length of at most 5 cm.
- Connect the shooting pipe (4.1.4) to the compressed air system and use the
reducing valve (4.1.3) to set the pressure of the compressed air at 0.5 bar (as
indicated by the manometer (4.1.2)).
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- Record the setting on the counter of the gas meter (S1) and simultaneously start
the stopwatch (4.5).
- Record the position of the counter of the manometer (S2) after, for example
exactly 300 seconds.
- Calculate the throughput in m 3 /hour (Q1) from the amount of air passing through
in m3 (S2 –S1) and the time in seconds.
- Using the gas meter, measure the amount of air at pressures of 1.0 and 1.5 bar
on the manometer (4.1.2) and then calculate the amount of air in m3/hour (Q2
and Q3 respectively)
- Close off the compressed air pipe, carefully remove the gas meter and connect
the plate holder back (4.1.6) to the shooting pipe (4.1.4).
- Plot the amount of air (m3/hour) against the pressure (bar).
- Calculate the amount of air (Q) required to create the specified air velocity of 21
m/s in the shooting pipe (4.1.4) on the basis of the inside diameter of the shooting
pipe (4.1.4) using the formula:
Q= 1/5 p (d)2 * 21 * 10-6 * 3600
Where: Q= the amount of air in the shooting pipe in m3/hour

d: the inside diameter of the shooting pipe in mm (usually 17.7 mm)
- Calculate, using linear regression, the pressure corresponding to the calculated

amount of air.
9. Reference
G:\skill centre\organisation\analytical method\doc\418v1.doc

AGRO 1032
10. Remarks
10.1 The equipment must preferably be installed in a conditioned area with a

Upgrade from AGRO 1032 to SCM Analytical Method
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12. Attachments
1. Equipment to determine the rolling tendency of fertilizers and dimensions of the

chute.
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Attachment 1: Equipment for determination of the shock resistance of (fertilizer)

prills
1: metering device
2: manometer
3: reducing valve
4: shooting pipe (glass)
5: metal plate
6: holder (perspex) for the metal plate
7: receiver
8: plastic stopper with seal (rubber ring)
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Analytical method 419, version 1 Date: 10 March 2004
DETERMINATION OF OIL IN LIQUID AMMONIA

(infrared spectrophotometric method)
Authorisation :
(signature)
Keywords: Liquid Ammonia, oil, infrared spectrophotometric, tetrachloroethylene
1. Scope
Determination of oil in liquid ammonia, in concentrations from 0.5 mg/kg upwards.
2. Safety
n-Hexadecane
Tetrachloroethylene
Sulphuric acid
Liquid Ammonia
Liquid ammonia is highly corrosive and toxic. Liquid ammonia irritates the eyes
and the skin and causes serious chemical burns by frostbite.
Its vapour is strongly irritant to the mucous membrane and eyes, and produces a
suffocating effect on the respiratory tract.
Another person should always accompany a person taking samples.
When sampling, use thick rubber gloves, a facial shield and a helmet.
A gas mask with an ammonia filter should be within reach and ready for use.
Never work solitaire with the liquid ammonia at the laboratory till after the
evaporation of the liquid ammonia.
Never use materials made of polyethylene.
Handling with tetrachloroethylene always in a fume hood.
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3. Principle
- Sampling of the liquid ammonia in a conical flask

- Evaporation of the ammonia
- Extraction of the residue with tetrachloroethylene
- Determination of the oil concentration in the solution by measurement of the
absorbance of the CH2-band at a wave number of 2925 cm-1 (= wavelength 3.42 µm)
with an infrared spectrophotometer.
4. Apparatus
4.1 PTFE outside coated conical flask of about 750 ml, provided with a normal-ground-
joint adapter tube and a 500 ml mark, see appendix 11.1. Use clamps to connect
the loose components with the conical flask.
4.2 Rack for at least 2 flasks (see 4.1).
4.3 Water bath with circulation-pump thermostat, capable of being set to 30°C.
4.4 Electronic thermometer with a long measuring probe and suitable for measuring
temperatures till –30°C.
4.5 Infrared spectrophotometer, e.g. Perkin Elmer 1310
4.6 Recorder paper
4.7 Seal able quartz cuvettes (e.g. quality Infrasil – QI – fa. Helma), with an optical path
length of 10 mm (see 9.2).
4.8 Separating funnel of at least 250 mL with ground stopper, provided with PTFE
stopcock (see 9.2).
4.9 Measuring flask, 50 and 100 mL made of glass (see 9.2).
4.10 Cotton wool, oil-free
5. Chemicals
5.1 Tetrachloroethylene,
5.2 Sulphuric acid, c(H2SO4) = 0.5 mol/L
5.3 n-Hexadecane,
5.4 Calibration solution: introduce 100 mg n-Hexadecane (5.3) (melting point 18.2°C;
heat to approx. 30°C on a water bath (4.3) and mix well before use) in a dry oil-free
measuring flask of 100 ml (4.1), make up to the mark with tetrachloroethylene (5.1)
and mix (1 ml = 1 mg oil)
6. Procedure
6.1 Sampling
- Place two dry conical flasks (4.1) (see 9.2) in the rack (4.2), one to purge the sample
line and one to take the sample.
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- Close the inlet and the outlet of the two flasks (4.1) with rubber stoppers pierced
through with a capillary (e.g. a syringe needle) having a inside diameter of 1 mm (see
9.1). Close all glass connections with clamps.
- Install (when necessary) a sample line with a control valve.
- Remove the capillary-pierced stoppers from the inlet and the outlet of the flasks (4.1).
- Connect the inlet of the purge flask (4.1) to the sampling point and the outlet to the
purge line.
- Cautiously open the valve of the liquid-ammonia line so that in about 1 minute 500 ml
of liquid ammonia flows into the purge flask (4.1).
- (Note: If 500 ml is not sufficient to purge the sample line, adjust the purging procedure
to the operating conditions)
- Close the valve, disconnect the purge flask (4.1) and now collect the sampling flask
(4.1) to the sampling point and the purge line.
- At the sampling point, record the pressure or the temperature of the liquid ammonia to
be sampled, in order to be able to determine the evaporation factor during sampling;
see table appendix 11.2.
- Cautiously open the valve and take a sample by allowing 500 ml (=V1 ml) of liquid
ammonia to flow into the flask (4.1) in about 1 minute.
- Close the valve, disconnect the sampling flask (4.1) and place the capillary-pierced
stoppers on the inlet and outlet of the two flasks (4.1).

- In the fume-hood, remove the capillary-pierced stoppers from the conical flasks (4.1)
and place the rack (4.2) with the flasks (4.1) in the water bath (4.3) so that only the
bottom of the flasks is in contact with the water (temperature approx. 30 °C).
Place the flask (4.1) in that way, that eventually spouting liquid ammonia from the
flask (4.1), cannot hit a person.
- Completely evaporate the liquid ammonia (in approx. 30 minutes).
- Remove the rack (4.2) from the water bath (4.3) immediately after the ammonia has
evaporated, dry the sampling flask (4.1) on the outside.
- Introduce 100 ml of sulphuric acid (5.2) into the sampling flask (4.1) and mix.
- Measure in a measuring cylinder 50 ml tetrachloroethylene (5.1).
- Add 25 mL of tetrachloroethylene (5.1) to the sampling flask and swirl for 1 minute
- Transfer the contents of the flask to the separating funnel (4.8).
- Wash the flask with the second 25 ml of tetrachloroethylene (5.1) and add the wash
liquid to the contents of the separatory funnel (4.8).
- Close the separating funnel (4.8) and shake the solution intensively for approx. 10
sec.
- Wait until the liquid mixture has fully separated into two layers.
- Filter the organic phase through a funnel containing a plug of cotton wool (4.10).
- Discard the first 20 ml of the filtrate and collect the remainder in a dry cuvette (4.7).
- Seal the cuvette (4.7) and place it in the sample beam of the infrared
spectrophotometer (4.5).
- Fill another cuvette (4.7) with tetrachloroethylene (5.1) seal the cuvette (4.7) and
place it in the reference beam of the infrared spectrophotometer (4.5).
- Set the infrared spectrophotometer (4.5) to 100% transmission at 3200 cm-1.
- Record the spectrum from 3200 to 2700 cm-1.
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- Measure the band height, in mm, at 2925 cm-1 and read the corresponding amount
of oil from the calibration graph (= a mg). See appendix 11.2.
- Calculate the amount of oil using the formula given in 7.1.
6.3 Preparation of the calibration graph (see appendix 11.2).

- Pipette 0.5, 1, 2, 3, 4 and 5 ml of calibration solution (5.4) into a dry, oil-free
measuring flasks of 50 ml (4.9). These solutions contain 0.5, 1, 2, 3, 4 and 5 mg n-
hexadecane (5.3) respectively.
- Make up to the mark with tetrachloroethylene (5.1) and mix.
- Measure the band height, in mm, as described in section 6.2.
- Prepare the calibration graph with the values found by plotting the band heights (in
mm) against the amounts of n-hexadecane (in mg/50 ml tetrachloroethylene). This is
not a linear graph (see appendix 11.2).
7. Calculation
7.1 Calculation of the amount of oil, expressed in mg n-hexadecane/kg
b * f * 1000
----------------
v * 0.68
Where:
b : the amount of n-hexadecane, in mg, read from the calibration graph.
f : the evaporation factor (see table, appendix 11.3) which is a correction factor for the
amount of liquid ammonia which evaporates during sampling.
v : the amount of liquid ammonia used, in mL.
0.68: The density of liquid ammonia at –33°C and 1 bar.
Accuracy of the analysis method determined by analysing 1 sample 9 times, based on

only the oil determination without sample preparation.
The relative standard deviation = 0.04 % (based on 1 times s) and only for the oil
determination without sample preparation. The relative standard deviation of the total
analysis with the sample preparation included is not determined, but is much larger then
the mentioned relative standard deviation.
8. Reference
AGRO 0013-E
POLYCHEMLAB 1549v3
(ISO 7106)
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9. Remarks
9.1 The capillary is necessary because pressure build-up in the flask owing to
evaporation ammonia must be prevented and the release of ammonia vapour during
transportation of the sample from the sampling point to the fume-hood of the laboratory
should be a minimum.
9.2 Glasswork: all the glasswork has to be cleaned with tetrachloroethylene (5.1) till oil-
free, before used.
9.3 The calibration solution of n-hexadecane with tetrachloroethylene has an infrared
absorption pattern which is virtually the same as the absorption patterns of the types of
oil which are used in UKF plants.
The translation from an AGRO analytical method to a SCM analytical method
11. Attachments
11.1 Conical flask for sampling liquid ammonia, scale 1:14

11.2 Example of a calibration graph.
11.3 Relation between the pressure, temperature and evaporation factor of liquid
ammonia.
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Appendix 11.1: Conical flask for sampling liquid ammonia
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DSM Melamine
Appendix 11.2: Example of a calibration graph.
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DSM Melamine
Appendix 11.3: Relation between the pressure, temperature and evaporation factor of
liquid ammonia
Temp Over- Evapor. Temp Over- Evapor.

pressure factor pressure factor
°C kg/cm2 bar F °C kg/cm2 bar F
+35 12.56 12.32 0.769 +02 3.66 3.59 0.880

+34 12.27 12.03 0.772 +01 3.51 3.44 0.883
+33 11.96 11.73 0.775 +00 3.36 3.29 0.886
+32 11.65 11.42 0.779 -01 3.21 3.15 0.890
+31 11.32 11.10 0.782 -02 3.07 3.01 0.893
+30 10.99 10.78 0.785 -03 2.94 2.88 0.897
+29 10.65 10.45 0.789 -04 2.80 2.75 0.900
+28 10.32 10.12 0.792 -05 2.68 2.62 0.903
+27 9.98 9.79 0.796 -06 2.55 2.50 0.907
+26 9.64 9.46 0.799 -07 2.42 2.38 0.910
+25 9.30 9.13 0.802 -08 2.30 2.26 0.913
+24 8.98 8.80 0.806 -09 2.18 2.14 0.917
+23 8.65 8.48 0.809 -10 2.06 2.02 0.920
+22 8.33 8.17 0.812 -11 1.94 1.91 0.924
+21 8.02 7.86 0.816 -12 1.83 1.79 0.927
+20 7.71 7.56 0.819 -13 1.71 1.68 0.930
+19 7.41 7.27 0.822 -14 1.60 1.57 0.934
+18 7.12 6.98 0.826 -15 1.48 1.46 0.937
+17 6.84 6.71 0.829 -16 1.37 1.35 0.940
+16 6.57 6.44 0.833 -17 1.26 1.24 0.944
+15 6.31 6.18 0.836 -18 1.16 1.13 0.947
+14 6.05 5.93 0.839 -19 1.05 1.03 0.950
+13 5.81 5.69 0.843 -20 0.95 0.93 0.954
+12 5.57 5.46 0.846 -21 0.85 0.83 0.957
+11 5.35 5.24 0.849 -22 0.76 0.74 0.961
+10 5.13 5.03 0.853 -23 0.67 0.65 0.964
+9 4.92 4.82 0.856 -24 0.58 0.57 0.967
+8 4.72 4.63 0.860 -25 0.50 0.49 0.971
+7 4.52 4.44 0.863 -26 0.43 0.42 0.974
+6 4.34 4.25 0.866 -27 0.36 0.35 0.977
+5 4.16 4.08 0.870 -28 0.29 0.29 0.981
+4 3.99 3.91 0.873 -29 0.24 0.24 0.984
+3 3.82 3.75 0.876 -30 0.19 0.19 0.988
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Skill Centre
Analytical method 420 version 1 Date: 8 July, 2002
DETERMINATION OF UREA IN WATER

(xanthydrol method)
Authorisation :
(signature)
Jan Jaap Nusselder, manager PAR Melamine Skill Centre.
Keywords: Urea, Gravimetric, Xanthydrol
1. Scope
Gravimetric determination of 0.5-40 g/L of urea in water solutions.

Ammonia, carbamate, carbonate, cyanate and biuret (< 5 mg; see 8.1) do not
interfere with the determination.
2. Safety
Methanol
Xanthydrol
Sodium hydroxide
Hydrochloric acid
Acetic acid
Bromophenol blue
Urea
Work safely, especially with hazardous chemicals. Use the guidelines of e.g. Material
Safety Data Sheets (MSDS) or a local equivalent.
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3. Principle
- Reaction of urea with xanthydrol in acetic acid medium, in the presence of

methanol, forming an insoluble compound.
- Filter through a crucible.

- Dry crucible and its contents.
- Weigh crucible and its contents.
4. Apparatus
4.1 Drying oven, e.g. Heraeus type T6120

4.2 Glass filter crucible (G4) with sintered bottom (pore 4) or a porcelain filter crucible
with perforated bottom and a filter paper.
5. Chemicals
5.1 Xanthydrol (9-hydroxyxanthene), 99 %, Acros

5.2 Xanthydrol/methanol slurry, 10 % (m/m) xanthydrol in methanol (5.9).
5.3 Sodium hydroxide (1 mol/L), e.g. titrisol Merck
5.4 Sodium hydroxide (0.1 mol/L), e.g. titrisol Merck
5.6 Bromophenol blue, 95 %, Aldrich
5.7 Bromophenol blue solution, grind 0.4 g (5.6) with 6.0 ml of sodium hydroxide
solution (0.1 mol/L) (5.4), dilute to 1 litre with demi water and mix.
5.8 Acetic acid, p.a., Merck
5.9 Methanol, p.a. Merck
5.10 Washing liquid: methanol, saturated with urea-xanthydrol-precipitate.
- Transfer 40 mg of urea (5.11) to 1 250 mL beaker.
- Dilute to 30 mL with demi water.
- Add 10 mL of methanol (5.9) and mix.
- Whilst stirring first add 80 mL of acetic acid (5.8) and then 22.5 mL
xanthydrol/methanol slurry (5.2).
- Allow the beaker to stand for 1 hour.
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- Filter the contents of the beaker through a crucible.

- Transfer the precipitate to a 100 mL volumetric flask and fill up to 100 mL
with methanol (5.9).
- Filter the contents of the flask through a crucible.
5.11 Urea, ≥ 99.5 %, Fluka
6. Procedure
6.1 If the amount of sample is at most 8 ml and contains 5-40 mg of urea.

- Transfer a suitable amount (usually between 1 and 8 mL) of sample to a 100 mL
beaker and dilute, if necessary, to at most 8 mL with demi water.
- Add 2 drops of bromophenol blue (5.7; see 8.2) and whilst stirring, neutralize drop
wise with hydrochloric acid (5.5).
Careful; possible carbon dioxide release.
- Cool, if necessary, and add 1 mL of hydrochloric acid (5.5) in excess.
- Allow the solution to stand for 5 minutes and then neutralize with sodium
hydroxide solution (5.3).
- Dilute to 10 mL with demi water, add 3.5 mL of methanol (5.9) and mix.
- Whilst stirring, first add 26.5 ml of acetic acid (5.8) and then xanthydrol/methanol
slurry (5.2) in 5 portions of 1.5 mL each; wait 5 minutes after each addition.
- After the last addition allow the beaker to stand for 1 hour (see 8.1) and proceed
as described under 6.3.
6.2 If the amount of sample is more than 8 mL, but at most 25 mL, and contains
10-40 mg of urea.
- Transfer a suitable amount (usually between 8 and 25 mL) of sample to a 250 mL
beaker.
- Add 2 drops of bromophenol blue (5.7; see 8.2) and whilst stirring, neutralize drop
wise with hydrochloric acid (5.5)
Careful; possible carbon dioxide release.
- Cool, if necessary, and add 1 mL of hydrochloric acid (5.5) in excess.
- Allow the solution to stand for 5 minutes and then neutralize with sodium
hydroxide solution (5.3).
- Dilute to 30 mL with demi water, add 10 mL of methanol (5.9) and mix.
- Whilst stirring, first add 80 ml of acetic acid (5.8) and then xanthydrol/methanol
slurry (5.2) in 5 portions of 4.5 mL each; wait 5 minutes after each addition.
- After the last addition allow the beaker to stand for 1 hour (see 8.1) and proceed
as described under 6.3.
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6.3 Collecting the precipitate.
- Dry a glass crucible (G4, pore 4) for 1 hour in a drying oven at 105 °C, allow to
cool the crucible in a desiccator and weigh the crucible (m0 mg).
- Filter the contents of the beaker through the crucible (do not draw off till dryness).
- Wash beaker and crucible with about 20 mL of washing liquid (5.10).
- Finally, suck off till dryness, dry the crucible with its contents for 1 hour at 105 °C,
allow to cool the crucible with its contents in a desiccator and weigh (m1 mg)
7. Calculation
Calculate the urea content in mg/L, using the formula:
( m1 - m0 ) Murea
-------------- * ------------- * 1000
a Murea-xanthydrol-precipitate
Where:
m0 = weight of crucible, empty and dried, in mg
m1 = weight of crucible with its contents after drying, in mg
a = the sample amount of the original sample in ml
Murea = molar mass of urea (60 g/mol)
Muea-xanthydrol-precipitate = molar mass of urea-xanthydrol-precipitate (420 g/mol)

(including sample preparation). The relative standard deviation = 0.5 %.
8. Remarks
8.1 Biuret may also give a precipitate with xanthydrol. However, biuret reacts much
more slowly than urea. An amount of less than 5 mg of biuret does not
interfere, provides the length of time between the last addition of reagent and
the filtration is not longer than 1 hour.
8.2 The treatment with hydrochloric acid can be omitted if no ammonia, carbamate,
carbonate and cyanate are present in the sample.
8.3 The quality of the xanthydrol/methanol slurry (10 % in methanol) shall be
checked by means of a determination with urea p.a. The solution is stable for 3
months, if stored in a properly closing brown flask.
8.4 Remove the precipitate from the crucible with a spatula. Clean the crucible with
methanol.
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8.5 The method is also applicable for the determination of the urea content of the
liquid from desorber to sewer.
8.5.1 Sample
Use the sample solution obtained after sampling the product and pretreating the
sample, as described in sampling method SCM 401v2.
- Pipette vi mL (usually 25 mL) of solution A (for this sample solution see sampling
method SCM 400v1.
8.5.2 Procedure
- Pipette vi mL of the sample into a 250 mL beaker.
- Proceed as described under 6.2.
8.5.3 Calculation
Calculate the urea content in % (m/m), using the formula:
(m1 - m0) * 0.1428 * 2000 = 28.56 * (m1 – m0)

------------------------- ------------------ ----------------------
vi 10(m4 – m3) vi * (m4 – m3)
where :
m0 = mass of the empty crucible, in mg
m1 = mass of crucible plus precipitate, in mg
vi = pipetted amount of solution A, in mL
m3 = mass of the bladder before sampling (see sampling method 400v1, DSM
Melamine Skill Centre), in g
m4 = mass of the bladder after sampling (see sampling method 400v1, DSM
Melamine Skill Centre), in g
9. Reference
G:\methods\doc\ 420v1.doc
DSM method 0207-E
DSM method 0207 24-E
Upgrade.
11. Attachments
No attachments.
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DSM Melamine
Analytical method 421, version 1 Date: 14 May 2004
DETERMINATION OF DUST IN PRILLING-TOWER OFF GASES

(Isokinetic Particulate sampling, In-stack, Gravimetric method)
Authorisation :
(signature)
Keywords: Dust, Urea, Off gases, Isokinetic sampling, In-stack, Gravimetric
1. Scope
Determination of the dust content of prilling-tower off gases as a measurement of dust

emissions by isokinetic, in-stack sampling.
This method is only an introduction. The method that has to be used is the international
standard:
- ISO 9096: Stationary source emissions .
- or EPA method 5: Determination of Particulate (Pm) Emissions from stationary
sources Isokinetic Particulate Sampling, Testing & Analyses.
The use of isokinetic sampling makes the sample representative for the process
stream in the duct.
2. Safety
Acetone
3. Principle
- Isokinetic sampling of an amount of dust-laden off gas from the gas duct (in-stack).
- Measurement of the volume of the collected gas.
- Separation of the dust from the off gas with a previously dried and weighed filter.
- Determination of the mass of the dust by weighing.
- Calculation of the gas particulate concentration.
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DSM Melamine
4. Reference
DSM 1209-E
ISO 9096:2003
EPA, method 5
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DSM Melamine
Analytical method 422, version 1 Date: 5 December 2003
DETERMINATION OF CHLORIDE IN STEAM CONDENSATE

Authorisation :
(signature)
Keywords: Chloride, Boiler Feed Water, Spectrophotometric
1. Scope
Determination of the chloride content of steam condensate in concentrations from 0,1

mg/L.
A concentration of 0,1 mg/L of Silver (Ag+),Chroom (Cr6+), Titan (Ti4+), Bromide (Br-),
Iodide (I-), Fluoride (F-), Sulphide (S2-), Nitrite (NO2-), Cyanide (CN-), Thiosulfate
(S2O32-)and tartrate have an influence of +10% on the chloride result.
For other interferences see on the method sheet delivered with the MERCK reagent kit.
For interference by cyanide, see 9.1.
The determination can also be performed by means of filter photometry.
2. Safety
Mercury(II)thiocyanate,
Iron(III)nitrate
Methanol
Dimethylsulfoxid
Nitric acid
Sodiumhydroxide
Sodiumchloride
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DSM Melamine
3. Principle
In an acid medium chloride reacts with mercury(II)thiocyanate to form undissociated

mercury(II)chloride, during which reaction an equivalent amount of thiocyanate is
released.
Reaction of the released thiocyanate with iron(III) to form a red-coloured
iron(III)thiocyanate complex.
4. Apparatus
4.1 Spectrophotometer or filter photometer e.g. Dr. Lange Lico 300. In case of a filter
photometer it should have a filter with a maximum transmission at app. 460 nm.
4.2 Glassware: Use dedicated glassware. Before it is used, the glassware should first be
rinsed with nitric acid (1 mol/L) (5.4) and then a number of times with millipore water
(5.1).
4.3 Plastic rectangular cuvettes with a path length of 5 cm e.g. LZM130, Dr. Lange.
4.4 pH indicator strips, pH 0-2,5, e.g. MERCK
5. Chemicals
5.1 Millipore water, free from chloride (<0.01 mg/L), conductivity 0.1 µS
5.2 Spectroquant chloride, 1.14755. e.g. MERCK. This reagent kit contains two reagents
5.2.1 Reagent Cl-1A, contains nitric acid (5-20 %) and Iron(III)nitrate (10-20 %)
5.2.2 Reagent Cl-2A, contains mercury(II)thiocyanate (0,5-2 % as Hg), methanol
(0,1-3 %) and dimethylsulfoxid (>50 %).
5.3 Nitric acid 65 %, e.g. MERCK
5.4 Nitric acid solution c(HNO3)= 1 mol/L: dilute 97,0 g nitric acid (5.3) into 900 ml
millipore water (5.1) in a 1L measuring flask. Mix and fill up to 1000,0 mL with
millipore water (5.1) and mix again.
5.5 Sodiumhydroxide (NaOH) pellets p.a. e.g. MERCK
5.6 Sodiumhydroxide solution c(NaOH) = 1 mol/L: dissolve 40,0 g sodiumhydroxide (5.5)
into 1000 ml millipore water (5.1).
5.7 Sodiumchloride (NaCl), pa, ± 99,5 % e.g. MERCK
6. Calibration
– Dissolve in millipore water (5.1) in a 1L measuring flask (4.2), 164,8 mg of

sodiumchloride (5.7), fill up with millipore water (5.1) and mix (= solution I).
– Dissolve in millipore water (5.1) in a 500 ml measuring flask (4.2), 82,4 mg of
sodiumchloride (5.7), fill up with millipore water (5.1) and mix (= solution II).
– Pipette 50,00 ml of solution I into a 1 L measuring flask, fill up with millipore water
and mix (= solution A). (conc 5,0 mg/L chloride)
– Pipette 25,00 ml of solution II into a 500 ml measuring flask, fill up with millipore
water and mix (= solution B). (conc 5,0 mg/L chloride)
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DSM Melamine
–
– Take 18 plastic cuvettes (4.3).
– Pipette into the plastic cuvettes 1,00, 3,00, 5,00 ml of solution A and 0,00, 2,00, 4,00
ml of solution B. Because of the high risk of contamination with chloride, perform
from each standard a triplet.
– Pipette so much millipore water (5.1) in each cuvette that each cuvette contains 5,00
mL liquid.
– Introduce into the six cuvettes:
6 drops of reagent CL-1A (5.2.1)
Mix carefully with a stirring rod.
length of 5 cm using a spectrophotometer (4.1).
– Adjust the photometer to 100% transmission relative to Millipore water, and measure
the extinction of the standard solution
– Measure the pH of the sample with the pH indicator strips (4.4). Not with a pH-meter
and an electrode because of the risk of contamination with the chloride of the KCl-
solution of the electrode.
– Adjust the pH with nitric acid (1 mol/L) (5.4) or with sodiumhydroxide solution
(1 mol/L) (5.6) to a pH of app. 1,0. Weight the sample before (m1) and after (m2) the
adjustment to correct later for the dilution.
– Pipette a ml (accurate to 0,01 ml) of sample into a plastic cuvette (4.3), with a
maximum of 5,00 ml. Usually 5,00 ml of sample is used so that 0 – 0,025 mg of
chloride will be present in the extinction measurement. Because of the high risk of
contamination with chloride, perform from each sample a triplet.
– Pipette so much Millipore water (5.1) in each cuvette that each cuvette contains 5,00
mL liquid.
– Introduce into the cuvettes:
Mix carefully with a stirring rod.
length of 5 cm using a spectrophotometer (4.1).
– Adjust the photometer to 100% transmission relative to Millipore water, and measure
the extinction of the sample solution (Ei= extinction of sample solution).
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8 Calculation
8.1 Calculation of the chloride calibration curve.
Cs
fs= -----------
Es – E0
Where: fs = calibration factor for standard solution s

Cs= chloride concentration of standard solution s in mg/L
E0= extinction of standard solution containing no chloride.
Es= extinction of standard solution containing chloride.
calibration curve (see attachment 1). Leave out results that look contaminated with
chloride.
8.2 Calculation of the chloride content in mg/L using formula:
(Ei - E0) * fs * 5 m1
mg/L chloride= --------------------- * ----
a m0
Where:
a= amount of sample taken into investigation into the cuvette
(ml)
5= max volume in cuvette (ml)
m0= weight of sample before pH adjustment (g)
m1= weight of sample after pH adjustment (g)

sample preparation). The standard deviation on a level of 0,3 ml/l is 0,047 mg/L. The
relative standard deviation = 16% (based on 1 times s).
9. Remarks
9.1 The interference by cyanide can be neutralized by addition of 1 ml of formaldehyde

sodium hydroxide solution* on 10 ml of sample. In this way, about 80 mg/L of CN- can
be masked.
* Formaldehyde sodium hydroxide solution contains 2 ml of sodium hydroxide solution
(1 mol/L) on 25 ml of formaldehyde solution (37%wt).
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DSM Melamine
10. Reference
DSM method 0760-E

MERCK Spectroquant method 1.14755.
Website MERCK: http://www.merck.de/
Website Dr. Lange: www.langegroup.nl (www.langegroup.com is not ready yet)
New analytical method.
12. Attachments
An example of a chloride calibration curve.
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DSM Melamine
Attachment 1: Chloride calibration curve (wavelength 460 nm, optical path length 5
cm)
Calibration curve chloride

(wavelength: 460 nm, Optical path length: 5 cm)
6.000
Extinction (460 nm, 5 cm)
y = 1.0482x
5.000
R2 = 0.9982
4.000
3.000
2.000
1.000
0.000
0.000 1.000 2.000 3.000 4.000 5.000 6.000
Concentration chloride (mg/L)
[Chloride] (mg/L) Extinction

(*) (Es-E0)
0,000 0,000
0.000 0.000
1.027 1.130
1.027 1.003
2.054 2.184
2.722 2.756
3.082 3.259
3.082 3.378
4.109 4.359
5.136 5.551
5.136 5.335
5.443 5.569
5.443 5.630
(*): Photometer adjusted to 100% transmission relative to Millipore water and the
extinction of the standard solutions was measured and corrected for the extinction of
the standard solutions that contains no chlorid.
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DSM Melamine
Skill Centre
Sampling method 424, version 1 Date: 6 November 2002
DETERMINATION OF THE BULK DENSITY OF (FERTILIZER)

GRANULES/PRILLS
(Loose and Tapped)
Authorisation :
(signature)
1. Scope
Determination of the bulk density (loose and tapped) of granular products.

The method is applicable to dry, free flowing (see 8.6) granular product with at most
10 wt% of the particles > 5 mm and at most 5 wt% of the particles < 0.5 mm.
2. Safety
Work safely.
3. Principle
- The loose bulk density is the mass of the sample, in grams, filled into a 1-litre
vessel under specified conditions.
- The tapped bulk density is the mass, in grams, of 1-litre of sample under
continuous vibration compacted to constant volume.
4. Apparatus
4.1 Apparatus for the determination of bulk density preferably made of stainless steel
(see attachment 1).
- Funnel with valve, fixed with 3 legs on the bottom plate
- Movable 1 litre measuring vessel without spout
4.2 Vibrator (220 V/45W), amplitude 0.10 – 0.15 mm, under load e.g. Retsch AS 200
control G
4.3 Stainless steel or plastic ruler, about 120 * 20 * 2 mm
4.4 Glass stick with a diameter of about 3 to 4 mm
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DSM Melamine
Skill Centre
5. Chemicals
No additional chemicals.
6. Procedure
- Use the sample as received.
6.1 Determination of the loose bulk density

- Determine the empty weight of the 1-litre measuring vessel (see 8.2), accurate to
1 g (m0 g).
- Place the measuring vessel between the 3 legs of the equipment (4.1) on the
bottom plate and against the guided plate.
- Close the valve of the funnel.
- Fill the funnel with the sample.
- Open the valve of the funnel completely and allow the sample to flow into the
measuring vessel within 6 to 12 seconds (see 8.3).
- Remove with the ruler (4.3) the overflow and weigh the filled measuring vessel,
accurate to 1 g (m1 g).
- Repeat this procedure (m2 g)
- If the difference between m1 and m2 is larger than 10 g the procedure should be
repeated (m3 g).
6.1 Determination of the tapped bulk density

- Place the measuring vessel with weight m1 as determined under 6.1 on the
vibrator (see 8.2).
- Start the vibrator and add continuously sample until the measuring vessel starts
overflowing and no more compaction occurs (see 8.5).
- Stop the vibrator and remove with a ruler (4.3) the overflow.
- Weigh the filled measuring vessel, accurate to 1 g (ma g).
- Repeat this procedure (mb g)
- If the difference between ma and mb is larger than 10 g the procedure should be
repeated (mc g).
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DSM Melamine
Skill Centre
7. Calculation
7.1 Calculate the loose bulk density in g/L using the formula:
(m1 + m2)/2 - m0 (m1 + m2 + m3)/3 - m0

------------------------------ or -----------------------------------
v v
where:
m0 = mass of the empty measuring vessel, in g
m1 = mass of the filled measuring vessel, in g (first determination)
m2 = mass of the filled measuring vessel, in g (second determination)
m3 = mass of the filled measuring vessel, in g (third determination)
v = volume of the measuring vessel, in L
7.1 Calculate the tapped bulk density in g/L using the formula:
(ma + mb)/2 - m0 (ma + mb + mc)/3 - m0

------------------------------ or -----------------------------------
v v
where:
m0 = mass of the empty measuring vessel, in g
ma = mass of the filled measuring vessel after compaction, in g (first determination)
mb = mass of the filled measuring vessel after compaction, in g (second
determination)
mc = mass of the filled measuring vessel after compaction, in g (third determination)
v = volume of the measuring vessel, in L
8. Remarks
8.1 This apparatus is preferably to be set up in an area conditioned at a temperature

of 22 ± 2 °C and a relative humidity between 40 and 45 %.
8.2 Check at least once a year the volume of the 1-litre measuring vessel. Use for
this purpose water with a temperature of 22± 1°C.
Allowed deviation = 0.1 %
8.3 If the sample is not free flowing a glass stick (4.4) is used to keep the sample in
the funnel in motion.
8.4 Instead of using a vibrator also carefully tapping the measuring vessel on the
table can be used to compact the sample.
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DSM Melamine
Skill Centre
8.5 The waiting time is about 1 minute for prills, about 5 minutes for granulated
products.
The waiting time for unknown products must be found experimentally.
8.6 If moisture content of the sample is too high as result of moisture absorption
during storage or transport, the sample should be dried prior to analysis.
Sample is therefore stored in a room with constant low water vapour pressure.
9. Reference
UKF 1062-E
AGRO 1061
Upgrade
11. Attachments
Apparatus for the determination of the bulk density.
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DSM Melamine
Skill Centre
Attachment 1: Apparatus for the determination of the bulk density.
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Analytical method 425, version 1 Date: 25 February, 2002
DETERMINATION OF TOTAL AMMONIA IN UREA
Authorisation :
(signature)
Keywords: Urea, ammonia, Titrimetric, Indicator, Methyl Red, Methylene Blue
1. Scope
Determination of the ammonia content (NH3) in urea and other intermediate products
obtained in the production of urea.
Besides ammonia present as ammonia also ammonia bound as carbonate, hydrogen
carbonate, carbamate and other ammonia salts are determined.
All components together are considered “total ammonia”, defined by an equivalence
point of pH = 5.2.
2. Safety
Hydrochloric acid
Methyl Red
Methylene Blue
3. Principle

Titration of the ammonia with hydrochloric acid.
Indicating the endpoint of the titration with an indicator containing methyl red and
methylene blue.
4. Apparatus
4.1 Burette, 5 ml
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5. Chemicals

5.2 Methyl red, e.g. Merck
5.3 Methylene blue, e.g. Merck
5.4 Indicator solution: dissolve 0.5 g methyl red (5.2) and 0.3 g methylene blue (5.3) in
1 L demi water
6. Procedure

- Add a few drops of the indicator solution (5.4).
- Titrate with hydrochloric acid 0.01 mol/l (5.1) to colour change (V ml).
The pH at equivalence point is ± 5.2.
7. Calculation
Calculate the ammonia content using formula:
V * T * 17.03 * 1000
ppm NH3= ----------------------------
a


8. Remarks
8.1 This method is also applicable for e.g. urea melt. Urea melt is a melt of 95 % urea
and 5 % water with original temperature of 130°C. Only take care that solution A,
the measuring solution, contains about 15 g urea/100 ml.
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9. Reference
DSM 206
Chemlab 1605-OV-E
New colour indicator.
11. Attachments
No attachments.
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DSM Melamine
Analytical method 425, version 2 Date: 30 August, 2004
DETERMINATION OF TOTAL AMMONIA IN UREA

Authorisation :
(signature)
Keywords: Urea, ammonia, Titrimetric, Indicator, Methyl Red, Methylene Blue
1. Scope
Determination of the ammonia content (NH3) in urea and other intermediate products
obtained in the production of urea.
Besides ammonia present as ammonia also ammonia bound as carbonate, hydrogen
carbonate, carbamate and other ammonia salts are determined.
All components together are considered “total ammonia”, defined by an equivalence
point of pH = 5.2.
2. Safety
Hydrochloric acid
Methyl Red
Methylene Blue
3. Principle

Titration of the ammonia with hydrochloric acid.
Indicating the endpoint of the titration with an indicator containing methyl red and
methylene blue.
4. Apparatus
4.1 Burette, 5 ml
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5. Chemicals

5.2 Methyl red, e.g. Merck
5.3 Methylene blue, e.g. Merck
5.4 Indicator solution: dissolve 0.5 g methyl red (5.2) and 0.3 g methylene blue (5.3) in
1 L demi water
6. Procedure

- Add a few drops of the indicator solution (5.4).
- Titrate with hydrochloric acid 0.01 mol/l (5.1) to colour change (V ml).
The pH at equivalence point is ± 5.2.
7. Calculation
Calculate the ammonia content using formula:
V * T * 17.03 * 1000
ppm NH3= ----------------------------
a


8. Remarks
8.1 This method is also applicable for e.g. urea melt. Urea melt is a melt of 95 % urea
and 5 % water with original temperature of 130°C. Only take care that solution A,
the measuring solution, contains about 15 g urea/100 ml.
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9. Reference
DSM 206
Chemlab 1605-OV-E
Add a subtitle in the first page.
11. Attachments
No attachments.
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DETERMINATION OF FREE AND TOTAL AMMONIA IN UREA
Authorisation :
(signature)
Keywords: Urea, Ammonia, Free, Total, Potentiometric Titration
1. Scope
Potentiometric determination of the ammonia content (NH3) of urea and other

intermediate products obtained in the production of urea, by detection of equivalence
points.
Besides ammonia present as ammonia (free ammonia) also ammonia bound as
carbonate, hydrogen carbonate, carbamate and other ammonia salts are determined
(total ammonia).
This method is to be used in combination with sampling method SCM-400 and

SCM-401.
2. Safety
Hydrochloric acid
3. Principle

Potentiometric titration of the ammonia with hydrochloric acid.
4. Apparatus

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5. Chemicals
5.1 Hydrochloric acid, 0.01 mol/L e.g. Titrisol from Merck.
6. Procedure
- Calibrate the titrator at pH 7.00 and 4.00 according to the instruction manual of the
titrator.
- Add into a 400 ml beaker a g, accurate to 0.01 g, of urea (usually ± 15g), or a g of
solution A (see 8.1)
- Add 200 ml of demi water and dissolve the sample (=solution B)
- Perform an endpoint titration with hydrochloric acid 0.01 mol/l (5.1) to pH 4.5.
- Determine the consumption of hydrochloric acid (5.1) at the equivalence points in
ml.
7. Calculation
7.1 Calculation of the free ammonia content as defined by the equivalence point at
pH ± 7.5, using formula:
V1 * T * 17.03 * 1000 * f
ppm NH3= -------------------------------
a
7.2 Calculation of the total ammonia content as defined by the equivalence point at
V2 * T * 17.03 * 1000 * f
ppm NH3= -------------------------------
a
Where: V1= titrated volume of hydrochloric acid in ml at first equivalence point

(pH 7.5)
V2= titrated volume of hydrochloric acid in ml at second equivalence
point (pH 5.2)
f = dilution factor (see SCM 400)

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8. Remarks
8.1 This method is also applicable for the following samples (solution A):
a. the urea solution of the outlet of the reactor.
b. the urea solution of the outlet of the stripper before the expansion valve.
c. the urea melt from the evaporation unit. Urea melt is a melt of approximately
95 - 99 wt-% urea and approximately 1 - 5 wt-% water with original
temperature of 130°C.
d. the urea solution of the outlet recirculation separator.
e. the carbamate solution from the low pressure carbamate condenser.
f. the liquid to the desorber.
g. the reflux condensor level tank.
h. the urea solution from the buffertank.
i. the liquid from desorber to sewer.
sample, as described in method SCM 400 and SCM 401.
- Pipet into a 400 ml beaker a ml of solution A.
- For sample a, e and g this is 5 ml.
- For sample b and f this is 25 ml.
- For sample c, d, h and i this is 100 ml.
- Continue as mentioned in par. 6.
Make sure that solution B, the measuring solution, contains about 15 g urea/200 ml.
9. Reference
SCM 400
SCM 401
DSM 381-34-E
Addition of sample streams.
11. Attachments
Titration curve of urea.
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Attachment 1: Example of a titration curve
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DETERMINATION OF FREE AND TOTAL AMMONIA IN UREA

(Titrimetric ,potentiometric)
Authorisation :
(signature)
Keywords: Urea, Ammonia, Free, Total, Potentiometric Titration
1. Scope
Potentiometric determination of the ammonia content (NH3) of urea and other

intermediate products obtained in the production of urea, by detection of equivalence
points.
Besides ammonia present as ammonia (free ammonia) also ammonia bound as
carbonate, hydrogen carbonate, carbamate and other ammonia salts are determined
(total ammonia).
This method is to be used in combination with sampling method SCM-400 and

SCM-401.
2. Safety
Hydrochloric acid
3. Principle

Potentiometric titration of the ammonia with hydrochloric acid.
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4. Apparatus

5. Chemicals
5.1 Hydrochloric acid, 0.01 mol/L e.g. Titrisol from Merck.
6. Procedure
- Calibrate the titrator at pH 7.00 and 4.00 according to the instruction manual of the
titrator.
- Add into a 400 ml beaker a g, accurate to 0.01 g, of urea (usually ± 15g), or a g of
solution A (see 8.1)
- Add 200 ml of demi water and dissolve the sample (=solution B)
- Perform an endpoint titration with hydrochloric acid 0.01 mol/l (5.1) to pH 4.5.
- Determine the consumption of hydrochloric acid (5.1) at the equivalence points in
ml.
7. Calculation
7.1 Calculation of the free ammonia content as defined by the equivalence point at
V1 * T * 17.03 * 1000 * f
ppm NH3= -------------------------------
a
7.2 Calculation of the total ammonia content as defined by the equivalence point at
V2 * T * 17.03 * 1000 * f
ppm NH3= -------------------------------
a
Where: V1= titrated volume of hydrochloric acid in ml at first equivalence point

(pH 7.5)
V2= titrated volume of hydrochloric acid in ml at second equivalence
point (pH 5.2)
f = dilution factor (see SCM 400)
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8. Remarks
8.1 This method is also applicable for the following samples (solution A):
a. the urea solution of the outlet of the reactor.
b. the urea solution of the outlet of the stripper before the expansion valve.
c. the urea melt from the evaporation unit. Urea melt is a melt of approximately
95 - 99 wt-% urea and approximately 1 - 5 wt-% water with original
temperature of 130°C.
d. the urea solution of the outlet recirculation separator.
e. the carbamate solution from the low pressure carbamate condenser.
f. the liquid to the desorber.
g. the reflux condensor level tank.
h. the urea solution from the buffertank.
i. the liquid from desorber to sewer.
sample, as described in method SCM 400 and SCM 401.
- Pipet into a 400 ml beaker a ml of solution A.
- For sample a, e and g this is 5 ml.
- For sample b and f this is 25 ml.
- For sample c, d, h and i this is 100 ml.
- Continue as mentioned in par. 6.
Make sure that solution B, the measuring solution, contains about 15 g urea/200 ml.
9. Reference
SCM 400
SCM 401
DSM 381-34-E
Add a subtitle in the first page.
11. Attachments
Titration curve of urea.
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Attachment 1: Example of a titration curve
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Analytical method 429, version 1 Date : 15 April 2003
DETERMINATION OF FORMIC ACID IN WATER.

(ionchromatographic method)
Authorisation :
(signature)
Keywords:
Formic acid, ion chromatograpy.
1. Scope
Determination of the concentration of formic acid in aqueous solutions, from 0.01

mg/kg upwards.
Concentrations of anions, cations or other compounds which are 100 to 10000 times
the concentration of the anion to be determined generally do not interfere with the
determination (depending on the difference in k’; see table, attachment 1)
Multivalent ions and compounds with a high affinity to the exchanger can be removed
by a washing procedure (see 7).
2. Safety
Formic acid
Sodium hydrogencarbonate
Sodium carbonate
A HPLC apparatus operates under high pressure (100 - 400 bar). In spite of the
use of small volumes, always wear safety glasses when working with HPLC.
Work safely, especially with hazardous chemicals. Use the guidelines of
Material Safety Data Sheets (MSDS) or a local equivalent.
3. Principle
- Injection of the sample solution into the continuous eluent flow, via a sample loop.
- Separation of formic acid on a column packed with a low-capacity anion
exchanger based on divinylbenzene-polystyrene.
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- Suppression of the total conductivity with the aid of a cation-exchanging

membrane.
- Detection of formic acid by measurement of the change of the electrical
conductivity of the eluent.
- Comparison of the value measured with the value obtained with a calibration
solution (external standard method).
4. Apparatus
4.1 Ion chromatograph (Dionex DX 500) with the following specifications:

4.1.1 Columns
pre-column separation column
- type code AG4A AS4A
- material rigid inert polymer
- inside diameter, mm 4.0 4.0
- outside diameter, mm 6.5 6.5
- length, cm 5.0 25
- temperature, °C ambient temperature (± 21 °C)
4.1.2 Column packing: Dionex patented low-capacity anion exchanger based on

divinylbenzene-polystyrene with particle size 0.015 mm.
4.1.3 Suppressor: Dionex ASRS
4.1.4 Sample injection: preferably use an auto sampler and auto injector with an
injection volume of 50-100 µl (for instance a Spark Marathon auto sampler).
4.1.5 Detector: Dionex conductivity detector (type ED 40 or CD 20).
4.2 Filter: with pores of 0.2 or 0.45 µm, e.g. Schleicher & Schull with nylon
membrane, item no 10463020.
4.3 Glassware: only use glassware especially reserved for ion chromatography
analyses and even clean this glassware before using it by rinsing it twice with
water (5.1) or the sample solution. If possible don’t use glass stoppers
because they are always contaminated. If possible close the volumetric flasks
with the same syringe that will be used to fill the vials of the auto sampler.
5. Chemicals
5.1 Water, HPLC quality, e.g. Milli-Q water.

5.2 Sodium bicarbonate (NaHCO3), p.a, e.g. Merck.
5.3 Sodium carbonate (Na2CO3), p.a., e.g. Merck.
5.4 Formic acid, > 98%, e.g. Merck
5.5 Washing liquid: Dissolve 1 g of sodium carbonate (5.3) in 1 litre of water (5.1)
5.6 Helium, free of organic impurities.
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6. Procedure
6.1 Preparation of the eluent solution

- Weigh 40 mg sodium bicarbonate (5.2) in a 1L measuring flask and dissolve in
1000 mL of water (5.1)
- Degass the eluent for 10 minutes with helium gas: flow approx. 100 mL/min (5.6)
Starting up procedure
- Pump eluent through, successively, the injector, the columns, the ASRS
suppressor (eluent in/out), the cell of the conductivity detector and again the
ASRS suppressor (regenerant in/out), at a rate of 2 ml per minute.
- Adjust flow through the column to 2.0 ml/min and immediately switch on the
ASRS. Be sure to switch the ASRS off when the flow over the column is
stopped.
- The base conductivity is about 5 µS/cm.
6.2 Preparation of the calibration solution

Stock solution formic acid (A):
- Weigh (accurate to 0.0001 g) into a 100.0 mL measuring flask approximately 100
mg formic acid (m1) (5.4).
- Fill up to 100 mL with water (5.1) and mix (= solution A1).
- Weigh (accurate to 0.0001 g) into a 200.0 mL measuring flask approximately 200
mg formic acid (m2) (5.4).
- Fill up to 200 mL with water (5.1) and mix (= solution A2).
- These solutions can be kept for at least several months.
-Weigh of stock solution A1; 0.05 – 0. 5 g (W a1) into measuring flasks of 200 mL.
-Fill up to 200 mL with water (5.1) and mix.
-Weigh of stock solution A2; 0.05 – 0. 5 g (W a2) into measuring flasks of 200 mL.
-Fill up to 200 mL with water (5.1) and mix.
-Calculate the concentration of formic acid from the calibration solutions (for
calculation see 8.1).
- Inject 50 – 100 µl (4.1) of each calibration standard onto the columns.
- Determine the peak surface of the component (Ac) (for an example of a
chromatogram see attachment 2).
- Prepare these solutions always freshly.
6.3 Determination
- If necessary, dilute a g of sample solution with water (5.1) to a mass of b g (=
solution B). The concentration of formic acid in solution B needs to be between
0.2 and 2.5 mg/L.
- Inject 50 – 100 µl (4.1) of solution B onto the columns.
- Determine the peak surface of the component (As).
- Inject the next sample as soon as the base conductivity has returned to its original
level and no interfering peaks of slowly eluting components are to be expected.
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- Apply the washing procedure (7) if it is found that on account of the presence of
irreversible components in the column or very slow elution of the components the
next determination would be interfered with.
7. Washing procedure
- Replace the eluent by washing liquid (5.5).

- After 10 minutes, when the base conductivity has returned to a value of 30-40
µS/cm via a very high value, replace the washing liquid (5.5) by water (5.1) and
about 2 minutes later the water by eluent.
- Inject the next sample as soon as the base conductivity has returned to its original
level.
8. Calculation.
8.1 Calculation of the calibration factor

Calculate, the calibration factor of formic acid, using the formula:
f = Cc / Ac
Where: f: calibration factor for formic acid

Cc: concentration of calibration solution of formic acid in mg/kg
Cc: m1/100 * W a1 * 5 or m2/200 * W a2 * 5
W a1: weight in g of stock solution A1 (6.2) into measuring flask of 200.0 ml.
W a2: weight in g of stock solution A2 (6.2) into measuring flask of 200.0 ml.
m1: weight of formic acid in mg
m2: weight of formic acid in mg.
Ac: peak surface area from formic acid
Calculate the average factor, or use linear regression caculation (see attachment 3).
8.2 Calculation of the concentration of formic acid in the sample

Calculate, the concentration of formic acid in the sample solution using the formula:
Cs = f * As * b / a
Where: Cs: the concentration of formic acid in the sample in mg/kg

f: calibration factor for formic acid
As: sample peak surface area from formic acid
a: the amount of sample solution, in g.
b: the mass of solution B, in g.
Accuracy of the analysis method is determined by analysing 1 sample 10 times

(including sample preparation). The relative standard deviation is about 2 %.
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9. Remarks
9.1 If solution B is turbid, filter with a 0.2 or 0.45 µm filter (4.2)

9.2 The vials which are used in the auto sampler should always be rinsed twice with
sample solution or calibration solution
10. Reference.
DSM_CRO 0648-E version 2

G:\skillcentre\organization\analytical methods\doc\429v1.doc
New method.
12. Attachments.
- Table with k’ of some ions

- Chromatogram of a calibration solution of formic acid in water.
- An example of a calibration curve of formic acid
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Attachment 1 : Table with k’ of some ions.
Composition of eluent
40 mg/L NaHCO3
Ion k’
fluoride <1
Acetate 1.5
Formiate 2.5
Chloride > 10
Nitrite > 10
Nitrate > 10
bromide > 10
Phosphate > 10
sulfate > 10
t r - t ro
k' =
t ro
tr = retention time of the ion

tro = retention time of the unretained components
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Attachment 2: An example of a chromatogram of a calibration solution of formic acid

in water.
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Attachment 3: An example of a calibration curve of formic acid.
Calibration curve of formic acid in water
3000
2500 y = 1110.4x
2
R = 0.998
area (counts)
2000
1500
1000
500
0
0 0.5 1 1.5 2 2.5 3
concentration formic acid (mg/L)
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Analytical method 430, version 1 Date: 02 November, 2002
DETERMINATION OF THE ROLLING TENDENCY OF (FERTILIZER)

GRANULES/PRILLS
Authorisation :
(signature)
Keywords: Urea, granules, prills, rolling tendency
1. Scope
Determination of the rolling tendency of fertilizer granules and prills. This method
provides a measure of the roundness of the granules and prills.
2. Safety
Work safely.
3. Principle
- Feeding an even and slow flow of sample onto a rotating, slightly inclined, flat disc
in such a way that the particles do not hinder each other’s movement.
- The particles roll down and change direction because of the rotary motion of the
disc. The particles with the highest rolling tendency will deviate the least from their
original direction.
- Catching the particles that roll off the disc within an arbitrarily chosen area.
- Weighing the particles caught and calculating the rolling tendency from the mass
of the particles caught.
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4. Apparatus
4.1 Equipment (see 9.1) for the determination of the rolling tendency of fertilizers
see attachments 1 and 2
Equipment consists of:
4.1.1 Stainless steel funnel
4.1.2 V-shaped feed chute, the drop by the particles from the chute onto the
disc is
10 mm
4.1.3 Vibrator, e.g. Retsch AS 200 Control G
4.1.4 Melamine coated Pertinax disc (trade name Trespa) inclined at 7°30’
from the
horizontal
4.1.5 Disc drive set at 16 rpm
4.1.5 Compressed air supply
4.2 Level (calibrated)
4.3 Stopwatch
4.4 Protractor (calibrated)
4.5 “Eindmaten”, stainless steel blocks with fixed (calibrated) dimensions with sizes
1, 2, 3, 4 and 5 mm
4.6 Stainless steel woven wire sieve of 1.4 mm e.g. Retsch
5. Chemicals
6. Procedure

- Sieve the sample through a 1.4 mm wire sieve (4.6) for 5 minutes.
- Use a g (approximately 100 g) of the fraction > 1.4 mm.
6.2 Determination of the rolling tendency

- Check that the equipment for the determination of the rolling tendency (4.1) is
level (4.2). (see 9.2)
- Start the disc drive and open the compressed air valve.
- Place the funnel as low a possible above the feed chute and set the vibrator to
the lowest frequency.
- Place a g of sample, weighed to the nearest 0.1 g, in the funnel.
- Increase the vibrator frequency and if necessary increase the distance between
the funnel and the feed chute so that the particles leave the feed chute in a
steady, continuous flow without interfering each other.
- Check that the unround particles are blown away. Increase the amount of
compressed air if necessary.
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- At the end of the test, weigh, to the nearest 0.1 g, the mass (= m g) of the
particles caught in the tray for round product.
- Clean the funnel, feed chute and disc with alcohol if necessary.
7. Calculation
Calculation the rolling tendency of the sample in wt% using the formula
m
--------- * 100
a
Where: a : amount of sample used in g

m : mass of product caught in g
Accuracy of the analysis method, including sample preparation determined by

analysing 1 sample 10 times. The relative standard deviation = 1.2 % (based on 1
times s)
8. Reference
AGRO 1081
03162001.doc
9. Remarks

9.2 Check every 6 months:
- The horizontal position of the equipment using a level (4.2)
- The rotation speed of the disc drive with a stopwatch (4.3) Allowed deviation=
none
- The angle of the coated disc drive with a protractor (4.4 ). Allowed deviation=
10%
- The height of drop of the particles with “eindmaten” (4.5). Allowed deviation=
10%
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Upgrade.
11. Attachments
Equipment to determine the rolling tendency of fertilizers and dimensions of the

chute.
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Attachment 1: Equipment for determination of the rolling tendency of fertilizers
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DSM Melamine
Attachment 2: Dimensions of the chute
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Analytical method 431, version 1 Date: 20 January, 2004
DETERMINATION OF pH, BUFFERVALUE AND AMMONIUM

SALTS OF UREA
Authorisation:
(signature)
Keywords: urea, pH, Buffer value, Ammonium salts, Titration
1. Scope
Determination of the pH of a 25% solution of urea in water, the buffer value and the
amount of ammonium salts of urea. Under buffer value in this method is
understood: the amount of mmol acid/kg urea that is required to bring the pH of a
25% solution of urea in water to 5.4.
The method is only applicable to well hang urea: In the production area (e.g. silo)
urea should be stored for at least 7 days at a temperature of 35 – 40°C.
A laboratory equivalent will be the next treatment of a fresh produced urea sample:
Stabilize a sample in a closed bottle (filled up to 80%) for 24 hours at 60°C.
2. Safety
Formaldehyde
Sodium hydroxide
Sulphuric acid
Potassium chloride
Urea
Work safely. Use the guidelines of e.g. Material Safety Data Sheets (MSDS) or a
local equivalent.
3. Principle
· Measurement of the pH of a 25% solution of urea in water.

· Measurement of the amount of mmol acid needed to bring the pH of a 25%
solution of urea in water to a pH of 5.4.
· Reaction of formaldehyde with ammonium ions and titration of the formed acid
with sodium hydroxide.
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4 Apparatus
4.1 pH meter, e.g. Mettler Toledo DL25 provided with a combi electrode e.g. Thermo
Orion Sure flow electrode type 91-72BN
5. Chemicals
5.1 Sodium hydroxide p.a., e.g. Merck

5.2 Sodium hydroxide solution, c(NaOH)= 0.1 mol/L, titre T1
5.3 Sulphuric acid p.a, e.g. Merck
5.4 Sulphuric acid solution, c(H2SO4)= 0.05 mol/L, titre T2
5.5 Formaldehyde solution p.a 37% e.g. Merck
5.6 Potassium chloride, p.a. e.g. Merck
5.7 Potassium chloride solution, 10 g/L
5.8 Demi water free of carbondioxide.
6. Procedure
- Transfer 100 ± 0.5 g sample to a 800 ml beaker.

- Add 300 ml water (5.8), 3 ml potassium chloride solution (5.7) and dissolve while
stirring with a magnetic stirrer, warm, if necessary to at most 20°C.
- Perform the pH and titration measurement at 20 ± 0.2° C.
6.1 Determination of the pH

- Calibrate the pH meter and a combi electrode (4.1) using buffer solution of pH
7.00 and 4.00.
- Rinse the electrode and determine the pH to a stabile reading.
- Proceed according to 6.2.
6.2 Determination of the buffer value

- Titrate the urea solution with sulphuric acid (5.4) to pH 5.4 (= v ml).
- Proceed according to 6.3
6.3 Determination of the amount of ammonium salts

- Bring the pH of the urea solution to 7.5 by addition of sodium hydroxide (5.2).
- Add 2.5 ml formaldehyde solution (5.5).
- Stir the solution and wait for 5 minutes.
- Titrate the formed acid with sodium hydroxide (5.2) to pH 7.5 (= v1 ml)
6.4 Perform a blank without urea

- Reference 6.2 (= v0 ml).
- Reference 6.3 (= v2 ml).
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7. Calculation
7.1 Calculate the buffer value in mmol/kg urea, using the formula:
(v - v0) * T2 * 1000
---------------------------
100
Where: v= ml sulphuric acid consumed in the titration according to 6.2

v0= ml sulphuric acid consumed in the titration according to 6.4
T2= normality of sulphuric acid
7.1 Calculate the amount of ammonium salts in mmol/kg urea, using the formula:
(v1 - v2) * T1 * 1000

---------------------------
100
Where: v1= ml sodium hydroxide consumed in the titration according to 6.3

V2= ml sodium hydroxide consumed in the titration according to 6.4
T1= normality of sodium hydroxide
8. Reference
DSM analytical method 602, CRO 700, DMG 261-B1

G:\skill centre\organization\analytical method\doc\431v1
New method.
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Analytical method 432, version 1 Date: 08 March, 2004
DETERMINATION OF THE FRIABILITY OF (FERTILIZER) GRANULES

(Ball mill technique)
Authorisation :
(signature)
Keywords: Urea, granules, ball mill, friability, abrasion and shatter resistance
1. Scope
Determination of the friability or abrasion and shatter resistance of (fertilizer) granules

under a dynamic pressure load so as to assess granule resistance to the various
forces acting on the product during handling.
In the context of this method, friability means the amount of product that crushes
under a dynamic pressure load under defined conditions.
Dynamic pressure load means the exertion of pressure, impact and shear forces
on the granules.
This method is applicable to all granular fertilizers.
2. Safety
Work safely.
3. Principle
- Sieving the sample.

- A number of granules are made to rotate in an inclined steel, flighted drum
containing steel balls.
- Sieving the sample thus treated.
- Calculation of the friability.
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4. Apparatus
4.1 Steel drum provided with six flights and a sealable cover. Its axis of rotation is
at an angle of 30° to the horizontal. The drum is driven by a DC motor whose
speed is set to 60 ± 1 r.p.m. (see 6.2) (Reference: shop drawing CL 14534
d.d. 21-06-1989).
4.2 25 stainless steel balls, diameter 7.925 ± 0.025 mm, mass 2.015 ± 0.005 g
(see 6.2) (see 9.3).
4.3 Timer set to 15 minutes or stopwatch.
4.4 Sieve shaker, woven wire sieves and bottom pan according to method SCM
416.
5. Chemicals
6. Procedure

- Sieve the sample for 5 minutes on a 2.8 mm (see 9.2) wire sieve according to
SCM 416 (4.4)
- Use the material retained on the sieve.
- Sieve out an amount of product such that 100 g of analysis material is available
for each determination.
6.2 Inspection of apparatus

- Check the drum speed prior to analysis.
- Fill the drum with 100 g of analysis material (6.1) and add the 25 stainless steel
balls (4.2).
- Close the drum (4.1), start the motor and the timer or stopwatch (4.3).
- Count the drum’s number of revolutions for 60 seconds. This count should be
60 ± 1.
- Check the mass of the balls once every year. This should be 2.015 ± 0.005
grams.
6.3 Determination of the friability

- Place the 25 stainless steel balls (4.2) in the drum (4.1).
- Add 100 ± 1 g (= a g) of analysis material (6.1) and close the drum (4.1).
- Start the motor (4.1) and the timer or stopwatch (4.3).
- Stop the drum after 15 minutes, automatically or by hand.
- Use a brush to transfer the analysis material to a sieve of 2.36 mm with sieve
bottom (4.4) and sieve again for 5 minutes.
- After sieving, determine the amount of product on the sieve bottom (= b g).
- Always perform the determination in duplicate.
Volgnummer: fscm042

DSM Melamine
Skill Centre
7. Calculation
Calculate the friability in wt% of the analysis material using the following formula:
b
--------- * 100
a
Where: a = mass of the amount of material tested before the determination, in g.

b = mass of sieved amount material after the determination, in g.
Average the two results and round off to 0.01 %.

The friability figures must not differ by more than 10 %(relative). The average value
is reported as the friability of the material tested. Where the difference exceeds
10%, a third analysis should be carried out and the average value of 3 analyses
should be reported.
8. Reference
G:\skill centre\organisation\analytical method\doc\432v1.doc

AGRO 1035
CRO ME 84 1363 KMO, Th. Evers, Onderzoek naar de vergruisbaarheid van
gecompacteeerde ZA
CRO MK 85 28 KMO, Th. Evers, M. Willems, De vergruisbaarheid van gekorrelde
kunstmeststoffen
Chemlab D&A, IC, SP&F d.d. 15-2-1995
9. Remarks

9.2 Always use a sieve with aperture size 2 sizes smaller than the d50 of the
sample.
9.3 In some cases it could be necessary to use 5 stainless steel balls instead of
25. In this case the 5 stainless steel balls have a diameter of 16 mm and a
weight of 16.4 ± 0.2 g. The timer should be set at 5 minutes.
New method.
Volgnummer: fscm042

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Stamicarbon bv

P.O. Box 53 - 6160 AB Geleen, The Netherlands

rev. by description checked date scanned

- LPO First Issue MEE Jan 2008

prepared by date pertaining drawings project

Number Version Date Title

305 1 September 2003 Determination of formaldehyde in water

401 2 September 2002 Sampling of product from the urea plant

402 1 May 2000 Determination of biuret in urea

403 1 September 2001 Determination of carbon dioxide in

404 1 May 2000 Determination of urea in urea solutions

405 1 September 2001 Determination of urea

406 2 July 2004 Determination of water in urea

407 1 February 2004 Determination of water in liquid ammonia

408 3 July 2004 Determination of formaldehyde in urea

410 3 August 2004 Determination of free ammonia in urea

411 2 January 2003 Determination of ammonia in water

412 1 February 2004 Determination of ammonia in gas

415 1 October 2002 Determination of the crushing strength or

416 1 October 2002 Determination of the particle size

417 1 March 2004 Determination of total nitrogen in urea

Analytical Methods Urea drawing nr A4-00000

Number Version Date Title

418 1 March 2004 Determination of impact (shock) of final

419 1 March 2004 Determination of oil in liquid ammonia

420 1 July 2002 Determination of urea in water

421 1 May 2004 Determination of urea in off gas prilling

422 1 December 2003 Determination of chloride in steam

424 1 November 2002 Determination of the bulk density of

425 2 August 2004 Determination of total ammonia in urea.

427 3 August 2004 Determination of free and total ammonia

429 1 April 2003 Determination of formic acid in water

430 1 November 2002 Determination of the rolling tendency of

431 1 January 2004 Determination of pH, Buffervalue and

Analytical Methods Urea drawing nr A4-00000

Analytical method 305, version 1 Date: 30 September 2003

DETERMINATION OF FORMALDEHYDE IN WATER

Jan Jaap Nusselder, Manager PAR Melamine Skill Centre

Keywords: Formaldehyde, HPLC, fluorescence detection

Determination of the formaldehyde concentration in water by means of a HPLC

Method 305v1 page 1 of 9

Dissolution of the sample in buffer solution.

4.1. HPLC system complete, containing:

5.1. Phosphoric acid 85% e.g. Baker Chemicals

Method 305v1 page 2 of 9

5.12. Eluent solutions

6.1 Preparation of the buffer solution A (see 8.1)

6.2 Preparation of the Hantz reagent

6.3 Preparation of the standard formaldehyde solution

6.4 HPLC start-up

Method 305v1 page 3 of 9

6.5 Shutting down

6.6 Analysis of formaldehyde in water

Method 305v1 page 4 of 9

7.1 Calculate, the calibration factor of formaldehyde using the formula:

Where: fm: calibration factor for formaldehyde

Calculate the average factor, or use linear regression calculation.

Where: Cs: the concentration of formaldehyde in the sample in mg/kg