Decree No 222 / 2004 Coll.
Decree establishing, for chemicals and chemical preparations, basic methods for testing physicochemical properties, explosive properties and environmental hazards
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Effective from 01.05.2004
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222
DECLARATION
of 14 April 2004
establishing, for chemicals and chemical preparations, basic methods for testing physicochemical properties, explosive properties and environmental hazards
According to § 8 (5) (c) of Act No. 356 / 2003 Coll., on Chemicals and Chemicals, and on the amendment of certain laws, the Ministry of Environment provides for:
Methods for testing the physicochemical and explosive properties of chemicals (hereinafter referred to as "substances') and chemical preparations (hereinafter referred to as" preparations') listed in Annex 1 shall be used for the determination of:
(a) melting / freezing points;
(b) boiling point;
(c) relative density;
(d) vapour pressure;
(e) surface tension;
(f) solubility in water,
(g) the distribution coefficient;
(h) explosive properties;
(i) numerically average molecular weight and molecular weight distribution of polymers;
(j) the content of low-weight molecules in polymers;
(k) the behaviour of polymers during dissolution / extraction in water.
Methods for testing the properties of substances and preparations hazardous to the environment listed in Annex 2 shall be used for the determination of:
(a) acute toxicity to fish;
(b) acute toxicity to Daphne;
(c) inhibition of algae growth,
(d) "easy" biodegradable
- the loss of dissolved organic carbon (DOC),
- DOC loss modified by screening test,
- the release of carbon dioxide (CO2) modified by the Sturm test,
- manometric respirometry,
- tests in closed bottles,
- MITI tests,
(e) degradability - biological oxygen consumption,
(f) degradability - chemical oxygen consumption,
(g) abiotic degradation - hydrolysis as a function of pH,
(h) worm toxicity - artificial soil test,
(i) biodegradability - Zahn-Wellens test,
(j) biodegradability - activated sludge simulation test;
(k) biodegradability - test for inhibition of breathing of activated sludge,
(l) biodegradability - modified SCAS test;
(m) bioaccumulation - flow test on fish,
(n) growth in juvenile fish;
(o) toxicity to fish embryos and spawn - short-term test,
(p) acute oral toxicity to honey bees;
(r) acute contact toxicity for honey bees;
(s) steady state adsorption / desorption,
(t) estimation of the adsorption coefficient (KOU) for soil and sewage sludge by HPLC;
(u) reproductive toxicity to the Daphne magna;
(v) the activity of soil micro-organisms in the transformation of nitrogen;
(w) activity of soil micro-organisms in carbon transformation;
x) aerobic and anaerobic transformation in soil,
y) aerobic and anaerobic transformation in water-sediment systems.
The following shall be deleted:
1. Decree No. 299 / 1998 Coll., laying down methods for the detection of the physico-chemical and chemical properties of chemicals and chemical products and properties of chemicals and chemical products dangerous to the environment.
2. Decree No. 316 / 1998 Coll., laying down a method for detecting explosives of chemicals and chemical preparations.
This decree shall take effect on the date of the entry into force of the Treaty of Accession of the Czech Republic to the European Union.
Minister:
RNDr. Ambrozek v. r.
Příloha č. 1
Annex No 1 to Decree No 222 / 2004 Coll.
METHODS FOR TESTING PHYSICAL CHEMICAL AND EXPLOSIVE CHARACTERISTICS
I. METHODS FOR DETERMINING THE DIMENSION POINT / POINT - Methods referred to in point A.1 of the Annex to Commission Directive 92 / 69 / EEC of 31 July 1992 adapting for the seventeenth time to technical progress Council Directive 67 / 548 / EEC on the approximation of the administrative provisions relating to the classification, packaging and labelling of dangerous substances (hereinafter referred to as "Directive 92 / 69 / EEC")
METHOD
Most of the methods described below are based on OECD Test Guidelines (1). Their basic principles are given in the literature (2) and (3).
INTRODUCTION
The methods and instruments described are designed to determine the melting point of the substances without restriction in terms of their degree of purity.
The choice of the method depends on the nature of the substance to be examined. Therefore, the restriction will be whether the substance can be easily, easily or easily diluted or not.
For some substances, determination of the freezing or crystallization points is preferable and standardised methods for these determinations are also indicated in this method.
If none of the above parameters is well established due to the specific properties of the substance, it may be appropriate to establish a point of fluid.
I.1.2 DEFINITIONS AND UNIT
The melting point is defined as the temperature at which the transition from a solid to a liquid state occurs under atmospheric pressure and which corresponds to a freezing point under ideal conditions.
Since many substances have a phase transition within the temperature range, this range is often called the melting range.
Conversion of units (K to ° C):
t = T − 273,15
t - Celsius temperature, degrees Celsius (° C)
T - Thermodynamic temperature, Kelvin (K)
I.1.3 REFERENCE SUBSTANCES
It is not always necessary to use reference substances when investigating a new substance. They should, first and foremost, serve to check the implementation of the method on an occasional basis and to compare the results obtained by other methods.
Some calibration agents are listed in the literature (4).
I.1.4 CONDITIONS OF TEST METHODS
The temperature (temperature range) of the phase transition from solid to liquid or liquid to solid is determined. In practice, when heating / cooling the test substance sample under atmospheric pressure, the melting / freezing temperatures and the melting / freezing end are determined. Five types of methods, namely capillary method, methods using heating blocks, determination of freezing points, methods of thermal analysis and determination of fluid point (developed for mineral oils) are described.
In some cases it may be appropriate to measure the freezing point instead of the melting point.
I.1.4.1 Capillary method
I.1.4.1.1. Equipment for determining melting point with liquid bath
A small amount of finely diluted substance is injected into the capillary and threaded. The capillary is heated with a thermometer, setting the temperature rise rate during melting to less than 1 K · min-1. The temperature of the beginning and end of melting is determined.
I.1.4.1.2. Metal block melting point equipment
It shall be performed in the same way as in paragraph 1.4.1.1, except that the capillary and thermometer are located in a metal heated block and the holes in the block are observed.
I.1.4.1.3. Photocopying
The sample in the capillary is automatically heated in a metal cylinder. The hole in the cylinder passes through the material of the light beam on a precisely calibrated photocell. When melting, most substances change optical properties and turn from opaque to transparent. At this point, the intensity of the light falling on the photocell will increase and a signal to stop recording is sent to the device reading the temperature of the platinum resistance thermometer located in the heating chamber. This method is not suitable for some highly coloured substances.
I.1.4.2. Heating blocks
I.1.4.2.1 Kofler heating table
The Kofler heating table consists of two metal parts with different thermal conductivity, is heated electrically and is designed so that the temperature gradient is almost linear over its length. The temperature of the table may vary from 283 to 573 K; the table is equipped with a special temperature reading device, made up of a rider with an indicator and a scale designed for the table. To determine the melting point, the substance shall be applied in a thin layer directly to the surface of the table. Within seconds, a sharp dividing line is formed between a liquid and a rigid phase. The temperature at the point of the dividing line is subtracted after setting the indicator to this dividing line.
I.1.4.2.2 Melting microscope
Different types of microscopes with a heating table are used to determine the melting point of very small quantities. Most heating tables use sensitive thermocouples to measure temperature, but mercury thermometers are also used. The typical melting point device using a microwave with a heating table has a heating chamber with a metal plate on which the sample is placed on the slide. In the centre of the metal plate is an opening through which the light beam can be reflected by the light mirror of the microscope. When measured, the heating chamber shall be covered with a glass plate to limit the air circulation at the location of the sample.
The heating of the sample shall be controlled by the regulatory resistance. Polarized light can be used for very accurate measurements of optical anisotropic substances.
Mensk method
This method is mainly used for polyamides.
Visually determine the temperature at which the meniscus of silicone oil, closed between the heating block and the glass plate placed on the sample of polyamide tested, is clearly moved.
I.1.4.3. Method for determining the freezing point
The sample shall be placed in a special test tube, which shall be placed in a freezing device. During cooling, the sample is constantly mixed and the temperature is subtracted at appropriate intervals. As soon as the temperature is constant after several readings (after the corresponding thermometer correction), it is recorded as a freezing point.
The hypothermia must be avoided by maintaining balance. between the rigid and the liquid phase.
Thermal analysis
I.1.4.4.1. Differential thermal analysis (DTA)
This technique shall record the temperature difference between the substance and the reference substance that are subject to the same controlled temperature programme. If the sample has a phase transition associated with a change in enthalpy, this change is recorded as endothermic (melting) or exothermic (freezing) deviation from the baseline temperature record.
I.1.4.4.2. Differential scanning calorimetry (DSC)
In this technique, the substance and the reference substance shall be subjected to the same controlled temperature programme and the energy difference absorbed by the substance and the reference substance shall be recorded as the temperature function. This energy is the energy needed to maintain the zero temperature difference between the substance and the reference substance. If the sample has a phase transition associated with a change in enthalpy, this change is recorded as endothermic (melting) or exothermic (freezing) deviation from the base line of the heat flow recording.
I.1.4.5. Liquid point
The method has been developed for mineral oils and is suitable for measuring low melting oils.
After initial heating, the sample is cooled at a certain rate and its fluid is determined at intervals of 3 K. The lowest temperature at which the movement of the substance is still observed shall be recorded as a liquid point.
I.1.5 QUALITY CRITERIA
The applicability and accuracy of the different methods of determining the melting point / range are given in the table below.
TABLE: EXPIRY DATE OF THE METHOD
A. Capillary methods
| Metoda měření | Látky, které lze rozmělnit na prášek | Látky, které nelze snadno rozmělnit na prášek | Rozsah teplot | Odhadnutá přesnost1) | Existující norma |
|---|---|---|---|---|---|
| Zařízení pro stanovení bodu tání s kapalinovou lázní | ano | pouze pro několik látek | 273 až 573 K | ±0,3 K | JIS K 0064 |
| Zařízení pro stanovení bodu tání s kovovým blokem | ano | pouze pro několik látek | 293 až > 573 K | ±0,5 K | ISO 1218 (E) |
| Detekce fotočlánkem | ano | pro některé látky s použitím přídavných zařízení | 253 až 573 K | ±0,5 K |
1) Depending on the type of device and the degree of purity of the substance
B. Heating blocks and determination of freezing point
| Metoda měření | Látky, které lze rozmělnit na prášek | Látky, které nelze snadno rozmělnit na prášek | Rozsah teplot | Odhadnutá přesnost1) | Existující norma |
|---|---|---|---|---|---|
| Koflerův zahřívací stolek | ano | ne | 283 až > 573 K | ±1,0 K | ANSI/AST M D 3451-76 |
| Tavicí mikroskop | ano | pouze pro několik látek | 273 až > 573 K | ±0,5 K | DIN 53736 |
| Menisková metoda | ne | především pro polyamidy | 293 až > 573 K | ±0,5 K | ISO 1218 (E) |
| Metoda stanovení bodu tuhnutí | ano | ano | 223 až 573 K | ±0,5 K | např. BS 4695 |
1) Depending on the type of device and the degree of purity of the substance
C. Thermal analysis
| Metoda měření | Látky, které lze rozmělnit na prášek | Látky, které nelze snadno rozmělnit na prášek | Rozsah teplot | Odhadnutá přesnost1) | Existující norma |
|---|---|---|---|---|---|
| Diferenční termická analýza | ano | ano | 173 až 1 273 K | do 600 K ±0,5 K do 1 273 K ±2,0 K | ASTM E 537-76 |
| Diferenční skenovací kalorimetrie | ano | ano | 173 až 1 273 K | do 600 K ±0,5 K do 1 273 K ±2,0 K | ASTM E 537-76 |
1) Depending on the type of device and the degree of purity of the substance
D. Liquid point
| Metoda měření | Látky, které lze rozmělnit na prášek | Látky, které nelze snadno rozmělnit na prášek | Rozsah teplot | Odhadnutá přesnost1) | Existující norma |
|---|---|---|---|---|---|
| Teplota tekutosti | pro minerální oleje a olejovité látky | pro minerální oleje a olejovité látky | 223 až 323 K | ±3,0 K | ASTM D 97-66 |
1) Depending on the type of device and the degree of purity of the substance
I.1.6. DESCRIPTION OF METHOD
The procedures of almost all these test methods are described in national and international standards (see Appendix 1).
Capillary methods
When the temperature rises slowly, the melting rates shown in Figure 1 can usually be distinguished for finely powdered substances.
Figure 1
Stage A (Start of melting): The inside of the tube is held evenly by fine droplets.
Phase B As a result of the shrinkage of the sample, there is a gap between the inner wall and the sample.
Phase C The shrinking sample begins to collapse down and becomes liquid.
Phase D A complete meniscus is formed on the surface, but a large part of the sample is still solid.
Phase E (Final Melting Phase): The sample no longer contains solid particles.
The melting temperature and the final phase shall be recorded during the determination of the melting point.
I.1.6.1.1. Equipment for determining melting point with liquid bath
Figure 2 shows standard glass apparatus for determining melting point (JIS K 0064); all dimensions are given in millimetres.
Figure 2
Liquid bath:
Appropriate liquid should be selected. The choice of liquid depends on the melting point to be determined, for example, by the liquid paraffin for the determination of melting point below 473 K, by the silicone oil for the determination of melting point below 573 K.
For the determination of a melting point of more than 523 K, a mixture of three parts by weight of sulphuric acid and two parts by weight of potassium sulphate may be used. This type of mixture should be handled with due care.
Thermometer:
Only thermometers meeting the requirements of ASTM E 1-71, DIN 12770, JIS K 8001 or equivalent standards should be used.
Procedure:
The dry substance shall be finely cleaved in a friction bowl and placed in a capillary sealed at one end so that after compaction the capillary is filled up to approximately 3 mm. If uniform compaction is to be achieved, the capillary should be allowed to fall from a height of approximately 700 mm through a glass tube onto a clock slide.
The filled capillary shall be placed in the bath so that the middle part of the mercury bulb of the thermometer touches the capillary at the location of the sample. The capillary is usually placed in the bath at about 10 K below the melting point.
The bath is heated to approximately 3 K · min-1. The bath is mixed. About 10 K below the expected melting point is adjusted to a maximum of 1 K · min-1.
Calculation:
The melting point shall be calculated as follows:
T = TD + 0,00016TD-TEN
where:
T = corrected melting point in K
TD = temperature reading on the D in K thermometer
TE = temperature reading on the temperature meter E in K
n = the number of degrees by which the mercury column of the thermometer D protrudes from the liquid.
I.1.6.1.2. Metal block melting point equipment
Apparatus:
It's made
- a cylindrical metal block whose upper part is hollow and forms a chamber (see Figure 3),
- a metal housing plate with two or more holes which can be inserted into the metal block,
- a metal block heating system, such as an electric heating resistance closed in a metal block,
- the regulatory resistance to control power when electric heating is used,
- four windows of refractory glass in the side walls of the heating chamber, oriented towards each other at right angles. In front of one of these windows is placed the ocular for the observation of the capillary tube. The other three windows are used to illuminate the inner space with bulbs,
- a capillary tube of refractory glass sealed at one end (see 1.6.1.1).
Thermometer:
See standards in 1.6.1.1. Thermoelectric measuring instruments of comparable accuracy may also be used.
Figure 3
Photograph detection
Device and procedure:
The apparatus consists of a metal chamber with an automatic heating device. The three capillary tubes shall be filled according to paragraph 1.6.1.1 and placed in the heating chamber.
For calibration of the apparatus, several linear temperature growth modes are available, with suitable linear temperature growth set electrically by a pre-selected constant. The recording equipment shows temperature in the heating chamber and temperature of the substance in capillaries.
I.1.6.2 Heating blocks
I.1.6.2.1 Kofler heating table
See addendum.
I.1.6.2.2 Melting microscope
See addendum.
I.1.6.2.3. Meniscus method (for polyamides)
See addendum.
In the melting zone the heating rate should be less than 1 K · min-1.
I.1.6.3. Methods for determining the freezing point
See addendum.
Thermal analysis
I.1.6.4.1. Differential thermal analysis
See addendum.
I.1.6.4.2 Differential scanning calorimetry
See addendum.
Determination of the liquid point
See addendum.
Date
In some cases it is necessary to correct the thermometer.
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Regulation Information
| Citation | Decree No 222 / 2004 Coll., establishing, for chemicals and chemical preparations, the basic methods for testing physicochemical properties, explosive properties and environmental hazards |
|---|---|
| Regulation Type | - |
| Author | - |
| Collection | Code of Laws |
| Date of Promulgation | 29.04.2004 |
|---|---|
| Effective from | 01.05.2004 |
| Effective until | - |
| Status | Valid |
The regulation text is for informational purposes only.
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