MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 71 SOLUBILITY IN SODIUM HYDROXIDE

71.1 Phenoxyalkanoic acids

REAGENT
Sodium hydroxide (NaOH) 0.5 mol/l (0.5N)

APPARATUS
Stoppered test tube 30 ml
Pipettes 2 and10 ml
Test sieve 150 µm, 100 mm diameter

PROCEDURE
Weigh 1 g of sample, transfer to the test tube, and dissolve in sodium hydroxide
(12 ml) by shaking. Examine the resulting solution to see whether it is free from
sediment. If there is considerable sediment, shake the solution and pour it
through the test sieve. Determine the amount of residue left on the sieve by a
gravimetric procedure.

71.2 Cresols (Note 1)

REAGENT
Sodium hydroxide solution (NaOH); dissolve sodium hydroxide (5 g) in distilled
water (95 ml).

APPARATUS
Stoppered conical flask 250 ml
Measuring cylinder 100 ml BS 604:1982

PROCEDURE
Weigh the flask, add approximately 10 g of sample and reweigh. Calculate the
volume of sodium hydroxide required, to the nearest ml, on the basis of 90 ml of
sodium hydroxide to 10 g of cresol. Measure the required volume in the measuring
cylinder and transfer to the flask. Shake the stoppered flask until the sample has
dissolved and then leave it for 30 min at the specified temperature. Examine for
clarity and freedom from insoluble matter.

200
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

71.3 Bromoxynil and Ioxynil

SCOPE
The method is suitable for determining the fractions of acidic technical materials
insoluble in sodium hydroxide.
OUTLINE OF METHOD
The material is dissolved in sodium hydroxide and the insoluble material is
determined by sieving.
REAGENT
Sodium hydroxide (NaOH) 0.2 mol/l (0.2N)
APPARATUS
Test tube 50 ml, with stopper
Test sieve 150 µm; 100 mm diameter, tared
PROCEDURE
Weigh (to the nearest mg) 1.00 g of sample, transfer to the test tube, and dissolve in
sodium hydroxide solution (35 ml). Examine the resulting solution to see whether it
is free from appreciable sediment. Shake the solution and pour it through the test
sieve. Note whether there is any residue left on the sieve. If there is, dry the sieve at
105°C, and determine the mass of the residue.

Note 1 The method is technically identical to PC 16-67 of the STPTC.

MT 73 HARDNESS OF WATER

REAGENTS

Magnesium chloride (MgCl2 · 6H2O) not less than 98% magnesium chloride,
hexahydrate
EDTA, disodium salt (disodium dihydrogen ethylenediaminetetra-acetate) not less
than 99%. Dry for 2 h at 80°C before use.
Calcium carbonate (CaCO3) not less than 99% m/m. Dry for 4 h at 105°C before
use.
Hydrochloric acid (HCl) 1 mol/l (1N)

201
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

Ammonium hydroxide (NH4OH) d20 0.880,

- 2 mol/l (2N) solution
Ammonium chloride (NH4Cl) not less than 99% ammonium chloride
Methyl red aqueous indicator solution; RE 28.1
Mordant black II; RE 53
Solochrome dark blue [sodium 3-hydroxy-4-(2-hydroxy-1-naphthylazo)-7-
nitronaphthalene-2-sulphonate] C.I. 15705
Diethylamine (CH3CH2NHCH2CH3)
Ethanol (CH3CH2OH) or Industrial Methylated Spirit
Sodium sulphide (Na2S · x H2O)
Methanol (CH3OH)
APPARATUS
Volumetric flasks 1000 ml
Conical flasks 250 and 500 ml
Pipettes
Burette 50 ml
PROCEDURE
(a) Preparation of working solutions
(i) EDTA solution 0.01 mol/l (0.01M).
Dissolve EDTA, disodium salt (3.723 g) and magnesium chloride, hexahydrate (0.05
g) in de-ionized water (Note 1), transfer quantitatively to a 1000 ml volumetric flask
and make up to volume with de-ionized water. The prepared solution should be stored
in a polyethylene container.

(ii) Standard calcium solution.

Weigh 1.000 g of dried calcium carbonate and transfer to a 500 ml conical flask,
using a little water. Slowly add hydrochloric acid (21 ml) and swirl the content of the
flask until all the carbonate is dissolved. Add water (200 ml), boil to expel the carbon
dioxide, and cool. Add a few drops of methyl red indicator and adjust to an
intermediate orange colour with 2 mol/l ammonium hydroxide solution or 1 mol/l
hydrochloric acid, as required. Transfer quantitatively to a 1000 ml volumetric flask
and dilute to volume.
1.00 ml of solution contains 1 mg calcium carbonate, and is equivalent to 1000 ppm
hardness.

(iii) Buffer solution pH 10.0.

202
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

Dissolve ammonium chloride (67.5 g) in water (300 ml), add 0.880 ammonium
hydroxide solution (570 ml) and make up to 1000 ml with distilled water.
(iv) Mordant black II indicator solution.
Dissolve 0.5 g of the dyestuff in 20 ml of ethanol and dilute to 100 ml with water.

(v) Solochrome dark blue indicator solution.

Dissolve 0.5 g of the dyestuff in methanol (100 ml).

(vi) Sodium sulphide solution.

Dissolve sodium sulphide (3.7 g) in water (100 ml).

(b) Standardization of EDTA solution.

Pipette standard calcium solution (25 ml) into a 250 ml conical flask and dilute to
100 ml with de-ionized water. Warm to 40°C. Add buffer solution (1 ml), sodium
sulphide solution (2 ml), and Mordant Black II solution (six drops). Titrate
immediately with the EDTA solution to a distinct blue end point.
Adjust the concentration by subsequent dilution so that 1 ml of the EDTA solution is
equivalent to 1 mg of calcium carbonate.

(c) Determination of total hardness in water.

Pipette the sample (25 ml) into a 250 ml conical flask and dilute to 100 ml with de-
ionized water. Warm to 40°C. Add buffer solution (1 ml), sodium sulphide solution
(2 ml), and Mordant black II indicator solution (six drops).
Titrate with standardized EDTA solution to a distinct blue end point (t ml).

Hardness as calcium carbonate = 40t ppm

(d) Determination of calcium (Note 2) in hard water in the presence of magnesium.

Pipette the sample (25 ml) into a 250 ml conical flask and dilute to 100 ml
with water. Add diethylamine (5 ml) to give a pH of 12.5, sodium sulphide
solution (1 ml), and Solochrome dark blue indicator solution (six drops).
Titrate with standardized EDTA solution to a distinct blue end point.
1 ml 0.01 mol/l (0.01M) EDTA solution is equivalent to 0.4008 mg calcium

Note 1 De-ionized distilled water should be used for all solutions involved in
EDTA titrations.
Note 2 The hardness due to magnesium may be calculated by subtracting the
volume of EDTA solution required for the calcium hardness, from the

203
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

volume required for the total hardness, for equal volumes of the sample.1 ml
0.01 mol/l (0.01M) EDTA solution is equivalent to 0.2432 mg magnesium
MT 74 NEUTRALITY

OUTLINE OF METHOD (Note 1)

The sample is shaken with distilled water to which an acid-base indicator has been
added. The colour of the aqueous layer is compared with that of a neutral solution of
the indicator.

REAGENTS

Distilled water freshly boiled and cooled in an atmosphere free from carbon
dioxide. See RE 130.
Mixed indicator colours: yellow (acid), grey-green (neutral) and blue-violet
(alkaline). Dissolve bromocresol green [α,α-bis(3,5-dibromo-4-hydroxy-o-
tolyl)toluene-2,α-sultone] (0.04g) in ethanol (10 ml) and alizarin red S [sodium
9,10-dihydro-3,4-dihydroxy-9,10-dioxoanthracene-2-sulphonate] (0.04 g) in
distilled water. Mix the two solutions and dilute to 100 ml with the distilled water.
If required, add 0.01 mol/l (0.01N) hydrochloric acid or 0.01 mol/l (0.01N) sodium
hydroxide to the solution until 0.3 ml of the indicator so treated gives the neutral
colour when added to the distilled water (10 ml).
APPARATUS
Stoppered measuring cylinders 100 ml BS 604:1982, of good quality glass, inert to
the contents under the conditions of this test.
White light cabinet for use when a good north light is not available.
PROCEDURE
Put 10 ml of the distilled water in a clean measuring cylinder and add the indicator
solution (0.3 ml). Add the sample (50 ml), stopper, shake thoroughly, and allow the
mixture to settle. Compare the colour of the aqueous layer with the colour of the
contents of a similar cylinder containing the distilled water and indicator, but without
the addition of sample.
Report the result of the test as acid, neutral, or alkaline, as the case may be. The
sample is considered acid when the indicator changes to a yellow shade matching
that produced when the indicator is added to water adjusted to a pH value of 4.5.
Similarly, the sample is deemed to be alkaline when the indicator changes to a violet
shade matching that produced when the indicator is added to water adjusted to a pH

204
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

value of 9.0.

Note 1 The method is technically identical to RLB 5-67 of the STPTC.

MT 75 DETERMINATION OF pH VALUES

75.1 General method

DEFINITION

The pH value of an aqueous liquid is defined as the common logarithm of the

reciprocal of the hydrogen ion concentration expressed in g/l.

OUTLINE OF METHOD

The pH value of a liquid is determined by means of a pH meter and a glass electrode.

REAGENTS

Potassium hydrogen phthalate (COOH · C6H4 · COOK) 0.05 mol/l (0.05M).

Dissolve 10.21 g in freshly boiled and cooled distilled water, and make up to 1000
ml. Do not keep the solution for longer than one month.
diSodium tetraborate (Na2B4O7 · 10H2O) 0.05 mol/l (0.05M). Dissolve 19.07 g in
freshly boiled and cooled distilled water and make up to 1000 ml. Do not keep the
solution for longer than one month.
Water freshly boiled and cooled distilled water of pH 5.5 to 7.0. See RE 130.

APPARATUS

pH meter to comply with BS 3145:1978 or equivalent.

Glass electrode and reference electrode to comply with BS 2586:1979 or equivalent

PROCEDURE

Operate the pH meter and electrode system according to the manufacturer's

instructions. Standardize the meter and electrodes with the 0.05 mol/l phthalate
(pH 4.00) when an acid solution is being measured or 0.05 mol/l borate when an
alkaline solution is being measured (see Table 13). The reading should not differ
by more than 0.02 pH units from the original value at which the apparatus was
standardized. If the difference is greater than 0.05, then repeat the measurements.

205
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

Check the pH/mV relationship of the glass electrode daily as follows:

Standardize with the 0.05 mol/l (0.05M) phthalate and measure the pH value of the
0.05 mol/l borate. If the reading is higher by 0.02 or more, or lower by 0.05 or more,
than the appropriate value in Table I, correct the pH values of all solutions measured
that day, assuming the potential of the glass electrode to be in a linear relationship
with the pH of the solution being measured.

TABLE I pH values of 0.05 mol/l (0.05M) disodium tetraborate

Temperature °C 10 15 20 25 30
pH 9.32 9.28 9.22 9.18 9.14

Unless otherwise specified, all solutions must be brought to laboratory temperature

before measurement.

The temperature coefficient of the 0.05 mol/l phthalate can be neglected but that of
the 0.05 mol/l borate must be taken into account (see Table I).

When measuring pH values above 10, use a glass electrode designed for use at the
alkaline end of the pH scale and apply any necessary correction.

75.2 pH of aqueous dispersions

REAGENTS

As for MT 75.1

APPARATUS

As for MT 75.1 together with:

Stoppered measuring cylinder 100 ml

PROCEDURE

Weigh 1 g of sample, transfer to the measuring cylinder containing water (about

50 ml), make up to 100 ml with water, and shake vigorously for 1 min. Allow
any suspension to settle for 1 min and then measure the pH of the supernatant
liquid.

206
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 76 SOLUBILITY IN AQUEOUS TRIETHANOLAMINE

REAGENT

Triethanolamine (2,2',2''-nitrilotriethanol) 5% v/v solution in distilled water

APPARATUS

Stoppered test tube 30 ml

Measuring cylinder 25 ml
Test sieve 106 µm

PROCEDURE

Weigh out 1 g of the acid, transfer to the test tube, and dissolve in the triethanolamine
solution (16 ml) by shaking. Examine the resulting solution to see whether it is free
from appreciable sediment. Shake the solution and pour it through the test sieve.
Note the amount of residue left on the sieve.

MT 77 DETERMINATION OF 1-CHLORO-2,3-EPOXYPROPANE

OUTLINE OF METHOD

The 1-chloro-2,3-epoxypropane is reacted with trimethylamine hydrochloride, and

the liberated trimethylamine is titrated with perchloric acid.

REAGENTS

Acetic acid (CH3COOH) glacial

Perchloric acid c(HClO4): 0.1 mol/l (0.1N) standardized solution in acetic acid; RE
43.1
1-Naphtholbenzein {4,4'-(α-hydroxybenzylidene)di-1-naphthol} indicator solution;
RE 54.1
Trimethylamine hydrochloride {(CH3)3NHCl} 10% m/v in glacial acetic acid;
neutral to 1-naphtholbenzein, adjust if necessary with either the perchloric acid or
sodium acetate solution.
Sodium acetate (CH3COONa) 0.1 mol/l (0.1N) solution in glacial acetic acid. This

207
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

solution should be standardized with 0.1 mol/l standardized perchloric acid.

APPARATUS

Conical flask 200 ml

Water bath
Burette 25 ml

PROCEDURE

Weigh accurately about 2 to 3 g(w g) of sample, transfer to the flask, add glacial
acetic acid (30 ml), and neutralize with the perchloric acid to 1-naphtholbenzein. Add
trimethylamine hydrochloride solution (10 ml), and place the flasks on the boiling
water bath for 1 min.
Remove and titrate the warm solution with the perchloric acid until the first
appearance of the green colour. Repeat the warming and continue the titration until
the light green colour becomes permanent. Cool in ice water until the green colour
intensifies, add sodium acetate solution (3.0 ml), and complete the titration (total titre
= t ml)

0.925 ⋅ (t ⋅ c1 − 3c2 )
Content of 1-chloro-2,3-epoxypropane = % m/m
w

where:
c1 = c(HClO4), mol/l (normality) of the perchloric acid
c2 = c(CH3COONa), mol/l (normality) of the sodium acetate solution

MT 78 HYDROGEN SULPHIDE AND THIOLS

REAGENTS
Potassium plumbite solution; RE 75
Sulphur (S) sublimed ('flowers of sulphur'), dry, and store in a closed container.
Cadmium chloride (CdCl2) solution containing cadmium chloride (100 g) dissolved
in 36% m/m hydrochloric acid (10 ml) and made up to 1000 ml with distilled
water.
Potassium iodide (KI) 10% m/m solution, freshly prepared
Starch indicator solution, RE 27.1 freshly prepared
Acetic acid (CH3COOH) 10% v/v solution

208
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

APPARATUS

Stoppered measuring cylinder 50 ml and several unstoppered cylinders –

BS 604:1982, about 25 mm internal diameter.

PROCEDURE

(a) Preliminary test.

Measure the sample (10 ml) and potassium plumbite solution (5 ml) into the cylinder
and shake them together vigorously for 15 sec. Observe the appearance of the
mixture and continue the procedure as indicated in the table below:

Observation Interference Continue test as

described in
Black precipitate forms immediately Hydrogensulphide (b)
present
Brown precipitate forms slowly Peroxides present (c)
During the shaking period the solution (d)
becomes opalescent and then darkens Thiols and
in colour elementary sulphur
No change occurs or a yellow colour present (d)
produced

(b) If hydrogen sulphide is present.

Shake a fresh quantity of sample with cadmium chloride solution (5% of sample
volume) to remove the hydrogen sulphide. Separate the treated sample and make a
further preliminary test (a).

(c) If peroxides are believed to be present.

To confirm the presence of peroxide in sufficient concentrations to invalidate the

test, shake a fresh portion of the sample with 20% of its volume of the potassium
iodide solution and a few drops of starch solution. A blue colour in the aqueous layer
confirms the presence of peroxides.

209
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

(d) Final test.

To the mixture obtained in (a) above, add a small quantity of sulphur, not more than
will cover the interface between the sample and the potassium plumbite solution,
shake the mixture for 15 sec, and allow to settle for 1 min.
If a yellow colour is formed after the initial shaking in (a), followed by the formation
of a brown or black precipitate, thiols are present.
Note The method is technically identical to IP 30/81 of the Institute of Petroleum.

MT 79 ACID WASH

OUTLINE OF METHOD (Note 1)

Equal volumes of the sample and sulphuric acid (95% m/m) are shaken together.
The colour of the acid is compared with solutions of standard colour (Note 2).
REAGENTS
Potassium dichromate (K2Cr2O7)
Sulphuric acid (H2SO4) 98% m/m, concentrated
- 95 ± 0.5% m/m checked by titration
Potassium permanganate c(1/5KMnO4): 0.1 mol/l (0.1N): prepare as described in
RE 22.1 but do not standardize.
APPARATUS
Water bath maintained at 20 ± 1°C
White light cabinet for use when a good north light is not available.
Cylinders. Three cylinders made of thin-walled colourless glass tubing of internal
diameter 13 ± 0.05 mm. The cylinders should be about 100 mm in height from the
base to the shoulder and are encircled with two marks. The upper mark is ± 1 mm
from the outside of the base of the cylinder and the lower mark is so placed that the
content of the cylinder from the base to that mark differs from that between the upper
and lower marks by not more than 0.1 ml. The three cylinders must be identical in all
other respects including colour and must be clean and dry at the start of the test.
PROCEDURE
(a) Preparation of colour standards.
The colour standards for comparison are made by dissolving potassium dichromate in
sulphuric acid and water. In their preparation careful attention must be given to the

210
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

following details:

(i) The standard solutions have oxidizing properties and must be made and stored in
glass stoppered bottles, entirely free from dust and grease.
(ii) Prepare a stock dilute acid solution containing equal volumes of water and 98%
m/m sulphuric acid, and cool to room temperature before use.
(iii) Check the water and the sulphuric acid for absence of oxidizable matter by
adding two drops (0.1 ml) of the potassium permanganate solution to 100 ml of the
stock dilute solution. The permanganate should not be decolourized in 5 min.
(iv) Prepare a stock potassium dichromate solution containing 10 g per 1000 ml in
49% sulphuric acid solution. This amount of dichromate dissolves only very slowly.
Prepare the standard solutions for comparison by diluting portions of this standard
solution with the appropriate quantities of the standard stock acid solution as in the
table below.
(v) The standard solutions for comparison must be used only on the day in which
they are prepared.
(vi) The stock acid solution, the stock dichromate solution, and the standard solutions
for comparison must be kept in the dark when not in actual use.

(b) Testing the sample.

The test must not be carried out in direct sunlight.

Fill one of the cylinders to the upper mark with the specified standard dichromate
solution, and a second cylinder with a dichromate solution of concentration higher
than the specified standard by the precision figure R (See 'Precision' below). Prepare
these solutions (as described above) so that they contain the specified amount of
dichromate to the nearest 0.01 g per 1000 ml.
Filter the sample through a filter paper about 15 cm in diameter and reject the first 10
ml of filtrate. Fill the third cylinder to the lower mark with the filtered sample, insert
the stopper, and place it in the water bath. Place sufficient 95% m/m sulphuric acid in
a suitable container and leave it in the water bath until it reaches the bath
temperature, and then pour the acid into the cylinder until the contents are level with
the upper mark.
Stopper the cylinder, shake vigorously for exactly 2 min, return it to the water bath,
and leave it undisturbed for exactly 10 min. Immediately compare the colour of the
acid layer with the contents of the other cylinders by the illumination of a good north
light, or by means of the white light cabinet.
Report the result as equal to the standard, paler than the standard, darker than the
standard but within the precision of the test, or as failing (Note 3).

211
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

(c) Precision.

Repeatability, r. Duplicate results by the same operator should be considered suspect

if they differ by more than the values of r given in the table below.

Reproducibility, R. Single results submitted by each of two operators should be

considered suspect if they differ by more than the values of R given in the table
below.

Colour standard r R
g/l K2Cr2O7 g/l K2Cr2O7 g/l K2Cr2O7
0.1 to 0.40 0.05 0.10
0.50 0.10 0.20
1.00 0.10 0.50
1.50 0.20 0.60
2.00 0.40 1.00
3.00 0.80 1.80
5.00 2.00 3.50

Note 1 The method is technically identical to the Acid Wash RLB-67 of the
STPTC.

Note 2 The comparison gives some indication of the extent to which acid refining
has been carried out. It is not a precise measurement of unsaturated
compounds in the product, as different unsaturated compounds produce
different colourations with sulphuric acid.

Note 3 Some samples, especially if acid when tested by neutrality test using NBA
screened indicator, may give a higher acid wash result as the age of the
sample increases.

212
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 80 RESIDUE ON EVAPORATION

80.1 Low boiling products

OUTLINE OF METHOD

Seventy five per cent of the sample is distilled. The residue in the flask is transferred
to a weighed dish, and the evaporation completed on a water bath; the residue
remaining on completion of the test is determined by weighing.

REAGENTS

Potassium dichromate (K2Cr2O7) a saturated solution in approximately 95%

sulphuric acid (H2SO4)
Acetone {(CH3)2CO}; RE 34

APPARATUS

Round bottomed flask 250 ml borosilicate glass

Liebig condenser with bent end
Distillation head
Crow receiver 100 ml
Board 150 × 150 mm, with a central hole 40 mm in diameter
Dishes made of borosilicate glass, hemispherical in shape, 64 to 70 mm external
diameter
Oven at 98 - 105°C
Water bath with cover holes 63 mm in diameter

PROCEDURE

Clean the dishes by immersing them in the dichromate solution for 12 h, wash with
distilled water until free from acid, and then dry with acetone. Put them in a drying
oven for 20 min and allow to cool in a suitable vessel without desiccant for not less
than 30 min. Handle the cleaned dishes with metal tongs and weigh to the nearest 0.2
mg.
Pass the sample through a filter paper, reject the first 10 ml, and measure 100 ml into
the flask. Connect up the apparatus and bring the contents of the flask to the boil with
a bunsen flame, avoiding any sudden evolution of vapour, and distil at the rate of 4 to
5 ml/min (about 2 drops/sec) until 75 ml has collected in the Crow receiver.

213
 MISCELLANEOUS TECHNIQUES AND IMPURITIES

Disconnect the flask from the distillation head and pour the contents into one of the
dishes, which has previously been heated to 98 - 105°C, cooled and weighed as
above. Allow the flask to drain into the dish for 15 sec. Put the dish on a vigorously
boiling water bath for 1.5 h, keeping it protected from dust.
For samples distilling less than 95% by volume at 160°C, continue evaporating, if
necessary, for longer than 1.5 h until evaporation is complete, but not longer than 3 h.
Transfer the dish to the oven and leave at 98 to 105°C for 1 h; allow to cool in a
dust-free atmosphere for 15 to 20 min, and reweigh.
Express the results as mg/100 ml of sample.

80.2 Cresols

OUTLINE OF METHOD

The weight of residue is determined after evaporation of the sample, first on a boiling
water bath and then in an oven at 105°C.

APPARATUS

Dishes borosilicate glass, hemispherical in shape, 80 mm in external diameter

Water bath with cover hole approximately 60 mm in diameter
Oven at 105 ± 2°C

PROCEDURE

Heat the dish in the oven to constant weight. Weigh between 9.5 and 10.5 g (0.1
g) of sample, and transfer to the dish. Heat on the water bath in a fume cupboard
for 3 h and then in the oven for 1 h. Cool the dish and contents to room
temperature in a desiccator and weigh. Determine the weight of residue by
difference and calculate the percentage of residue in the sample.

214