Ethylene oxide (EO) is a very versatile compound with considerable energy in its ring structure. Its reactions proceed mainly via ring opening and are highly exothermic. Under some conditions, it is known to undergo a variety of reactions, such as isomerization, polymerization, hydrolysis, combustion and decomposition Due to its very reactive characteristic and widely industrial applications, EO has been involved in a number of serious incidents such as Doe Run 1962, Freeport 1974, Deer Park 1988 and Union Carbide Corporation’s Seadrift 1991. The impacts can be severe in terms of death and injury to people, damage to physical property and effects on the environment. For instance, the Union Carbide incident in 1991 caused one fatality and extensive damage to the plant with the property damage of up to 80 million dollars. Contamination has a considerable impact on EO reactivity by accelerating substantially its decomposition and playing a key role on EO incidents. In this work, the reactivity of EO with contaminants such as KOH, NaOH, NH4OH, and EDTA is evaluated. Useful information that is critical to the design and operation of safer chemical plant processes was generated such as safe storage temperatures (onset temperature), maximum temperature, maximum pressure, temperature vs. time, heat and pressure generation rates as a function of temperature and time to maximum rate using adiabatic calorimetry. A special arrangement for the filling-up of the cell was constructed due to the gaseous nature and toxicity of EO. A comparison of their thermal behavior is also presented since several contaminants are studied.

Due to strict placement time and strength constraints during the construction of concrete pavement repair slabs, accelerators must be incorporated into the mixture design. Since the most common accelerator, calcium chloride, promotes corrosion of concrete reinforcement, a calcium nitrate-based accelerator was studied as an alternative. To replicate mixtures used in the field, commercial accelerators commonly used in concrete pavement repair slabs were used in the current study. Crack risk of different mixtures was assessed using modeling and cracking frame testing. HIPERPAV modeling was conducted using several measured mixture properties; namely, concrete mechanical properties, strength-based and heat of hydration-based activation energies, hydration parameters using calorimetric studies, and adiabatic temperature rise profiles. Autogenous shrinkage was also measured to assess the effect of moisture consumption on concrete volume contraction. The findings of the current study indicate that the cracking risk associated with calcium nitrate-based accelerator matches the performance of a calcium-chloride based accelerator when placement is conducted during nighttime hours.

Adiabatic calorimetry provides accurate and precise specific heat (Cp) data. From this data, thermodynamic functions may be calculated. Cu2OCl2, melanothallite, became of interest as part of a study of a particular thermochemical cycle. The experimental specific heat data and the calculated thermodynamic functions are reported here. Free energies of formation, calculated from the thermodynamic functions, suggest the particular cycle of interest with this compound as an intermediate is not feasible; uncertainty as to the accuracy of CuO and CuCl2 data used in the calculations indicate further study may be necessary. Upon collection of the specific heat data, an antiferromagnetic transition was observed at 70 K; this led to examination of the magnetic heat capacity and entropy of the transition in melanothallite. The entropy of the transition was estimated to be 18.1 % and 7.5 % of 2Rln2 by two methods. A theoretical calculation using an Ising model produced a result of 39 %. This is consistently low when compared to the entropies of the antiferromagnetic transitions of CuO and CuCl2. This suggests geometric frustration. This thesis reports the thermodynamic functions calculated from the specific heat; the examination of the magnetic entropy; and repairs to an adiabatic apparatus involved in the collection of this data.

Student Number : 9900772K - MSc research project - School of Civil and Environmental Engineering - Faculty of Engineering and the Built Environment / The hydration of cement is an exothermic reaction, which begins almost immediately upon contact with water. This produces a large amount heat that subsequently raises the temperature of the concrete mixture, creating a temperature gradient across the member. The temperature rise associated with hydration induces thermo-mechanical stresses. These stresses can cause damage to the structure, affecting the durability and in extreme cases the functionality of the structure. If the maximum rate of heat evolution experienced can be minimised through the selection of the constituents of a concrete mixture, then the thermal stresses that develop in the concrete can be reduced. The main aim of this research is to develop a knowledge of how the heat evolution characteristics of concrete are affected by changing certain concrete mixture parameters and ingredients. The focus is on the addition of three different cement extenders and varying the water/cement ratio. This will be a step towards the development of a model for predicting the thermal properties of concrete. As a part of this investigation, a prediction model for the change in heat rate in concrete was developed. The model is intended to predict the contribution of the individual clinker crystallographic phases in cement and the heat liberated in concrete during hydration.