MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 18 STANDARD WATERS

INTRODUCTION (Note 1)

Instructions for the preparation of Standard Waters and of waters of any desired
hardness are given in CIPAC Monograph 1. For the Standard Waters A to G,
stock solutions of Ca++ and Mg++ are prepared; the working solutions are then
made by dilution of these stock solutions.
All solutions should be stored in polyethylene containers.
Working solutions should be freshly prepared immediately before use.
A method for the determination of the hardness of water by EDTA titration is
given in MT 73.

18.1 Preparation of Standard Waters A to G (MT 18.1.1 to 18.1.7)

REAGENTS

Calcium carbonate (CaCO3) containing not less than 99% calcium carbonate;
dry for 2 h at 105 °C before use
Magnesium oxide (MgO) containing not less than 99% magnesium oxide; dry
for 2 h at 105 °C before use
Sodium hydrogen carbonate (NaHCO3) containing not less than 99% sodium
hydrogen carbonate
Ammonia solution ( NH4OH) approximately 1 mol/l (1N)
Hydrochloric acid c (HCl) : 1 mol/l (1N) and 0.1 mol/l (0.1N) standardized
solutions; RE 14.2 and 14.1
Sodium hydroxide c (NaOH) : 0.1 mol/l (0.1N) standardized solution; RE 25.1
Methyl red indicator 0.1% m/v aqueous solution; RE 18

STOCK SOLUTIONS

Solution I. 0.04M Ca++ solution

Weigh accurately calcium carbonate (4.000 g), and transfer to a 500 ml conical
flask with a minimum of distilled water. Place a small filter funnel in the mouth of
the flask and add slowly 1 mol/l hydrochloric acid (82.0 ml, measured from a
burette), swirling the contents. When all the calcium carbonate has dissolved, dilute
the solution to approximately 400 ml with distilled water, and boil gently to expel
excess carbon dioxide. Cool the solution, add methyl red (2 drops) and neutralize to
an intermediate orange colour with 1 mol/l ammonia solution, added drop wise.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

Transfer the solution quantitatively to a 1000 ml volumetric flask and make up

to volume with distilled water. The solution should be stored in a polyethylene
container.
One ml of this solution when diluted to 1000 ml gives a water containing 4 ppm
hardness expressed as calcium carbonate.

Solution II. 0.04M Mg++ solution

Weigh accurately magnesium oxide (1.613 g), and transfer to a 500 ml conical
flask with a minimum of distilled water. Place a small filter funnel in the mouth
of the flask and add slowly 1 mol/l hydrochloric acid (82.0 ml, measured from a
burette), swirling the contents. When all the magnesium oxide has dissolved,
dilute the solution to approximately 400 ml with distilled water. Add methyl red
(2 drops) and neutralize to an intermediate orange colour with 1 mol/l ammonia
solution, added drop wise. Transfer the solution quantitatively to a 1000 ml
volumetric flask and make up to volume with distilled water. The solution
should be stored in a polyethylene container.
One ml of this solution when diluted to 1000 ml gives a water containing 4 ppm
hardness expressed as calcium carbonate.

Solution III. 1.0M sodium hydrogen carbonate solution

Weigh accurately sodium hydrogen carbonate (84.01 g), dissolve in 800 ml

distilled water, transfer to a 1000 ml volumetric flask and make up to volume
with distilled water.
One ml of this solution when diluted to 1000 ml gives a water containing the
equivalent of 23 ppm of sodium.

Solution IV. 0.2M Ca++ solution.

Weigh accurately calcium carbonate (20.00 g), and transfer to a 1000 ml

conical flask with a minimum of distilled water. Place a small filter funnel in
the mouth of the flask and add slowly 1 mol/l hydrochloric acid (410 ml),
swirling the contents. When all the calcium carbonate has dissolved, dilute the
solution to approximately 800 ml with distilled water, and boil gently to expel
excess carbon dioxide. Cool the solution, add methyl red (2 drops) and
neutralize to an intermediate orange colour with 1 mol/l ammonia solution,
added drop wise. Transfer quantitatively to a 1000 ml volumetric flask and
make up to volume with distilled water. The solution should be stored in a
polyethylene container.
One ml of this solution when diluted to 1000 ml gives a water containing
20 ppm hardness expressed as calcium carbonate.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

Solution V. 0.2M Mg++ solution

Weigh accurately magnesium oxide (8.065 g), and transfer to a 1000 ml conical
flask with a minimum of distilled water. Place a small filter funnel in the mouth
of the flask and add slowly 1 mol/l hydrochloric acid (410 ml), swirling the
contents. When all the magnesium oxide has dissolved, dilute the solution to
about 800 ml with distilled water. Add methyl red (2 drops) and neutralize to an
intermediate orange colour with 1 mol/l ammonia solution, added drop wise.
Transfer quantitatively to a 1000 ml volumetric flask and make up to volume
with distilled water. The solution should be stored in a polyethylene container.
One ml of this solution when diluted to 1000 ml gives a water containing 20 ppm
hardness expressed as calcium carbonate.

APPARATUS

pH meter with suitable electrode assembly

PREPARATION OF WORKING SOLUTIONS (Notes 2 and 3)

18.1.1 Standard Water A

20 ppm hardness
pH 5.0 - 6.0
Ca++: Mg++ = 1:1

Pipette Solution I (2.5 ml) and Solution II (2.5 ml) into a 1000 ml beaker and
dilute to about 800 ml with de-ionized water. Using a pH-meter, adjust to pH 5.0
to 6.0 (Note 4) by the drop wise addition of 0.1 mol/l sodium hydroxide or 0.1
mol/l (0.1N) hydrochloric acid as appropriate. Transfer the solution quantitatively
to a 1000 ml volumetric flask and make up to volume with de-ionized water (Note
3).

18.1.2 Standard Water B

20 ppm hardness
pH 8.0 - 9.0
Ca++.: Mg++ = 4:1

Pipette Solution I (4.0 ml) and Solution II (1.0 ml) and Solution III (2.0 ml) into
a 1000 ml beaker and dilute to about 800 ml with de-ionized water. Using a pH-
meter, adjust to pH 8.0 to 9.0 (Note 4) by the drop wise addition of 0.1 mol/l
sodium hydroxide. Transfer the solution quantitatively to a 1000 ml volumetric
flask and make up to volume with de-ionized water (Note 3).

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

18.1.3 Standard Water C

500 ppm hardness
pH 7.0 - 8.0
Ca++.: Mg++ = 4:1

Pipette Solution I (100 ml) and Solution II (25 ml) into a 1000 ml beaker and
dilute to about 800 ml with de-ionized water. Using a pH-meter, adjust to pH 7.0
to 8.0 (Note 4) by the drop wise addition of 0.1 mol/l sodium hydroxide.
Transfer the solution quantitatively to a 1000 ml volumetric flask and make up
to volume with de-ionized water (Note 3).

18.1.4 Standard Water D

342 ppm hardness
pH 6.0 - 7.0
Ca++.: Mg++ = 4:1

Measure, from a burette, Solution I (68.5 ml) and Solution II (17.0 ml) into a
1000 ml beaker and dilute to about 800 ml with de-ionized water. Using a pH
meter, adjust to pH 6.0 - 7.0 (Note 4) by the drop wise addition of 0.1 mol/l
sodium hydroxide. Transfer the solution quantitatively to a 1000 ml volumetric
flask and make up to volume with de-ionized water (Note 3).

18.1.5 Standard Water E

1500 ppm hardness
pH 7.0 - 8.0
Ca++.: Mg++ = 4:1

Measure, from a burette, Solution IV (60 ml) and Solution V (15.0 ml) into a
1000 ml beaker and dilute to about 800 ml with de-ionized water. Using a pH
meter, adjust to pH 7.0 - 8.0 (Note 4) by the drop wise addition of 0.1 mol/l
sodium hydroxide. Transfer the solution quantitatively to a 1000 ml volumetric
flask and make up to volume with de-ionized water (Note 3).

18.1.6 Standard Water F

5000 ppm hardness
pH 6.0 - 7.0
Ca++ only

Transfer Solution IV (250 ml) to a 1000 ml beaker and dilute to about 800 ml with
de-ionized water. Using a pH meter, adjust to pH 6.0 - 7.0 (Note 4) by the drop
wise addition of 0.1 mol/l sodium hydroxide. Transfer the solution quantitatively to
a 1000 ml volumetric flask and make up to volume with de-ionized water (Note 3).

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

18.1.7 Standard Water G

8000 ppm hardness
pH 6.0 - 7.0
Mg++ only

Transfer Solution V (400 ml) to a 1000 ml beaker and dilute to about 800 ml with
de-ionized water. Using a pH meter, adjust to pH 6.0 - 7.0 (Note 4) by the drop
wise addition of 0.1 mol/l sodium hydroxide. Transfer the solution quantitatively to
a 1000 ml volumetric flask and make up to volume with de-ionized water (Note 3).

18.2 Preparation of salted waters H and J.

Standard waters with properties which are intended to simulate waters occurring
in Argentina and Brazil. The method of preparation was supplied by E V Pineda.

REAGENTS

Calcium chloride anhydrous (CaCl2) not less than 95%; dry for 2 h at 105 °C
before use
Magnesium sulphate (MgSO4 ⋅ 7 H2O) not less than 99.5% magnesium sulphate
heptahydrate
Sodium sulphate (Na2SO4) not less than 99.5%; dry for 2 h at 105 °C before use
Sodium chloride (NaCl) not less than 99.9%; dry for 2 h at 105 °C before use
Hydrochloric acid c (HCl) : 0.1 mol/l (0.1N) standardized solution; RE 14.1
Sodium hydroxide c (NaOH) : 0.1 mol/l (0.1N) standardized solution; RE 21

STOCK SOLUTION

Weigh accurately into separate vessels 2.00 g calcium chloride; 1.80 g magnesium
sulphate; 5.00 g sodium sulphate and 10.0 g sodium chloride. Dissolve each of the
reagents in about 150 ml distilled water and transfer quantitatively to the same
1000 ml volumetric flask, mix the solution thoroughly, make up to volume with
distilled water and mix again.
This solution should be stored in a polyethylene container and has a total hardness
of 2535 ppm as calcium carbonate with Ca++.: Mg++ ratio about 2.5 : 1. Working
solutions with total hardness 634 ppm and 63.4 ppm are prepared by dilution from
this stock solution.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

APPARATUS

pH meter with suitable electrode assembly

PREPARATION OF WORKING SOLUTIONS (Notes 2 and 3)

18.2.1 Standard Water H

634 ppm hardness
pH 6.0 - 7.0
Ca++.: Mg++ about 2.5 : 1

Transfer 250 ml of stock solution to a 1000 ml beaker and dilute to about 800 ml
with de-ionized water. Using a pH meter, adjust to pH 6.0 - 7.0 (Note 4) by the
drop wise addition of either 0.1 mol/l sodium hydroxide or 0.1 mol/l hydrochloric
acid. Transfer the solution quantitatively to a 1000 ml volumetric flask and make
up to volume with de-ionized water (Note 3).

18.2.2 Standard Water J

63.4 ppm hardness
pH 6.0 - 7.0
Ca++.: Mg++ about 2.5 : 1

Transfer 100 ml of Standard Water H to a 1000 ml beaker and dilute to about

800 ml with de-ionized water. Using a pH meter, adjust to pH 6.0 - 7.0 (Note 4)
by the drop wise addition of either 0.1 mol/l sodium hydroxide or 0.1 mol/l
hydrochloric acid. Transfer the solution quantitatively to a 1000 ml volumetric
flask and make up to volume with de-ionized water (Note 3).

18.3 Non-CIPAC Standard Waters

18.3.1 WHO Standard Hard Water

342 ppm hardness (Note 5)
Ca++.: Mg++ 4 : 1 (Note 6)

Dissolve calcium chloride (0.304 g) and magnesium chloride (0.139 g of

MgCl2.⋅ 6 H2O) in distilled water and make up to 1000 ml.

18.3.2 GB Standard Water

400 ppm hardness
Ca++.: Mg++ about 1 : 1

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

Dissolve calcium carbonate (1.85 g) and magnesium oxide (0.74 g) in 2 mol/l

hydrochloric acid. Evaporate to dryness and dissolve in distilled water, making
up to 100 ml. Add 10 ml of this solution to sufficient distilled water to give a
final volume of 1000 ml when the specified amount of sample is added.

18.3.3 AOAC Standard Water

Theoretical hardness varies according to dilution
Ca++.: Mg++ about 7 : 3
(a) Dissolve calcium chloride (73.99 g) in 400 ml boiled, distilled water.
Dissolve magnesium chloride (67.76 of MgCl2 ⋅ 6 H2O) in 400 ml boiled,
distilled water. Mix the solutions in a 1000 ml volumetric flask and make up to
volume.
(b) Dissolve sodium hydrogencarbonate (56.03 g) in boiled distilled water
and make up to 1000 ml. Waters of differing hardness may be made by
combining x ml of (a) with 4 ml of (b) and making up to 1000 ml.
One ml of (a) diluted to 1000 ml gives a water containing 100 ppm of hardness
expressed as calcium carbonate.

18.3.4 US Navy Hard Water

500 ppm hardness
Ca++.: Mg++ about 6 : 4
Dissolve calcium chloride dihydrate (CaCl2 ⋅ 2 H2O; 0.235 g) and magnesium
chloride hexahydrate (MgCl2 ⋅ 6 H2O; 0.268 g) in water and make up to 1000 ml.

18.3.5 Synthetic Nile Water

170 ppm hardness
Ca++.: Mg++ 4 : 1
Dissolve magnesium chloride hexahydrate (0.1024 g) and sodium hydrogen-
carbonate (0.1600 g) in 400 ml distilled water. Dissolve calcium oxide hydrate
[Ca(OH)2; 0.0910 g] in 150 ml distilled water. Mix the two solutions in a 1000 ml
flask and make up to the mark. Adjust the pH of the solution to 8.4 by the addition
of small pieces of solid carbon dioxide.

18.3.6 ASTM Hard Water

300 ppm hardness
Ca++.: Mg++ about 3 : 2
Dissolve calcium chloride dihydrate (CaCl2 ⋅ 2H2O; 1.764 g) and magnesium
sulphate (1.968 g) in distilled water and make up to 1000 ml. Dilute 150 ml of
this solution to 1000 ml for the working solution.

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18.4 Preparation of Standard Waters of required hardness

By use of stock solutions I, II, IV and V waters of any hardness up to 20000 ppm
can be prepared with any Ca++.: Mg++ ratio.

18.4.1 Dilution of stock solutions

Waters of the following hardness are obtained when 1 ml of the individual stock
solution is diluted to 1000 ml.

Stock solution Hardness (as ppm CaCO3) Cation

I 4 Ca++ only
II 4 Mg++ only
IV 20 Ca++ only
V 20 Mg++ only

18.4.2 Preparation of waters with a hardness of up to 600 ppm. Use stock

solutions I and/or II only.
To prepare 1000 ml of a Standard Water of hardness H ppm calcium carbonate,
the total volume of stock solution(s) required is H /4 ml.
Thus, to prepare 1000 ml of a standard water of hardness H ppm containing
Ca++ or Mg++ only, the volumes of stock solution required are H /4 ml of stock
solution I or II respectively. To prepare 1000 ml of a Standard Water of
hardness H ppm containing both Ca++ and Mg++ and where a ratio of Ca : Mg =
C : 1 is required, the volumes of stock solutions required are respectively:

H C
× ml of stock solution I
4 C +1
and
H C
× ml of stock solution II
4 C +1

For example:

Prepare 1000 ml of Standard Water with a hardness of 575 ppm and where
Ca++.: Mg++ = 4 : 1

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

575
Total volume of stock solutions required = = 143.75 ml
4
575 4
Volume of stock solution I required = × = 115 ml
4 4 +1
575 1
Volume of stock solution II required = × = 28.75 ml
4 4 +1

18.4.3 Preparation of waters with a hardness greater than 600 ppm. Use stock
solutions IV and/or V only.
To prepare 1000 ml of a Standard Water of hardness H ppm calcium carbonate,
the total volume of stock solution(s) required is H/20 ml.
To prepare 1000 ml of a Standard Water of hardness H ppm containing Ca++ or
Mg++ only, the volumes of stock solutions required are H/20 ml of stock solution
IV or V respectively. To prepare
1000 ml of a standard water of hardness H ppm and where a ratio of Ca++ : Mg++
= C : 1 is required, the volumes of stock solutions required are respectively:

H C
× ml of stock solution IV
20 C + 1

H C
× ml of stock solution V
20 C + 1

For example:

Prepare 1000 ml of Standard Water with a hardness of 2300 ppm and where
Ca++ : Mg++ = 4 : 1

2300
Total volume of stock solutions required = = 115 ml
20
2300 4
Volume of stock solution IV required = × = 92 ml
20 4 +1
2300 1
Volume of stock solution V required = × = 23 ml
20 4 +1

18.5 Units of measurement for the hardness of water and their conversion

The unit used in this method is ppm calcium carbonate.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

Other units which may be encountered are:

The milliequivalent per 1000 ml (me/l)
1 me/l Ca hardness = 20.04 mg Ca++ / l
1 me/ l Mg hardness = 12.16 mg Mg++/l

The English degree of hardness (°gb), corresponding to 1 grain calcium

carbonate in an Imperial gallon.

The German degree of hardness (°d), corresponding to 10 mg calcium oxide in

1 litre.

The French degree of hardness (°f), corresponding to 100 g calcium carbonate

in 10 m3.

The American degree of hardness (°usa), corresponding to 1 grain calcium

carbonate in an American gallon.

1 grain = 0.064798918 g 1 gallon (Imp) = 4.54596 l 1 gallon (US) = 3.7853 l

TABLE I Comparison of Units of Measurement of Hardness of Water

ppm me/l
CaCO3 Ca++ °gb °d °f °usa
1 ppm calcium carbonate 1.00 0.020 0.0702 0.0560 0.100 0.0585
1 mol/l Ca++ 50.0 1.00 3.51 2.80 5.00 2.925
1 English degree 14.3 0.285 1.00 0.798 1.43 0.829
1 German degree 17.8 0.357 1.25 1.00 1.78 1.044
1 French degree 10.0 0.200 0.702 0.560 1.00 0.583
1 American degree 17.1 0.342 1.20 0.958 1.71 1.00

Note 1 For further information see CIPAC Monograph 1, Standard Waters;

Recommendations for the preparation of standard waters used for
testing pesticidal and other formulations and an FAO survey of
naturally occurring waters, R de B Ashworth & B Crozier, edited G R
Raw, 1972. W Heffer & Sons Ltd, Printers, King's Hedges Road
Cambridge, England.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

Note 2 All working solutions should be stored in polyethylene containers and

must be freshly made up before use, as Ca++ and Mg++ will be lost from
solution on standing.

Note 3 It is recommended that de-ionized water be used for the preparation of

all working solutions, since distilled water may have a pH 5.0,
requiring excessive addition of sodium hydroxide for pH adjustment.

Note 4 The pH after adjustment should be near the middle of the stated range,
to allow for any slight pH change on standing.

Note 5 The total hardness of water is calculated by the following formula: Total
hardness as ppm calcium carbonate = 2.495 × ppm Ca++ + 4.115 × ppm
Mg++.

Note 6 Ca++ and Mg++ are expressed as their contribution to the total hardness in
terms of calcium carbonate and not as their individual ionic contributions.

MT 19 PHOSPHATE BUFFER SOLUTIONS

REAGENTS

Sodium dihydrogen orthophosphate (NaH2PO4 ⋅ 2 H2O) (Note 1)

diSodium hydrogen orthophosphate (Na2HPO4 ⋅ 12 H2O) (Note 1)
Hydrochloric acid c (HCl) : 0.25 mol/l (0.25N) standardized solution; RE 14.5
Bromocresol green 0.4% indicator solution; RE 55.1
Sodium hydroxide c (NaOH) : 0.25 mol/l (0.25N) standardized solution; RE 25.8
Thymol blue 0.04% indicator solution; RE 30.2
Sodium chloride (NaCl) 0.25 mol/l solution

APPARATUS

Two weighing bottles

Four volumetric flasks 250 ml
Class A burette 100 ml
Burette 50 ml
Four conical flasks 250 ml
Two polyethylene bottles 250 ml

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

METHOD

(a) Preparation of standard phosphate solutions

Weigh accurately 23.0 g of disodium hydrogen orthophosphate and 10.0 g of

sodium dihydrogen orthophosphate. Dissolve each salt separately in distilled water,
recently boiled and cooled, and make both solutions up to 250 ml in volumetric
flasks (Note 2). Titrate 25 ml disodium hydrogen orthophosphate solution with
hydrochloric acid using three drops of bromocresol green solution as indicator.
Match the colour at the end point with that of a mixture of sodium dihydrogen
orthophosphate solution (25 ml), bromocresol green solution (3 drops), and sodium
chloride solution (25 ml). Calculate the exact amount of disodium hydrogen
orthophosphate needed to give a 0.25 mol/l solution in 250 ml of water. Dissolve
this exact amount in 250 ml water and check the concentration of the solution by
titration with hydrochloric acid as before.
Similarly, titrate 25 ml sodium dihydrogen orthophosphate solution with the
sodium hydroxide solution, using three drops of thymol blue solution as indicator.
Match the colour at the end point with that of a mixture of the disodium hydrogen-
orthophosphate solution (25 ml), thymol blue solution (3 drops), and water
(25 ml). Hence, calculate the exact amount of sodium dihydrogen ortho-
phosphate required to give 250 ml of exactly 0.25 mol/l solution. Dissolve
exactly this amount in 250 ml water and check the concentration of the
solution by titration with hydrochloric acid as before.

(b) Preparation of buffer solutions

(i) MCPA analysis

Prepare the buffer solution by mixing 112 ml of exactly 0.25 mol/l disodium
hydrogen orthophosphate and 83 ml of exactly 0.25 mol/l sodium dihydrogen-
orthophosphate solutions, using a Class A burette to measure the volumes, and
mix well (Note 2).

(ii) Dinoseb analysis

Mix 100 ml of 0.25 mol/l disodium hydrogen orthophosphate

solution and 10 ml of 0.25 mol/l sodium dihydrogen orthophosphate solution.

Note 1 As the percentage of water of crystallization in these salts is variable,

approximately 0.25M solutions are made up and standardized.
Note 2 Store all phosphate solutions in polyethylene bottles at 0 °C to prevent
mould growth and chemical contamination. Always shake the bottle
and bring to room temperature before use.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

MT 20 STABILITY OF DILUTE EMULSION

REAGENT

Standard Water MT 18, (Note 1)

APPARATUS

Beakers 250 ml, 6 cm internal diameter

Two burettes 50 ml graduated in 0.1 ml
Measuring cylinders 100 ml graduated in 1.0 ml

PROCEDURE

To Standard Water (70 ml) at the specified temperature (Note 2) in a beaker,

add the formulation under test at the rate of about 5 ml per 12 seconds, from a
burette. During the addition, stir with a glass rod at the rate of about 3 turns per
second, and direct, continuously, the flow of the concentrate towards the centre
and not against the wall of the beaker. Sufficient formulation is added so that
when subsequently the solution is diluted to 100 ml, it will be as recommended
for use by the supplier. Make up the volume to 100 ml by adding distilled water
from the other burette, as above. Transfer the emulsion immediately to a clean,
dry measuring cylinder and keep at the specified temperature ± 1 °C (Note 2) for
1 h without disturbing in any way the cylinder or its contents. At the end of 1 h
Note any changes in the emulsion and the volume of any separated material.
Repeat the whole operation using distilled water instead of Standard Water.

Note 1 Use CIPAC Standard Water D (MT 18.1.4) unless otherwise specified.
Note 2 If no temperature is specified, the temperature used should be 30 ± 1 °C.

MT 21 SILICA FOR CHROMATOGRAPHY

21.1 Silica

REAGENTS

Sodium silicate solution; d20 about 1.70

Methyl orange indicator solution; RE 17.1
Hydrochloric acid (HCl) concentrated, d20 1.18
- 0.2 mol/l (0.2N) solution
Ethanol (CH3CH2OH) or Industrial Methylated Spirit 95%

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

APPARATUS

Beaker 10000 ml
Burette 100 ml
Buchner flask and funnel large
Oven at 110 °C
Oven at 400 °C
Sieve 75 µm
Sieve 53 µm

PREPARATION

Dilute the sodium silicate solution (1500 ml) with two volumes of water containing
a little methyl orange solution and cool to 8 °C. Stir the solution and add
concentrated hydrochloric acid from a burette until the solution is just acid.
Allow the precipitated silica gel to settle for 3 h. Filter through a large Buchner
funnel and wash the gel with water, using approximately 10 l. Suspend the gel in
sufficient 0.2 mol/l hydrochloric acid to form a thin slurry and allow to stand for
two days. Again filter through a Buchner funnel.
Transfer the silica to the original container, add water (2500 ml), stir mechanically
for 30 min and filter through a Buchner funnel. Repeat this washing operation 15
times to remove all the sodium chloride then repeat twice with ethanol (2500 ml)
instead of water, filtering through the Buchner funnel after each washing. Drain
the material thoroughly in the filter and remove most of the ethanol by vacuum
drying in a desiccator. Transfer the silica in open trays to an oven at 100 °C and
dry for 2 days. Break down any lumps with a glass rod and ignite in open trays
at 400 °C for 4 days.
Pulverize the silica until most of the material passes through a 75 µm sieve.
Store in sealed bottles, rejecting any material not passing the sieve.
The material thus prepared is adequate for most purposes, but slightly better
performance is obtained with silica which passes a 75 µm sieve and is retained by a
53 µm sieve. The separation of this fraction is, however, very time consuming.

21.2 Sorbisil® M 60

Sorbisil® M 60 is a selective adsorption grade of silica gel which has been specially
developed for use in separating aromatics from aliphatic and cycloparaffins.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

PHYSICAL DATA

Particle size 90% passing a 200µm sieve and retained

on a 75µm sieve
Loss on ignition at 1000 °C Maximum: 7.0%
Alcohol/ether solubles Maximum 0.01%
Surface area (BET N2 ads) 575 ± 75 m2/g
Pore volume 0.4 - 0.5 cm3
Bulk density 0.6 g/cm3
pH (extraction to 5 to 6
equilibrium)

CHEMICAL DATA (ANHYDROUS MATERIAL)

Silica as SiO2 99.8%
Sulphate as SO42- 0.1%
Sodium as Na+ 0.04%
Iron as Fe3+ 0.04%

PERFORMANCE

For hydrocarbon separation Sorbisil® M 60 complies with the ACS toluene

adsorption test (D H Mair method). Typical runs with a 50/50% v/v mixture of
toluene and n-heptane gave the following results:

Recovery

Column Depth Toluene n-Heptane

25 cm 49.8 % 50.2 %

30 cm 50.2 % 49.8 %

®´Sorbisil´ is a registered trade mark of Crosfield Chemicals Ltd, Warrington,

England.

21.3 Florisil (Note 1)

INTRODUCTION

Florisil is a synthetic magnesium oxide-silica gel adsorbent widely used in

chromatography. In pesticide chemistry, it is often of value in instances where the
compound under examination breaks down on silica gel, for example, endrin.

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MISCELLANEOUS TECHNIQUES AND IMPURITIES

The material consists of hard, porous, white granules, stable in water and
organic solvents and having the following average composition:

MgO 15.5 ± 0.5% m/m

SiO2 84.0 ± 0.5% m/m
Na2SO4 0.5% m/m (1.0% m/m maximum)

PHYSICAL DATA

Particle size 150 - 250 µm

pH (aqueous slurry, 20%) 8.4
Bulk density 0.47 g/cm3
Surface area (BET nitrogen 300 m2/g
adsorption)

PERFORMANCE

The following references give some idea of the capabilities of Florisil as a

chromatographic adsorbent.

(a) 'Official Methods of Analysis of the Association of Official Analytical

Chemists' 14th edition (1984), page 533. Method of calibrating Florisil
columns for mixed pesticide residue analysis based on the separation of
fenchlorphos, ethion, heptachlor epoxide, dieldrin, endrin and malathion into
groups.

(b) Residue Reviews (published by Springer Verlag), 1971, 34, p. 37. 'Separation of
chlorinated pesticides from polychlorobiphenyls'.

Note 1 Florisil is a registrated trade mark of the Floridin Company, Pittsburgh,

USA.

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