DKS 2471:2013

KENYA STANDARD DKS 2471:2013

Methanol for Industrial Use —

Specification
DKS 2471:2013
DKS 2471:2013

TECHNICAL COMMITTEE REPRESENTATION

The following organizations were represented on the Technical Committee:

University of Nairobi
Government Chemist
MOR-Materials Dept.
Agro Chemical and Food Company
Kenyatta University
Spectre International
Associated Battery Manufacturers
Marshall Fowler
Agrochemical Association of Kenya
Galaxy Paints
Tata Chemicals Magadi
Associated Battery Manufacturers
Athi River Mining
KIRDI
Eastern Chemical Industries
Unilever
Pan Africa Chemicals Ltd
Consumer Information Network
Kenya Medical Services
Kenya Bureau of Standards Secretariat

REVISION OF KENYA STANDARDS

In order to keep abreast of progress in industry, Kenya Standards shall be regularly reviewed. Suggestions for improvements to published standards,
addressed to the Managing Director, Kenya Bureau of Standards, are welcome.

© Kenya Bureau of Standards, 2013

Copyright. Users are reminded that by virtue of section of the Copyright Act, Cap. 12 of 2001 of the Laws of Kenya, copyright subsists in
all Kenya Standards and except as provided under section 26 of this Act, no Kenya Standard produced by Kenya Bureau of Standards
may be reproduced, stored in a retrieval system in any form or transmitted by any means without prior permission in writing from the
Managing Director.

ISBN 9966-07-140-7
DKS 2471:2013

DKS 2471:2013

PREFACE

This Kenya Standard was prepared by the Technical Committee on Industrial Solvents and Chemicals
under the authority of Kenya Bureau of Standards.

Methanol, with a chemical formula, CH3OH is a light, volatile colourless simple flamable liquid with a
distinctive odor. It is used as an antifreeze, as fuel, solvent and as a denaturant for ethanol. It also finds
use in producing biodiesel through transesterification.

Its similarity to ethanol in terms of appearence and odour and its relative low price to ethanol makes it
prone to misuse. It has adverse health effects including causing permanent blindness and even death,

The standard has addressed safety concerns, test methods including determination of sulphur
compounds. It has captured marking requirements as well.

During the development of this standard, reference was made to the following publications:

• BS 506-1:1987 Methanol for industrial use- Part 1: Specification for methanol

• BS 506-2 1984 – Methanol for industrial use – Part 2: Methods of test

Assistance from these sources is greatly acknowledged.

DKS 2471:2013

DKS 2471:2013

Methanol for Industrial Use – Specification

1. Scope:

This Kenyan Standard specifies requirements and methods of test for methanol for industrial use.

2. Requirements

Requirements
i. Appearance Clear and free from Visual
matter in suspension
ii. Colour in Hazen Units 15 maximum KS 1180
o
iii. Density at 20 C, g/ml 0.791-0.794 KS 1180

o
iv. Distillation range at 1013mbar, C Initial 64.0 KS 1180

Dry point 65.0

v. Residue on evaporation %m/m 0.001 maximum KS 1180
vi. Miscibility with water Shall not show Annex A
opalescence when
mixed with distilled
water.
vii. Acidity %m/m 0.003 maximum and Annex B
shall not be alkaline to
phenolphthalein
viii. Aldehydes and ketones %m/m as acetone 0.005 Annex E
CH3COCH3
ix. Sulphur compounds % m/m 0.0001 maximum Annex D
x. Permanganate test Shall not cause Annex C
potassium
permanganate solution
to fade in 30 minutes to
match or be lighter than
matching solution
xi. Water content% m/m of water 0.1maximum KS 1180
DKS 2471:2013

Marking and packaging

Methanol shall be packed in suitable and serviceable containers and marked indelibly with the
following information.

(i) Name of product

(ii) Manufacturer’s name and/or registered trade mark; and address.

(iii) Net content

(iv) The word ‘inflammable’ plus its international symbol.

(v) Country of origin.

(vi) Batch/Lot number
(vii) The precautionary measures do not inhale or ingest

Annex A

Test for miscibility with water

A.1 Principle

Addition of water to a test portion, under specified conditions and examination for opalescence.

A.2 Reagent

During the analysis, use only distilled water.

A.3 Apparatus

Ordinary laboratory apparatus and two matched Nessler cylinders, of capacity 100ml.

A.4 Procedure

Test portion:of the sample, place the test portion in one of the nessler cylinders and dilute with water to
o
the 100ml mark. Mix and adjust the temperature to about 20 C. Place 100ml of water in the other nessler
cylinder.

Examine the cylinder containing the test solution vertically for opalescence, against a black background
with side illumination, using the second nessler cylinder containing water as the standard.

Report the dilution-ratio of the test portion and the presence of or absence of opalescence.
DKS 2471:2013

Annex B

Detection of Alkalinity or determination of acidity to phenolphthalein

B.1 Principle

Dilution of a test portion with carbon dioxide-free water. Checking whether the test portion is alkaline or
acidic to phenolphthalein , and if appropriate, determination of acidity by titration with standard volumetric
sodium hydroxide solution.

B.2 Reagents
During the analysis, use only reagents of recognized analytical grade and only distilled water or water of
equivalent purity, carbon dioxide-free, recently prepared.

B.2.1 Water, carbon dioxide-free. Boil distilled water and allow it to cool in a flask fitted with a stopper
carrying a soda-lime guard-tube.

B.2.2 Sodium hydroxide, standard volumetric solution, c(NaOH) = 0,1 mol/l.

B.2.3 Phenolphthalein, 5 g/l ethanolic solution. Dissolve 0,5 g of phenolphthalein in 100 ml of 95 % (V/V)
ethanol and add the sodium hydroxide solution until a pale pink coloration is obtained.

B.3 Apparatus
Ordinary laboratory apparatus, and

B.3.1 Conical flask, of borosilicate glass, of capacity 500 ml, fitted with a ground glass stopper carrying a
soda-lime guard-tube.

B.3.2 Burette, of capacity 10 ml, graduated in 0.02 ml.

B.4 Procedure
B.4.1 Test portion
Take 100 ± 0,1 ml of the laboratory sample.

B.4.2 Determination
Place 100 ml of the water in the conical flask add 0.5 ml of the phenolphthalein solution and restore the
pale pink coloration by the addition of 1 or 2 drops of the sodium hydroxide solution. Add the test portion
and a further 0.5 ml of the phenolphthalein solution and note whether the solution is alkaline; if acid,
titrate the test solution with the sodium hydroxide solution stoppering the flask and swirling its contents
after each addition, until a pink coloration, persisting for about 15 s, is obtained. Shake the contents of the
flask, with the stopper in position, after each addition of sodium hydroxide solution.

B.4.3 Alkaline products

Indicate whether the product is alkaline to phenolphthalein.

B.4.4 Acidic products

The acidity, expressed as a percentage by mass of formic acid (HCOOH), is given by the formula
where
DKS 2471:2013

V is the volume, in millilitres, of the sodium hydroxide solution used for thedetermination;

is the density, in grams per millilitre, of the sample at 20 °C

0.0046 is the mass, in grams, of formic acid corresponding to 1.00 ml of sodium hydroxide solution,
c(NaOH) = 0.100 mol/l.

NOTE: If the concentration of the standard volumetric solution used is not exactly as specified in the list
of reagents, an appropriate correction should be made.

Annex C

Determination of Permanganate time

C.1 Permanganate time is the number minutes required, after adding 2ml of 0.2g/l potassium
permanganate solution to 50ml of the sample, for the colour to match that of a colour standard [(cobalt(II)
chloride and Uranyl nitrate colour standard].

C.2 Reagents

C.2.1 Potassium Permanganate, 0.2g/L solution. Use water previously boiled for 30min with sufficient
dilute potassium permanganate solution to give a stable faint pink coloration . Cool the water to ambient
temperature before preparation of the solution. Prepare this solution immediately before use and protect
from light.

C.2.2 Cobalt(II) Chloride and Uranyl nitrate, colour standard.

To 5ml of a 50g/l solution of cobalt(II) chloride hexahydrate (COCl2.6H2O), add 7ml of a 40g/l solution of
Uranyl nitrate hexahydrate [UO2(NO3)2.6H2O], and dilute with water to 50ml. Prepare this solution on the
day of use.

C.3 Apparatus
C.3.1 Ordinary laboratory apparatus
o
C.3.2 Water bath, capable of being controlled at 15±0.2 C

C.3.3 Two matched cylinders, of capacity 100ml, of transparent and colourless glass, graduated at
50ml and fitted with ground glass stoppers

C.3.4 Burrete of capacity 10ml, graduated at 50ml divisions

DKS 2471:2013

C.4 Procedure

C.4.1 Carry out the test as soon as possible after receiving the sample. Rinse one of the cylinders first
with 15-20ml of hydrochloric acid, approximately 1.19g/ml, about 38%(m/m) solution, then six times with
tap water, twice with distilled water and finally with some of the laboratory sample.
o
Immediately fill the cylinder to the mark with more of the laboratory sample at 15 C

Fill the second cylinder to the mark with the colour standard.

Place the cylinder containing the test portion in the water bath controlled at 15 ±0.2oC so that the water
level in the bath is approximately 25mm below the neck of the cylinder. After 15 min, remove the cylinder
from the water bath and using the burrete, add 2ml of potassium permanganate solution. Note the time.
Immediately, stopper the cylinder, shake and replace it in the water bath.

Remove the cylinder from the water bath, at intervals of 1min and compare the colour, viewing vertically
downwards against a white background with the colour of the colour standard. Avoid exposing the test
solution to strong daylight.

Note the time at which the colour of the test solution matches that of the colour standard.

Report the time in minutes from the addition of the potassium permanganate solution for the colour of the
test solution to match that of the colour standard.

Annex D

Determination Of Sulphur Compounds

D.1 Applicability

The method determines all sulphur compounds normally encountered in methanol for industrial use.It
does not dertermine alkyl sulphones and other oxygen bounded sulphur compounds.

D.2 Principle

Reaction with Raney nickel of sulphur compounds in a test position to form nickel sulphide which is then
decomposed with hydrochloric acid;the hydrogen sulphide evolved is absorbed in sodium hydroxide
solution before being titrated with standardized mercury [11]acetate solution in the presence of dithizone
as indicator.

D.3 Apparatus

D.3.1 Ordinary laboratory apparatus and reduction apparatus as shown in figure 1.Burette,of capacity
10ml,graduated in 0.02ml

During the analysis, use only reagents of recognized analytical grade and only distilled water or water of
equivalent purity.
DKS 2471:2013

D.3.2 Nitrogen, gas free from carbon dioxide.

D.3.3 Acetone,

D.3.4 Raney nickel

WARNING-Raney nickel is spontaneously flammable in air. After use, it is essential to dispose of it

immediately by dissolving in dilute hydrochloric acid.

Treat 10g of 50/50 nickel/aluminium alloy with 100ml of 100g/l sodium hydroxide solutions, cooling with
ice while the reaction proceeds. Wash the Raney nickel three times with water ,remove the water by
decantation and store the Raney nickel under 100ml of propan-2-ol.Raney nickel prepared in this way
retains its activity for about 3 days.5ml of this suspension will reduce quantitatively 1,0 to 1,5mg of
organic sulphur to hydrogen sulphide.

D.3.5 A stabilized form of Raney nickel is available commercially in pellet form.

D.3.6 Sodium hydroxide, approximately 40 g/l solution.

D.3.7 Hydrochloric acid solution.

Dilute 3 volumes of concentrated hydrochloric acid, approximately 1.19 g/ml, with 2 volumes of water

D.3.8 Mercury[11] acetat solutions

WARNING-mercury compounds are very toxic.lt essential that adequate precautions are taken
including a voidance of inhalation of mercury oxide dust. The disposal of mercury compounds
may be subject to local restrictions.

Dissolve 0,200g of mercury (II) oxide in 25 ml of water containing 1 ml of glacial acetic acid, and dilute to
1 000 ml with water.

D.3.9 Methanol, sulphur-free.

Into a 2 litre round bottom flask with two necks, measure 10 ml of the Raney nickel suspension;
alternatively, measure 20 ml of acetone into the flask, add 0.5 g (1 pellet) of Raney nickel, warm until the
pellet has disintegrated and decant the acetone. Add 1 500 ml of methanol, place the flask into a heating
mantle and fix it with reflux condenser. Insert the nitrogen lead into the second neck and pass in gas at
the rate of two bubbles per second.

Heat until slight effervescence is observed on the methanol surface and continues for 30 min. Turn off
the gas flow and the heating, and allow the nickel to settle. Decant the methanol into a flask, and distil .
reject the first 250 ml and collect the next 1 000 ml, rejecting the remainder.

D.3.10 Dithizone, 1 g/l solution in acetone.

D.4 Procedure

D.4.1 Transfer 5ml of the Raney nickel suspension to the flask of reduction apparatus; alternatively
,measure 10ml of the acetone into the flask, add 0.25g(½ pellet)of Raney nickel and warm until the pellet
has disintegrated and decant the acetone. Add 100ml of the sample, place the flask into a heating mantle
and pass the nitrogen through at the rate of about 31h.Adjust the temperature of the heating mantle until
DKS 2471:2013

slight effervescence appears on the surface (just below boiling point). Continue for 30 min, swirling the
flask at intervals.

Transfer 10 ml of the sodium hydroxide solution and 10 ml of the acetone to the absorber. Add two drops
of the dithizone solution and, by means of the burette, one drop of the mercury (II) acetate solution to the
absorber.

NOTE: The colour change should be from yellow to pink. Liberation of hydrogen sulphide will reverse this
colour change.

D.4.2 Transfer 15 ml of the hydrochloric acid solution to the dropping funnel, switch off the heating
mantle, and attach a second nitrogen lead to the glass tube in the top of the dropping funnel so as to
apply a slight gas pressure. Admit the acid, a few millimetres at a time, to the flask and begin titrating the
contents of the absorber with the mercury (II) acetate solution, as necessary to restore the pink colour.
When all the acid has been added disconnect the nitrogen supply to the top of the dropping funnel ,
increase the nitrogen flowrate to about 12 l/h, switch on the heating mantle again and continue heating
for a further 20 min. When all the hydrogen sulphide has apparently been titrated, switch off the heating
mantle, divert the flow of nitrogen momentarily, cool the flask by blowing on it, allow the absorbent to
travel up the delivery tube in the absorber (to recover any hydrogen sulphide which may be absorbed on
its surface) and complete the titration.

D.4.3 Carry out a blank test by following the same procedure and using the same quantities of reagents
as in the determination but using 100 ml of the sulphur-free methanol in place of the test portion.

D.4.4 Standardization of the mercury(II) acetate solution

Add a known amount of an aliphatic sulphur compound (e.g. di-iosoamyl sulphide), equivalent to 0.65 mg
to 0,85 mg of sulphur-free methanol. Carry out a determination by the method using 100 ml of this
solution. From the volume of the mercury(II) acetate solution required in the titration, calculate the mass,
in micrograms, of sulphur equivalent to 1 ml of the mercury(II) acetate solution.

D.5 Expression of results

The sulphur compound content expressed as a percentage by mass of sulphur (S) is given by the
formula.
DKS 2471:2013

Where m is the mass in micrograms, of sulphur equivalent to 1 ml of mercury(II)acetate solution.

T1 is the volume, in millilitres of the mercury (II) acetate solution required in the test determination;

T2 is the volume, in millilitres, of mercury(II) acetate solution required in the blank test;

ρ is the density, in grams per millilitre, of the sample at 20°C.

DKS 2471:2013

Figure 1 — Reduction apparatus for the determination of sulphur compounds

Annex E
Estimation of content of carbonyl compounds present in small
amounts — Spectrometric method

E.1 Applicability
The method is applicable to products having carbonyl compounds contents, expressed as formaldehyde,
between 0.000 2 and 0.01 % (m/m). Reaction in acid medium of the carbonyl compounds in a test portion
with 2,4-dinitrophenylhydrazine. Formation of the corresponding 2,4-dinitrophenylhydrazones, which, after
DKS 2471:2013

making the solution alkaline, take on a yellowish-red coloration. Spectrometric measurement of this red
coloration at a wavelength of about 445 nm.

E.2 Reagents

During the analysis, use only reagents of recognized analytical grade and only distilled water or water of
equivalent purity.

E.2.1 Methanol, free from carbonyl compounds, purified as follows.

Boil under reflux 1 000 ml of methanol with 10 g of 2,4-dinitrophenylhydrazine and 10 drops of the
hydrochloric acid solution for 2 to 3 h. Distil the methanol slowly using a Widmer distillation column, about
300 mm long and about 25 mm in diameter, or any other suitable column. Reject the first 75 ml of
distillate and collect the next 850 ml, rejecting the remainder. If the distillate is coloured, redistil it.

E.2.2 2,4-Dinitrophenylhydrazine, saturated solution in the methanol (11.3.1) at ambient temperature

[about 0,06 % (m/m) solution].

WARNING. 2,4-dinitrophenylhydrazine is harmful if inhaled, if in contact with skin or eyes, or if

swallowed and carries the risk of explosion by shock, friction, heat or by other sources ofignition,
particularly when dry. Inhalation of dust and contact with skin and eyes should be avoided.
Particular care should be taken when using the dry material.

E.2.3 Hydrochloric acid, Q approximately 1.19 g/ml, about 38 % (m/m) solution.

E.2.4 Potassium hydroxide, 100 g/l solution in a 70 % (V/V) solution of the methanol

E.2.5 Carbonyl compounds, standard solution corresponding to 0.030 g of carbonyl compounds,

expressed as formaldehyde, per litre. Weigh, to the nearest 0.000 1 g, 1.200 g of acetophenone, and
dissolve it in a little of the methanol . Transfer quantitatively to a 100 ml one-mark volumetric flask, dilute
to the mark with the methanol and mix. Take 5.0 ml of this solution, transfer it to a 500 ml one-mark
volumetric flask, dilute to the mark with the methanol and mix. 1 ml of this standard solution contains 30
4g of carbonyl compounds, expressed as Formaldehyde.

E.3 Apparatus
Ordinary laboratory apparatus, and

E.3.1 Water bath, capable of being controlled at 50 ± 2 °C.

E.3.2 Test tubes, fitted with ground glass stoppers.

E.3.3 Spectrometer with a radiation selector for continuous variation, fitted with cells of optical path
length 1 cm, or

E.3.4 Spectrometer with a radiation selector for discontinuous variation, fitted with filters providing
maximum transmission at a wavelength of about 445 nm.

E.4 Procedure
E.4.1 Test portion
Take 1.0 ml of the laboratory sample and place it in one of the test tubes
DKS 2471:2013

E.4.2 Blank test

Carry out a blank test at the same time as the determination, following the same procedure and using the
same quantities of all the reagents used for the determination, but replacing the test portion by 1.0 ml of
the methanol

E.4.3 Preparation of the calibration graph

E.4.3.1 Preparation of dilute standard solutions, with a view to preparation of standard colorimetric
Solutions Into a series of seven 25 ml one-mark volumetric flasks, introduce the volumes of the standard
carbonyl compounds solution indicated in the following table and dilute to the mark with the methanol

Standard Carbony Compounds Corresponding mass of Mass of carbonyl compounds

Solution carbonyl compounds, in 1 ml of dilute standard
expressed as solution
HCHO

ml µg µg
a
0 0 0
1.5 45.0 1.8
2.5 75.0 3.0
5.0 150.0 6.0
7.5 225.0 9.0
10.0 300.0 12.0
12.5 375.0 15.0

a
Compensation solution.

E.3.3.2 Preparation of standard colorimetric solutions, for spectrometric measurements carried

out in cells of optical path length 1 cm place 1.0 ml of each of the dilute standard solutions and treat the
contents of each tube according to the procedure E.3.3.3.

E.3.3.3 Colour development

Add 1,0 ml of the 2,4-dinitrophenylhydrazine solution and one drop of the hydrochloric acid solution
Stopper the tubes and heat for 30 min using the water bath controlled at 50 ± 2 °C. Allow to cool, add 5.0
ml of the potassium hydroxide solution mix, and allow to stand for 5 min.

E.3.3.4 Spectrometric measurements

Immediately carry out the spectrometric measurements on each of the standard colorimetric solutions,
using either the spectrometer set at a wavelength of about 445 nm, or the spectrometer fitted with
appropriate filters, after having first adjusted the instrument to zero absorbance against the methanol

E.3.3.5 Plotting the graph

Deduct the absorbance of the compensation solution from those of the standard colorimetric solutions.
Plot a graph having, for example, the masses, in micrograms, of carbonyl compounds, expressed as
HCHO, in 1 ml of each dilute standard solution as abscissae, and the corresponding corrected values of
absorbance as ordinates.
DKS 2471:2013

E.4 Determination

E.4.1 Colour development

Treat the test portion in the test tube, following the procedure specified in E.3.3.3.

E..4.2 Spectrometric measurements

Immediately carry out the spectrometric measurements on the coloured test solution and the blank test
solution following the procedures specified in E.3.3.4, after having adjusted the instrument to zero
absorbance against the methanol
NOTE If the absorbance exceeds the maximum of the calibration graph, repeat the determination using
as the test portion 1.0 ml of a test solution prepared by diluting 1.0 ml of the laboratory sample with an
appropriate volume (not more than 4.0 ml) of the methanol

E.5 Expression of results

By means of the calibration graph determine the masses of carbonyl compounds corresponding to the
values of the spectrometric measurements. The carbonyl compounds content, expressed as a
percentage by mass of formaldehyde (HCHO), is given by the formula

where

m0 is the mass, in micrograms, of carbonyl compounds found in the blank test

solution

m1 is the mass, in micrograms, of carbonyl compounds found in the test solution;

is the density, in grams per millilitre, of the sample at 20 °C

rD is the ratio of the volume of the diluted test solution to the volume of the aliquot portion taken for the
determination (if the test portion was not diluted, rD is equal to 1);

1,0 is the volume, in millilitres, of the test portion. The results can also be expressed as a percentage by
mass of acetone [(CH3)2CO] by multiplying the above results by 1,93.