6 Adiabaticcalorimetry PDF

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HarsNet HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS
6. Adiabatic calorimetry
This HarsBook text has been prepared by a HarsNet working group for
use by HarsNet partners. 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: Runaway, exotherm, adiabatic calorimetry, thermodynamic, kinetic, phi factor,

pressure and temperature measurement, reaction enthalpy, vent sizing.
6.1. Introduction
A chemical reaction leads to a runaway when its own heat production rate is faster than heat
E
-
losses. In most cases, chemical reactions follow an Arrhenius law ( Rate µ Z × exp RT ), where
the heat production rate increases exponentially with temperature, whilst the heat removed by
the jacket is proportional to the temperature difference between the reactor and jacket
( Rate = UA× (Tj - Tr ) ).
This is well described by either the theory of Semenov (in which an uniform temperature
within the reactor is assumed) or the Frank Kamenetskii theory (which allows for a
temperature distribution for an unstirred system).
The worst real case and the easiest to understand is when a runaway reaction occurs under
adiabatic conditions, that is to say without any heat exchange with the surroundings. (For
present purposes the even worse case of loss of cooling with a continued external heat input is
ignored.) To study such a case at laboratory scale is not easy because natural cooling changes
dramatically with scale. Heat losses are proportional to surface area (i.e. r²) and mass to
volume (i.e. r3), so heat loss per unit mass is proportional to 1/r (i.e. it reduces dramatically
with reactor scale up). Some typical heat loss data are summarised in table 6.1. Note that a
one litre Dewar flask has very similar heat loss characteristics to a 12.7 m3 reactor.
6-1
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Item Volume Cooling time Cooling rate Heat loss*

for 1°C (°C/min) (Watts / kg)
test tube 10 ml 11 s 5,5 385
Beaker 100 ml 20 s 3 210
Flask 1000 ml 2 min 0,5 35
Reactor 2,5 m3 21 min 0,047 3,29
Reactor 5,0 m3 43 min 0,023 1,61
Reactor 12,7 m3 59 min 0,0169 1,18
Dewar 1000 ml 62 min 0,0161 1,13
Reactor 25 m3 233 min 0,0043 0,3
Table 6.1. Typical cooling rates and heat loss data. Laboratory and industrial scale
equipment, 60°C hotter than surroundings
(* for an 80% fill level with water)
So as to reproduce exactly what occurs during a run-away and learn from laboratory
experiments, we can use a technique called adiabatic calorimetry. Ideal adiabatic tests at a
PHI factor of 1 give results that are independent of the mass investigated.
6.2. Information required
Information that is needed includes thermodynamic and kinetic data that can be applied to real
large-scale run-away scenarios (that is to say in the correct range of temperature). With a
small number of experiments, and as little calculation as possible, we should be able to
determine: adiabatic temperature rise, rate of change of pressure, rate of change of
temperature and system characterisation (vapour pressure, gassy or hybrid).
We want to answer the following questions :
Thermal behaviour. Is there a thermal hazard ?

Detected “Onset” temperature. At what temperature is reaction detected ?
Induction time. What is the Time to Maximum Rate (TMR)?
Adiabatic temperature rise. What temperature can be reached under adiabatic
conditions?
System characterisation. Is the pressure rise due to vapour pressure or non-
condensable gas production?
Rate of change of temperature How many reactions occur?
How fast are they?
What are the kinetic and Arrhenius parameters?
Rate of change of pressure How rapid is the pressure rise?
Is it pressure dependent?
So we want to quantify both the potential thermal hazard and the vent size that may be
required required to protect a batch or semi-batch reactor vessel.
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6.3. Techniques available
Different techniques are used to detect and characterise decomposition of a reaction mixture:
some of these such as DSC and DTA are well described in Chapter 3 of HarsBook, so we will
now focus on adiabatic and pseudo-adiabatic techniques.
A suitable adiabatic calorimeter, for measuring data for the worst case runaway will:
a) Be adiabatic
Adiabatic conditions can be realised either by using an adiabatic shield (an oven), or by
putting the sample into a container having good thermally insulated walls. The second
technique was first used with a Dewar flask (silvered and evacuated double-glass wall).
Experiments have shown that of all vessels with an insulated wall, Dewar flasks are the best.
Better measurements, however, can be obtained by using a combination of the Dewar flask
and an adiabatic temperature control system. In most modern adiabatic devices (ARC /
Accelerating Rate Calorimeter, VSP / Vent Sizing Package, PHI-TEC, APTAC / Automatic
Pressure Tracking Adiabatic Calorimeter.), the experimental set-up is usually able to
minimise heat loss from the test cell by maintaining the temperature of the surroundings equal
to that of the sample temperature (or to the test cell wall temperature). Test cell volume is
typically from 10 to 100 ml, batch introduction of liquid can be performed, threshold
detection is about 0.02 °C/min for the self-heating rate, and a wide range of temperatures (20-
400/500°C) and pressures (0-100/150 bar) can be used. Another calorimeter (that is difficult
to classify) must be mentioned here: with the RSST (Reactive System Screening Tool), the
test is non-adiabatic and relies on a constant small heat input to the sample. So the worst-case
runway data can be obtained and vent sizing calculations can be performed.
Methanol / Acetic Anhydride
16 175
Pression en bar a
14 Température en °C 155
12 Initial Temperatute=20,2°C 135

Final Temperature=165,2°C
Temperature (°C)
Pressure (bara)
Final pressure =14,8 bara

10 115
8 95
6 75
4 55
2 35
0 15
0 50 100 150 200 250
Time (mn)
Figure 6.1. Adiabatic experiment with low PHI factor; Acetic anhydride / Methanol
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b) Have a thermal inertia, f, close to unity.
Both the sample and the vessel are under adiabatic conditions, so the heat produced by the
sample causes not only an increase in its own temperature but also in the vessel temperature.
On the small scale, the thermal mass of the reactor vessel (or cell) is usually a much larger
fraction of the total thermal mass than for large scale operation. This can be expressed by the
PHI factor:
Thermal mass of sample and test cell

f= [Eq. 6.1]
Thermal mass of sample alone
Phi factors in a large chemical plant are often between 1 and 1.05. The concept of a phi factor
can be applied not only to reactors but also to storage vessels, evaporators, distillation
columns, etc. It is important to realise that runaway reactions can, and do, occur in these types
of equipment as well as in reactors. One must also take into account that “static” PHI factors
can be easily calculated by the previous formula but “dynamic or real” PHI factors (due to
heat transfer limitation through the walls of the vessel) are difficult to evaluate. This is true
for both industrial reactor and laboratory test cells.
The phi factor is very important. For example, in the case of f = 2, the observed adiabatic
temperature rise in the adiabatic instrument will be only half the true adiabatic temperature
rise for the chemicals alone. The consequence is that the experiment is not performed over the
correct range of temperature; failure to detect consecutive reactions and gross underestimates
of the rates of reaction may result. Thus it is better to work with f close to unity and normally
in the range 1.05 to 1.1. In the case of experimentation at a high Phi factor, data
correction is required before vent sizing calculations and kinetic or thermodynamic
evaluations can be made. This may involve data extrapolation over a large range of
temperature and this is not recommended. To achieve the objective of a low phi factor, the
test cell mass must be as low as possible. As a result it will not be very strong, yet it must be
able to be used at high pressure. It is therefore necessary to match or balance the pressure
outside the test cell to that in the head space above the sample so as to avoid rupture of the
cell. This method of operation is used in the cases of the VSP, PHI TEC and APTAC
equipment.
c) Work with a Heat, Wait and Search routine.
In order to obtain a better sensitivity for runaway detection, a Heat, Wait and Search routine
should be performed. This procedure consists of Heating the sample to the required
temperature, Waiting for stabilisation and then Searching, to detect if any exothermic
phenomenon is occurring. If no exotherm is detected, the sample is Heated to a new
temperature and the process repeated. This continues step by step until a runaway is detected
or a maximum temperature is reached. This routine can be applied flexibly to allow
isothermal or ramped temperature modes to be used. Autocatalytic behaviour can be studied.
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120
100
Température en °C
80
60
Search
Track
Heat
Search
Cool
Wait
Heat
Heat
Wait
Search
Wait
Search
Heat
Wait
Heat
Wait
Search
Wait
Search
40
Initialisation
20
0
0 2000 4000 6000 8000 10000 12000 14000 16000
temps en s
Figure 6.2. Heat-Wait-Search experiment
d) Work at conditions close to the industrial ones
Accurate results can be obtained only if the user takes care to perform laboratory experiments
analogous to industrial conditions. That is to say using a glass test cell when reactions are
performing in a glass reactor in order to avoid catalysis, under nitrogen or air, with good
agitation, etc...
All industrial conditions may be difficult to reproduce at the laboratory scale but keep in mind
that one must work as close as possible to them
Comparison Comparison Kinetic

Laboratory adiabatic calorimeter / Pilot scale test (350 litres) Adiabatic calorimeter / Pilot plant experiment
140 6
130
5
120 Relief Temperature in pilot experiment
4
110
LN (dT/dt) (°C/min)
Temperature (°C)
100
3
Pilot Vapor Temperature
Laboratory test
90 Pilot Liquide Temperature
Pilot test
LaboratoryTemperature 2
80
70 1
60
0
50
40 -1
0 200 400 600 800 1000 1200 -3.2 -3 -2.8 -2.6 -2.4 -2.2 -2
Time (s) -1000 / T (°K)
Figure 6.3. Comparison between a laboratory adiabatic experiment and a pilot plant
experiment
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6.4. Comparison of techniques and relative merit
a) Dewar Flask.
Typically, a calorimeter comprises a 1-litre stainless steel Dewar inside an oven that is
programmed to follow the temperature inside the Dewar to achieve adiabaticity. But you can
also use a cheap domestic item (sold by Thermos or Camping Gaz) in which the original
plastic cap is replaced by welding a thread to hold a cap equipped with thermocouples, a
pressure gauge (and an optional agitator, rupture disk and blow-down valve). Dewar
calorimeters have a good sensitivity because of the large amount of chemicals used, and the
mixing can be very good with mechanical agitation. The f factor is typically 1.1 for a
stainless steel vessel, and 1.8 for a glass one. Only the stainless steel vessel can be used for
pressure experiments and these must be performed in a laboratory equipped with blast cells
from which personnel are excluded during experiments. The results are comparable to those
from VSP or PHI TEC but maximum pressures are limited to the order of 25 bar (as opposed
to ~140 bar) and maximum temperature tracking rates are ~ 20 to 30omin-1.
The Dewar flask can be recommended for reactions with a moderate final pressure
b) ARC. Accelerating Rate Calorimeter.
The sample is placed in a small bomb and heated until the initial runaway temperature. The
external heater then tracks the sample temperature to ensure adiabaticity (in fact 3 different
modes can be used, Heat Wait and Search, isothermal and Ramp Wait Search procedures).
Due to the heat capacity of the bomb (to avoid its rupture), the f factor for the ARC is high:
typically 2 or 4 (extreme values are 1.2 to 9). In some cases, this can allow a better
understanding of complex kinetics. These f factor values prohibit the use of data directly for
vent sizing and, as we said before, can lead to wrong determination of the adiabatic
temperature rise. ARC data needs careful correction (see use of data). Also the thermocouple
is located outside the cell and this can lead to wrong interpretation of data in the case of a
viscous solution or very fast reaction. Runaway detection is very good, and a low “onset”
temperature is detected; sensitivity can be down to 0.02°C/min.
No mixing and no remote feeding is possible: the use of metal cells may present chemical
compatibility problems in some circumstances. Kinetic results can be obtained only if the
experiment goes to completion (no cell rupture) so it is recommended to use techniques such
as DSC, DTA, RSST or an Autoclave to define experiments. The ARC is the most commonly
used adiabatic equipment for thermal run-away detection; recent improvements in the
software have been made.
The ARC is very good for detecting runaways, and understanding decomposition, but
correction of data is necessary for scale-up. The latter requires some modelling or
assumptions about the reaction kinetics. The equipment has physical limits (feeding, mixing,
etc.)
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c) VSP – PHITEC – APTAC
The concept is the same for these three different bench scale calorimeters. Low thermal inertia
is achieved by using a very thin-walled test cell within a larger pressure containment vessel.
The weakness of the test cell is compensated for by maintaining the pressure in the
containment vessel essentially equal to that in the test cell so as to prevent cell rupture. A
pressure control system which can either add or vent nitrogen from the containment vessel is
provided for this purpose.
These calorimeters have a very low f factor, good exotherm detection sensitivity (of the order
of 0.02°C/min) and a wide range of both temperature (up to 500°C) and pressure (up to 200
bar). The Heat Wait Search routine, relatively good mixing, open or closed cell tests and
remote feeding possibilities are all features. These devices give very accurate and useful data
to characterise runaways and to use for designing reactor venting systems. Nevertheless, a
high level of expertise is required to operate the equipment and to interpret results. One must
ensure good calibration of the different sensors for heat loss compensation (which is both
temperature and pressure dependent) and oven regulation. One should also try to avoid any
cell rupture. Other screening devices with pressure information may need to be used for initial
tests. Testing using these types of calorimeter is expensive and time-consuming.
These types of calorimeter offer perhaps the best technique to obtain very accurate data, but
they can only be used as a complement to other tests in a well-equipped laboratory. Detailed
adiabatic testing is often carried out at a fairly late stage of process development.
d) RSST – Reactive System Screening Tool
As its name implies, this calorimeter is useful for screening purposes and is smaller and than
those described above. The test is non-adiabatic, but relies on a constant small heat input to
the sample which compensates for heat losses and which raises the sample temperature. Tests
are performed in a 10 ml open cell test with low f factor (1.05) and magnetic stirrer. Nitrogen
pressure in the containment vessel is used to suppress boiling from the sample: feeding is
possible. The new version called ARSST can work with the Heat Wait Search procedure,
although the earlier equipment only works with a constant heating ramp (as is often used in
DSC). Temperature and pressure information are obtained and round robin tests showed good
agreement between RSST and VSP experiments. When used with special formulae, the results
should be safe (but might be over conservative) for relief system sizing. Due to its design,
RSST can easily be used for screening up to 500°C. All spare parts can be changed for each
test.
Given that adiabatic conditions are difficult to produce and that so many details may influence
the heat rate and gas generation rate data, the results obtained from RSST experiments seem
surprisingly good.
RSST is a useful tool for screening, but data must be used very carefully, and in some cases,
genuine adiabatic tests are required.
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6.5 How to use data
To use data from adiabatic experiments, one must be very careful about:
- How the data was obtained (type of calorimeter, adiabaticity, acquisition rate etc.)
- How the data was reduced, smoothed or processed (to avoid noise but to keep vital
features and to generate derived data)
- Problems occurring during the experiment (lack of adiabaticity, leaks between the test cell
and containment vessel, cell rupture, oven regulation problems, etc.)
A high level of expertise is needed to interpret the results and it is of course better when the
same person can perform the experiment and interpret results.
“Onset” temperature determination must be expressed with the experimental conditions used
to determine it and always quoted together with the threshold detection rate.
For kinetic and thermodynamic results, two cases must be described:

In both cases it is assumed that the temperature rise observed is proportional to the degree of
conversion and that the rate constant depends on the temperature according to the Arrehnius
law.
6.5.1. In the case of a low f factor (< 1.1)
a) Thermodynamics
The adiabatic increase of temperature can directly be deduced from experimental data:
DTad = (Tend - Tonset ) [Eq. 6.2]
From this value, it is possible to estimate global decomposition enthalpy (assuming a mean
value for the specific heat of the reaction mixture):
- DH dec = m × c v × DTad [Eq. 6.3]
b) Kinetics
(T - Tonset )
Thermal conversion can be expressed by a: a =
(Tend - Tonset )
So the classic kinetic expression: v = f (T ) × g (a ) expressed assuming Arrhenius dependency
æ -E ö
da ç ÷
= Z × e è RT ø g(a ) can be written in the case of a unique nth order reaction :
dt
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æ -E ö æ -E ö
dT ç ÷ Z ç ÷
= Z × e è RT ø × (1 - a ) = × e è RT ø × (Tend - T )
n n
[Eq.6.4]
dt (DTad ) n -1
Or rewritten as
æ dT ö æ Z ö
lnç ÷ = lnç ÷ - E + n × ln (Tend - T ) [Eq. 6.5]
ç n -1 ÷
è dt ø è (DTad ) ø RT
æ dT ö 1
So, when performing multilinear regression with lnç ÷ as dependant variable and and
è dt ø RT
ln (Tend - T ) as independent variables, one can determine E (activation energy) and n (order of
reaction)
As a final step, the Time to Maximum Rate (TMR) can be calculated:
E æ 4 × n × R × Tend ö
TMR = × çç 1 + - 1÷÷ [Eq. 6.6]
2×n×R è E ø
Other methods can be used to determine kinetic parameters, assuming first or second order
reactions (or more complex kinetics) and useful information can also be obtained for auto-
catalytic systems.
6.5.2. In the case of a high f factor (> 1.1)
a) Thermodynamics
The adiabatic increase of temperature can be calculated from the experimental temperatures
and the f factor :
DTad ,ideal = f × (Tend - Tonset ) [Eq. 6.7]
b) Kinetics
In relation to the ARC a method (proposed by D.I. Townsend and J.C. Tou) for phi factor
correction for exotherm data near the “onset” temperature, or for zero order kinetics, is:
æ dT ö æ dT ö
ç ÷ = f×ç ÷ [Eq. 6.8]
è dt ø ideal è dt ø mesl
A method was proposed to correct the whole heat rate curve, but this method is not generally
satisfactory.
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It is necessary to be familiar with the theory by Townsend and Tou to have a good
understanding of the correction methods.
When the experimental heat rate data must be corrected to adiabatic conditions at a
temperature far from the onset temperature, and when the reaction is not zero order, a method
was proposed by Fisher, after Huff.
In this method, the “onset” temperature is first re-calculated:
1 1 R
= + × ln [Eq. 6.9]
T0 To, mes E
This correction takes into account the fact that for a given onset detection sensitivity of the
experimental device, the onset temperature would have been lower if the f factor was 1.
Then an adjusted temperature Ta for f=1 is calculated:
Ta = T0 + f × (Tmes - T0 ) [Eq. 6.10]
The corrected heat rate for f=1 is obtained from the measured heat rate by :
é dT ù éE æ 1 1 ö ù é dT ù
ê dt ú = f × EXP ê × çç - ÷÷ ú × ê ú [Eq. 6.11]
ë û F =1 ëê R è Tmes Ta ø ûú ë dt û F >1
Other methods are available to correct data obtained with a high f factor, but for each one you
need kinetic information (a good kinetic fit to the data and an activation energy) to recalculate
the temperature heat rates for phi = 1.
6.5.3. Pressure information
Kinetic modelling is also possible from pressure measurements after correction for the initial
presence of any inert gases (assuming the ideal gas law). For high vapour pressure systems,
the corrected pressure when plotted on a log scale is often a linear function of reciprocal
absolute temperature (i.e. an Antoine type relationship is followed).
A deviation from what was initially a vapour pressure type curve may indicate the production
of non-condensable gases. Pressure increases resulting from production of non-condensable
gases can be expressed as a function of conversion. The kinetics of both temperature and
pressure development can be compared to validate reaction details (e.g. order of reaction,
single/multiple reactions, etc.)
6.6. How to use data for vent sizing
At a final step, a reactor pressure relief vent may need to be designed to protect an industrial
installation in the event of a thermal runaway. A good safety vent must be designed to avoid
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increase of pressure above the maximum allowable pressure of the reactor. In order to predict
the two phase mass flux, pressure and temperature during venting, one needs to consider the
following equations: overall mass balance, gas component balance, energy balance and
equation of state.
Data from adiabatic calorimetry allows determination of:

· System classification; Vapour pressure (pressure developed as a consequence of
increasing vapour pressure), Gassy (pressure developed as a consequence of non
condensable gas production) or Hybrid (a combination of the two).
· Rate of heat generation. dT/dt and dP/dt under real adiabatic conditions. To be used
these values must be obtained with a very low phi factor (close to unity).
· Type of discharge from the vent. Foamy, bubbly, churn turbulent or all gas/vapour.
This determination at the laboratory scale is topic of ongoing discussion. Extrapolation
to the large scale requires care and is subject to some uncertainty.
Examples of equations used for vent sizing for a vapour system Leung, J.C. (1986):
m0q
[Eq. 6.12]
A ideal = 2
éæ 1
ù
v h fg ö÷
2
G êç + (cpf DT ) 2 ú
1
×
êç m0 v fg ÷ ú
ëè ø û
[Eq. 6.13]
m 0q
A ideal = 2
éæ 1
ù
æ dP ö ö
2
v
× Ts ç ÷ ÷÷ + (c pf DT ) 2 ú
1
G êçç
êè m 0 è dT ø ø ú
ë û
A = 1.510 -5 ×
m 1 æ dT ö
×ç ÷ (T = Ts ) [Eq. 6.14]
F Ps è dt ømanip1
This equation can only be used with RSST values
Examples of equations used for vent sizing for a Gassy system :
m r V0bm [Eq. 6.15]

A ideal =
æ Pm ö V0
Gçç ÷÷ ×
è a 0 ø mr
Leung, J.C. (1987)
m r V0bm [Eq. 6.16]

A ideal =
æP ö
G çç m × V1÷÷ + bm V0 Dt (1 - x1 )
a
è 0 ø
Singh, J (1994)
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Vent sizing must be done with care: account must be taken of the experimental conditions at
which raw data were obtained and extrapolability of this raw data. (Extensive extrapolation
without additional verification should never be made). The worst credible maloperation must
be defined and the range of validity of formula checked.
Actually for a complex system (e.g. in which the physical properties of the chemicals
involved are not well known) results from vent sizing calculations must be taken as
indicative. A safety factor may be required so as not to underestimate the correct vent size:
(this factor is already included in simplified formula given above).
6.7. Tabulated comparison
Apparatus Adiabatic Low Pressure Heat Closed Easy to Stirring

f factor compensati Wait cell test use
on Search
Carius tube X
Dewar flask X X X X X
RSST X X X X
ARC X X X X X
VSP – X X X X X X
PHITEC
APTAC
6.8. Nomenclature :
Z : pre-exponential factor
E : Activation energy
R : Ideal gas constant
Tr : Reaction temperature
Tj : Jacket temperature
DTad : Adiabatic temperature rise
Tend : Final temperature of the experiment
DHdec : Decomposition enthalpy
mr : reaction mass
Cv : specific heat at constant volume
a : Thermal conversion
n : order of reaction
Tideal : Temperature in real adiabatic condition
Tmes : Temperature measured during experiment
To = Tonset = Initial temperature of a “run away” – detected by the instrument
Vent sizing formula :

M0 : Initial mass (batch)
Q : Specific heat release rate
G : Mass flux
v : Specific volume
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hfg : Latent heat of vaporisation

vfg : Specific volume difference between vapour and liquid
cpf : Liquid specific heat at constant pressure
DT : “over-temperature” corresponding to over pressure
A : Vent area
F : Flow reduction factor
Ps : Set pressure
dT/dt : Temperature rise rate, self-heat rate
Ts : Set temperature
dP/dt : pressure rise rate
m = mr : Mass of reactant
bm : Maximum rate of pressure rise per unit mass of reactant
Pm : Turnaround pressure
a0 : Void fraction
x1 : Mass fraction of vapour
Dt : tm-tv, difference in time corresponding to Pm – Pv
V1 : Specific volume
V0 : Vessel internal volume
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6.9. References :
Etchells, J.; Wilday, J. Workbook for chemical reactor relief system sizing, HSE Books,
Contract research report 136/1998
Townsend, D.I.; Tou, J.C. Thermochimica Acta no 37, pp 1-30, 1980
Fisher, H.G. 5th DIERS Users Group Meeting Seattle, May 1989
Huff, J.E. Plant Operations Progress, Vol 1 no 4, pp 221-229, October 1992
Gustin, J.L. 6th Symp Loss Prevention and safety Promotion in the process Industry, Oslo
Norway, June 19-22 1989, paper no 75
Fauske, H.C.; Leung, J.C. CEP August 1985, p10
Rogers, R.L. The advantages and limitations of adiabatic Dewar calorimetry in chemical
hazard testing, International symposium on runaway reactions March 7-9, 1989 – Cambridge
Massachusetts, ppP 281-292
Fauske, H.K.; Clare, G.H.; Jo Creed, M. Laboratory tool for characterizing chemical systems
Ibid p.364-371
Singh, J. PHI TEC: Enhanced vent sizing calorimeter – application and comparison with
existing devices, International symposium on runaway reactions, March 7-9 1989,
Cambridge, Mass, USA (AIChE)
Ottaway, M.R. Thermal hazard evaluation by accelerating rate calorimetry, analytical proc,
23:116, 1986
DIERS Reports : Bench scale ERS Sizing Tools : Equipment details and test procedures :
FI/84-4, 1984 (AIChE, USA)
Semenov, N.N. 1928, Z Phys Chem, 48/571.
Frank Kamenetskii, DA, 1989, Diffusion and heat transfer in chemical Kinetics, 2nd edition
(Plenum Press, London, UK).
Barton, J.; Rogers, R. Chemical reaction hazards, IChemE. ISBN 0-85295-341-0
Leung, J.C. (1986), AIChE Journal, October 1986, Vol 32, no 10
Leung, J.C. (1987), AIChE Journal, June 1987, Vol 33, no 6
Singh, J. J. Loss Prevention in the Process Industries, 1994, Vol 7, no 6
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HarsNet HAZARD ASSESSMENT OF HIGHLY REACTIVE SYSTEMS

Keywords: Runaway, exotherm, adiabatic calorimetry, thermodynamic, kinetic, phi factor,

Item Volume Cooling time Cooling rate Heat loss*

6.2. Information required

We want to answer the following questions :

Thermal behaviour. Is there a thermal hazard ?

6.3. Techniques available

Methanol / Acetic Anhydride

12 Initial Temperatute=20,2°C 135

Final pressure =14,8 bara

b) Have a thermal inertia, f, close to unity.

Thermal mass of sample and test cell

c) Work with a Heat, Wait and Search routine.

Figure 6.2. Heat-Wait-Search experiment

d) Work at conditions close to the industrial ones

Comparison Comparison Kinetic

120 Relief Temperature in pilot experiment

6.4. Comparison of techniques and relative merit

b) ARC. Accelerating Rate Calorimeter.

c) VSP – PHITEC – APTAC

d) RSST – Reactive System Screening Tool

6.5 How to use data

For kinetic and thermodynamic results, two cases must be described:

6.5.1. In the case of a low f factor (< 1.1)

DTad = (Tend - Tonset ) [Eq. 6.2]

- DH dec = m × c v × DTad [Eq. 6.3]

As a final step, the Time to Maximum Rate (TMR) can be calculated:

6.5.2. In the case of a high f factor (> 1.1)

DTad ,ideal = f × (Tend - Tonset ) [Eq. 6.7]

In this method, the “onset” temperature is first re-calculated:

Ta = T0 + f × (Tmes - T0 ) [Eq. 6.10]

6.5.3. Pressure information

6.6. How to use data for vent sizing

Data from adiabatic calorimetry allows determination of:

This equation can only be used with RSST values

Examples of equations used for vent sizing for a Gassy system :

m r V0bm [Eq. 6.15]

Leung, J.C. (1987)

m r V0bm [Eq. 6.16]

6.7. Tabulated comparison

Apparatus Adiabatic Low Pressure Heat Closed Easy to Stirring

Vent sizing formula :

hfg : Latent heat of vaporisation

Townsend, D.I.; Tou, J.C. Thermochimica Acta no 37, pp 1-30, 1980

Huff, J.E. Plant Operations Progress, Vol 1 no 4, pp 221-229, October 1992

Fauske, H.C.; Leung, J.C. CEP August 1985, p10

Semenov, N.N. 1928, Z Phys Chem, 48/571.

Barton, J.; Rogers, R. Chemical reaction hazards, IChemE. ISBN 0-85295-341-0

Leung, J.C. (1986), AIChE Journal, October 1986, Vol 32, no 10

Leung, J.C. (1987), AIChE Journal, June 1987, Vol 33, no 6

Singh, J. J. Loss Prevention in the Process Industries, 1994, Vol 7, no 6

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