Thermally degrading polyethylene studied by means of factor-jump thermogravimetry

Degradation of polyethylene in both linear (NBS 1475) and branched (NBS 1476) form has been studied in the range 410–475°C using factor-jump thermogravimetry. In vacuum, the rate of weight loss was erratic because of bubbling in the sample. The apparent overall activation energy was determined to be 65.4 ± 0.5 kcal/mol (273 ± 2 kJ/mol). There was no distinguishable difference between linear and branched samples. In slowly flowing N₂ at 8 mmHg (1 mmHg = 133 Pa), the overall activation energy was determined to be 64.8 ± 0.3 kcal/mol (271 ± 1 kJ/mol) for linear PE and 64.4 ± 0.2 kcal/mol (269 ± 1 kJ/mol) for a sample of PE with one percent branches. In N₂ at 800 mmHg, the values were 62.6 ± 0.5 kcal/mol for linear PE and 61.2 ± 0.6 kcal/mol for the branched sample, the rate of weight loss being smooth in both cases. Changing the linear flow velocities over the range 1–4 mm/sec at 800 mmHg did not affect the results. From the insertion of typical values in the equation relating the overall activation energy for weight loss from linear polyethylene to the activation energies of the component steps, a degradation mechanism involving scission β to allyl groups, with rapid hydrogen abstraction, slower subsequent β scission, and bimolecular termination, is indicated. The activation energy of β scission for secondary alkyl radicals is estimated to be 33 kcal/mol. The reason for the lower activation energies in N₂ is related to the effects of preformed molecules. The average molecular weights of the volatiles in vacuum and for 8 and 800 mmHg N₂ have been shown to be in the ratios 1 to 1/4 to 1/10, respectively, at these imposed rates of weight loss. The activation energies to use for the initial stage of degradation are 70.6 kcal/mol (295 kJ/mol) in vacuum and 67.8 kcal/mol (284 kJ/mol) at atmospheric pressure.     

Thermal degradation and oxidation of polystyrene studied by factor-jump thermogravimetry

Factor-jump thermogravimetry has been used to study the activation energy of polystyrene degrading in a vacuum, in N₂ flowing at 4 mm/s and in $\text{N}{}_2\text{O}{}_2$ mixtures. The results show the activation energy to be 44·9 ± 0·2 kcal/mole (188 ± 0·8 kJ/mole) for degradation above 350°C in vacuum or in flowing N₂. This agrees well with work reported in 1949 by Jellinek⁷ but with few results reported subsequently.The apparent activation energy for polystyrene losing weight above 280°C in an atmosphere of abundant O₂ is 21·5 ± 0·2 kcal/mole (90·2 ± 0·8 kJ/mole). In all cases where O₂ was deliberately introduced (partial pressures >4 mm Hg), the sample degraded to a black tar and the activation energy was ≤30 kcal/mole, depending on the amount of oxygen present and on the thermal history of the sample.     

Thermal degradation of polyisobutylene studied using factor-jump thermogravimetry

The overall activation energy of the thermal degradation of polyisobutylene has been measured using factor-jump thermogravimetry to be 206±1 kJ/mole over the range 365 to 405° in N₂ at 800 mm Hg pressure and flowing at 4 mm/s over the sample. This is consistent with some values reported for thermal degradation in vacuum and in solution. In 5 mm Hg of N₂, an apparent activation energy of 218±2 kJ/mole was found, and in vacuum the apparent activation energy is 238±13 kJ/mole. Troublesome bubbling made the vacuum values difficult to measure. Substitution of reasonable values for the activation energies of initiation,E _i , termination,E _t , and the activation energy,E _a , for vacuum degradation in the equationE _a =E _i /2E _d -E _t /2 yields an activation energy E_d=84 kJ/mole for the unzipping reaction. This equation presupposes a degradation mechanism of random initiation, unzipping, and bimolecular termination. Substitution of reasonable values for the heat of polymerization, ΔH, in the definition ΔH=E _p ?e _d suggests that the activation energy of the polymerization reaction at 375° is approximately 30 kJ/mole.     

Ethylbenzene solubility,diffusivity, and permeability in poly(dimethylsiloxane)

The pure‐gas sorption, diffusion, and permeation properties of ethylbenzene in poly(dimethylsiloxane) (PDMS) are reported at 35, 45, and 55 °C and at pressures ranging from 0 to 4.4 cmHg. Additionally, mixed‐gas ethylbenzene/N₂ permeability properties at 35 °C, a total feed pressure of 10 atm, and a permeate pressure of 1 atm are reported. Ethylbenzene solubility increases with increasing penetrant relative pressure and can be described by the Flory–Rehner model with an interaction parameter of 0.24 ± 0.02. At a fixed relative pressure, ethylbenzene solubility decreases with increasing temperature, and the enthalpy of sorption is −41.4 ± 0.3 kJ/mol, which is independent of ethylbenzene concentration and essentially equal to the enthalpy of condensation of pure ethylbenzene. Ethylbenzene diffusion coefficients decrease with increasing concentration at 35 °C. The activation energy of ethylbenzene diffusion in PDMS at infinite dilution is 49 ± 6 kJ/mol. The ethylbenzene activation energies of permeation decrease from near 0 to −34 ± 7 kJ/mol as concentration increases, whereas the activation energy of permeation for pure N₂ is 8 ± 2 kJ/mol. At 35 °C, ethylbenzene and N₂ permeability coefficients determined from pure‐gas permeation experiments are similar to those obtained from mixed‐gas permeation experiments, and ethylbenzene/N₂ selectivity values as high as 800 were observed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1461–1473, 2000     

The thermodynamic properties of magnesium uranoborate

The standard enthalpy of formation of crystalline Mg(BUO₅)₂ at 298.15 K (?4347.5 ± 8.0 kJ/mol) was determined by reaction calorimetry. The heat capacity of magnesium uranoborate was studied by adiabatic vacuum calorimetry over the temperature range 8–330 K. The thermodynamic functions of the compound were calculated. The standard entropy and Gibbs energy of formation at 298.15 K were found to be ?903.0 ± 2.1 J/(mol K) and ?4078.5 ± 9.0 kJ/mol, respectively.     

Homogeneous decomposition of vinyl ethers. The heat of formation of ethanal-2-yl

The thermal unimolecular decomposition of three vinylethers has been studied in a VLPP apparatus. The high-pressure rate constant for the retro-ene reaction of ethylvinylether was fit by log k (sec^?1) = (11.47 + 0.25) - (43.4 ± 1.0)/2.303 RT at <T> = 900 K and that of t - butylvinylether by log k (sec^?1) = (12.00 ± 0.27) - (38.4 ± 1.0)/2.303 RT at <T> = 800 K. No evidence for the competition of the higher energy homolytic bond-fission process could be obtained from the experimental data. The rate constant compatible with the C? O bond scission reaction in the case of benzylvinylether was log k (sec^?1) = (16.63 ± 0.30) - (53.74 ± 1.0)/2.303 RT at <T> = 750 K. Together with ΔH_f,300⁰(benzyl·) = 47.0 kcal/mol, the activation energy for this reaction results in ΔH_f,300⁰(CH₂CHO) = +3.0 ± 2.0 kcal/mol and a corresponding resonance stabilization energy of 3.2 ± 2.0 kcal/mol for 2-ethanalyl radical.     

Molecular motions of tactic poly(2-hydroxyethyl methacrylate) in solutions studied by 13C-NMR relaxation measurement

The spin-lattice relaxation time and the nuclear Overhauser enhancement were measured using Bruker AM 300 spectrometer operating at 75.5 MHz for ¹³C to investigate the molecular motional characteristics and its tacticity effect for tactic poly(2-hydroxyethyl methacrylate) (PHEMA) as a function of temperature in dimethyl sulfoxide and methanol solvents. The observed relaxation data have been analyzed for both backbone motion and methyl internal rotation according to the log-χ² distribution model and the diamond-lattice model. The correlation times thus obtained for the molecular motions show that isotactic PHEMA is more flexible than syndiotactic counterpart. The syndiotactic PHEMA seems to have intramolecular hydrogen bonding which restricts the motion of C-2 carbon at temperatures below 35°C, whereas the isotactic one indicated no hydrogen bonding at all temperatures examined in this study. The methyl group of isotactic PHEMA shows a greater degree of freedom for the internal rotation than that of syndiotactic one. From the temperature dependence of correlation times, the activation energies for both backbone segmental motion and methyl internal rotation are obtained. The activation energies, 20 kJ/mol for backbone motion and 19 kJ/mol for methyl internal rotation, for isotactic PHEMA are substantially lower than the corresponding activation energies of 30 and 32 kJ/mol obtained for syndiotactic one. An examination of these energies indicates that methyl side group and backbone motions in tactic PHEMA are linked together.     

The thermodynamic properties of magnesium uranoborate tetrahydrate

The standard enthalpy of formation of crystalline Mg(BUO₅)₂ · 4H₂O at 298.15 K (?5563 ± 10 kJ/mol) was determined by reaction calorimetry. The heat capacity of the compound was studied over the temperature range 8–340 K by adiabatic vacuum calorimetry, and its thermodynamic functions were calculated. The standard entropy and Gibbs function of formation at 298.15 K (?1692.2 ± 3.4 J/(mol K) and ?5059 ± 11 kJ/mol, respectively) were determined.     

Desorption kinetics of model polar stratospheric cloud films measured using Fourier Transform Infrared Spectroscopy and Temperature‐Programmed Desorption

This study combines Fourier transform infrared (FTIR) spectroscopy and temperature‐programmed desorption to examine the evaporation kinetics of thin films of crystalline nitric acid hydrates, solid amorphous H₂O/HNO₃ mixtures, H₂O–ice, ice coated with HCl, and solid HNO₃. IR spectroscopy measured the thickness of each film as it evaporated, either at constant temperature or during a linear temperature ramp (temperature‐programmed infrared, TPIR). Simultaneously, a mass spectrometer measured the rate of evaporation directly by monitoring the evolution of the molecules into the gas phase (temperature‐programmed desorption, TPD). Both TPIR and TPD data provide a measurement of the desorption rate and yield the activation energy and preexponential factor for desorption. TPD measurements have the advantage of producing many data points but are subject to interference from experimental difficulties such as uneven heating from the edge of a sample and sample‐support as well as pumping‐speed limitations. TPIR experiments give clean but fewer data points. Evaporation occurred between 170 and 215 K for the various films. Ice evaporates with an activation energy of 12.9 ± 1 kcal/mol and a preexponential factor of 1 × 10^32±1.5 molec/cm² s, in good agreement with the literature. The beta form of nitric acid trihydrate, β–NAT, has an E_des of 15.6 ± 2 kcal/mol with log A = 34.3 ± 2.3; the alpha form of nitric acid trihydrate, α–NAT, is around 17.7 ± 3 kcal/mol with log A = 37.2 ± 4. For nitric acid dihydrate, NAD, E_des is 17.3 ± 2 kcal/mol with log A = 35.9 ± 2.6; for nitric acid monohydrate, NAM, E_des is 13 ± 3 kcal/mol with log A = 31.4 ± 3. The α–NAT converts to β–NAT during evaporation, and the amorphous solid H₂O/HNO₃ mixtures crystallize during evaporation. The barrier to evaporation for pure nitric acid is 14.6 ± 3 kcal/mol with log A = 34.4 ± 3. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 295–309, 2001     

The thermodynamic properties of uranyl metaborate

The standard enthalpy of formation of crystalline UO₂(BO₂)₂ at 298.15 K was determined by reaction calorimetry (?2542.5 ± 3.5 kJ/mol). The heat capacity of this compound was measured over the temperature range 6–302 K by adiabatic vacuum calorimetry. The thermodynamic functions were calculated, including the standard entropy (502.8 ± 2.1 J/(mol K)) and Gibbs function of formation (?2392.5 ± 4.0 kJ/mol) at 298.15 K. The standard thermodynamic functions of reactions with the participation of uranyl metaborate were determined and analyzed.     

Kinetics of CN reactions with N2O and CO2

The rate constants for the reaction of CN with N₂O and CO₂ have been measured by the laser dissociation/laser-induced fluorescence (two-laser pump-probe) technique at temperatures between 300 and 740 K. The rate of CN + N₂O was measurable above 500 K, with a least-squares averaged rate constant, k = 10^−11.8±0.4 exp(−3560 ± 181/T) cm³/s. The rate of CN + CO₂, however, was not measurable even at the highest temperature reached in the present work, 743 K, with [CO₂] ⩽ 1.9 × 10¹⁸ molecules/cm³. In order to rationalize the observed kinetics, quantum mechanical calculations based on the BAC-MP4 method were performed. The results of these calculations reveal that the CN + N₂O reaction takes place via a stable adduct NCNNO with a small barrier of 1.1 kcal/mol. The adduct, which is more stable than the reactants by 13 kcal/mol, decomposes into the NCN + NO products with an activation energy of 20.0 kcal/mol. This latter process is thus the rate-controlling step in the CN + N₂O reaction. The CN + CO₂ reaction, on the other hand, occurs with a large barrier of 27.4 kcal/mol, producing an unstable adduct NCOCO which fragments into NCO + CO with a small barrier of 4.5 kcal/mol. The large overall activation energy for this process explains the negligibly low reactivity of the CN radical toward CO₂ below 1000 K. Least-squares analyses of the computed rate constants for these two CN reactions, which fit well with experimental data, give rise to for the temperature range 300–3000 K.     

The thermodynamic properties of calcium uranoborate

The standard enthalpy of formation of crystalline Ca(BUO₅)₂ at 298.15 K was determined by reaction calorimetry (?4491.0 ± 3.5 kJ/mol). The heat capacity of the substance was measured over the temperature range 7–304 K by adiabatic vacuum calorimetry, and its thermodynamic functions were calculated. The standard entropy and the Gibbs function of formation at 298.15 K were found to be ?887.1 ± 2.1 J/(mol K) and-4226.5 ± 4.0 kJ/mol, respectively. The standard thermodynamic functions of calcium uranoborate synthesis reactions were calculated and analyzed.     

The heat of formation of C2F4

The CCSD(T) atomization energies are extrapolated to the complete basis set limit, and are corrected for zero-point energy, spin–orbit, core-valence, and scalar relativistic effects. Our best heats of formation at 298 K for CF₄ and C₂F₄ are −223.1±1.1 and −160.5±1.5 kcal/mol, respectively. The CF₄ value is in excellent agreement with experiment (−223.04±0.18 kcal/mol), while the C₂F₄ result suggests that the experimental value (−157.6±0.6 kcal/mol) has a larger error than believed. Our value for C₂F₄ also shows that the G3 value has the expected error of ±2 kcal/mol.     

Thermal degradation study of phenolphthalein polycarbonate

Phenolphthalein polycarbonate underwent complicated thermal degradation which included random scission, rearrangement, hydrolysis, Friedel-Crafts acylation, and cross-linking. The carbonate group and lactone ring were both susceptible to thermal deterioration. Kinetic parameters were determined from the dynamic TGA thermograms. During early stages of degradation the measured reaction order was nearly 1, which suggested a random chain scission mechanism. The measured activation energy was 42.6 kcal/mol, compared with 41.2 kcal/mol calculated from isothermal aging. The Arrhenius preexponential constant was 3.09 × 10¹¹ min^?1. Below 80% weight residue the plot of fractional weight against 1/T revealed that complicated reactions with different activation energies occurred simultaneously and resulted in a final overlap of TGA curves for different heating rates indicative of cross-linking and a lower preexponential constant. The reaction order changed and kept increasing in the last stages of degradation. Pyrolysis of this polymer was performed at 350°C under vacuum, followed by GC-mass spectroscopic identification of products. The volatile products (17.5%) contained CO₂, CO, O₂, H₂O, phenol, fluorenone, diphenyl carbonate, xanthone, anthraquinone, 2-hydroxylanthraquinone, 2-benzoxyanthraquinone, phenolphthalein, and trace amounts of benzoxyphenol and hydroquinone; the other 82.5% of products was insoluble gel. Functional group changes were examined by Fourier transform infrared spectroscopy (FT-IR). Lactone, carbonate, and aromatic absorptions decreased during degradation. Increasing absorptions at 1739, 1728, 1280–1200, and 1138–1075 cm^?1 were believed to result from aromatic ester (1728 cm^?1) and phenyl aromatic ester (1739 cm^?1) cross-linkages ortho to the aromatic ether group (increases at 1155 cm^?1 and 1280–1200 cm^?1). Existence of 2-hydroxyanthraquinone and xanthone contained in the crosslinked polymer matrix were also detected. Mechanisms for random scission, rearrangement, Friedel-Crafts acylation, hydrolysis, and cross-linking were suggested.     

Kinetics and equilibria in the system Br + t-BuO2H ⇆ HBr + t-BuO2. OH bond dissociation energy in t-BuO2-H

The kinetics and equilibria in the system Br + t-BuO₂H ? HBr + t-BuO₂· have been measured in the range of 300–350 K using the very low pressure reactor (VLPR) technique. Using an estimated entropy change in reaction (1) ΔS₁ = 3.0 ± 0.4 cal/mol·K together with the measured ΔG₁, we find ΔH₁ = 1.9 ± 0.2 kcal/mol and DHº (t-BuO₂-H) = 89.4 ± 0.2 kcal/mol ΔH_f·(tBuO₂·) = 20.7 kcal/mol and DH^º (t-Bu-O₂) = 29.1 kcal/mol. The latter values make use of recent values of ΔH_f·(t-Bu) = 8.4 ± 0.5 kcal/mol and the known thermochemistry of the other species. The activation energy E₁ is found to be 3.3 ± 0.6 kcal/mol, about 1 kcal lower than the value found for Br attack on H₂O₂. It suggests a bond 1 kcal stronger in H₂O₂ than in tBuO₂H.     

Very-low-pressure pyrolysis of N-methyl aniline and N,N-dimethyl aniline. Enthalpy of formation of the anilino and N-methyl anilino radicals

The kinetics of the thermal unimolecular decompositions of N-methyl aniline and N,N-dimethyl aniline into anilino and N-methyl anilino radicals, respectively, have been studied under very low-pressure conditions. The enthalpies of formation of both radicals, ΔH°_f,298°K(Ph?H,g) = 55.1 and ΔH°_f,298°K(Ph?Me,g) = 53.2 kcal/mol, which have been derived from the experimental data, lead to BDE(PhNH-H) = 86.4 ± 2, BDE[PhN(Me)-H] = 84.9 ± 2 kcal/mol and to a value of 16.4 kcal/mol for the stabilization energy of the PhNH radical (relative to MeNH). These results are discussed in connection with earlier work. At high temperatures, the anilino radical loses HNC and forms the very stable cyclopentadienyl radical, a decomposition comparable to that of the phenoxy radical.     

The thermodynamic properties of Ba2SrUO6

The standard enthalpy of formation of crystalline Ba₂SrUO₆ at 298.15 K was determined by reaction calorimetry (-2940.0 ± 8.5 kJ/mol). The heat capacity of the compound was measured over the temperature range 8-330 K by adiabatic vacuum calorimetry. The thermodynamic functions of Ba₂SrUO₆ were calculated. The standard entropy (-558.6 ± 2.1 J/(mol K)) and Gibbs function of formation at 298.15 K (-2773.5 ± 9.0 kJ/mol) were determined.     

Radical heterogeneous polymerization behavior of N‐methyl‐α‐fluoroacrylamide in benzene

The polymerization of N‐methyl‐α‐fluoroacrylamide (NMFAm) initiated with dimethyl 2,2′‐azobisisobutyrate (MAIB) in benzene was studied kinetically and with electron spin resonance. The polymerization proceeded heterogeneously with the highly efficient formation of long‐lived poly(NMFAm) radicals. The overall activation energy of the polymerization was 111 kJ/mol. The polymerization rate (R_p) at 50 °C is given by R_p = k[MAIB]^0.75±0.05 [NMFAm]^0.44±0.05. The concentration of the long‐lived polymer radical increased linearly with time. The formation rate (R_p?) of the long‐lived polymer radical at 50 °C is expressed by R_p? = k[MAIB]^1.0±0.1 [NMFAm]^0±0.1. The overall activation energy of the long‐lived radical formation was 128 kJ/mol, which agreed with the energy of initiation (129 kJ/mol), which was separately estimated. A comparison of R_p? with the initiation rate led to the conclusion that 1‐methoxycarbonyl‐1‐methylethyl radicals (primary radicals from MAIB), escaping from the solvent cage, were quantitatively converted into the long‐lived poly(NMFAm) radicals. Thus, this polymerization involves completely unimolecular termination due to polymer radical occlusion. ¹H NMR‐determined tacticities of resulting poly(NMFAm) were estimated to be rr = 0.34, mr = 0.48, and mm = 0.18. The copolymerization of NMFAm(M₁) and St(M₂) with MAIB at 50 °C in benzene gave monomer reactivity ratios of r₁ = 0.61 and r₂ = 1.79. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2196–2205, 2001     

Aqueous Polymerization of Methyl Methacrylate

Aqueous polymerization of methyl methacrylate (MMA), initiated by the potassium bromate-thioglycollic acid (TGA) redox system, has been studied at 30 ± 0.2° C under positive pressure of nitrogen. The rate is given by K[MMA] [TGA] ⁰[KBrO₃]^x where × = 1 for lower KBrO₃ concentrations and 0.5 for higher KBrO₃ concentrations. The reaction has been studied over the 20–45°C range. The activation energy was found to be 65.72 kJ/mol (15.71 kcal/mol) in the investigated range of temperature. Inorganic electrolytes except MnSO₄·4H₂O and Na₂C₂O₄ depress both the rate of polymerization and the maximum conversion. All the alcohols (viz., MeOH, EtOH, iso-PrOH, tert-BuOH) and acetone depress the rate of polymerization as well as the maximum conversion.     

The very low-pressure pyrolysis of phenyl ethyl ether,phenyl allyl ether,and benzyl methyl ether and the enthalpy of formation of the phenoxy radical

A value of the enthalpy of formation of the phenoxy radical in the gas phase, ΔH°_,298K (?O·, g) = 11.4 ± 2.0 kcal/mol, has been obtained from the kinetic study of the unimolecular decompositions of phenyl ethyl ether, phenyl allyl ether, and benzyl methyl ether

1 Trivial names for ethoxy benzene, 2-propenoxy (allyloxy) benzene, and α-methoxytoluene, respectively

at very low pressures. Bond fission, producing phenoxy or benzyl radicals, respectively, is the only mode of decomposition in each case. The present value leads to a bond dissociation energy BDE(?O—H) = 86.5 ± 2 kcal/mol,

2 1 kcal = 4.18674 kJ (absolute)

in good agreement with recent estimates made on the basis of competitive oxidation steps in the liquid phase. A comparison with bond dissociation energies of aliphatic alcohols, BDE(RO—H) = 104 kcal/mol, reveals that the stabilization energy of the phenoxy radical (17.5 kcal/mol) is considerably greater than the one observed for the isoelectronic benzyl radical (13.2 kcal/mol). Decomposition of phenoxy radicals into cyclopentadienyl radicals and CO has been observed at temperatures above 1000°K, and a mechanism for this reaction is proposed.