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E
IMO
SUB-COMMITTEE ON DANGEROUS
GOODS, SOLID CARGOES AND
CONTAINERS
14th session
Agenda item 3
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17 July 2009
Original: SPANISH
SUMMARY
Executive summary:
Strategic direction:
High-level action:
5.2
Planned output:
5.2.3
Action to be taken:
Paragraph 10
Related documents:
Introduction
1
In the IMDG Code, sodium nitrate and potassium nitrate mixture (UN No. 1499) is
classified as class 5.1, oxidizing substance, packing group III.
2
Sodium nitrate and potassium nitrate mixture, regardless of its chemical state (ratio of
sodium nitrate to potassium nitrate), is marketed in the form of prilled nuggets or beads.
For reasons of economy, this document is printed in a limited number. Delegates are
kindly asked to bring their copies to meetings and not to request additional copies.
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-2-
3
Sodium nitrate and potassium nitrate mixture is used in agricultural applications.
The 67:33 mixture of NaNO3 : KNO3 is a useful source of K and N for use in feeding plants,
fruits and industrial crops. It is mainly applied directly to the soil, either on its own or in
combination with other fertilizers. To differentiate it from other nitrates, it is normally stained
with inorganic red pigment.
4
The Chilean company, SQM S.A., is one of the worlds leading producers of sodium and
potassium nitrates.
Discussion
5
In June 2009 the TNO Prins Maurits Laboratory, of the Netherlands, tested a sodium
nitrate/potassium nitrate mixture produced by SQM in the form of beads or nuggets, in
accordance with Test No. O.1 (Test for oxidizing solids) from the UN Manual of Tests and
Criteria.
The results are shown in the table below:
Substance
Reference
Sodium nitrate and potassium
nitrate mixture: agricultural
grade, beads
*
Substance/cellulose ratio
3:7
1:1; 4:1
6
In the tested sample, the 1:1 mixtures had a greater mean burning time than
the 3:7 reference mixtures. The 4:1 mixtures did not fully react, and the time given in the table
indicates the end of the combustion period. A considerable quantity of sample material did not
burn, signifying that the sample was not capable of reacting within the allowed time limit for the
reference mixture.
7
According to the UN Manual of Tests and Criteria, any substance which, for mixtures of
sample/cellulose in proportions of both 1:1 and 4:1, has mean burning times greater than
a 3:7 potassium bromate/cellulose mixture, is not classified in class 5.1 as an oxidizing
substance. On the basis of these results, TNO concluded that prilled sodium nitrate/potassium
nitrate does not have oxidizing properties which meet these criteria.
8
For reference, the IMDG Code contains the following special provisions for substances
with similar characteristics, including nitrates:
.1
Sulphur (UN No. 1350, class 4.1, packing group III), Special Provision 242:
Sulphur is not subject to the provisions of this Code when it has been formed to a
specific shape (such as prills, granules, pellets, pastilles or flakes).
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-3.2
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Calcium nitrate (UN No. 1454, class 5.1, packing group III), Special
Provision 208:
The commercial grade of calcium nitrate fertilizer, when consisting mainly of a
double salt (calcium nitrate and ammonium nitrate) containing not more than 10%
ammonium nitrate and at least 12% water of crystallization, is not subject to the
provisions of this Code.
.3
Magnesium nitrate (UN No. 1474, class 5.1, packing group III), Special
provision 332:
Magnesium nitrate hexahydrate is not subject to the provisions of this Code.
The IMDG Code contains the following information on the properties of
potassium nitrate: White crystals or powder. Soluble in water. Mixtures with
combustible material are readily ignited and may burn fiercely. Harmful if
swallowed. Considering the information which has been provided, this does not
take into account all the physical forms in which the product is marketed.
Proposal
9
On the basis of the information provided, the following Special Provision is proposed for
sodium nitrate and potassium nitrate mixture in the form of beads, for inclusion in column 6 of
the entry for UN No. 1499 in the Dangerous Goods List in the IMDG Code:
SP XXX:
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ANNEX
1.
Chemical name:
Description:
Molecular formula:
CAS No.:
Uses:
Producer:
Technical advice:
Value
~ 33%
~ 67%
0.05 2%
0.01 2%
0.005 0.5%
1.28 ton/m3
29
~ 2.3 - 2.5
> 240C
Not determined
TNO DV 2009-C294
Oxidizing properties of three grades of prilled sodium/potassium nitrate
Date:
3 July 2009
Author:
W.A.Mak
Contractor: SQM Industrial SA, Antofagasta, Chile
Project No.: 032.18618/10
Classification: Restricted
No. of pages: Three
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ANNEX
Page 2
1.
Introduction
SQM Industrial SA, Antofagasta, Chile requested TNO Defence, Security and Safety, of
Rijkswijk, Netherlands, to evaluate the oxidizing properties of three grades of prilled sodium
nitrate/potassium nitrate mixture.
Samples of the following grades of sodium nitrate/potassium nitrate were sent for testing:
SPO sodium nitrate and potassium nitrate, prilled.
The objective of the study was to determine the oxidizing properties of the samples, i.e. the
materials capacity to increase combustion in a combustible material. It was agreed to determine
the oxidizing properties using the conical pile test. This method of testing and the associated
criteria are described in the Manual of Tests and Criteria (Fourth ed. rev., test no. O.1) in the
United Nations Recommendations on the Transport of Dangerous Goods. The result of the test
determines whether the material does or does not have oxidizing properties according to
established criteria.
2.
Description of samples
The sample, weighing 2 kg, was sent from Chile to the Netherlands by Intertek Caleb Brett
Chile S.A. on 12 May 2009 and received by TNO in Rijswijk on 20 May 2009. The sample was
wrapped in a sealed plastic bag with a unique seal identification number. Following receipt, the
sample was recorded and stored under ambient conditions. The seal was not broken until it was
time to test the sample. At the request of the contractor a basic determination of particle size was
performed by fractional analysis between 0.85 mm and 3.0 mm, in order to categorize the
material by size. The samples were identified as follows:
SPO
3.
The UN Manual of Tests and Criteria states that if the substance to be tested breaks easily into
smaller pieces, the whole sample must be ground into powder prior to testing, to allow for
reduction in particle size during handling and transportation. After careful inspection of the
beads, it was established that the material does not break easily. Accordingly, the samples were
tested in the form in which they were received. Five separate mixtures of sample and cellulose,
in proportions of 1:1 and 4:1, were prepared and tested. The results are shown in table 1.
For reference purposes, five individual samples of potassium bromate and cellulose were
prepared and tested. The results are shown in table 1.
Table 1 Results of testing
Substance
Ratio
SPO
1:1
4:1
3:7
Reference
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Test 1
148
35
119
Test 2
146
46
108
Burning time(s)
Test 3
Test 4
156
109
63
32
110
119
Test 5
124
35
125
mean
137
42
116
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ANNEX
Page 3
For the sample tested, the 1:1 mixtures had a greater mean burning time than the 3:7 reference
mixtures. The 4:1 mixtures did not fully react, and the time given in the table indicates the end
of the combustion period. A considerable quantity of sample material did not burn, signifying
that the sample was not capable of reacting within the allowed time limit for the reference
mixture.
4.
Conclusions
On the basis of the results of this study, it is concluded that the tested sample of prilled sodium
nitrate and potassium nitrate mixture (SPO) has no oxidizing properties within the meaning of the
criteria established by the Manual of Tests and Criteria in the United Nations Recommendations
on the Transport of Dangerous Goods, section 34.4.1.4. These conclusions apply to the grade
tested (composition and particle size).
5.
Signature
This study was performed by A.E.A van Gijzel-Koning and supervised by W.A. Mak.
Rijswijk, TNO Defence, Security and Safety.
H.L.J Keizers
Director of Department
W.A. Mak
Project leader, Author
___________
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