GVS Cibatech Pvt. Ltd.

,
Firex Testing Laboratory,
A Wing, Ground Floor, LBS Marg,
Bhaichand Textile Compound,
Bhandup (West),
Mumbai – 400 078
Tel:+91-22-25961246

ACCELERATING RATE CALORIMETER

EXPERIMENTAL REPORT

REPORT NO.: CAL/A0421811 Date: 02/11/2018

PAGE NO. : 1 OF 11

SAMPLE NAME : Reaction Mass Step-3

BATCH NO. : -

SAMPLE DESCRIPTION : Slurry

: Excel Crop Care Limited

SAMPLE SOURCE
6/2, Ruvapari Road,
Bhavnagar – 364005.

Mr. Bhavesh Shah

DATE OF SAMPLE RECEIPT : 30/10/2018

PARAMETER REQUESTED : Thermal stability and TMRAD

------------------------------------------------------------------------------------------------------------------------------

Authorised Signatory
V.V.Bhujle
Senior Vice President-Technical
These results are valid only for the sample tested. The test results reported are valid under the stated conditions of measurements. Any correction invalidates
this report. The test report shall not be reproduced except in full, without written approval of the laboratory.Report is submitted without legal responsibility.
 PAGE 2 OF 11

SCHEMATIC DIAGRAM OF ARC (ACCELERATING RATE CALORIMETER)

 PAGE 3 OF 11

EXPERIMENTAL PROCEDURE

Accelerating rate calorimetry aids in the evaluation of hazard prediction for reactive chemicals. The
Accelerating Rate Calorimeter permits a small sample of a chemical to undergo thermal decomposition
due to self-heating. The primary data given in this report are the temperature and pressure variations
as a function of time during such a 'thermal runaway' reaction. Secondly, certain modelling functions
based upon the experimental values are presented.

The specified amount of sample is introduced into the sample container (or 'bomb'), which is in turn
mounted in the calorimeter, and the temperature and pressure sensors are attached.

The calorimeter is then rapidly heated to the 'Start Temperature' after which either an Isothermal Age
mode or a Heat-Wait-Seek sequence is entered, to determine onset of sample self-heating. After each
'Heat' step there is a 'Wait' period intended to allow the sample-bomb system to reach thermal
equilibrium. This in turn is followed by a self-heating 'Seek' period.

When less than the present self-heat rate threshold ('Slope Sensitivity') is observed during the Seek
mode, or at the end of the Isothermal Age time, a Heat step is applied to the sample and bomb. The
Heat-Wait-Seek sequence is repeated until the 'End Temperature' is reached or until self-heating is
detected above the 'Slope Sensitivity' threshold. At this point the reaction is allowed to proceed under
very closely controlled adiabatic conditions and time, temperature and pressure data are collected and
stored. Detailed procedures and information can be found in the Accelerating Rate Calorimeter
Instruction Manual.

TMRAD : The Time to maximum rate under adiabatic condition is defined as the time gap at the given
temperature to the point of the maximum decomposition reaction.

TMR indicates the time it takes for a reaction mass to reach the maximum rate of heat release for a given
starting temperature. In an adiabatic system, no heat exchange occurs between the material and the
surroundings; this means that the total heat generated remains in the system and increases its
temperature.

The TMR value provides operating personnel a measure of “response time”. It allows one to make
decisions concerning possible actions to be taken in case heat transfer is lost during processing.
Knowledge of the TMR allows decisions to be based on an understanding of the time frame available for
corrective measures.

……CONTINUED
 PAGE 4 OF 11

PROBABILITY

Probability can be evaluated using time scale after cooling failure, whether enough time left to take safety
measures.

HIGH < 8 hr – Case 2

MEDIUM 8 hr < TMRAD < 24 hr – Case 1
LOW > 24 hr

TMRAD < 8 hr not generally recommended

GENERAL PRECAUTIONS

Accelerating rate calorimetry is useful for evaluating exothermic runaway processes. However, caution
should be used when relating accelerating rate calorimetry data to an actual plant process especially if
significant extrapolations of the data or in the thermal inertia, Φ, are involved. Also, many of the
mathematical relationships used herein are assumed valid only for non-autocatalytic, simple, single
reactions. It is strongly recommended that predictions for full scale chemical processing, storage or
handling procedures should not be based solely upon the results of this report.

DISCLAIMER

The work carried out and reported herein has been obtained with all due care and competence by the
signatory or other professionally qualified and fully trained person. The Accelerating Rate Calorimeter
used in this work has been utilised in as expert a way as possible. The method conforms to the method
described in ASTM E1981-98 Standard Guide for Accessing the Thermal Stability of Materials by
Methods of Accelerating Rate Calorimetry procedure. The results submitted on the basis that they
constitute and are considered to be a reliable representation of the received material and its behaviour in
the test. Further to this no warranty can be given to the data and its application. Acceptance of the data
implies agreement with this. Whilst every effort will be given to aid the Customer in understanding and
interpreting the data, help will not be given on the specific application of the data.

……CONTINUED
 PAGE 5 OF 11

1. SAMPLE DATA

1.1 Chemical Reaction mass Step-3

1.2 Formula -

1.3 Molecular Weight -

1.4 Density -

1.5 Purity -

1.6 Diluent/Solvent -

1.7 Test sample mass 2.857 g

1.8 Comments -

2. BOMB DATA

2.1 Type Bomb

2.2 Material Hastelloy

2.3 Bomb Volume (approx.) 9ml

2.4 Sample Volume (approx.) 2.8ml

2.5 Sample Atmosphere Air

……CONTINUED
 PAGE 6 OF 11

3. THERMAL INERTIA

(Mb) x (Cb)
Φ = 1 + ___________

(Ms) x (Cs)

where: Φ = Thermal Inertia

M = Mass (g)
C = Specific Heat (J/g 0C)

and subscripts: b = bomb

s = sample

Mb = 15.714g
Cb = 0.423 J/g ºC
Ms = 2.857 g
Cs = 1.8 J/g ºC

Φ = 2.29

4. EXPERIMENTAL CONDITIONS

PARAMETER VALUE

4.1 Start Temperature 60 ºC

4.2 End Temperature 450 ºC

4.3 Slope Sensitivity 0.02 ºC/min

4.4 Heat Step Temperature 3 ºC

4.5 Driver Heater Power 20 %

4.6 Wait Time 10 min

4.7 Seek Time 10 min

4.8 Data Step Temperature 1.0 ºC

4.9 Data Step Time 0.5 min

……CONTINUED
 PAGE 7 OF 11

5. EXPERIMENTAL RESULTS

During the test Exotherm was observed

Exotherm: The Exotherm starts at 126.1°C.

For First Exotherm:

The values below are for Bomb/Sample system, i.e. not phi - corrected.

5.1 Observed Onset Temperature (To) 126.1°C

5.2 Self Heat Rate at To 0.02°C/min
5.3 Temperature at Maximum Rate 196.24°C
5.4 Maximum Self Heat Rate 0.65°C/min
5.5 Maximum Pressure 47bar
5.6 Maximum Pressure Rate 0.32/min
5.7 Final Adiabatic Temp. (Tad) sys 210.28°C
5.8 Overall Adiabatic Temp. Rise (∆Tad) sys 84.18°C
5.9 Residual Pressure at 30°C 6 bar

Where (∆Tad) sys = (Tad) sys - To

The values below are for Bomb/Sample system, i.e. phi Φ - corrected.
5.11.1 Overall Adiabatic Temp. Rise (∆Tad) 192.77 °C

5.11.2 Final Adiabatic Temp. (Tad) 318.87 °C

5.11.3 Heat of Reation ∆H 346.98 J/g

5.11.4 TMRAD 8 hour 105°C

5.11.5 TMRAD 24 hour 83°C

Where (∆Tad) = (∆Tad) sys X Φ

∆H = (∆Tad) X Cs

……CONTINUED
 PAGE 8 OF 11

APPENDICES

6. REAL TIME DATA

6.1 Temperature as a function of Time

6.2 Temperature and Pressure as a function of Time
6.3 Pressure as a function of Temperature
6.4 Raw data of Time to maxmimum rate
6.5 Predicted Time to maximum rate (Phi Corrected)

……CONTINUED
PAGE 9 OF 11
 PAGE 10 OF 11

TMR

……CONTINUED
 PAGE 11 OF 11

Main Findings:
1. The material starts decomposing at 126.1 °C.
2. Overall Heat of Reation (∆H) is 346.98 J/g.
3. Temperature for TMRAD 8 hours (Time for maximum rate under adiabatic codition at 8 hours)
is approximately 105 °C.
4. Temperature for TMRAD 24 hours (Time for maximum rate under adiabatic codition at 24 hours)
is approximately 83 °C.
5. Maximum Pressure reached during exothermic decomposition is 47 bar.
6. At 30°C, Residual Pressure is 7 bar.
7. TMRAD at different temperatures:

TMRAD at 8 hour 105°C

TMRAD at 24 hour 83°C
TMRAD at 80°C ~ 29.1 hours
TMRAD at 70°C ~ 51.4 hours
TMRAD at 60°C ~ 93.7 days
TMRAD at 50°C ~ 177.2 days
TMRAD at 40°C ~ 349 days

------------------------------------------------------------------------------------------------------------------------------

Analyst
These results are valid only for the sample tested. The test results reported are valid under the stated conditions of measurements. Any correction invalidates
this report. The test report shall not be reproduced except in full, without written approval of the laboratory.Report is submitted without legal responsibility.