Period, induction

The induction period is one of the specific features of chain reactions. It has been studied in detail for the hydrogen combustion inside the ignition peninsula [239]. 

The induction period is manifested in that the reaction rate, increasing according to exp 9t becomes at a certain moment measurable by the experimental technique used. Note that the induction period depends on the technique sensitivity or on the replacement of one technique by another. 

In terms of a simplified hydrogen combustion mechanism, the overall rate of the pressure (p) variation is represented by the sum of variations in the partial pressures of Hg, Og, HgO, HgOg, H, 0, OH, and HOg. 

With Till given by Eq. (39.2) the time dependence of the pressure increment Ap is [230] 

if Apmin is the minimally measurable (at the technique sensitivity) value of Ap at the time t = t corresponding to the induction period, then with exp(9T) 1, 9T 

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Finally, the determination of the induction period (NF M 07-012) also reveals the potential of gum formation during storage. The fuei sampie is contained in a bomb filled with oxygen at 100°C, under a pressure of 7 bar and the oxygen pressure is monitored with time. The time corresponding to the first drop in pressure is noted, symptomatic of incipient oxidation. If no further events take place, the test is stopped after 960 minutes. This time corresponds thus to the maximum induction period. 

The European specification for unleaded gasoline has set a minimum induction period of 360 minutes. 

Stability to oxidation (induction period method) Oxygenates content... 

Oxidation stability (gasoline) (induction period) NFM 07-012 ISO/DlS 7536 ASTM D 525 Time necessary for a sample bomb under oxygen pressure to reach the critical induction point... 

Figure A3.14.2. Characteristic features of a clock reaction, illustrated for the Landolt reaction, showing (a) variation of product concentration witii induction period followed by sharp reaction event (b) variation of overall reaction rate witli course of reaction.

The Landolt reaction (iodate + reductant) is prototypical of an autocatalytic clock reaction. During the induction period, the absence of the feedback species (Irere iodide ion, assumed to have virtually zero initial concentration and fomred from the reactant iodate only via very slow initiation steps) causes the reaction mixture to become kinetically frozen . There is reaction, but the intemiediate species evolve on concentration scales many orders of magnitude less than those of the reactant. The induction period depends on the initial concentrations of the major reactants in a maimer predicted by integrating the overall rate cubic autocatalytic rate law, given in section A3.14.1.1. 

The bromate-ferroin reaction has a quadratic autocatalytic sequence, but in this case the induction period is detennined primarily by the time required for the concentration of the hiliibitor bromide ion to fall to a critical low value tlirough the reactions... 

Clock-type induction periods occur in the spontaneous ignition of hydrocarbon-oxygen mixtures [2], in the setting of concrete and the curing of polymers [3]. A related phenomenon is the induction period exhibited... 

Hansen L D and Hart R M 1978 Shelf-life prediction from Induction period J. Electrochem. Soc. 125 842... 

In addition to the initial reaction between nitric acid and acetic anhydride, subsequent changes lead to the quantitative formation of tetranitromethane in an equimolar mixture of nitric acid and acetic anhydride this reaction was half completed in 1-2 days. An investigation of the kinetics of this reaction showed it to have an induction period of 2-3 h for the solutions examined ([acetyl nitrate] = 0-7 mol 1 ), after which the rate adopted a form approximately of the first order with a half-life of about a day, close to that observed in the preparative experiment mentioned. In confirmation of this, recent workers have found the half-life of a solution at 25 °C of 0-05 mol 1 of nitric acid to be about 2 days. ... 

Experimental results are in general conformity with the Avrami equation, but the interpretation of various observations is still complicated in many instances. One intriguing observation is that the induction period for nucleation is inversely proportional to the length of time the liquid is held in the liquid state after previous melting. This dependence on prior history may be qualitatively understood... 

Inhibitors and retarders differ in the extent to which they interfere with polymerization, and not in their essential activity. An inhibitor is defined as a substance which blocks polymerization completely until it is either removed or consumed. Thus failure to totally eliminate an inhibitor from purified monomer will result in an induction period in which the inhibitor is first converted to an inert form before polymerization can begin. A retarder is less efficient and merely slows down the polymerization process by competing for radicals. 

Reactivity Acrolein is a highly reactive chemical, and contamination of all types must be avoided. Violent polymerization may occur by contamination with either alkaline materials or strong mineral acids. Contamination by low molecular weight amines and pyridines such as a-picoline is especially hazardous because there is an induction period that may conceal the onset of an incident and allow a contaminant to accumulate unnoticed. After the onset of polymeriza tion the temperature can rise precipitously within rninutes. 

Properties. Silver difluoride melts at 690°C, bods at 700°C, and has a specific gravity of 4.57. It decomposes in contact with water. Silver difluoride may react violently with organic compounds, quite often after an initial induction period. Provisions must be made to dissipate the heat of the reaction. Small-scale experiments must be mn prior to attempting large-scale reactions. 

However, reaction 7 suffers other shortcomings, eg, entropy problems. Other proposals range from trace peroxidic contaminants to ionic mechanisms for generating peroxides (1) to cosmic rays (17). In any event, the initiating reactions are significant only during the induction period (18). 

Above about 250°C, the vapor-phase oxidation (VPO) of many organic substances becomes self-sustaining. Such oxidations are characterized by a lengthy induction period. During this period, peroxides accumulate until they can provide a source of new radicals to sustain a chain reaction. Once a critical threshold peroxide concentration is reached, the reaction accelerates very rapidly. 

Cool Flames. An intriguing phenomenon known as "cool" flames or oscillations appears to be intimately associated with NTC relationships. A cool flame occurs in static systems at certain compositions of hydrocarbon and oxygen mixtures over certain ranges of temperature and pressure. After an induction period of a few minutes, a pale blue flame may propagate slowly outward from the center of the reaction vessel. Depending on conditions, several such flames may be seen in succession. As many as five have been reported for propane (75) and for methyl ethyl ketone (76) six have been reported for butane (77). As many as 10 cool flames have been reported for some alkanes (60). The relationships of cool flames to other VPO domains are depicted in Figure 6. 

Propane. The VPO of propane [74-98-6] is the classic case (66,89,131—137). The low temperature oxidation (beginning at ca 300°C) readily produces oxygenated products. A prominent NTC region is encountered on raising the temperature (see Fig. 4) and cool flames and oscillations are extensively reported as compHcated functions of composition, pressure, and temperature (see Fig. 6) (96,128,138—140). There can be a marked induction period. Product distributions for propane oxidation are given in Table 1. 

Catalysts and Promoters. The function of catalysts in LPO is not weU understood. Perhaps they are not really catalysts in the classical sense because they do not necessarily speed up the reaction (25). They do seem to be able to alter relative rates and thereby affect product distributions, and they can shorten induction periods. The basic function in shortening induction periods appears to be the decomposition of peroxides to generate radicals (eq. 33). 

The free radicals initially formed are neutralized by the quinone stabilizers, temporarily delaying the cross-linking reaction between the styrene and the fumarate sites in the polyester polymer. This temporary induction period between catalysis and the change to a semisoHd gelatinous mass is referred to as gelation time and can be controUed precisely between 1—60 min by varying stabilizer and catalyst levels. 

In the absence of zinc oxide, cross-linking proceeds through an accelerator polysulfide. With TBSI (14) and other sulfenamides, the accelerator decomposes upon heating during the induction period (before cross-linking) as shown in Figure 2 (13). 

Fig. 5. Cure characteristics of accelerators A, thiuram B, dithiocarbamate C, sulfenamide D, thiazole and E, guanidine. The induction period represents...

To assist in control of the onset of vulcanization, a retarder or prevulcanization iuhibiter (PVI) is used. Retardation of the onset of cure does not mean that the rate of cure is slowed, in fact cure rate may actually be increased. Rather, there is an induction period prior to cure. 

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