MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 35 OIL INSOLUBLE MATERIAL

REAGENT
Mineral oil; RE 36.2

APPARATUS
Sieve 150 µm
Weighing bottle
Stoppered measuring cylinder 250 ml

METHOD
Weigh sufficient of the sample to contain 0.5 g of active ingredient, transfer to the
measuring cylinder, add the oil (100 ml) and stopper. Mix by shaking and allow to
stand at 20 1°C for 1 h. At the end of this period the solution should be
homogenous and clear. Of not clear, or insoluble material is present, pour it
through the sieve. Report if there is any solid matter left on the sieve.

MT 36 EMULSION CHARACTERISTICS OF EMULSIFIABLE

CONCENTRATES

The (existing ) methods are not always suitable for emulsifiable concentrates
containing solid active ingredients. For these and for products used in very low
concentrations alternative methods are under consideration.

36.1 Five per cent v/v oil phase

36.1.1 Hand shaking

SCOPE.
The procedure described in this method is applicable to any emulsifiable concentrate,
which gives rise, on dilution with water, to oil in water emulsions
OUTLINE OF METHOD.
Five ml of the emulsifiable concentrates are mixed with a Standard Water to give
100 ml of aqueous emulsion. The stability of this emulsion is then in terms of the
amounts of free 'oil' or 'cream' which separates while the emulsion is allowed to
stand undisturbed for 24 h. The ability of the system to re-emulsify at the end of the

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24 h period is also determined.

If required, the test is repeated on a fresh sample of the concentrate which has
previously been treated by MT 46.1.3, Accelerated storage procedure for emulsifiable
concentrates.

REAGENTS

Standard water MT 18.1.4, unless otherwise specified

APPARATUS

Measuring cylinders 100 ml, Glass stoppered - The volume between the 100 ml
graduated mark and the bottom of the stopper should not more than 40 ml and not
less than 35 ml. The apparatus must be clean and free from grease.
Constant temperature bath large enough to allow several 100 ml measuring
cylinders to be immersed in an upright position in the water to the neck;
maintained at 30 ± 1°C (Note 1).
Adjustable lamp fitted with a 60 watt bulb
Measuring cylinder, 5 ml

PROCEDURE
(i) Initial emulsification. Fill a 100 ml measuring cylinder to the 95 ml mark with
standard water at 30 ± 1°C unless otherwise specified. The emulsifiable
concentrate (5 ml at the same temperature as the Standard Water) is gently
poured on to the surface of the water; the stopper is replaced and the cylinder is
inverted once (Note 2).
After 30 sec observe whether the mixture has emulsified spontaneously giving
100 ml of an emulsion which appears, on visual examination, to be uniform.
Note any froth produced.

(ii) Emulsion stability on standing. Invert the cylinder 10 times (Note 2), and allow
the cylinder and its contents to stand undisturbed in the constant temperature bath
at 30 ± 1 °C (Note 3) for 24 h. Record the volume (Note 3), if any, of free oil (Note
4), froth and 'cream' formed either at the top or the bottom of the emulsion, after
standing for 30 min, 2 h and 24 h.

(iii) Re-emulsification after standing for 24 h. At the end of the 24 h period invert
the cylinder 10 times (Note 2). Allow to stand for 30 sec, then observe whether any
free oil, froth, 'cream' or solid matter found after standing for 24 h is re-emulsified
giving 100 ml of an emulsion which appears, on visual examination (Note 3), to be

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uniform.

(iv) Final emulsion stability. Allow the cylinder to remain undisturbed for a further
period of 30 min.
Record the volume, if any, of free oil, froth, 'cream', or solid matter present at the
end of the 30 min period.

36.1.2 Machine shaking (Note 5)

REAGENTS

Standard water MT 18.1.4, unless otherwise specified.

APPARATUS. As for 36.1.1 together with:

Shaking apparatus. See Figs 20 and 21; the plate should rotate at 30 rpm.

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Figure 20 Shaking apparatus - front view

Figure 21 Shaking apparatus - side view

PROCEDURE

(i) Initial emulsification. Fill a 100 ml measuring cylinder to the 95 ml mark with
standard water at 30 ± 1 °C. Pour the emulsifiable concentrate (Note 4), gently (5
ml from a measuring cylinder) on the surface of water, replace the stopper and
invert the cylinder once (Note 2).
After 0.5 min observe whether the mixture has emulsified spontaneously giving
100 ml of an emulsion which appears, on visual examination, to be uniform. Note
any froth produced.

(ii) Emulsification stability on standing. Shake the cylinder for 20 sec in the
shaking machine (i.e.., 10 inversions) and allow the cylinder and its contents to
stand undisturbed in the constant temperature bath at 30 ± 1°C for 24 h. Record the
volume (Note 3), if any, of free oil, froth and the total volume of 'cream' formed
either at the top or the bottom of the cylinder, after standing for 30 min, 2 h and
24 h.

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(iii) Re-emulsification after s6tanding for 24 h. At the end of the 24 h period shake
the cylinder for 20 sec as before.
Record whether any free oil, froth, 'cream' or solid matter, found after standing for
24 h is re-emulsified giving 100 ml of an emulsion which appears, on visual
examination (Note 3), to be uniform.
(iv) Final emulsion stability. Allow the cylinder to remain undisturbed for a further
period of 30 min. Observe the volume, if any, or free oil, froth, 'cream', or solid
matter present at the end of the 30 min period.

36.2 1 per cent v/v oil phase (Note 6)

36.2.1 Preliminary examination. Prepare a 5% v/v dilution of the emulsifiable
concentrate in water and allow to stand in a 100 ml measuring cylinder. Allow to
remain undisturbed at room temperature to determine whether top or bottom
creaming occurs.
If the sample does not separate no further testing is required.
If it does separate after 24 h, continue the test by the appropriate section of
MT 36.2.2.

36.2.2 Dispersion stability

OUTLINE OF METHOD
Two ml of the concentrate are mixed with standard water in a standard-stoppered
measuring cylinder to give 200 ml of dilute emulsion which is allowed to stand in a
water bath, at a given temperature, for a given time. If the sample top creams, the
pesticide content of the top 100 ml is determined; if the sample bottom creams, the
pesticide content of the bottom 100 ml is determined. The dispersion is then
calculated.
REAGENT
CIPAC Standard water D MT 18.1.4
APPARATUS
Measuring cylinder 250 ml fitted with stopper, and with dimensions of between
20 and 21.5 cm from the bottom, i.e..., the 0 ml mark to the 250 ml mark.
Water bath at 30 ± 1°C unless otherwise specified
Sampling tube. A piece of small bore tubing 2 mm internal diameter, about 30 cm
long, fitted at one end with a two way-stopcock. One of the arms of the stopcock is
connected to a Drechsel bottle with nylon tubing; the outlet from the bottle is

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connected to a vacuum source via a second stopcock. The tube is fitted with a bung
to act as a stop.
Pipette 2 ml

PROCEDURE

(i) Active ingredient in initial dispersion. Determine the content of active

ingredient in 100 ml of the initial dispersion. (Note 7). Express the result in
grams (x g) per 100 ml of the dilute emulsion

(ii) Top creaming (Removal of 100 ml of emulsion from the bottom of the
cylinder, i.e.., between 0 and 100 ml marks). Adjust the stop on the glass tube so
that the tip of the tube is below the 10 ml graduation mark near the bottom of the
cylinder. Remove the tube and fill the cylinder to the 100 ml mark with water. Fill
the sampling tube to the top with water and close the two way-stopcock. Calibrate
the cylinder by inserting the tube into the cylinder (i.e., near the bottom) and mark
the new level of water on the side of the cylinder.
Pour the standard water (198 ml at 30 °C unless otherwise specified) into the
cylinder 30 times (Note 2), and put the cylinder in the water bath at 30 ± 1 °C
(Note 1).
At the end of the specified time place the sample tube, filled with water, in
position in the cylinder, open the stopcocks, and remove the dilute emulsion until
the surface of the liquid reaches the calibration mark of the cylinder. Close the
stopcock on the tube, remove the tube from the cylinder, and wash any material
adhering to the outside of the tube directly into the cylinder. Open the stopcock,
suck the remainder of the liquid into the bottle, and wash the tube and leads to the
bottle by inserting the tube in distilled water, and applying suction.
Determine the pesticide content (y g) of the dilute emulsion remaining in the
cylinder. (Note 8)

(iii) Bottom creaming (Removal of 100 ml of emulsion from the top of the cylinder
i.e., between the 100 and 200 ml graduations). Pour standard water (198 ml at 30
°C unless otherwise specified) into the cylinder and add the emulsifiable
concentrate (2.0 ml). Insert the stopper, invert the cylinder 30 times, and place in
the water bath at 30 ± 1 °C. At the end of the specified time insert the sampling
tube into the cylinder and draw the dilute emulsion over into the Drechsel bottle,
until the surface of the liquid on the cylinder reaches the 100 ml mark, maintaining
the tip of the tube just below the sinking level of the liquid. Withdraw the sampling
tube and wash the tube and leads to bottle by inserting the tube into distilled water
and applying suction.

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Determine the pesticide content (y g) of the dilute emulsion remaining in the

cylinder (Note 8).

DISPERSION STABILITY

100 (2 x − y )
Dispersion stability = % m/m
x

Note 1 Any vibration can alter the properties of the dilute emulsion in the cylinder.
The cylinder should, therefore, be supported or clamped in such a way that
it is not in contact with the body of the water bath. The stirrer assembly
should preferably be clamped independently of the water bath.
Note 2 The expression 'invert the cylinder' implies that the stoppered cylinder is
tipped by hand through 180 degrees, and is then brought back to its original
position, the whole operation being completed in approximately 2 sec.
Note 3 An adjustable lamp fitted with a 60 watt pearl bulb, should be used to
illuminate the cylinder. The position and angle of the light should be
adjusted for optimum viewing of the phase boundary. It is often easier to
see this by reflected, rather than by transmitted light.
Note 4 If, initially, difficulty is experienced in distinguishing between oil and
cream a dye soluble in the oil phase may be used, but the final tests should
be carried out without the addition of dye. It has been found that dyes which
give a deep blue solution in aromatic hydrocarbon solvents, e.g. Oil Blue
SWS 1,4-bis(isopropylamino)anthraquinone (CI 61551), are most suitable
for this purpose. The dye (0.1g/100 ml) should be added to the emulsion
concentrate before carrying out the test. If oil is present then the dye will
colour it deep blue; if extensive creaming has occurred, the dye will give a
pale blue layer; if little or no creaming has occurred then no definite colour
band will be produced.
Note 5 Method developed by A McCormick, Instituto de Investigaciones
Technologicas, Bogota, Colombia.
Note 6 The method is not suitable for formulations intended for low volume
spraying and/or aerial application; it may not be suitable for 'invert'
emulsions.
Note 7 The content of active ingredient in the initial dispersion must be determined
by the same method as is used for determination of the active ingredient in
the dilute emulsion after estimation of dispersion stability. If MT 65 is used
for organochlorine pesticides, take all the sample for the analysis and do not
sub-sample at any stage.

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Note 8 The pesticide content of the emulsion drawn into the Drechsel bottle may
also be determined (z g) to check the recoveries of the active ingredient,
since y + z should equal 2x.

MT 37 ISOLATION OF ACTIVE INGREDIENT

37.1 Extraction with acetone

OUTLINE OF METHOD
The active agent is extracted with acetone in a continuous extraction apparatus.

REAGENTS
Acetone (CH3COCH3) anhydrous; RE 34
Filter aid

APPARATUS
Continuous solvent extraction apparatus e.g. consisting of a 500 ml flask, straight
through extractor and double surface condenser.
Extraction thimbles
Conical flask 250 ml, tared
Flame-proof oven at 100 °C

PROCEDURE
Weigh to 1 mg, in a suitable extraction thimble, the prescribed amount of
sample (m g; Notes 1 and 2). Add filter aid (4:1) and mix.
Pour acetone (200 ml) into the extraction flask, assemble the apparatus with the
thimble in the extractor, and extract under reflux for 6 h, unless otherwise directed.
Transfer the acetone extract, filtering, if necessary, through a Whatman No 42
filter paper, or equivalent, to the tared conical flask (x g), rinse the extraction flask
with acetone, and add the rinsings to the conical flask. Distil off the acetone and
then dry the residue to constant weight (y g) at 100 °C, unless otherwise directed.
100 ( y - x)
Content of acetone-extracted material = % m/m
m
37.2 Extraction with petroleum spirit

REAGENT

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Petroleum spirit, boiling point range 40 to 60 °C, unless otherwise specified

APPARATUS As for MT 37.1.

PROCEDURE
Extract the prescribed amount (m g) of sample with petroleum spirit, as for MT
37.1.
37.3 Removal of solvents by distillation

OUTLINE OF METHOD
The solvent is distilled off under vacuum, at room temperature, into a trap cooled
with solid carbon dioxide. The residue is washed with water, and dried to constant
weight.

REAGENT
Carbon dioxide (CO2) solid
Acetone (CH3COCH3) anhydrous; RE 34

APPARATUS
Vacuum pump rotary pattern to produce a vacuum of about 0.1 mm of mercury
Vacuum gauge
Round bottom flasks, 25 ml B14/23 cone necks
Manifold to fit; see Figure 22
Vacuum flasks wide mouth to contain the 25 ml flasks
Sintered glass crucible porosity P160 (pore size 100-160 µm), tared
Filter flask and crucible adapter
Vacuum desiccator containing phosphorus(V) oxide (MT 24) as desiccant
Weighing bottle

PROCEDURE
Weigh accurately the specified amount (m g) of sample, and transfer to one of the
25 ml flasks. Assemble the apparatus as shown in Figure 22. Close both taps and
immerse the bulbs of the flasks in solid carbon dioxide dissolved in acetone in the
vacuum flasks. Open the tap to the vacuum pump, evacuate, and maintain a
pressure of about 0.1 mm of mercury in the apparatus. Close the tap to vacuum,
remove the vacuum flask of refrigerant from the flask containing the sample, and
allow the latter to warm to room temperature (Note 3). Leave until no further

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solvent passes into the cold trap. Cool both flasks, evacuate again, and repeat the
procedure until all the solvent has distilled over (Note 4). Remove both vacuum
flasks, allow the apparatus to reach room temperature, release the vacuum by
opening tap B, and disconnect the flask containing the residue of pesticide and
wetting agents. Wash this residue into the tared sintered crucible (x g) with water,
and continue washing until free from wetting agents. Transfer the crucible to the
vacuum desiccator and dry to constant weight (y g).
100 ( y - x)
Residue = % m/m
m

Figure 22 Manifold for distillation of solvents

Note 1 If no amount is prescribed, then use sufficient material to provide a final

extract of at least 0.1 g.

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Note 2 It may be necessary to use several thimbles to obtain sufficient active

ingredient if the content of the sample is low or if the required amount of
residue is high.
Note 3 In some cases it may be necessary to raise the temperature above room
temperature. A temperature of 50 °C has been found to be satisfactory for
products containing HCH, gamma-HCH or DDT.
Note 4 The whole operation may take up to 36 h.

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