4.thermal Screening

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THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS
4. Thermal Screening
This HarsBook text has been prepared by a HarsNet working group. The text has been prepared in good faith but the authors accept no responsibility for the consequences of application of the information contained herein. The HarsNet Thematic network is European Community Project BET2-0572 funded in part by contract number BRRT-CT98-5066. Keywords: thermal, screening, stability, exotherm, onset, decomposition, kinetics, enthalpy 4.1. Introduction The general objective of thermal screening of chemicals and mixtures is to identify whether the sample can undergo an exotherm process and the temperature range of its occurrence, which provides a preliminary indication of potential chemical reaction hazards. The focus lies here on secondary reactions. Depending on the calorimeter used additional information on the amount and rate of released heat, kinetics (normal or autocatalytic) and pressure build up can be obtained. Thermal screening is the first experimental stage in a hazard assessment. 4.2. Principle Calorimeters for thermal screening are available from various producers in different specifications, including DSC and various forms of DTA (single and twin set-up). All screening calorimeters are characterised by the small sample size they require (mg- to gscale) and by the speed at which measurements can be performed. They are particularly useful for: Screening of a large number of samples. Screening of highly unstable substances. Screening of samples, which are only available in laboratory quantities, such as reactants, isolated intermediates, products and reaction mixtures. Unintended mixtures, e.g. contamination with rust In a typical screening apparatus a small amount of sample is placed in a pressure resistant metal or glass container and is heated at a constant rate (0.1 to 10K/min) in the temperature range of -20 to 500C. Besides this scanning mode, isothermal experiments are also used for certain applications. Sensors measure the temperature of the sample or sample container relative to a reference. In most of the available apparatuses this temperature difference can be calibrated in units of rate of heat generation. Samples which absorb a known amount of heat at a specific temperature, for instance the melting
4-1 PROJECT: BET2-0572 INDUSTRIAL AND MATERIALS TECHNOLOGIES PROGRAMME OF THE EUROPEAN COMMISSION. COORDINATION: Prof. Dr. R. Nomen Tel. +34-93-267 20 00 Fax. +34-93-205 62 66 http://www.iqs.url.es/harsnet
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of a known quantity of indium, are used for calibration. There is either no mixing or only very limited mixing in the test cells. A tabulated comparison of some screening calorimeters can be found in section 5. Near-adiabatic gram-scale methods, such as RSST or ARC may also be used for screening, but are not considered here. These methods are described in chapter 5 on Adiabatic calorimetry. 4.3. The sample and sample container For screening experiments closed high-pressure containers are typically used to suppress/limit vaporisation and keep volatile decomposition products contained, which may contribute to further decomposition. To ensure all compounds are kept in the sample container, the mass of the filled sample container should be weighed before and after a screening experiment. The decomposition of a sample can depend strongly on its impurity profile. It is therefore important that the screened chemicals or mixtures stem from the investigated process. A sample taken from a heterogeneous mixture most likely does not represent the mixture. This must be considered in the evaluation. The preparation of a heterogeneous mixture in the sample container can generate more meaningful information. A disadvantage of using small sample sizes is that the sample has an unfavourable ratio of surface to volume, which makes interactions with the container wall, the surrounding air, etc. more likely. Catalytic as well as stabilising effects are possible, so that the measured effect may not represent properties of the sample itself. For instance, many compounds containing chlorine give artificial peaks when using steel or gold containers. This kind of interaction can usually be eliminated by running screening experiments with two containers of different material, e.g. steel and glass (Grewer, 1994). Interactions with the surrounding air etc. can be eliminated by preparing the sample in a glove-box with an inert atmosphere. 4.4. Evaluation The previous section makes clear, that inherent features of thermal screening measurements are considerable uncertainties and that an ideal evaluation should not be based on one measurement only. The interpretation and evaluation of screening experiments are often difficult because the peak limits can not be clearly recognised and only rarely does an exothermic peak appear independent from other peaks. However, using a different heating rate can sometimes separate previously unseparated peaks. An illustration and interpretation of different combinations of several peaks in screening experiments using some typical examples of substances and mixtures can be found in /1, page 68/. The following subsections describe the evaluation of a single peak.
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4.4.1. Qualitative Evaluation The most obvious result of a screening test is the direction of the resulting peak indicating an exothermic or endothermic process. The other information is the onset temperature1, Tonset, the peak temperature and the peak shape, where the onset temperature characterises the thermal stability, and the peak shape (size and sharpness) gives an indication on the hazard potential of the sample (figure 4.1).
TO = Onset temperature TP = Peak temperature Q = Heat of reaction
TP
heat generation rate
exo Area Q TO
temperature / time
Figure 4.1. Idealised screening curve of an exothermic reaction
In general, the larger and sharper the peak, the more hazardous the decomposition reaction. However, low activation energy processes, which cause broad peaks, should be considered when extrapolating the data to adiabatic conditions. The preliminary assessment of the thermal stability of chemicals or mixtures at production scale is often based on a rule-of-thumb using Tonset of the secondary reaction2. Such a rule-of-thumb states that if the maximum operating temperature of a process is X Kelvin lower than Tonset, the operation will not experience this secondary reaction, and it is not necessary to obtain more detailed information by other means. For instance, a safety margin of 100K is often used for DSC measurements. This kind of rule-of-thumb can easily be misused, since the value of Tonset depends on the sensitivity of the apparatus, the sample container, the heating rate and is sometimes difficult to determine - especially if the signal is noisy and/or curvy. The DSC safety margin of 100K is based on the assumption that the decomposition follows zeroth order kinetics and has a defined temperature dependence. It has been shown that reactions with activation energies below 80kJ/mol will violate the 100K rule (Hofelich, 1989). Hence, the 100K rule was extended to ensure that low activation energy decompositions are excluded. Beside the 100K safety margin, a shift of the peak temperature of less then 40K is demanded when changing the heating rate by a factor of ten (Steinbach, 1995).
The observed Tonset is the temperature at which the sample shows the first observable instrumental response due to a reaction 2 See remark at the end of this subsection!
1
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Another rule-of-thumb for DSC measurements has been proposed. It assumes a comparatively low activation energy of 50kJ/mol, zeroth order kinetics and a detection limit of 20W/kg for the DSC (Keller, 1997). The maximum allowable process temperature Tp,max is regarded as safe if the adiabatic time to maximum rate of the secondary reaction is greater than or equal to 24 hours, which leads to the following correlation:
TP ,max = 0.65 Tonset + 50K .
[Eq. 4.1]
A more general correlation between Tp,max and Tonset of a DSC measurement assuming zeroth order kinetics (Dransfeld, 2001) is:
TP ,max = Tonset
2 tmr24 E A q onset R Tonset ln 2 c R (T EA + 50 K ) onset P
[Eq. 4.2]
where R is the universal gas constant, EA the activation energy, tmr24 the adiabatic time to maximum rate of 24 hours, qonset the detection limit of the DSC and cp the heat capacity. The kind of kinetics (normal or autocatalytic) of the heat generation can be qualitatively determined using the peak profile of an isothermal measurement. Remark: The definition of an upper safe temperature limit using a safety margin or an adiabatic time to maximum rate is based on zeroth order kinetics. This simplifying assumption is conservative for normal (nth order) kinetics but not necessarily for autocatalytic kinetics. This means, that the interpretation of screening traces to large scale manufacture requires great care and experience in identifying reactions or decompositions that are not proceeding via normal kinetics, i.e. screening tests are not like running a melting point determination, where one just reads off the number from the trace! 4.4.2. Quantitative Evaluation 4.4.2.1. Heat Flow Profile The measured heat flow contains the heat generation rate of the chemical reaction and other thermal effects3 - the baseline. However, for evaluation only the heat generation rate of the chemical reaction is of interest. Hence, the heat flow must be corrected prior to an evaluation.
E.g. many neat solvents reach their critical temperature (Acetone: 235C; Isopropanol: 235C; toluene: 319C; water: 374C) during screening measurements which causes an abrupt change in the baseline profile. The same effect can be encountered when testing solutions.
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a) Baseline Correction The baseline represents the theoretical profile, which would have been measured if the reaction/decomposition would have taken place without any heat release. The difference between the measured heat flow and the baseline is the heat production rate of the reaction. For a baseline correction the peak limits have to be fixed, which can be quite difficult - especially with a noisy and/or curvy heat flow profile. In the reaction interval the unknown baseline must be interpolated, which is often an error prone task. Commercial evaluation software often offers a large variety of interpolation methods, e.g. linear, integral, spline, horizontal etc. The baseline type determines the obtained results and should be chosen carefully. For normal scanning experiments an integral baseline, which shows a smooth profile, is recommended (figure 4.2). For normal isothermal measurements a baseline horizontal from the peak end is recommended. If there is any doubt about the peak limits or the baseline profile, a second experiment on the sample may help with the determination of the peak limits and baseline profile.
heat generation rate
exo
tem perature / tim e
Figure 2: Idealised screening curve with integral baseline Peak limits and interpolated baseline should be plausible and chosen in a way to give rather conservative results, i.e. lowest onset temperature and largest heat of reaction or decomposition. b) Deconvolution Ideally, the difference between measured heat flow and baseline, although representing the heat production rate of the chemical reaction, should not directly be used for a kinetic or TMR evaluation. This is caused by the convoluting effect of the sample container acting as a heat buffer, which leads to a broader peak. However, it has to be pointed out that a TMR evaluation without deconvolution usually leads to conservative results. The convolution is usually characterised by a time lag constant, tsignal, which can be obtained by the evaluation of the rising part of a negative melting peak. The true & , can be recalculated (Hemminger, heat production rate of the chemical reaction, q & b using tsignal according to: 1989) from the baseline-corrected heat flow q
& (t) = q & b ( t ) + t signal q &b q
[Eq 4.3]
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c) Heat of reaction
The integration of the baseline-corrected heat flow over time gives the heat of reaction, which is a measure of the thermal hazard. Based on the amount of released heat decisions are made how to proceed with further investigations. The thermal hazard is usually related to the adiabatic temperature rise, which can be calculated by dividing the heat of reaction with the heat capacity of the sample. An adiabatic temperature rise of 50K, which equals a heat of reaction of about 100J/g for a typical organic liquid, is often used as lower hazard limit. This means, if an exothermic process generates less than 100J/g than this process is regarded as not hazardous providing gaseous products or vapour are not generated in significant amounts. If the sample undergoes several exothermic processes, the generated heat of each peak relative to the temperature differences of their onset temperatures has to be considered. The investigated sample may be subject to transport regulations. The UN committee on transport of dangerous goods has defined a value of 300J/g as the energy limit for tests on self-reactivity. If this limit is exceeded, further tests are needed as outlined by the United Nations recommendations. If the heat of decomposition exceeds 500J/g, especially in combination with a sharp peak, the sample may be an explosive4. If the decomposition energy is higher than 500J/g further tests on explosibility are recommended. d) Kinetics In principle, screening calorimeters offer the capability to determine kinetic parameters from isothermal and scanning experiments. Calculation methods for establishing reaction kinetics from several scanning experiments are proposed in the literature e.g. /8-10/. It was shown that reliable kinetic parameters can be obtained by quantitative screening methods, such as DSC (Wagner, 1996). However, the determination of reliable kinetic parameters is limited to simple homogenous reactions. Kinetic parameters obtained from complex reactions give only an indication and can not be used for quantitative interpretations or predictions. From one scanning measurement an estimation of an overall activation energy can be obtained when plotting the natural logarithm of the corrected heat flow vs. the reciprocal absolute temperature. The initial slope represents the negative activation energy divided by the universal gas constant. From several scanning measurements at different heating rates an estimated activation energy can be obtained using the Ozawa plot (Ozawa, 1970) - the natural logarithm of the heating rate vs. the reciprocal absolute peak temperature. The slope of the resulting straight line represents the negative activation energy divided by the universal gas constant.
4This
energy limit is based on the experience that an explosive with a decomposition energy of less than 500J/g is not known (Grewer. 1994).
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In isothermal mode the activation energy can be obtained by plotting the natural logarithm of the maximum heat production rate versus the reciprocal absolute temperature. The slope of the resulting straight line represents the negative activation energy divided by the universal gas constant. e) Time to Maximum Rate (TMR) TMR can be used as an alternative to the use of a safety margin in order to define an upper safe temperature limit of a process. The calculation of TMR is based on several isothermal measurements at different temperatures. Using the maximum heat production rate and the isothermal temperature, the TMR for a given set-temperature Ts can be approximated by extrapolation, assuming a reaction of second (Townsend, 1980) or zeroth order (Grewer. 1994):
c R TS TMR = P & (TS ) E A q
2
[Eq. 4.4]
& (Ts) the heat production where cp is the heat capacity, R the universal gas constant, q rate at Ts and EA the activation energy. Even though the application of TMR seems to be straightforward, one has to consider that EA is typically determined from three & (Ts) is obtained by isothermal measurements, i.e. from three data points, and q extrapolation far outside the regression interval. Taking the temperature where TMR equals 24 hours and a correlation coefficient for three points of 0.999, the time span can have an uncertainty of three hours. For a correlation coefficient of 0.99 the uncertainty may be as big as eight hours! As a rule-of-thumb: A secondary reaction does not generally pose a threat to the process if TMR is longer than 24 hours at the highest attainable process temperature. 4.4.2.2. Pressure Profile Some calorimeters enable the measurement of the pressure on-line indicating the amount and rate of gas generation, which can afford valuable information about hazardous gas production. The plot of the logarithm of the pressure vs. the reciprocal absolute temperature gives an indication whether the investigated sample generates gaseous products. An approximately straight line in such an Antoine plot indicates that the pressure, in the sample container, rises due to vaporisation rather than the generation of non-condensable products. Considerable deviations of the slope from 10.5 times the absolute boiling temperature of the liquid5 indicate possible generation of non-condensable products.
Many organic (non-polar) liquids follow the Trouton rule reasonably well, i.e. the heat of evaporation over the universal gas constants is approx. 10.5 times the absolute boiling temperature of the liquid.
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Since the pressure measurement is not convoluted, the time lag constant, tsignal, can be checked or determined by measuring a simple gas producing reaction, e.g. an azo decomposition. The profile of the heat production rate and pressure rate should be identical if the correct tsignal was used for deconvolution.
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Calorimeter Typical sample size
4.5. Comparison of Thermal Screening Calorimeters

Temperature range in C Raw data as function of time
Sensitivity Tabulated in mW/kg
Mode of operation
DSC Heat Flow
2-10 mg 2-10 mg 0.5-2 g 0.5 1.5 g 5-20 g
Power Comp. Twin DTA TAM C80 IET Single DTA Carius tube DPT Sikarex Radex Sedex
-50 to 700 -50 to 700 20 to 80 20 to 300 20 to 400 20-400 0-400
Isothermal T-ramp Isothermal T-ramp Isothermal Isothermal T-ramp T-ramp T-ramp T-ramp
no no yes yes6
T, q T, q Q T, q, p T, DT
20 20 10-4 1
35 35 70 60
no
T, DT, p T, p
1 T-ramp no T, DT yes 80 Isothermal T, DT, p T-ramp Adiabatic u 26 TS 17g 20 to Isothermal & no T, DT, p 400 Several T ramps 6 Mixing performance is limited. On-line pressure measurement not possible when mixing. 1-3 g 2-100 g
Price in kEuro
4-9
Stirring
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4.6. References
Grewer, T. Thermal Hazards of Chemical Reactions; Elsevier B.V., 1994 Hemminger, W.F.; Cammenga, H.K. Methoden der thermischen Analyse. SpringerVerlag, 1989 Hofelich, T.C.; Thomas, R.C. Int. Symp. on Runaway Reactions; AIChE 1989; p.74 Hugo, P. et al; Z. Naturforsch. 50a (1995); p.549 Keller, A. et al; J. Loss Prev. Ind. 10 (1997); p. 31 Kissinger, H.; Anal. Chem. 29 (1957); p.1702 Ozawa, T.; J. Therm. Anal. 2 (1970); p. 301 Ozawa, T.; J. Therm. Anal. 9 (1976); p.369 Steinbach, J.; Chemische Sicherheitstechnik; VCH, 1995 Townsend, D.I..; Tou, J.C.; Thermochim. Acta 37 (1980); p. 1 United Nations; Recommendations on the transport of dangerous goods; Test and criteria, 2nd revised Edition, 1995 Wagner, S.; Experimental and theoretical investigations of the use of Differential Scanning Calorimetry as a thermokinetic measuring method (in German); PhD Thesis; TU Berlin, 1996

4.thermal Screening

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HarsNet

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

TO = Onset temperature TP = Peak temperature Q = Heat of reaction

heat generation rate

Figure 4.1. Idealised screening curve of an exothermic reaction

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

2 tmr24 E A q onset R Tonset ln 2 c R (T EA + 50 K ) onset P

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

heat generation rate

tem perature / tim e

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

4.5. Comparison of Thermal Screening Calorimeters

Sensitivity Tabulated in mW/kg

DSC Heat Flow

2-10 mg 2-10 mg 0.5-2 g 0.5 1.5 g 5-20 g

-50 to 700 -50 to 700 20 to 80 20 to 300 20 to 400 20-400 0-400

THEMATIC NETWORK ON HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

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