Decree No. 299 / 1998 Coll.
Ordinance of the Ministry of the Environment laying down methods for the detection of physico-chemical and chemical properties of chemicals and chemical products and properties of chemicals and chemical products hazardous to the environment
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22.12.1998
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299
DECLARATION
Ministry of Environment
of 2 December 1998
laying down methods for the detection of physico-chemical and chemical properties of chemicals and chemical products and properties of chemicals and chemical products dangerous to the environment
The Ministry of the Environment provides pursuant to § 4 (1) (d) of Act No. 157 / 1998 Coll., on Chemicals and Chemical Products and on the amendment of certain other laws (hereinafter referred to as "the Act"):
(1) The detection of physico-chemical and chemical properties of chemicals and chemical products shall be carried out in accordance with the procedures set out in Annex 1.
(2) The detection of the properties of chemicals and chemical products hazardous to the environment, which, after penetration into the environment, constitute or may constitute an immediate or delayed danger, shall be carried out in accordance with the procedures set out in Annex 2.
This Decree shall take effect on 1 January 1999.
Minister:
RNDr. Kužvart v. r.
Příloha č. 1
Annex No 1 to Decree No 299 / 1998 Coll.
INTRODUCTION
The methods of testing the physico-chemical properties of substances and preparations described in this Annex of the MŽP Ordinance are the same as those laid down in the Annex to Commission Directive 92 / 69 / EEC. The correlation of methods is as follows:
| Označení metody podle přílohy k vyhlášce MŽP | Označení metody podle přílohy směrnice ES |
|---|---|
| I | A. 1 |
| II | A. 2 |
| III | A. 3 |
| IV | A. 4 |
| V | A. 5 |
| VI | A. 6 |
| VII | A. 8 |
Note:
If a valid Czech legal or technical regulation (e.g. CSN) meets the general conditions of the MŽP test, it is possible to proceed when testing according to this Regulation. This shall be indicated in the test report. On request, the test laboratory shall demonstrate that the measurement procedure used provides it with the same results in accordance with the procedure laid down in the MRU Decree.
I TEMPERATURE _
1 DESCRIPTION OF THE METHOD
Most of the methods described below are based on OECD recommendations (1).
Their basic principles are given in the literature (2), (3).
1.1 INTRODUCTION
The methods and instruments described are intended for determining the melting temperature of the substances, without restriction in terms of their purity.
The choice of the most appropriate method depends on the nature of the test substance, whether the substance can be easily, easily or not.
It is preferable for some substances to determine the temperature of solidification or crystallization; these procedures were included in the description of methods.
If none of the above parameters can be well measured due to the properties of the studied substance, a liquid temperature may be used.
1.2 DEFINITIONS AND UNIT
The melting temperature is the temperature at which the transition between rigid and liquid phases occurs at normal atmospheric pressure. Under ideal conditions, this temperature corresponds to the freezing temperature.
Conversion of units (K to ºC):
t = T - 273,15
| kde | t = Celsiova teplota, stupně Celsia (°C), |
| T = termodynamická teplota, kelvin (K). |
1.3 REFERENCE SUBSTANCES
When a new substance is studied, it is not always necessary to use reference substances. Reference substances should be used primarily for the occasional control of the measurement method and for the comparison of results obtained by different methods.
Some calibration agents are listed in the literature (4).
1.4. PRINCIPLE OF TEST METHODS
The temperature or temperature range of phase conversion is determined from solid to liquid or liquid to solid. When heating / cooling the sample of the study substance under atmospheric pressure, the melting / freezing temperatures and the melting / freezing end shall be determined. Five types of methods are described: capillary methods, methods using heating blocks, determination of freezing temperatures, methods of thermal analysis and determination of freezing points (as introduced for mineral oils). In some cases it may be appropriate to measure the freezing temperature instead of melting temperature.
1.1 Capillary method
1.1 Equipment for determining melting temperature with liquid bath
A small amount of finely diluted substance is injected into the capillary and threaded with a tap. The capillary shall be heated with the thermometer, with the temperature rise rate during melting being less than 1K.min-1. The temperature of the beginning and end of melting shall be determined.
1.2 Equipment for determination of melting temperature with metal block
It is done in the same way as 1.4.1.1, with the difference that capillary and thermometer are located in a metal block where holes in the block are observed.
1.4.1.3 Detection by photolink
The sample of the substance in the capillary is automatically heated in a metal cylinder. The hole in the cylinder and the sample of the substance placed in this hole shall be guided by a focused beam of light 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 is sent to the measuring device to record the temperature of the platinum resistance thermometer located in the heating chamber. This method is not suitable for some highly coloured substances.
1.2 Heating blocks
1.4.2.1 Kofler heating table
The Kofler heating table consists of two metal parts with different thermal conductivity. It is constructed by creating a linear temperature gradient along the table length. The temperature of the table can vary from 283 to 573 K. The table is equipped with a special temperature reading device, consisting of a rider with an indicator and a particularly dimensioned scale. For the determination of melting temperature, the substance shall be applied in a thin layer directly to the surface of the table. Within seconds, a sharp dividing line appears between a liquid and a rigid phase. The temperature is subtracted after setting the indicator to this dividing line.
1.2 Melting microscope
Different types of microscopes with a heating table are used to determine melting temperature of very small quantities. Most heating tables use sensitive thermocouples to measure temperature, but mercury thermometers are also used. The typical apparatus for determining the melting temperature by a microscope 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 reduce the cooling of the sample by air.
The heating of the sample shall be controlled by the regulatory resistance. For very accurate measurements of optically anisotropic substances, polarised light can be used.
1.3 Meniscus method
This method is mainly used for polyamides.
The temperature at which the silicone oil meniscus, closed between the heating block and the glass plate placed on the sample of the polyamide tested, shall be determined visually.
1.3 Method for determination of freezing temperature
The sample shall be placed in a special test tube, which shall be placed in a freezing apparatus. During cooling, the sample is constantly mixed and the temperature is subtracted at appropriate intervals. The temperature at which a further drop in temperature suddenly stops (i.e. remains constant after several readings) is recorded as freezing temperature (after the corresponding correction of the thermometer).
When maintaining the balance between the rigid and liquid phases, hypothermia must be avoided.
1.4 Thermal analysis
1.4.1 Differential thermal analysis (DTA)
The study and reference substance shall be treated with the same (controlled) temperature programme and the temperature difference between the two samples shall be recorded as a temperature function. If the study substance has a phase transition associated with a change in enthalpy, this change is indicated as endothermic (melting) or exothermic (freezing) deviation from the baseline of the record.
1.4.2 Differential chanting calorimetry (DSC)
The study and reference substance shall be treated with the same (controlled) temperature programme and the difference of energy input between the two samples shall be recorded as a function of temperature. The measured energy is the energy required to maintain the zero temperature difference between the study and the reference substance. If the study substance has a phase transition associated with a change in enthalpy, this change is indicated as endothermic (melting) or exothermic (freezing) deviation from the baseline of the record.
1.5 Fluid temperature
The method has been developed for mineral oils and is suitable for measuring oil substances with low melting temperatures.
After initial heating the sample shall be cooled and its liquid determined at intervals of 3 K. The lowest temperature at which the movement of the substance is still observed is recorded as liquid temperature.
1.5 QUALITY CRITERIA
The area of application and the accuracy of the melting temperature / temperature range methods 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 rozmělnit na prášek | Rozsah teplot | Odhadnutá přesnost a) | Existující norma |
|---|---|---|---|---|---|
| 1. 4. 1. 1 | ano | jen málo látek | 273 až 573 K | ± 0,3 K | JIS K 0064 |
| 1. 4. 1. 2 | ano | jen málo látek | 293 až 573 K | ± 0,5 K | ISO 1218 (E) |
| 1. 4. 1. 3 | ano | některé látky s použitím přídavných zařízení | 273 až 573 K | ± 0,5 K | |
| a) Závisí na použitém typu zařízení a stupni čistoty látky | |||||
B: Heating blocks and determination of freezing point
| Metoda měření | Látky, které lze rozmělnit na prášek | Látky, které nelze rozmělnit na prášek | Rozsah teplot | Odhadnutá přesnost a) | Existující norma |
|---|---|---|---|---|---|
| 1. 4. 2. 1 | ano | ne | 273 až 573K | ± 1,0K | ANSI/AS TM D 3451-76 |
| 1. 4. 2. 2 | ano | jen málo látek | 293 až 573K | ± 0,5K | DIN 53736 |
| 1. 4. 2. 3 | ne | speciálně pro polyamidy | 293 až 573 K | ± 0,5K | ISO 1218 (E) |
| 1. 4. 3. | ne | ano | 273 až 573K | ± 0,5K | např. BS 4695 |
| a) Závisí na použitém typu zařízení a stupni čistoty látky | |||||
C. Thermal analysis
| Metoda měření | Látky, které lze rozmělnit na prášek | Látky, které nelze rozmělnit na prášek | Rozsah teplot | Odhadnutá přesnost a) | Existující norma |
|---|---|---|---|---|---|
| 1. 4. 4. 1 | ano | ano | 173 až 1273 K | do 600 K ± 0,5 K do 1273 K ± 2,0 K | ASTM E 537 - 76 |
| 1. 4. 4. 2 | ano | ano | 173 až 1273 K | do 600 K ± 0,5 K do 1273 K ± 2,0 K | ASTM E 537 - 76 |
| a) Závisí na použitém typu zařízení a stupni čistoty látky | |||||
D. Friction point
| Metoda měření | Ropné produkty a olejovité látky | Rozsah teplot | Odhadnutá přesnosta) | Existující norma |
|---|---|---|---|---|
| 1. 4. 5 | ano | 223 až 323 K | ± 3,0 K | ASTM D 97 - 66 |
| a) Závisí na použitém typu zařízení a stupni čistoty látky | ||||
1.6 DESCRIPTION OF THE METHOD
Practices of almost all test methods listed here are described in national and international standards (see Annex 1).
6.1 Methods with capillaries
When the temperature rises slowly, the melting rates shown in Figure 1 can usually be distinguished for finely powdered substances.
Figure 1
Stage A: Fine droplets cling evenly to the inner wall of the tube.
Phase B: As a result of the sample shrinkage, a gap is formed between the inner wall and the sample.
Phase C: The shrinkled sample begins to collapse downwards and becomes liquid.
Stage D: A complete meniscus is formed on the surface, but a significant part of the sample is still rigid.
Stage E: (End of melting): The sample no longer contains any solid particles.
The temperature of the melting process shall be recorded when determining the melting temperature.
1.1 Equipment for determining melting temperature with liquid bath
Figure 2 shows a standardised glass apparatus for determining melting point (JIS K 0064). All dimensions are given in millimetres.
Figure 2
A: Measuring flask
B: Cork stopper
C: Pressure compensation
D: Thermometer
E: Auxiliary thermometer
F: Liquid bath
G: Glass capillary tube 80-100 mm long, with inside diameter 1,0 ± 0,2 mm and wall thickness 0,2 to 0,3 mm
H: Side throat
Liquid bath
The choice of suitable liquid depends on the expected melting temperature, e.g. liquid paraffin for melting temperatures not exceeding 473 K, silicone oil for melting temperatures not exceeding 573 K.
For melting temperatures exceeding 523 K, a mixture of three parts by weight of sulphuric acid and two parts by weight of potassium sulphate may be used. Special care should be taken when dealing with this type of medium.
Thermometer
Only thermometers meeting the requirements of ASTM E 1-71, DIN 12770, JIS K 8001 or other standards of the same level should be used.
Procedure
The dried substance is gently spread in the friction bowl and injected into the capillary tube at one end of the sealed. After compaction, the capillary should be filled up to about 3 mm. In order to achieve standard compaction, the capillary is allowed to fall from a height of about 700 mm through a glass tube on a clock slide.
The filled capillary is inserted into the bath so that the middle part of the mercury bulb of the thermometer touches the capillary tube at the location of the sample. The capillary is inserted into the bath at about 10 K below the expected melting point.
The liquid bath is heated so that the rise in temperature is about 3 K per minute. The bath must be mixed. About 10 K before the expected melting temperature is reached, the temperature growth is reduced to a maximum of 1 K per minute.
Calculation
The melting temperature shall be calculated using the formula:
T = TD + 0,00016 (TD-TE) .n
| kde | |
| T = | korigovaný bod tání v K |
| TD = | odečet teploty na teploměru D v K |
| TE = | odečet teploty na teploměru E v K |
| n = | počet stupňů, o které rtuťový sloupec teploměru D vyčnívá z kapaliny. |
1.6.1.2 Metal block device for determination of melting temperature
Apparatus:
It consists of:
- a cylindrical metal block whose upper part is hollow and forms a heating chamber (see Figure 3),
- a metal housing plate with two or more holes which can be used to introduce tubes 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 at right angles to each other (one of these windows is placed in front of the ocular for viewing the capillary tube, the other three windows are used to illuminate the inner space with bulbs).
- a capillary tube of heat resistant glass sealed at one end (see 1.6.1).
Thermometer:
According to the standards in 1.6.1 Electrical measuring instruments of comparable accuracy may also be used.
Figure 3
1.6.3.
Device and procedure:
The apparatus consists of a metal chamber with an automatic heating device. Three capillary tubes are filled according to 1.6.1.1 and placed in the heating chamber.
Several linear temperature growth modes are available to calibrate the instrument, and an appropriate mode can be selected in advance. The temperature in the heating chamber and the temperature in the capillary shall be recorded.
1.2 Heating blocks
1.6.2.1 Kofler heating table
(see Annex)
1.2 Melting microscope
(see Annex)
1.6.3 Meniscus method (for polyamides)
(see Annex)
In the melting zone the heating rate should be less than 1 K.min-1.
1.6.3 Methods for determining freezing points
(see Annex)
1.6.4 Thermal analysis
1.6.4.1 Differential thermal analysis
(see Annex)
1.2 Differential chanting calorimetry
(see Annex)
1.5 Determination of temperature of fluid (pour point)
(see Annex)
2 RESULTS
In some cases it is necessary to correct the thermometer.
3 TEST PROTOCOL
The test report should include the following:
- the method used,
- precise specification of the sample (main component, impurities) and information on the cleaning carried out (if any),
- an estimate of accuracy.
The mean value of at least two measurements, the results of which lie within the approximate accuracy range, shall be given as the melting point (see tables). If the temperature difference of the initial and final melting phases lies within the accuracy limits of the method, the final temperature shall be given as the melting point, otherwise both temperatures shall be indicated.
Some substances decompose or sublimate before reaching the melting point. The temperature at which the observed event occurs shall then be indicated.
All information and comments necessary for the evaluation of the results should be provided, in particular where they concern impurities and the physical state of the substance.
4 LITERATURE
(1) OECD, Paris, 1981, Test Guideline 102, Decision of the Council C (81) 30 final.
(2) IUPAC, B. Le Neindre, B. Vodar, eds. Experimental thermodynamics, Butterworth, London 1975, vol. II, 803 - 834.
(3) R. Weissberger ed.: Technique of organic Chemistry, Physical Methods of Organic Chemistry, 3rd ed., Interscience Publ. New York, 1959, vol. I, part I, Chapter VII.
(4) I U P A C, Physical chemical measures: Catalogue of reference materials from national laboratories, Pure and applied chemistry, 1976, Vol. 48, 505 - 515.
ANNEX
Further technical details can be found, for example, in the following standards:
| 1 | Kapilární metody | ||
| 1.1 | Přístroje pro stanovení bodu tání s kapalinovou lázní | ||
| ASTM E 324-69 | Standard Test Method for Relative Initial and Final Melting Points and the Melting Range of Organic Chemicals (Standardní metody pro stanovení počáteční a koncové teploty tání a teplotního intervalu tání organických látek) | ||
| BS 4634 | Method for the Determination of Melting Point and/or Melting Range (Metoda pro stanovení bodu tání a teplotního intervalu tání) | ||
| DIN 53181 | Bestimmung des Schmelzintervalles von Harzen nach Kapillarverfahren (Stanovení teplotního intervalu tání pevných látek kapilární zkouškou) | ||
| JIS K 00-64 | Testing Methods for Melting Point of Chemical Products (Metody stanovení bodu tání chemických produktů) | ||
| 1.2 | Přístroje pro stanovení teploty tání s kovovým blokem | ||
| DIN 53736 | Visuelle Bestimmung der Schmelztemperatur von teilkristallinen Kunstoffen | ||
| ISO 1218 (E) | Plastics - polyamides - determination of "melting point" | ||
| 2 | Zahřívací bloky | ||
| 2.1 | Koflerův zahřívací stolek | ||
| ANSI/ASTM D 3451-76 | Standard recommended practices for testing polymeric powder coatings | ||
| 2.2 | Tavicí mikroskop | ||
| DIN 53736 | Visuelle Bestimmung der Schmelztemperatur von teilkristallinen Kunstoffen | ||
| 2.3 | Menisková metoda | ||
| ISO 1218 (E) | Plastics - polyamides - determination of "melting point" | ||
| ANSI/ASTM D | Standard recommended practices for testing | ||
| 3451-76 | polymeric powder coatings | ||
| NF T 51-050 | Résines de polyamides. Détermination du "point de fusion". Méthode du ménisque | ||
| 3 | Metody stanovení bodu tuhnutí | ||
| BS 4633 | Method for the determination of crystallizing point | ||
| BS 4695 | Method for Determination of Melting Point of petroleum wax (Cooling Curve) | ||
| DIN 51421 | Bestimmung des Gefrierpunktes von Flugkraftstoffen, Ottokraftstoffen und Motorenbenzolen | ||
| ISO 2207 | Cires de pétrole: détermination de la temperature de figeage | ||
| DIN 53175 | Bestimmung des Erstarrungspunktes von Fettsauren | ||
| NF T 60-114 | Point de fusion des paraffines | ||
| NF T 20-051 | Méthode de détermination du point de cristallisation (point de congélation) | ||
| ISO 1392 | Method for determination of freezing point | ||
| 4 | Termická analýza | ||
| 4.1 | Diferenční termická analýza | ||
| ASTM E 537-76 | Standard method for assessing the thermal stability of chemicals by methods of differential thermal analysis | ||
| ASTM E 473-85 | Standard definitions of terms relating to thermal analysis | ||
| ASTM E 472-86 | Standard practice for reporting thermoanalytical data | ||
| DIN 51005 | Thermische Analyse, Begriffe | ||
| 4.2 | Diferenční skanovací kalorimetrie | ||
| ASTM E 537-76 | Standard method for assessing the thermal stability of chemicals by methods of differential thermal analysis | ||
| ASTM E 473-85 | Standard definitions of terms relating to thermal analysis | ||
| ASTM E 472-86 | Standard practice for reporting thermoanalytical data | ||
| DIN 51005 | Thermische Analyse, Begriffe | ||
| 5 | Stanovení bodu tekutosti | ||
| NBN 52014 | Echantillonnage et analyse des produits du pétrole: Point de trouble et point d'écoulement limite - Monsterneming en ontleding van aardolieproducten: Troebelingspunt en vloeipunt | ||
| ASTM D 97-66 | Standard test method for pour point of petroleum oils | ||
| ISO 3016 | Petroleum oils - Determination of pour point | ||
_
1 DESCRIPTION OF THE METHOD
Most of the methods described below are based on OECD recommendations (1).
Their basic principles are given in the literature (2), (3).
1.1 INTRODUCTION
The methods and equipment described here can be used for liquids and substances with low melting temperature, unless they are subject to chemical reactions below boiling temperature (e.g. autooxidation, overwash, decomposition, etc.). Methods can be applied to both clean and contaminated liquids.
Priority should be given to photocoplay detection methods and thermal analysis methods, as they allow the determination of both melting and boiling temperatures. In addition, these measurements may be made automatically.
"Dynamic method" has the advantage that it can also be used to determine vapour tension. The boiling temperature does not need to be corrected for normal pressure (101, 325 kPa) because it can be adjusted by manostat during measurement.
Remarks
The effect of impurities on boiling temperature determination depends largely on their nature. If the sample contains volatile impurities that may affect the results, the substance may be purified.
1.2 DEFINITIONS AND UNIT
The standard boiling temperature is defined as the temperature at which the vapour tension of the fluid is 101,325 kPa.
If the boiling temperature is not measured under normal pressure, the vapour tension may be applied to the temperature described by Clausius-Clapeyron equation:
logos oftenop = ΔHv2,3RT + konst.
| kde | |
| p | = tenze par látky v Pa, |
| ΔHv | = výparné teplo v J mol-1, |
| R | = univerzální molární plynová konstanta =8,314 J mol-1 K-1, |
| T | = termodynamická teplota v K. |
The boiling temperature shall be reported with the ambient pressure reading.
Recalculations:
Pressure (unit: kPa)
100 kPa = 1 bar = 0,1 MPa
("bar 'unit is still permissible but its use is not recommended).
133 Pa = 1 mm Hg = 1 torr
(units "mm Hg 'and" torr' are not allowed).
1 atm = standard atmosphere = 101 325 Pa
(not allowed).
Temperature (unit: K)
t = T-273,15
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Regulation Information
| Citation | Decree of the Ministry of the Environment No. 299 / 1998 Coll., laying down methods for the detection of physico-chemical and chemical properties of chemicals and chemical products and properties of chemicals and chemical products dangerous to the environment |
|---|---|
| Regulation Type | Order |
| Author | - |
| Collection | Code of Laws |
| Date of Promulgation | 22.12.1998 |
|---|---|
| Effective from | 01.01.1999 |
| Effective until | - |
| Status | Valid |
The regulation text is for informational purposes only.
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