MS 417 : PART 7 : 2001

MALAYSIAN
STANDARD
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THE ANALYSIS OF FERTILIZERS :

PART 7 : METHOD FOR THE
DETERMINATION OF BORON
(SECOND REVISION)

ICS : 65.080

Descriptors : fertilizers, boron, colorimetric, titrimetric

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 DEVELOPMENT OF MALAYSIAN STANDARDS
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 MS 417 : PART 7 : 2001

CONTENTS

Page

Committee representation....................................................................................... ii
Foreword................................................................................................................. iii
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1 Scope...................................................................................................................... 1

2 Referenced documents…………………………………………………………………. 1

3 Sampling and sample preparation........................................................................... 1

4 Quality of test reagents............................................................................................ 1

5 Calibrated volumetric glassware...................................................…........................ 1

6 Determination of boron.........................................................…................................ 2

Figure 1 Flow diagram for the determination of boron in borate fertilizer

on the autoanalyser…………………………………………………………………… 5

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 MS 417 : PART 7 : 2001

Committee representation

The Chemical and Materials Industry Standards Committee (ISC B) under whose supervision this Malaysian
Standard was developed, comprises representatives from the following organisations :

Department of Mineral and Geoscience

Department of Standards Malaysia
Federation of Malaysian Manufacturers
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Malaysian Ceramic Industry Group

Malaysian Institute of Chemistry
Malaysian Paint Manufacturers Association
Malaysian Pulp and Paper Manufacturers Association
Malaysian Textile Manufacturers Association
Ministry of Agriculture (Department of Agriculture)
Ministry of Defence (Defence Science and Technology Centre)
Ministry of Science, Technology and the Environment (Department of Chemistry, Malaysia)
Universiti Malaya

The Technical Committee on Fertilizers which developed this Malaysian Standard consists of representatives from
the following organisations:

Department of Agriculture, Peninsular Malaysia

Felda Agricultural Services Sdn. Bhd.
Fertilizer Industry Association of Malaysia
Malaysian Agriculture Research and Development Institute
Malaysian Palm Oil Association
Malaysian Palm Oil Board
Malaysian Rubber Board
Malaysian Rubber Producers’ Council
Malaysian Society of Soil Science
Rubber Industry and Smallholder Development Authority
SIRIM QAS Sdn Bhd
SIRIM Berhad (Secretariat)

Co-opted members :

CCM Fertilizers Sdn Bhd

Espek Agrotech and Advisory Services
Petronas Research and Scientific Services
Sabrinatech Agri Sdn. Bhd.

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 MS 417 : PART 7 : 2001

FOREWORD

This Malaysian Standard was developed by the Technical Committee on Fertilizers under the
authority of the Chemical and Materials Industry Standards Committee.

This Malaysian Standard is the second revision of MS 417 : Part 7 : 1994, The analysis of
fertilizers: Part 7: Method for the determination of boron.
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This Standard is based on the current practices and requirements of the local industries and
relevant authorities.

The major changes featured in this revision are the inclusion of :

a) azomethine method using UV/visible spectrophotometer; and

b) titration method, which was extracted from ISO 1916 : 1972, Disodium tetraborates
for industrial use – Determination of sodium oxide and boric oxide contents and loss
on ignition.

MS 417, The analysis of fertilizers, consists of the following parts :

Part 1 : Method of sampling and sample preparation

Part 2 : Method for the determination of moisture content, particle size and ash content

Part 3 : Method for the determination of nitrogen

Part 4 : Method for the determination of phosphorus

Part 5 : Method for the determination of potassium

Part 6 : Method for the determination of magnesium

Part 7 : Method for the determination of boron

Part 8 : Method for the determination of secondary properties

This revised Malaysian Standard cancels and replaces MS 417 : Part 7 : 1994.

Compliance with a Malaysian Standard does not of itself confer immunity from legal
obligations.

iii
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 MS 417 : PART 7 : 2001

THE ANALYSIS OF FERTILIZERS :

PART 7 : METHOD FOR THE DETERMINATION OF BORON
(SECOND REVISION)

1. Scope
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This part of MS 417 prescribes methods for the determination of boron in fertilizers.

2. Referenced documents

The following referenced documents contain provisions which, through reference in this text,
constitute provisions of this Malaysian Standard. For dated references, where there are
subsequent amendments to, or revisions of, any of these publications do not apply. However,
parties to agreements based on this Malaysian Standard are encouraged to investigate the
possibility of applying the most recent editions of the referenced documents. For undated
references, the latest edition of the publication referred to applies.

MS 417: Part 1: 1994, Method of sampling and sample preparation (First revision).

3. Sampling and sample preparation

3.1 The method of sampling fertilizers, both in packages and in bulk, shall be carried out
according to MS 417: Part 1.

3.2 Preparation of sample for analysis shall also be carried out according to MS 417 :
Part 1.

4. Quality of test reagents

4.1 Unless otherwise specified, the reagents used for analysis described in this standard
shall be of analytical reagent grade and shall not contain any impurities that will affect the
results of the analysis.

4.2 Unless otherwise specified, all references to water shall be understood to mean
distilled water or water of equal purity.

5. Calibrated volumetric glassware

Where high accuracy is required, calibrated volumetric glassware shall be used at the
temperature at which they are calibrated; if used at other temperatures, appropriate
corrections should be made.

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 MS 417 : PART 7 : 2001

6. Determination of boron

Boron shall be determined by one of the following methods, whichever applicable:

a) Carmine method;
b) Azomethine method; and
c) Titration method.
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In case of dispute (excluding disodium tetraborate), the carmine method shall be used.

6.1 Carmine method

6.1.1 Principle

Boron is measured colorimetrically in this method.

6.1.2 Apparatus

6.1.2.1 Spectrophotometer, capable of measuring at 585 nm.

6.1.2.2 Dry test-tube, soda glass/plastic.

6.1.3 Reagents

6.1.3.1 Hydrochloric acid, 6M

Mix 270 mL of concentrated hydrochloric acid and 230 mL of water. Store in a bottle.

6.1.3.2 Carmine in concentrated sulphuric acid, 0.05 % (v/w)

Weigh accurately 1.25 g of carmine into a freshly opened bottle of 2.5 L concentrated
sulphuric acid. Shake for two days on a shaking machine.

6.1.3.3 Boron standard solution

Weigh accurately 0.2860 g of boric acid into a 500 mL volumetric flask. Add water and make
to the mark. This solution contains 100 mg/L boron. Dilute to obtain working standard
solutions containing 1 mg/L to 5 mg/L boron.

6.1.3.4 Sulphuric acid, concentrated (S.G. = 1.84).

6.1.4 Procedure

6.1.4.1 Preparation of sample solution and analysis

Weigh to the nearest mg about 1 g of the sample and transfer into a 1 litre flask. Add about
500 mL of water to dissolve the sample. Make up to the mark and shake well.

Pipette 10 mL of the solution into a 500 mL flask and make up to volume. Pipette 2 mL of the
diluted solution into a dry test-tube.

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 MS 417 : PART 7 : 2001

Add slowly 10 mL of concentrated sulphuric acid. Cover the test-tube and set aside to cool.
When cool, add 10 mL of the 0.05 % carmine solution. Mix well by pouring from one test-tube
to another several times. Set aside for 2 h for colour development. Measure the absorption at
585 nm using a spectrophotometer.

Using the working standards, calibrate the spectrophotometer as stated by the procedure as
described above for the sample.
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6.1.5 Calculation

6.1.5.1 Total boron (as B2O3) content expressed as percentage of the sample:

C x D x 0.322
W

where,

C is the concentration of boron in mg/L of diluted sample solution;

D is the dilution factor; and

W is the weight in grammes of sample taken for determination.

6.2 Azomethine method

6.2.1 Principle

Azomethine-H forms a yellow complex with simple borates. This method has the advantage
over the carmine method for not using concentrated acid in the reaction. The buffer includes
masking agents to prevent interference by copper, iron or aluminium.

6.2.2 Using autoanalyser

6.2.2.1 Reagents

a) Buffer solution

Weigh 280 g ammonium acetate, 20 g potassium acetate, 20 g ethylenediaminetetraacetic

acid disodium salt (EDTA) and 8 g nitrilotriacetic acid and dissolve in 400 mL warm water.
Add 130 mL acetic acid and 2 mL of a suitable wetting agent. Filter the solution.

b) Azomethine solution

Weigh 4.5 g azomethine and 10 g L-ascorbic acid and dissolve in 500 mL water. Warm
gently to dissolve. Store in a dark bottle in a refrigerator.

The reagent should be discarded after two weeks.

NOTE. Advisable to use a fresh solution for each analysis

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 MS 417 : PART 7 : 2001

c) Boron standard solution

Dissolve 0.2860 g of boric acid (H3BO3) in water and dilute to 500 mL. Store in a
polyethylene bottle. The solution contains 100 mg/L boron.

d) Boron working standards

Dilute the standard boron solution with water to obtain a suitable range of standard solutions
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containing 1 mg/L to 10 mg/L boron.

6.2.2.2 Procedure

Preparation of sample solution and analysis

Weigh to the nearest mg about 1 g of the sample into a 1 litre volumetric flask. Add water to
dissolve, shake well and dilute to the mark. Filter if necessary.

Pipette 20 mL into a 500 mL volumetric flask. Add water, shake well and dilute to the mark.
Store about 15 mL in a test tube.

Calibrate the instrument with the boron solutions, over the range 0 mg/L to 10 mg/L boron,
after which unknown samples may be analysed at the rate of 40 samples per hour.

Figure 1 is a typical manifold diagram for the determination of boron. Other manifold
diagrams may also be used provided similar results are obtained.

6.2.2.3 Calculation

a) Total boron (as B2O3) content expressed as percentage of the sample:

C x D x 0.322
W

where,

C is the concentration of boron in diluted sample solution;

D is the dilution factor; and

W is the weight in grammes of the sample taken.

b) To obtain total boron (as B2O3) content of the dry sample, the moisture content
should be taken into consideration.

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 MS 417 : PART 7 : 2001
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Figure 1. Flow diagram for the determination of boron in borate fertilizer on the
autoanalyser

6.2.3 Using UV/Visible spectrophotometer

6.2.3.1 Reagents

a) Ammonium acetate buffer

Weigh 500 g ammonium acetate and make up to 1 liter with water. Adjust pH to 5.1 with 20
% sulphuric acid.

b) Ethylenediaminetetraacetic acid disodium salt (EDTA)

Weigh 18.61 g EDTA and make up to 1 liter with water.

c) Azomethine solution

Weigh 0.45 g azomethine and add 1 g L-ascorbic acid and then dissolved in 50 mL water.
Before use, add 25 mL ammonium acetate solution and make up to 100 mL with water.

NOTE. Advisable to use a fresh solution for each analysis.

d) Sulphuric acid, 0.35 M

Mix 20 mL of 98 % sulphuric acid with water and make up to 1 liter of solution.

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 MS 417 : PART 7 : 2001

e) Boron standard solution

Dissolve 2.8577 g of boric acid in 0.35 M sulphuric acid and make up to 1 liter. This solution
contains 500 mg/L boron.

f) Boron working solutions

Dilute the standard boron solution with 0.35 M sulphuric acid to obtain a suitable range of
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standard solutions containing 0.5 mg/L to 3.0 mg/L boron.

6.2.3.2 Procedure

Preparation of sample solution and analysis

Weigh to the nearest mg about 5 g of the sample into a suitable container. Add 10 mL of
concentrated hydrochloric acid and a suitable volume of water. Heat the solution until it boils.
Cool and transfer to a 500 mL volumetric flask and dilute to the mark.

Dilute the sample solution if necessary.

Pipette 1 mL of sample into a sample tube followed by 0.5 ML of EDTA and 1 mL of

ammonium acetate. Mix well and allow to stand for 15 min.

Add 1 mL of azomethine solution and allow the colour to develop for 90 min.

Measure the absorption at 420 nm using a spectrophotometer

Using the working standards, calibrate the spectrophotometer as stated by the procedure as
described above for the sample.

6.2.3.3 Calculation

Total boron as B2O3 content expressed as percentage of the sample:

C × D × 0.322
W

where,

C is the concentration of boron in mg/L of diluted sample solution;

D is the dilution factor (if any); and

W is the weight in gramme of sample taken for determination.

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 MS 417 : PART 7 : 2001

6.3 Titration method

6.3.1 Principle

The method is suitable for the determination of boron (as B2O3) content in disodium
tetraborate. An acidified sample is titrated against sodium hydroxide in the presence of
mannitol with phenolphthalein as an indicator.
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6.3.2 Apparatus

6.3.2.1 Conical flask

6.3.2.2 Weighing machine

6.3.3 Reagents

6.3.3.1 Mannitol, neutral (alternatively sorbitol, neutral)

6.3.3.2 Standard hydrochloric acid solution, 0.5 M

6.3.3.3 Standard sodium hydroxide solution, 0.5 M

6.3.3.4 Screened methyl red

Dissolve 0.5 g methyl red indicator solution in 500 mL methanol and dissolve 0.5 g methylene
blue in 500 mL methanol. Mix the two solutions.

6.3.3.5 Phenolphthalein indicator solution, 0.2 % (w/v)

Dissolve 2 g phenolphthalein in 600 mL methanol. Add 0.1 M sodium hydroxide until it is

neutral and make up to 1 litre with distilled water, when a very faint pink colour first appears.

6.3.3.6 Carbon dioxide-free distilled water or water of equal purity

6.3.4 Procedure

6.3.4.1 Weigh to the nearest mg about 1 g sample and transfer to a conical flask. Add about
70 mL distilled water.

6.3.4.2 Heat to dissolve sample and then allow to cool.

6.3.4.3 Add 6 to 8 drops of screened methyl red indicator solution followed by 25 mL of 0.5 M
hydrochloric acid solution.

6.3.4.4 Titrate with 0.5 M sodium hydroxide solution until colour changes from purple to
green.

6.3.4.5 Cool sample solution, add 15 g mannitol and 6 to 8 drops phenolphthalein indicator
solution.

6.3.4.6 Titrate with 0.5 M sodium hydroxide solution until colour changes to pink.

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 MS 417 : PART 7 : 2001

6.3.5 Calculation

6.3.5.1 Total boron (as B2O3) content expressed as percentage of the sample:

V
x 1.741
W

where,
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V is the volume (mL) of 0.5 M NaOH obtained in the titration after addition of
mannitol; and

W is the weight in grammes (g) of the test sample.

8
 Acknowledgements
Dr. Lau Chee Heng/Encik Lee San Chin (Chairman), Puan Nageswary I. (Secretary), Dr
Abdul Aziz Bidin, Encik Leong Cheng Woh, Encik Raja Subramaniam, Dr Zin Z. Zakaria, Dr
Alias Husin, Encik Tee Sze Peng, Encik R. Guna Seelan, Encik Amir Hamzah Yasak, Dr Che
Fauziah Ishak, Dr Leong Tat Thim, Dr Zainab Hamzah, Dr Ahmad Husni, Encik Hanifudin
Abdul Rahman, Dr Lim Chin Huat, Encik B. Thayananthan, Dr Ahmad Husni, Puan Sarifah
Rejab
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