MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 165 ULTRAVIOLET ABSORPTION TEST FOR EVALUATION OF

ETHYLENEBIS(DITHIOCARBAMATE)

OUTLINE OF METHOD
The ultraviolet spectrum is recorded in the range of 200-400 nm on the filtrate of an
ethylenebis(dithiocarbamate) water dispersion. Absorbance values are measured at
280-285 nm for the EBDC anion, using a linear baseline procedure.
Zineb, mancozeb, and mixtures of maneb and water-soluble zinc salts give an
absorbance not exceeding 0.05 absorbance units, whereas maneb, and mixtures of
maneb with zineb or insoluble zinc salts give an absorbance higher than 0.05
absorbance units (typically in the range of 0.1 to 0.7 absorbance units).

SCOPE
This method, measuring the water solubility of different EBDC compounds, is useful
to differentiate zineb, mancozeb, and mixtures of maneb and water- soluble zinc salts
from maneb, and mixtures of maneb with zineb or insoluble zinc salts.

REAGENTS
Distilled water (RE 130) de-oxygenated with nitrogen

APPARATUS
Beakers 25 and 600 ml
Volumetric flask 25 ml
Syringe 10 ml and hypodermic needle
Microsyringe filter holder with a 0.45 µm filter unit Millipore or equivalent
Buchner funnel
Magnetic stirrer
Spectrophotometer to measure over the range 200-400 nm
PROCEDURE
(a) Sample preparation.
Weigh 0.5 g of the material. Add distilled water (300 ml) to a 600 ml beaker and stir,
using a magnetic stirrer. The distilled water should be de-oxygenated with nitrogen
and should remain under nitrogen during the course of the experiment. Add the
weighed sample to the water in the beaker.
One hour after addition of sample, withdraw 10 ml of the supernatant liquid by means
of a hypodermic needle and a 10 ml syringe. Remove the needle and replace with a
Millipore micosyringe filter holder with a 0.45 µm filter unit, and filter the slurried

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sample into a 25 ml beaker.

Remove 1 ml of the filtrate by pipette and add it to a 25 ml volumetric flask. Adjust
to the mark with distilled water and record the UV spectrum as described in (b).

(b) UV spectrum measurement.

Fill a 1 cm path length UV absorption cell with the diluted filtrate and scan in the UV
region (200-400 nm) on a suitable spectrophotometer. Run the sample against a blank
cell filled with distilled water.
Use the absorption band at 280-285 nm of the EBDC anion for measuring the
absorbance value, according to a linear baseline procedure. Measure the height of the
peak after plotting the baseline.

RESULTS

The following observations can be made on typical EBDC compounds:

(a) Zineb, mancozeb, and mixtures of maneb with water soluble zinc salts give
absorbance values not exceeding 0.05 units (see Fig. 51b).

(b) Maneb, and mixtures of maneb with zineb or water insoluble zinc salts give
absorbance values greater than 0.05 absorbance units, typically in the range of 0.1 to
0.7 units (see Fig. 51a).

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Figure 51a Ultraviolet spectrum of maneb with zineb, or mixtures of maneb with water-insoluble zinc salts
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Figure 51b Ultraviolet spectrum of zineb, mancozeb or mixtures of maneb with water-soluble zinc salts
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 166 SAMPLING OF WATER DISPERSIBLE GRANULES

SCOPE

The method is suitable for preparing samples of water dispersible granules for the
determination of the amount of active ingredient content or the physical properties of
the formulation.

OUTLINE OF METHOD

Water dispersible granules (WG) may have a relatively broad particle spectrum so
that segregation into different particle sizes may occur during transportation or
handling of the products.
It is, therefore, essential to divide samples with great care. This may be achieved by
using a dividing apparatus or by standardized manual dividing.

APPARATUS

Mechanical sample divider conforming to ISO-R-607 (DIN 53911), Retsch sample

divider Type PTZ (Note 1)
Polyethylene bag size about 30 cm square
Laboratory spoon-spatula

PROCEDURE

(i) With the dividing apparatus

Mechanical sample division is most suitable for taking representative individual
samples. For the handling of the apparatus, refer to the instructions of the
manufacturer.

(ii) Manual
Put a representative sample of about 200 g (Note 2) of the WG into a sufficiently
large polyethylene bag, filling this by at least one third.
Mix the contents by turning the closed bag end over end at least 10 times. Put the
polyethylene bag on a flat surface and spread the granules within the bag over as large
an area as possible. The sample layer should be approximately 1 cm thick.
Take the required sub-sample from a minimum of five positions from the sample
layer.

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Note 1 Obtainable from: Firma RETSCH, Rheinische Straße 36, P.O.B. 1510,
W.-Germany, D-5657 Haan

Note 2 If the original sample is bigger than 200 g, start the manual sampling
procedure carefully. Spread out the contents of the entire container and take
sub-samples by spoon from 20 - 25 different positions per kg to get a
representative sample of 200 g.
For samples taken from large containers, a mechanical sample divider is
preferred.

MT 167 WET SIEVING AFTER DISPERSION OF WATER

DISPERSIBLE GRANULES
(See CIPAC MT 59.3)

SCOPE

The method is suitable for the determination of the amount of non-dispersible

material in water dispersible granules

OUTLINE OF METHOD

A sample of water dispersible granules is dispersed in water and the suspension is

transferred to a sieve and washed. Determination of the weight of the residue on the
sieve is done according to MT 59.3 which has been adapted to the requirements of
testing water dispersible granules.

APPARATUS

Beaker 250 ml
Glass rod of about 6 mm diameter - rubber capped
Sieve 20 cm diameter, 75 µm mesh size (200 mesh according to ASTM E 11-61,
0.075 mm according to DIN 4188, ISO 565, if not otherwise specified)

PROCEDURE

(i) Wetting of water Dispersible Granules

Weigh 10 g of the sample, to the nearest 0.1 g, into a 250 ml beaker and add 100
ml tap water (Note 1). Allow to stand for 60 sec. Then stir with a rubber capped
glass rod by hand for 30 sec at not more than three to four revolutions per sec,
making no deliberate attempt to break up any lumps.

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(ii) Wet Sieving

Transfer the slurry to the sieve, rinsing with tap water. Wash the material on the sieve
with an oscillating jet of tap water (Note 2) using a rubber hose of 10 mm i.d.
delivering 4-5 litres of water per min. Continue the washing for 10 min, directing the
water from the circumference of the sieve towards the centre and keeping the end of
the hose at a distance of between 2 - 5 cm from the surface of the sieve. Transfer the
residue to a tared glass dish with a jet of distilled water from a wash bottle. Dry to
constant weight (Note 3) and record the weight of the sample to the nearest 0.01 g.

(iii) Calculation
Express the weight of residue as a percentage of the sample weight and record the
result as a percentage retention on the stated test sieve.

Note 1 This method was developed using tap water of temperature from 5 - 15°C.
Note 2 The tap water may contain solids, and should be screened before use.
Note 3 A temperature of 60-70°C is recommended. If necessary, the temperature
must be varied to avoid decomposition or volatilization at the drying
temperature.

MT 168 DETERMINATION OF THE SUPENSION STABILITY OF

WATER DISPERSIBLE GRANULES

SCOPE AND OUTLINE OF METHOD

As for MT 15.1.
REAGENT

Standard Water MT 18.1.4, if not otherwise specified

APPARATUS
As for MT 15.1.

PROCEDURE
(a) Preparation of the suspension

As for MT 15.1, method b, except that a dispersing time of 4 min is used instead of
13 min.

(b) Determination of Sedimentation

As for MT 15.1.

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(c) Quantitative determination of the sediment

Determine the content of solids in the sediment gravimetrically . After removing

nine-tenths of the suspension, transfer the remaining tenth of the suspension at the
bottom of the test vessel into a tared Petri dish by rinsing with distilled water, and dry
to constant weight. Record the mass of the residue to the nearest 0.01 g (a).
a
Suspension stability = 111 ( 1 − )
w
where:

a = dry mass of the lower 25 ml of the suspension (g)

w = the mass of the sample taken (g)

MT 169 TAP DENSITY OF WATER DISPERSIBLE GRANULES

1 Standard-method (See CIPAC MT 58.4 and MT 33)

OUTLINE OF METHOD
The granules are put into a glass measuring cylinder of known weight which is then
raised and allowed to fall vertically through a distance of 2.5 cm on to a rubber pad;
the operation is repeated 50 times and the final volume of powder is measured.

DEFINITION
Tap density is the apparent density of a bed of granules formed in a container of
standard dimensions when a specified amount of granules is vibrated or tapped under
standard conditions.

APPARATUS

Dropping box firmly screwed to a rigid table or bench (Fig. 19)

Measuring cylinder glass cylinder without a spout and fitted with a rubber bung; the
base of the cylinder should be ground flat, and the weight of the cylinder and rubber
bung should be 250 ± 5 g. The cylinder should be graduated in 2 ml divisions over
the range 25 to 250 ml (Note 1). The distance between zero and the 250 ml
graduation on the cylinder shall be 22 to 25 cm. The distance between the flat-
ground part of the base of the cylinder and the rubber base pad, when the cylinder is
raised to the full height, shall be 25 ± 2 mm, i.e. the total lift of the cylinder shall be

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adjusted to 25 ± 2 mm by the application of a suitable packing to the underside of

the shelf.
Rubber base pad the rubber base pad shall have a BS hardness of 35 to 50 (Note 2).
Beaker 250 ml
Timing device to indicate seconds
Balance with an accuracy of at least ± 0.1 g.

PROCEDURE

Prepare a sample of 80 ± 2 g by appropriate division of the bulk sample. Weigh the

sample (to the nearest 0.1 g) into a beaker (W g), pour the sample slowly into the
measuring cylinder and fit the rubber bung into the cylinder without jolting. Put it
carefully in the dropping box and start the timing device.
With the thumb and forefinger of one hand, gently hold the upper part of the cylinder
and, during 1 second, lift it to the full extent of its travel. Avoid any undue impact
against the upper stop so that no jar is given to the sample. At the beginning of the
next second, smartly release the cylinder by quickly and completely withdrawing the
thumb and forefinger. Continue the process of lifting and dropping until 50 counted
drops are completed, the cylinder falling once every 2 seconds. Rotation of the
cylinder through an arc of about 10 degrees should be made during the lifting which
precedes each drop, as this will help to impart a level surface to the sample for the
final volume reading.
Immediately 50 drops have been completed, remove the cylinder from the dropping
box, raise it to eye level and note the volume to the nearest 1 ml (V ml). Any further
drop in level after standing should be ignored.

Calculation of Results

Calculate the apparent density after compaction (D in g/ml) of the sample to two
decimal places from the expression

D = W / V g/ml

Note 1 See ISO 4788: 1980

Note 2 BS 903 Part A26: 1969 Methods of Testing Vulcanised Rubber;
Determination of Hardness (ISO 48)

2 Method with dry substance jolting volumeter

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OUTLINE OF METHOD

The tap density is determined with a Dry Substance Jolting Volumeter according to
DIN 53194 (Note 1).
APPARATUS

Dry Substance Jolting Volumeter DIN 53194 (Note 2)

PROCEDURE

Prepare a sample of 80 ± 2 g by appropriate division of the bulk sample. Weigh the

sample (to the nearest 0.1 g) into a beaker (W g), pour the sample slowly into the
measuring cylinder, taking care that there are no cavities and the sample has a level
surface. Then fix the measuring cylinder with the sample in the cylinder support of the
Jolting Volumeter set for 1000 jolting strokes and start the apparatus.
Immediately after 1000 strokes are completed, remove the cylinder from the support,
raise it to eye level and note the volume to the nearest 1 ml (V ml). Any further drop in
the level after standing should be ignored.

CALCULATION OF RESULTS

Calculate the apparent density after compaction (D in g/ml) of the sample to two
decimal places from the expression

D = W / V g/ml

Note 1 DIN 53194 obtainable from: Beuth Verlag GmbH, D-1000 Berlin 30,
Germany
Note 2 Jolting Volumeter obtainable from: J. Engelmann AG, Frankenthaler Str.
137-141, D-6700 Ludwigshafen, Germany

MT 170 DRY SIEVE ANALYSIS OF WATER DISPERSIBLE GRANULES

SCOPE

The method is suitable for the determination of the particle size distribution of water
dispersible granules.

OUTLINE OF METHOD

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Sieve analysis consists of the quantitative separation of water dispersible granules into
fractions of different particle size ranges by use of the modified method MT 58.3
(machine sieving described under A). If the apparatus required is not available, a
simple method (hand sieving described under B) can be used.
APPARATUS
Test sieves about 20 cm diameter according (MT 59.1). Preferred sizes are 3350,
2000, 1000, 500, 250, 125 and 75 µm.
Lid and receiver pan for the above sieves
Soft brush (2.5 cm flat) - for cleaning the finer mesh sieves
Stiff brush for cleaning the coarser sieves.
Balance sensitive to 0.1 g, with a precision of ± 0.05 g.
Glazed paper sheets of not less than 38 cm square.
In addition for method A (machine sieving)

Inclyno test sieve shaker or equivalent equipment, described in MT 58.3.

In addition for method B (hand sieving)
Three retort stands
Three socket fittings
Three metal rods with diameter of about 1 cm and length of about 10 cm.
Hard-rubber sheet size min. 20 × 20 cm2 (Note 1)
Assembly of component parts see Fig. 52
PROCEDURE
Sampling should be done according to MT 166.
For each determination the mass M of the sample has to be calculated:

M = n ⋅ D ⋅ 20 g
where:

n = number of sieves used

D = tap density (g/ml) of the water dispersible granule according to MT 169.
The machine sieving method works with several sieves at the same time whereas the
hand sieving method has to be repeated for each sieve.

A. Machine sieving procedure

Assemble the nest of x sieves in the correct order with the coarsest at the top and the
finest at the bottom, and mount then on the receiver pan. Weigh a sample of specified

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weight (m g) to the nearest 0.1 g and transfer it to the coarsest sieve. Fit the lid to the
nest of sieves and put it in the sieving machine. Start the machine and let it run for a
period of 5 min.

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Figure 52 Assembly of dry sieve apparatus

Remove the nest of sieves from the machine after allowing time for airborne particles
to settle (about 2 min). Take off the lid carefully and invert each sieve over a separate
sheet of paper, tap the side of the sieve frame and carefully brush the uppermost
surface. Reverse the sieve and repeat the process to dislodge any loose particles
remaining. Add the brushings to the bulk of material taken from each sieve. Follow
this procedure for each sieve x and record the individual masses (gx) to the nearest 0.1
g.

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The residue rx on each sieve x is calculated:

gx
rx = ⋅ 100 % m/m
m
where:
gx = the amount of material retained by the sieve x
Rx = the calculated sum of residues on all the x sieves. Therefore the residue Rx on
sieve x and the residues on all coarser sieves must be summed.
n
Rx = ∑x rx % m/m

The particle size distribution of the water dispersible granules is specified by the range
[x1, x2] of two sieves where Rx ≥ 90% and Rx ≥ 10% (Note 2).

EXAMPLE 1

number of sieves n=6

tap density WG D = 0.5 g/ml
sample weight m = 60 g

sieve x mass gx residue rx sum of residues Rx

µm g % %
75 1.26 2.1 96.2
125 3.36 5.6 94.1
250 24.90 41.5 88.5
500 22.68 37.8 47.0
1000 5.52 9.2 9.2
2000 0 0.0 0.0

range : x1 = 125 µm where Rx ≥ 90 %

x2 = 1000 µm where Rx ≤ 10 %

B. Hand sieving procedure

(i) Put the test sieve x above the receiver pan into the sieve assembly according to
Fig. 52. Add the sample of specified weight (m g) carefully and quantitatively
on to the sieve and then fit the lid.

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(ii) Lift the assembly of sieve, lid and pan by hand until the lid touches the lower
surface of the metal rods. The sieve assembly should be symmetrical in the
apparatus.

(iii) Allow the sieve assembly to fall freely for 1 cm on to the hard-rubber sheet
(see Fig. 52).

Repeat the procedure (ii) to (iii) 25 times.

(iv) Take off the lid and the sieve and invert the receiver pan over a sheet of paper.
Record the mass to the nearest 0.1 g as the material passing the sieve (dx g).
Repeat procedures (i) to (iv) with all test sieves using fresh 10g samples.

The residue Rx is calculated: (Note 3)

d
Rx = 100 − ( mx ⋅ 100 ) %g

The calculation must be done for each sieve x. The range [x1, x2] of the two sieves
where Rx ≥ 90% and Rx ≥ 10% has to be estimated.

EXAMPLE 2

Tap density: 0.5 g/ml

Sample mass for each determination: 10.0 g

sieve x passage dx residues Rx

µm g %

75 0.5 95
125 1.2 88
250 7.5 25
500 9.8 2
1000 10.0 0

range: x1 = 75 µm where Rx ≥ 90%

x2 = 500 µm where Rx ≥ 10%

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Note 1 The rubber sheet shall have a B.S. hardness of 35 to 40. See BS 903 Part
A26 1969 Methods of testing vulcanized rubber; determination of
hardness. This is technically equivalent to ISO 48.

Note 2 80% or more of the mass of the water dispersible granule is in the range
[x1, x2].

Note 3 Because only one sieve is used in the hand sieving method, the residue Rx
should correspond to the sum of residues Rx in the machine sieving method,
assuming that no significant attrition occurs using the machine sieving
method.

MT 171 DUSTINESS OF GRANULAR PRODUCTS

DEFINITION

Dustiness in this method is defined as the property of a granular product to liberate

dust into the air when handled under specified conditions. These conditions are related
to typical handling in agricultural practice (i.e. measuring out and pouring the product
into the spray tank).
OUTLINE OF METHOD

The determination of the dustiness of a granular product involves two operations.

Firstly, a weighed amount of a granular product is allowed to fall under standard
conditions in a test chamber, thus releasing dislodgeable dust. The second operation is
the collection and/or assessment of the amount of airborne dust. This can be achieved
by a gravimetric method, in which the generated dust is removed by an airflow,
collected on a filter and weighed, or by an optical method in which the obscuration of
a light-beam by the airborne dust is measured (Note 1).

1 Gravimetric method
APPARATUS
Dust-measuring apparatus (see Fig. 53) consisting of a measuring box (1) and a
pouring tube (2). The top of the measuring box is a removable lid, connected with
the pouring tube. At the opening of the box there is a fitting (3) into which the glass
filter (4) is plugged. The glass filter is connected via and air flow meter (5) to a
vacuum pump (Note 2).
Sintered glass filter porosity P100 (pore size 40-100µm), diameter 40 mm

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Air flow meter range 10 l/min - 20 l/min

Filter discs diameter 35 mm (Note 3)
Balance sensitive to 0.1 mg with a precision of ± 0.1 mg
Stop watch
Beaker 100 ml
Tweezers

Figure 53 Apparatus for determining dustiness, gravimetric method,

dimensions in mm

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PROCEDURE

(a) Sampling
Take a sample according to MT 166. It is important to measure dustiness with the
sample 'as received'. Wherever possible, take the sample from previously unopened
commercial container. Changes in water content caused by 'conditioning' of the
sample under certain temperature and/or humidity conditions can change dustiness
significantly.
For each determination, take a representative sample of the granular products of
30.0 g, weighed to the nearest 0.1 g.

(b) Determination of dust

Weigh a filter disc to the nearest 0.1 mg (W1 g) and put it on the filter plate of the
glass filter. Connect the glass filter with tubing to an air flow meter and a vacuum
pump and then plug the glass filter into the fitting at the measuring box. Start the
vacuum pump and adjust the air flow to 15 l per min. In a glass beaker, weigh a
30.0 g sample to the nearest 0.1 g, and transfer it with a single action into the
pouring tube. At the same time start the stop watch.
The liberated airborne dust is sucked off for 60 sec and collected on the filter.
Remove the filter disc with tweezers and weigh it to the nearest 0.1 mg (W2 g). The
difference in weights (W2 - W1) is defined as the 'collected dust'.

2 Optical method
APPARATUS
(a) Instrument description and settings
Dust-measuring apparatus (see Fig. 54), Cassella Instrument or equivalent
In the electronic dust-measuring apparatus the change is measured in the intensity
of a light beam resulting from the introduction of airborne dust (Note 4). The
apparatus (Fig. 54) consists of an electronic measuring device (1) and a cubic box
with removable case (2). A tube (3) is fitted to the top of the cubic box. On its
upper part the tube has a funnel with trap (4) which is opened magnetically. The
sample drops to the bottom of the case, dust is released thus reducing the intensity
of a light-beam as measured by a photocell on the opposite side. The lamp (5) and
photocell (6) are positioned off-centre from the tube centre line.
The 'maximum-value' and 'dust-value' are then recorded and the values used to reset
the equipment when a new measurement is made.
Optical filters (7) for readjustment can be fitted in front of the photocell.

(b) Sampling. As for MT 171.1 (a)

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(c) Determination of dust

Before starting a measurement, adjust the meter reading of the dust measuring
apparatus. For each investigation, put 30 g of the sample-material in the funnel (4).
Start the machine, which opens the trap for 2 sec, and allows the sample to drop to
the bottom of the case, releasing dust and reducing the intensity of the light-beam
(see description of optical method, page 427).
Make the first measurement directly after the fall of the sample, the 'maximum-
value'.
Make the second measurement after 30 sec. and add this value to the 'maximum-
value'.
Take the sum of both values as the 'dust-value'. The difference between the 'dust-
value' and the 'maximum-value' gives an indication of the length of time the
generated dust is suspended in the air.

ASSESSMENT OF DUSTINESS
With the 'collected dust' (gravimetric method) and 'dust-factor' (optical method) the
dustiness of a granular product can be categorised as follows:
Category Range of results Interpretation

gravimetric optical
collected dust dust factor
mg
1 0 - 12 0 - 10 nearly dust-free

2 12 - 30 12 - 35 essential non
dusty

3 > 30 > 25 Dusty

Note 1 The optical method usually shows good correlation with the gravimetric
method and can therefore be used as an alternative where the equipment
is available. Where the correlation is in doubt, it should be checked with
the product to be tested. In cases of arbitration the gravimetric method
should be employed.

Note 2 The apparatus is not commercially available. It can, however, be easily

constructed. It should preferable be made of a non-corroding metal-sheet

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(1.5 mm gauge).

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Figure 54 Apparatus for optical dust measuring

Note 3 Any filter disc can be used which gives a complete separation of the
airborne dust at a constant air flow of 15 per min. The filter disc should
be checked for quantitative retention of fine dust.

Note 4 Recently a dust-measuring apparatus, which has improved calibration

and electronic facilities, has become commercially available: Hoechst
AG, Verfahrenstechnik/FE, D-6230 Frankfurt, Germany.

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MT 172 FLOWABILITY OF WATER DISPERSIBLE GRANULES AFTER

HEAT TEST UNDER PRESSURE (Note 1)

SCOPE

The method is suitable for assessing the flowability of water dispersible granules after
heat test under pressure.

OUTLINE OF METHOD
After the accelerated storage test according to MT 46.1, the amount of granules
remaining on a sieve is determined without any mechanical disturbance, and
afterwards with a standardized tapping.
APPARATUS

Cylinder of polyvinyl chloride - 5 to 5.5 cm internal diameter

Polyvinyl chloride compactor to fit into the cylinder. The compactor is filled with lead
or steel shot to make up a pressure of 25 g/cm2
Polyvinyl chloride bottom fitting to close the cylinder
Oven thermostatically controlled to the specified temperature (± 2°C)
Balance sensitive to 0.1 g with a precision of ± 0.05 g
Test sieve - a standard sieve of about 20 cm diameter and of 5 mm mesh size (ISO
565, DIN 4188, BS 410) or 4.75 mm mesh size (ASTM E 11)
Three retort stands
Three socket fittings
Three metal rods with diameter of about 1 cm and length of about 10 cm
Hard-rubber sheet size min. 20 × 20 cm2 (Note 2)
PROCEDURE
Assemble the component parts as shown in Fig. 52, MT 170. Place the cylinder on
the bottom fitting. Sampling should be done according to MT 166. Put the sample
(50 g) into the cylinder, and spread it, without using any pressure, in a smooth even
layer of constant thickness. Place the compactor on the surface of the granules in
the cylinder, and put it in the oven at 54 ± 2°C for 14 days (Note 3). After storage,
allow the cylinder to cool to room temperature in the desiccator without any
desiccant for 2 h. After cooling, turn the complete apparatus upside down and
remove the bottom fitting. Transfer the sample carefully on to the sieve, pushing
the cylinder downwards.
Assess the flowability of the sample by the procedure described in MT 170.

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REPORTING

Whether the sample drops through the sieve spontaneously; if not, report the
quantity of the sample which remains on the sieve after 5 and 20 liftings.

Note 1 The method is not suitable for products to which the manufacturer has
added water as a formulant.

Note 2 The rubber sheet shall have a B.S. hardness of 35 to 40. See B.S. 903 Part
A 26: 1969 'Methods of testing vulcanized rubber; determination of
hardness' (ISO 48)

Note 3 The relative humidity in the oven should be less than 30%.

MT 173 COLORIMETRIC METHOD FOR DETERMINATION OF THE

STABILITY OF DILUTE EMULSIONS

SCOPE
The method is suitable for determining the emulsion stability of dilute emulsions at
dilution rates from 0.1 to 2.0%. Alternative conditions concerning standing times,
volume of initial emulsion, may be fixed according to a given particular
specification.

OUTLINE OF METHOD
A dye is dissolved in the emulsifiable concentrate formulation (EC). A sample of
the dyed EC is added to a standard water to obtain an aqueous emulsion. At the end
of a specified time an aliquot is withdrawn from the emulsion, and transferred to a
flask to which propan-2-ol is added to clarify the emulsion. Then the absorbance of
the dyed solution is measured in a spectrophotometer and compared to the
absorbance of a similar aliquot taken under the same conditions but at t0 (initial
emulsion).

REAGENTS

Oil Red O oil soluble dye. C.I. no 26125 {1-[4-(xylylazo)xylylazo]-2-naphthol}

Maximum absorbance: 525 nm (FLUKA 75087 or equivalent) (Note 1)
Propan-2-ol {CH3.CH(OH).CH3}; RE 40
CIPAC standard waters MT 18
APPARATUS

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Spectrophotometer set at 525 nm, with glass cell of 1 cm

Glass-stoppered graduated cylinder 250 ml conforming to ISO 4788 (see CIPAC
Handbook 1C, p. 2295)
Pipettes 1, 2 or 5 ml, calibrated to 0.01 ml

PROCEDURE

Dissolve an amount (x mg) of Oil Red O depending on the dilution rate of the
emulsifiable concentrate (see Table I) in 10 ml of the sample (Note 2). Pour into a
250 ml glass-stoppered graduated cylinder a sufficient volume of appropriate
CIPAC Standard Water at 25°C for the preparation of 250 ml emulsion.
Add drop by drop keeping the tip of the pipette as close as possible to the surface
of the water an appropriate volume (y ml) - see Table I - of this dyed sample.
Replace the stopper, and immediately invert the cylinder 30 times through 180°
(Note 3).
Allow to stand at 25°C for 4 h, unless otherwise specified. At the end of this time,
transfer by pipette a 10 ml aliquot from the emulsion taken at mid-height (125 ml
marking), as shown in Fig. 55, into a 50 ml conical flask. In case of top creaming,
withdraw previously the cream layer by suction in order to avoid contaminating the
pipette. Add then to the flask propan-2-ol (15 ml) and mix well. Measure the
absorbance A of this red solution in a 1 cm cell in a spectrophotometer at 525 nm,
using water as reference.
Proceed exactly in the same way with another 250 ml glass-stoppered cylinder, but
transfer by pipette the 10 ml aliquot from the emulsion immediately after the 30
times inversion, into a 50 ml conical flask in order to determine the absorbance at
time t0 (absorbance A0) (Note 4).
In case of any instability, record in the report whether creaming or sediment is
formed.

CALCULATION

A
Emulsion stability = ⋅ 100 %
A0

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TABLE I Amount of Oil Red O to be added to 10 ml of the emulsifiable

concentrate according to the dilution rates and volume of sampling

Dilution rate Amount (x) of Oil Red O / Volume of sampling (y)

(% v/v) 10 ml EC (mg) (ml)

2.00 10 5.000
1.00 20 2.500
0.50 40 1.250
0.40 50 1.000
0.25 80 0.625
0.20 100 0.500
0.10 200 0.250

The amount of dye to be added cannot alter the emulsion stability. It is calculated
so that under the conditions of the method an absorbance of about 0.5 - 0.6 is
obtained at initial emulsion (t0). This level of absorbance is required to ensure good
repeatability and reproducibility. It is not necessary to record the amount of the dye
since the absorbance at t0 has to be measured for each dyed sample.

LIMITATION OF THE METHOD

The main limitations of this method are:
- The amount of dye to be added in the EC sample is too high to allow
determination of the emulsion stability at dilution rates below 0.1%.
- The solubility of the dye must be complete in the organic solvents of the EC, and
negligible in water.
- The active ingredient and solvents must be insoluble in the aqueous phase of the
emulsion. If not, a different partition of the dye and the active ingredient could
occur between the organic and the aqueous phases.
For each product, it must be established that the active ingredient has the same
partition between the organic and aqueous phases as the dye in the emulsion.

Note 1 If another dye is used, it is essential that it is completely soluble in the

organic phase and insoluble in the aqueous phase.

Note 2 The amount of dye to be added to the EC sample should not interfere with
the stability of the emulsion.

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Note 3 This procedure must be exactly followed to avoid any pre-emulsification

resulting from a mixing of the sample with the upper aqueous layers.

Note 4 The aliquot at t0 can be also taken from the same emulsion. In this case,
prepare the emulsion in 260 ml instead of 250 ml. This could be done if it
is known that the introduction of the pipette at t0 does not alter the
emulsion stability.
The preparation of an initial emulsion of 500 ml and its division into two
parts is not recommended, because this procedure could modify the
emulsion stability.

Figure 55 Marking the pipette to take an aliquot from the middle of the emulsion

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MT 174 DISPERSIBILITY OF WATER DISPERSIBLE GRANULES

OUTLINE OF METHOD

A known amount of a water dispersible granule (WG) is added to a defined

volume of water and mixed by stirring to form a suspension. After standing for a
short period, the top nine-tenths are drawn off and the remaining tenth dried and
determined gravimetrically. The method is virtually a shortened test of
suspensibility and is appropriate for establishing the ease with which a WG
dispersed uniformly in water.

APPARATUS

Beaker 1000 ml with a diameter of 102 ± 2mm (low form)

Stirrer motor with speed control
Stainless steel stirrer propeller type with four fixed stirrer blades twisted at an
angle of 45°. Particular care should be given to the construction of the stirrer
with dimensions conforming to those in Fig. 56.
Drying cabinet with temperature control
Rotary vacuum evaporator
Stopwatch
Glass suction tube about 40 cm long and about 5 mm i.d. drawn to a point at one
end with an opening of about 2 to 3 mm. The other end of the tube is connected
to a vacuum pump protected by a suitable reservoir.

PROCEDURE

Fill the tared beaker with 900 ml of CIPAC Standard Water D at 20°C ± 1°C. The
stirrer should be centrally located in the beaker and is positioned in such a way that
the bottom of the stirrer blades are 15 mm above the base of the beaker. The pitch
of the stirrer blades and the direction of rotation are such that the propeller pushes
the water upwards. Switch on the stirrer with the speed set to 300 rpm.
Add a sample (Note 1) of WG (approximately 9 g weighed to ± 0.1 g) to the stirred
water and continue the stirring 1 min. Then switch off the stirrer and allow the
suspension to stand undisturbed for 1 min. Withdraw, by means of a vacuum pump,
nine-tenths (810 ml) of the suspension. Carry out the operation in 30 to 60 s by
maintaining the tip of the glass tube just below the falling level of the suspension,
taking care to minimize any disturbance of the suspension (see also MT 15.1).

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Determine by gravimetric means the solids obtained in the remaining 90 ml in the

beaker. This can be done most conveniently by evaporating the liquid in the rotary
vacuum evaporator and drying to constant weight. If the manufacturer has not
specified the drying temperature, 60 to 70°C is recommended.

CALCULATION

Calculate the dispersibility of the WG by the formula:

10 m − W
Dispersibility = ⋅ ⋅ 100 %
9 m
where:
W = mass of residue after drying (g)
M = mass of sample taken

Report dispersibility to the nearest 1% and specify the following conditions:

(a) Water hardness (if other than Standard Water D)

(b) Water temperature

Note 1 The sample of WG may conveniently be obtained from a bulk sample by

using a sample divider (see MT 166).

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Figure 56 Propeller type stirrer ((mm) units of linear measure)

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