MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 38 ORGANIC CHLORINE

38.1 Potassium - xylene method

OUTLINE OF METHOD
The organic chlorine is converted by potassium in xylene to the chloride ion
which is then titrated by the silver nitrate/ammonium thiocyanate procedure, or
determined electrometrically.
REAGENTS
Xylene {C6H4(CH3)2}
Potassium (K) (Note 1)
Ethanol (CH3CH2OH) absolute
Nitric acid (HNO3) 50% v/v aqueous solution
Phenolphthalein 0.1% indicator solution; RE 19.1
Ammonium thiocyanate c(NH4SCN): 0.1 mol/l (0.1N) standardized solution;
RE 3.1
Nitrobenzene (C6H5NO2)
Ammonium iron(III) sulphate {FeNH4(SO4)2} indicator solution; RE 2.1
Silver nitrate c(AgNO3): 0.1 mol/l (0.1N) standardized solution; RE 24.1
Hydrogen peroxide (H2O2) 9% (30 volumes); see RE 56
Hydrazinium sulphate (H3N-NH3SO4)
APPARATUS
Weighing bottle
Flat bottom flask 150 ml with ground glass neck
Reflux condenser to fit
Conical flask 500 ml
Water bath
Measuring cylinders 10 ml and 25 ml
Burettes 50 ml
PROCEDURE
(a) Technical materials
(i) Total chlorine. Weigh (to the nearest mg) sufficient sample (w g) to contain 0.12
to 0.16 g of chlorine, transfer to the flat bottom flask containing xylene (5 ml), then
add potassium (about 1.5 g in 4 or 5 lumps; Note 1). Attach the condenser to the
flask. Heat the mixture gently to boiling point and reflux for 30 min. Allow to cool,

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

and remove the excess potassium by adding ethanol cautiously, a few drops at a time
down the reflux condenser, and boil for a further 10 min. Allow to cool, detach the
condenser, and dilute with distilled water (25 ml).
Add hydrogen peroxide, in small portions (10 ml), to the alkaline solution. Warm
gently to remove the excess of hydrogen peroxide. Cool, add hydrazinium sulphate
(100 mg) and phenolphthalein indicator solution (2 or 3 drops) to the solution,
neutralize with dilute nitric acid, then add 10 ml in excess. Cool the solution to
room temperature and add, from a pipette, silver nitrate solution in excess of that
required to precipitate all the chloride (s ml). Add nitrobenzene (5 ml) and
ammonium iron(III) sulphate indicator solution (1 to 2 ml), and swirl the flask to
coagulate the precipitate. Back-titrate the excess silver nitrate with the potassium
thiocyanate solution (t ml; Note 2).
(ii) Inorganic chloride. Weigh (to the nearest mg) about 1 g (x g) of the sample,
dissolve in acetone (10 ml) and add distilled water (100 ml). Keep the mixture at
room temperature for 10 min, and then filter. Add phenolphthalein indicator
solution (2 or 3 drops) and continue as above from 'neutralize the solution with
the nitric acid solution .....'
Inorganic chloride content =

Organic chloride content =

3.545 (u c1 b c2 )
I % m/m
x

3.545 ( s c1 t c2 )
- I = C % m/m
w

where:
u
b
c1
c2

= volume of silver nitrate added in the inorganic chloride determination (ml)

= volume of potassium thiocyanate used in the inorganic chloride
determination (ml)
= c(AgNO3), mol/l (normality) of the silver nitrate solution
= c(KCNS), mol/l (normality) of the potassium thiocyanate solution
Active ingredient = C F % m/m

where:
F =

HCH or gamma HCH

HEOD
DDT
methoxychlor

1.367
1.79
2.01
3.18

HHDN
heptachlor
chlordane
endrin

1.75
1.50
1.56
1.79

(b) Dried residues from extraction procedures. Determine the organic chlorine
as in (a), except that it is not normally necessary to correct for chloride.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

38.2 Stepanov method (Note 3)

38.2.1 Technical materials
REAGENTS
Propan-2-ol {(CH3)2CHOH} 99% dry; RE 40
- 50% aqueous solution
Sodium (Na) wire, ribbon or small pieces
Nitric acid (HNO3) 50% v/v aqueous solution
Phenolphthalein 0.1% indicator solution; RE 19.1
Ammonium thiocyanate c(NH4SCN): 0.1 mol/l (0.1N) standardized solution;
RE 3.1
Nitrobenzene (C6H5NO2)
Ammonium iron(III) sulphate {FeNH4(SO4)2} indicator solution; RE 2.1
Silver nitrate c(AgNO3): 0.1 mol/l (0.1N) standardized solution; RE 24.1
APPARATUS As for MT 38.1
PROCEDURE
Weigh (to the nearest 0.1 mg) about 0.2 g (w g) of sample. Transfer to the flat
bottom flask, add the propan-2-ol (25 ml of dry 99%), shake, and add sodium
(2.5 g). Attach the reflux condenser to the flask, heat the mixture gently until
boiling and reflux for at least 1 h, shaking the flask from time to time. Remove
the excess sodium, by cautiously adding the aqueous propan-2-ol (10 ml) a few
drops at a time down the condenser. Boil the mixture for a further 10 min, and
add distilled water.
Cool, and continue as under MT 38.1, paragraph 2, from 'Add hydrogen
peroxide in small portions ....'
38.2.2 Dusts and wettable powders
REAGENTS As for MT 38.2.1 together with:
Toluene (C6H5CH3); RE 152
APPARATUS As for MT 38.1 together with:
Volumetric flask 100 ml
Extraction apparatus
Pipette 10 ml

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

PROCEDURE
Weigh (to the nearest mg) sufficient sample (w g) to contain about 1 g of active
ingredient, and extract it quantitatively with toluene in a fume cupboard.
Concentrate the extract to such a volume that it can be transferred to the 100 ml
volumetric flask, make up to the mark with toluene, and mix thoroughly.
Transfer a 10 ml aliquot to the conical flask, add propan-2-ol (25 ml), shake the
flask, and continue by MT 38.2.1 from 'add sodium ....'
Total organic chlorine content =

35.45 ( s c1 t c2 )
C % m/m
w

where:
c1 = c(AgNO3), mol/l (normality) of the silver nitrate solution
c2 = c(KCNS), mol/l (normality) of the potassium thiocyanate solution
38.2.3 Emulsion concentrates and solutions
(i) Total chlorine
REAGENTS As for MT 38.2.1
APPARATUS As for MT 38.1
PROCEDURE
Weigh (to the nearest 0.1 mg) sufficient sample (w g) to contain about 0.1 g of
the active ingredient, transfer to the conical flask, and add propan-2-ol (25 ml).
Shake the flask, and continue as in MT 38.2.1 from line 3, 'add sodium ...'
(ii) Inorganic chloride. Weigh (to the nearest 0.1 mg) about 1 g (x g) of the
sample and transfer to the conical flask with distilled water (100 ml). Acidify
with nitric acid, cool, and continue as under MT 38.1, paragraph 2 from 'add
phenolphthalein indicator solution .....'
38.3 Oxygen flask method
OUTLINE OF METHOD (Note 4)
The material is burnt in oxygen, oxidized by neutral hydrogen peroxide solution
and the hydrochloric acid formed is determined by: (i) potentiometric titration
with silver nitrate solution, or (ii) the use of dimercury dicyanide oxide with a
comparative end point procedure, or (iii) in certain cases, direct titration with
standard alkali.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

SCOPE
The method is applicable to the determination of the chlorine content of
technical pesticides and their formulations, provided that the chlorine content of
the sample is in excess of about 5% (Note 5). The method is thus, unsuitable for
formulated products containing low levels of chlorine (about 0.5% or less) and a
high proportion of inorganic filler.
REAGENTS
Absorbent solution Mix distilled water (20 ml) and hydrogen peroxide (1 ml of
100 vol (30 % m/v), microanalytical reagent grade) directly in the combustion
flask, and neutralize exactly with 0.02 mol/l (0.02N) sodium hydroxide
solution, using screened methyl red as indicator.
Methyl red screened indicator solution; RE 18.2
Oxygen (O2)
Hydrogen peroxide (H2O2) 100 volumes (30 % m/v); RE 56
Potentiometric titration:
Sulphuric acid (H2SO4) concentrated, d20 1.84;
- dilute: carefully add concentrated sulphuric acid(1 volume) to distilled
water (6 volumes), slowly and with stirring.
Silver nitrate c(AgNO3): 0.02 mol/l (0.02N) standardized solution; RE 24.2
Oxycyanide titration:
Sodium hydroxide c(NaOH): 0.02 mol/l (0.02N) standardized solution; RE 25.7
Dimercury dicyanide oxide {Hg2(CN)2O} saturated solution; RE 154
Sulphuric acid c(1/2 H2SO4): 0.02 mol/l (0.02N) standardized solution; RE 28.3
Standard chloride solution 0.02 mol/l (0.02N); prepare from sodium chloride
(NaCl) which has been dried at 250 to 350C for 1 h.
APPARATUS
Combustion apparatus. See Fig 23. This consists of a 1000 ml flask with a
24/32 ground glass neck into which fits a glass stopper of the design shown in
Figure 23 (Note 6). To the 3 mm diameter glass extension rod below the stopper
is sealed a 30 mm length of platinum wire, 1 mm in diameter, terminating in a
15 20 mm piece of platinum gauze (420 m mesh or coarser) formed into a
cylindrical sheath. The lower end of the sheath should be located, centrally,
about 4 to 5 cm from the bottom of the flask.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

Filter paper Whatman No 44 or similar

Capillary dropper
Rubber gloves or finger stalls
Methylcellulose (preferred) or hard gelatine capsules
Whatman ashless floc
Glove stout canvas
Weighing tube long-handled

Figure 23 Oxygen flask combustion apparatus

For a potentiometric titration finish:
Potentiometric apparatus. A cell system, containing a glass reference electrode
and silver indicator electrode coupled to an electronic voltmeter or high
impedance pH/mV meter, together with a means for stirring the titration
solution.
Beaker 100 ml lipless, tall form
Measuring cylinder 25 ml
Microburette 10 ml
For an oxycyanide titration finish:
Measuring cylinder 25 ml
Two microburettes 10 ml

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

PROCEDURE
(i) Preparation of the sample. Prepare a representative
sample of the material being analysed and weigh out a portion according
to the following table:
Type

Approximate chlorine
content of sample
(%)

Mass of
sample
(mg)

Technical chemicals

50

15 to 25

Concentrated powders

25

25 to 35

Emulsifiable concentrates

10

35 to 50

Diluted powders

50 to 100

(a) Solid samples. Weigh (to the nearest 0.1 mg) the sample (w mg) on to a No 44
Whatman filter paper; use a 3 cm square for samples weighing less than 50 mg
and a 4 cm square for samples weighing 50 to 150 mg. Wrap the sample in the
paper and fix it securely in the gauze sheath (Note 7). Handle the paper as little
as possible and preferably wear rubber gloves or finger stalls.
(b) Liquid samples. Using a capillary dropper, weigh (to the nearest 0.1 mg) the
sample (w mg) into a methylcellulose or hard gelatine capsule, supported on the
balance pan in a small glass or metal thimble. Loss of liquid on combustion of
the capsule can be prevented by packing the lower half of the capsule with
Whatman ashless floc before adding the sample; about 15 mg of floc is adequate
for the absorption of 50 mg of liquid sample. Close the capsule, and fix securely
in the platinum gauze sheath.
(ii) Combustion. Insert a filter paper fuse, 3 30 mm, into the gauze sheath, set
light to it and quickly insert the stopper into the flask, which already contains
the absorbent solution, and which has previously been flushed out completely
with oxygen from a cylinder. Carefully invert the flask so that the neutralized
peroxide forms a seal round the stopper, which should be firmly held in place
while the combustion proceeds (Note 8). Protect the exposed hand and interpose
a safety screen between the flask and the face.
When combustion is complete, shake the flask intermittently for 10 to 15 min, to
ensure complete absorption of the combustion products. Rinse the stopper, wire,
and gauze with a little distilled water, collecting the rinsings in the combustion
flask. Boil the mixed solution and rinsings gently for 1 to 2 min, to destroy most of
the peroxide and to expel carbon dioxide. Cool to room temperature.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

Determine the chloride in the solution either by potentiometric titration using

standard silver nitrate solution, or by the dimercury dicyanide oxide comparative
procedure, given below.
(iii) Determination of chlorine
(a) Potentiometric titration. Transfer the boiled and cooled solution (Note 9), from
the combustion of the sample, quantitatively to the lipless beaker. Dilute the
solution to about 40 ml with distilled water and add dilute sulphuric acid (20 ml).
Stir the solution mechanically and titrate potentiometrically with the standard silver
nitrate solution from a micro-burette, using the silver/glass electrode system.
Plot the curve of emf against the volume of silver nitrate solution added, and
determine the end point (t ml; Note 10).
Content of chlorine in the sample =

3.545 t c'
% m/m
w

where:
c' = c(AgNO3), mol/l (normality) of the silver nitrate solution
1 ml of 0.02 mol/l (0.02N) silver nitrate is equivalent to 0.709 mg of chlorine
(b) Dimercury dicyanide oxide comparative procedure. To the boiled and
cooled solution from the combustion of the sample, add screened methyl red.
Neutralize with the 0.02 mol/l sodium hydroxide solution, matching the colour
with that of an equal volume of neutralized freshly boiled and cooled distilled
water (containing the same amount of screened indicator solution) in a similar
flask (Note 11).
Add dimercury dicyanide oxide solution (20 ml or more if necessary, Note 12) to
the test solution and titrate the liberated alkali with 0.02 mol/l sulphuric acid until
the colour again matches the neutral shade of the indicator in the control solution.
To the control flask add the same volumes of dimercury dicyanide oxide
solution and 0.02 mol/l sulphuric acid as were added to the test, and titrate the
mixture with the 0.02 mol/l sodium chloride (t ml) until the colour matches that
of the test solution at the end point. The volumes and temperature of both test
and control solutions must be the same. Calculate the chlorine content of the
sample from the volume of sodium chloride solution added (Note 13).
Content of chlorine in the sample =

70.9 t
w

% m/m

1 ml of 0.02 mol/l (0.02N) standard chloride solution is equivalent to 0.709 mg

of chlorine
(c) Direct alkalimetry. If a gelatine capsule has not been used, and the sample
contains no other interfering elements or components, e.g. nitrogen, sulphur, or

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alkalis, the hydrochloric acid in the boiled out and cooled solution from the
combustion of the sample may be titrated directly with 0.02 mol/l sodium
hydroxide solution (t ml) with screened methyl red indicator solution.
Content of chlorine in the sample =

3.545 t c'
% m/m
w

where:
c' = c (NaOH), mol/l (normality) of the sodium hydroxide solution
(iv) Blanks. Carry out blank determinations on appropriate amounts of filter
paper and ashless floc, and on the capsules. Significant blanks are to be expected
on some batches of gelatine capsules.
Note 1

Note 2

Note 3

Note 4

Note 5

Note 6

It is recommended that the handling, weighing and transferring of the

potassium should be carried out as follows: Transfer a lump of
potassium from clean, dry naphtha to clean, dry filter papers. Do not
attempt to remove the naphtha. Cut the lump of potassium with a
clean stainless steel blade, using naphtha as lubricant and a barrier for
moist air. Dry the small lumps of potassium with fresh dry filter
papers and weigh under petroleum spirit. The requisite weight of
potassium is transferred to the flask by difference. Shake each piece of
potassium to remove excess petroleum spirit.
Alternatively, the chloride ion may be determined electrometrically
but, in some formulations, the organic solvents prove troublesome as
they foul the electrodes.
With some HCH technical materials and formulations, based on HCH
of low gamma-isomer content, the use of the sodium method may not
give satisfactory results and MT 38.1 must be used.
The method is based on that developed by the Chlorine in Organic
Compounds Subcommittee of the Analytical Methods Committee of
the Royal Society of Chemistry, whose co-operation is gratefully
acknowledged.
For some routine purposes where high precision is not essential, the
method may be applied to materials containing less than 5% of total
chlorine. Where greater precision is required, the Stepanov procedure,
MT 38.2, is suitable.
For the combustion of solid samples, a 500 ml conical iodine flask is
satisfactory.

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Note 7

Note 8

Note 9

Note 10

Note 11
Note 12

Note 13

Normally, the sample can be wrapped in the middle of the paper,

which is folded into three and then doubled over. For the heavier
samples, when much inorganic matter is present, better combustion
may be achieved by spreading the sample carefully over the paper
before it is folded, so that interleaving of the sample and paper take
place. For samples that burn only with difficulty, the use of filter
paper pre-treated with a strong solution of potassium nitrate and then
dried, may be an advantage.
The flame of the burning sample should not impinge on the glass, as
carbon may be produced and a low result obtained. Should carbon
formation occur, the distance between the gauze and the bottom of the
flask may be increased. Carbon may also be formed if the flask has
not been adequately flushed out with oxygen, or too much sample has
been used.
If carbon or other insoluble residues (e.g. from inorganic filler) are
present, they should be filtered off, preferably by the use of a sintered
glass funnel.
Initially, a full plot of emf against the volume of silver nitrate added
will be necessary to establish the end point. Thereafter it is possible to
titrate directly to the predetermined potential and read off the end
point volume from the burette. The end point potential should be
redetermined whenever the electrodes are cleaned.
If the material contains an alkaline filler, the filtered solution will be
alkaline and must be neutralized by acid.
An excess of reagent must be used to allow the reaction to go to
completion. For 0 to 12 mg of chloride, use 20 ml of dimercury
dicyanide oxide solution and for 12 to 20 mg, use 30 ml.
Experience may show that, on this scale of working, the total chlorine
content of the sample, as calculated from the direct sulphuric acid
titration of the alkali, produced by addition of dimercury dicyanide
oxide to the test solution, should be identical with that obtained by the
comparative procedure given above. Confirmation of this fact should
enable the comparative titration procedure to be replaced by the
simpler direct dimercury dicyanide oxide titration method.
Content of chlorine in the sample =

3.545 b c'
w

where:
b
c'

= volume of sulphuric acid used (ml)

= c ( H2SO4), mol/l (normality) of the sulphuric acid

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% m/m

MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 39 STABILTY OF LIQUID FORMULATIONS AT 0C

39.1 Emulsifiable concentrates and solutions (Note 1)

OUTLINE OF METHOD
A sample is maintained at 0C for 1 h and the volume of any separated solid or
oily matter is then recorded. Storage at 0C is continued for 7 days, any solid
matter is settled by centrifuging and its volume recorded.
APPARATUS
Refrigerator capable of maintaining a temperature of 0 1C (Note 2)
Cone shaped centrifuge tubes 100 ml as specified in IP 75 or ASTM 96 (Note 3)
see Figure 25.
Centrifuge equipped with buckets capable of holding the specified tubes (Note 4).
Pipette 100 ml

Figure 25 Graduated centrifuge tube

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

PROCEDURE
Transfer 100 1.0 ml of a sample of the product to a centrifuge tube. Cool the
tube and its contents to 0 1C in the refrigerator. If the sample contains a
dissolved crystalline pesticide, add to the tube a small crystal of the pure or
technical pesticide (Note 5). Allow the tube and its contents to remain at 0 1C
for 1 h, and during this time stir the contents of the tube at intervals of
approximately 15 min, each time for approximately 30 s.
After this period examine the tube and record whether any solid or oily matter
is present. Replace the tube in the refrigerator and allow it to remain at 0 1C
for a total period of 7 days.
At the end of 7 days, remove the tube from the refrigerator, and allow it to
remain undisturbed at room temperature (Note 6) for 3 h. Invert the centrifuge
tube once, and centrifuge for 15 min at such a speed that the relative centrifugal
force (RCF) at the tips of the tubes is about 550 G (the acceleration due to
gravity = 981 cm sec-2; Note 7).
Record the volume of any separated material at the bottom of the tube to the
nearest 0.05 ml (Note 8).
39.2 Aqueous solutions
APPARATUS
Measuring cylinder 100 ml
Refrigerator at 0 1C (Note 2)
PROCEDURE
Put 100 ml of the material in the measuring cylinder and then put it in the
refrigerator for 48 h at 0 1C. At the end of this time, Note the amount of
separated material, if any, then allow the cylinder to reach room temperature and
again Note the amount of separated material.
Note 1
Note 2
Note 3

Based on Shell Method Series No 1410-2.

A domestic refrigerator is often unsuitable because the on/off cycle
covers a range greater than 2C.
Standard methods for analysis and testing of petroleum and related
products. Method IP 75/82. Produced by the Institute of Petroleum
London. [ASTM D1796-83]

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

Note 4
Note 5

Note 6
Note 7

Centrifuge suitable for Method 'IP 75, Water and Sediment'.

The crystal for seeding should be obtained from the formulation being
examined. Distil off the solvents from a portion of the concentrate by
MT 37, and use a crystal from the residue.
Not more than 20C.
(rpm) 2 d
RCF =
179000
rpm

98.45
10 3
d

where:
RCF

relative centrifugal force

d cm

diameter of swing measured from the tips of the opposite tubes

when in the position occupied during the centrifuging.

Note 8

If the liquid phase is not homogenous, record the volume of each

layer.

130