Organic liquid peroxides

It will, thus, be necessary here for us to confirm a posteriori, with reference to some concrete example, the validity of the linear approximation of the selfheating process or curve, in the early stages, of 2 cm of a chemical of the TD type charged in the open-cup cell, or confined in the closed cell, in accordance with the self-heating property of the chemical, and subjected to the adiabatic self-heating test started from a 7. The confirmation illustrated below is performed with reference to the experimental data which are determined for the ten organic liquid peroxides and are listed in Table 8 in Subsection 5.7.1. 

Secondly, let us assume the mean value of T, to be 60 °C in the adiabatic selfheating tests performed each for the ten organic liquid peroxides charged each in the open-cup cell, because the value of T,. ranges from 26 °C for 69.5 % tert-hexyl peroxyneodecanoate in isoparaffin (THPN) to 100 °C for 99 % d -tert-butyl peroxide (DTBP), as stated in Subsection 5.4.1,... 

And lastly, let us assume that, at the time when the adiabatic self-heating test was started from a T, of 60 °C for 2 cm of an organic liquid peroxide charged... 

For details of the experimental procedure performed for each of the ten organic liquid peroxides, refer to Section 5.4. 

It is also of course possible to calculate the A for an arbitrary volume of a liquid confined in an arbitrary closed container and placed in the atmosphere under isothermal conditions by applying the reduced form of the Semenov equation. It is, however, required in such a case to obtain both the heat generation data and the heat transfer data of the liquid under confined conditions. In this connection, the adiabatic self-heating tests were performed, in the present chapter, at atmospheric pressure for nine organic liquid peroxides, other than DTBP, respectively, because these nine peroxides are not very volatile or do not decompose to evolve corrosive and/or toxic gases while tested, respectively. 

The values of the BAM test thus calculated each for ten organic liquid peroxides, including TBPB, ranged from 22.7 °C for THPN to 92.4 °C for DTBP. 

For the abbreviations of organic liquid peroxides tested herein, refer to Table 7 in Subsection 5.7.1. 

The final decision has thus been made herein that, in order to measure the main heat transfer data of an arbitrary volume of an organic liquid peroxide charged in an arbitrary container and placed in the atmosphere under isothermal conditions, kerosene, a sort of nonconducting liquid, is used in place of every organic liquid peroxide. 

The values of c of the ten organic liquid peroxides were measured by the adiabatic scanning calorimetry and are presented in Table 8 in Subsection 5.7.1, respectively. As noted down at the end of Section 2.4, the value of c of every chemical bears some temperature dependence. In this regard, the temperature at which the value of c of each individual organic liquid peroxide was measured is presented in parentheses after the corresponding value of c in Table 8. 

In order to compare the values of Tc calculated each for the ten organic liquid peroxides charged each in the container and placed each in the atmosphere under isothermal conditions with one another, however, it is required to calculate the individual values of T assuming that these peroxides are each placed under the same conditions of shape and size. The same is true of powdery chemicals of the TD type and of gas-permeable oxidatively-heating substances. 

A decision was thus made herein to calculate the individual values of the BAM test for the ten organic liquid peroxides by applying Eq. (72), assuming that 400 cm each of these peroxides are each charged in the 500 cm Dewar flask used in the BAM test and are each placed in the atmosphere under isothermal conditions. 

The value of the BAM test thus calculated for TBPB, 67.95483 t, is finally rounded to 68.0 t and is presented as such, together with the values of the BAM test calculated each for the nine organic liquid peroxides, other than TBPB, in the same manner as performed for TBPB, in Table 8 in Subsection 5.7.1. 

The list of the ten organic liquid peroxides tested herein is given in Table 7. These peroxides are all products of NOF Corporation. Taketoyo, Aichi, Japan, and were tested without further purification. 

The adiabatic self-heating tests for the nine organic liquid peroxides, other than TBPB, were also performed in the same manner as done for TBPB, respectively. 

The ten plots of aAt versus 1/71, made each for the ten organic liquid peroxides, including TBPB, arc presented in Fig. 55. 

It is possible to see roughly from Fig. 55 the relative liability of these organic liquid peroxides to self-heating or ultimate thermal explosion. That is, we can tell that THPN and TBPD are relatively easy to explode thermally, but TBPB and DTBP are relatively hard to do so. In this regard, TPIC and TBPC are medium in the liability to theimal explosion. 

Organic Liquid Peroxide CoefficiefUs of Eq. (44) a b Specific heat capacity c cal/ g-K> specific gravity gfcm (7W The value of the The value of the BAM test BAM test ealed. heroin measurod pc] cal/min K Go No Go ... 

The values of the BAM test calculated each for the ten organic liquid peroxides, including TBPB, are summarized in Table 8 in the order of increasing value of the BAM test, together with the corresponding values measured each actually by a series of BAM heat-accumulation storage tests performed at NOT Corporation, for comparison [23]. 

At all events, however, it will be reasonable, in practice, to consider a temperature 30 K lower than the value of the BAM test calculated herein for an organic liquid peroxide as the upper limit temperature for the safe handling of the peroxide. For instance, -10 °C will be the upper limit temperature for the safe handling of THPN, 10 °C for BPOD, 20 °C for TPIC, and so forth. 

The main heat transfer data of 5 or 10 L of kerosene charged in the con espoiiding 5 or 10 L polyethylene practical container, which is set under conditions of no air circulation in an aluminium box maintained at a T ei-up near 50 and settled in a fairly large themiostat. have been measured in temperature differences of 1.25 K between the T , and the in almost the same manner as perfomicd for 400 mL of kerosene charged in the Dewar flask in Subsection 5.5.3 (Fig. 57). These containcis arc used by NOF Corporation, Japan, to deliver 5 or 10 kg each of organic liquid peroxides to the users, respectively. The measurements of the 10 L polyethylene practical container with a 1.5 mm thick wall arc shown in Fig, 56,... 

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