17 research outputs found
The Impact of Materials and Maintenance Considerations during the Design Stage of Public Buildings in Oman
The purpose of this study is to describe the experiences of architects and civil engineers in the Sultanate of Oman regarding building maintenance during the design of public buildings. This exploratory and descriptive study used a qualitative approach, drawing data from focus groups in particular, to develop a rich and in-depth description of the designers’ building maintenance experiences. Structured interviews were conducted with 15 participants from architecture and civil engineering fields, from which, the interviewees shared the viewpoint that maintenance functions entirely separate from the design and construction process itself, but that it is, in fact, an integral part of the design process and post-occupancy stage. The designer should plan for sufficient maintenance for the whole building life cycle. However, some elements are more difficult to maintain in Oman than in other regions such as roofs, facades and the substructure of buildings. The results showed that salt is the most challenging environmental factor that could cause building defects. This was followed by solar heat, moisture from below ground and, lastly, rain. Most of these defects occurred during the buildings’ post-occupancy phase and were related to inappropriate or poor design. The results also suggested that deficiencies caused by thermal expansion came in the form of cracks, followed by paint decay, dampness, and staining
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The reaction between silylene and ammonia: some gas-phase kinetic and quantum chemical studies
Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by 193 nm laser flash photolysis of silacyclopent-3-ene, have been carried out in the presence of ammonia, NH3. Second order kinetics were observed. The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas at each of the three temperatures, 299, 340 and 400 K. The second order rate constants (laser pulse energy of 60 mJ/pulse) fitted the Arrhenius equation:
log(k/cm3 molecule-1 s-1) = (-10.37 ± 0.17) + (0.36 ± 1.12 kJ mol-1)/RTln10
Experiments at other pressures showed that these rate constants were unaffected by pressure in the range 10-100 Torr, but showed small decreases in value at 3 and 1 Torr. There was also a weak intensity dependence, with rate constants decreasing at laser pulse energies of 30 mJ/pulse. Ab initio calculations at the G3 level of theory, show that SiH2 + NH3 should form an initial adduct (donor-acceptor complex), but that energy barriers are too great for further reaction of the adduct. This implies that SiH2 + NH3 should be a pressure dependent association reaction. The experimental data are inconsistent with this and we conclude that SiH2 decays are better explained by reaction of SiH2 with the amino radical, NH2, formed by photodissociation of NH3 at 193 nm. The mechanism of this previously unstudied reaction is discussed
Gas-Phase Kinetic Study of the Prototype Silylene Addition Reaction SiH2 + C2H4 over the Temperature Range 298-595 K. An Example of a Third-Body Mediated Association
The Impact of Materials and Maintenance Considerations during the Design Stage of Public Buildings in Oman
The purpose of this study is to describe the experiences of architects and civil engineers in the Sultanate of Oman regarding building maintenance during the design of public buildings. This exploratory and descriptive study used a qualitative approach, drawing data from focus groups in particular, to develop a rich and in-depth description of the designers’ building maintenance experiences. Structured interviews were conducted with 15 participants from architecture and civil engineering fields, from which, the interviewees shared the viewpoint that maintenance functions entirely separate from the design and construction process itself, but that it is, in fact, an integral part of the design process and post-occupancy stage. The designer should plan for sufficient maintenance for the whole building life cycle. However, some elements are more difficult to maintain in Oman than in other regions such as roofs, facades and the substructure of buildings. The results showed that salt is the most challenging environmental factor that could cause building defects. This was followed by solar heat, moisture from below ground and, lastly, rain. Most of these defects occurred during the buildings’ post-occupancy phase and were related to inappropriate or poor design. The results also suggested that deficiencies caused by thermal expansion came in the form of cracks, followed by paint decay, dampness, and staining
The effect of some variables on the removal of synthetic bentonite suspension in water by electrocoagulation using turbidity measurements
Direct Gas-Phase Kinetic Studies of Silylene Addition Reactions:  SiH2 + C3H6, SiH2 + i-C4H8, and SiMe2 + C2H4. The Effects of Methyl Substitution on Strain Energies in Siliranes
Time-resolved studies of the title reactions have been carried out over the pressure range 1−100 Torr (in SF6 bath gas) and at temperatures in the range 293−600 K, using laser flash photolysis techniques to generate and monitor the silylenes, SiH2 and SiMe2. All three reactions showed evidence of pressure dependence, consistent with third-body assisted association reactions to form silirane products. Extrapolation of the pressure-dependent rate constants gave the following Arrhenius parameters:  SiH2 + C3H6, log(A/cm3 molecule-1 s-1) = −9.79 ± 0.03, Ea (kJ mol-1) = −1.9 ± 0.3; SiH2 + C4H8, log(A/cm3 molecule-1 s-1) = −9.91 ± 0.04, Ea (kJ mol-1) = −2.5 ± 0.3; SiMe2 + C4H8, log(A/cm3 molecule-1 s-1) = −12.12 ± 0.02, Ea(kJ mol-1) = −8.5 ± 0.2. These parameters are consistent with fast, nearly collision-controlled processes for SiH2 but a tighter transition state for SiMe2. Rice, Ramsperger, Kassel, Marcus theory (RRKM) modeling, based on consistent transition states for silirane decomposition, and employing a weak collisional deactivation model, gave good fits to the pressure-dependent curves for each system, provided an appropriate value of Eo (fitting parameter) was used for each reaction. The kinetic results are consistent with an electrophilically led addition mechanism, although methyl substitution in the alkene hardly affects the rate constants. The RRKM-derived Eo values have been used to derive reaction enthalpies which are in reasonable agreement with values obtained by ab initio calculations at the G2 (MP2,SVP) level. The experimental ΔH° values yield strain energies of 190, 196, and 216 kJ mol-1 for 2-methyl-, 2,2-dimethyl-, and 1,1-dimethylsilirane, respectively. Compared to the strain enthalpy of 167 kJ mol-1 for silirane itself, this shows that methyl substituents in the silirane products substantially increase the strain energies. Theory supports this.Reprinted (adapted) with permission from Journal of Physical Chemistry A 102 (1998): 8564, doi:10.1021/jp981957f. Copyright 1998 American Chemical Society.</p
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Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with nitric oxide
Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with NO. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 299-592 K. The second-order rate constants at 10 Torr fitted the Arrhenius equation log(k/cm3 molecule-1 s-1) = (-11.66 ± 0.01) + (6.20 ± 0.10 kJ mol-1)/RT ln 10 The rate constants showed a variation with pressure of a factor of ca. 2 over the available range, almost independent of temperature. The data could not be fitted by RRKM calculations to a simple third body assisted association reaction alone. However, a mechanistic model with an additional (pressure independent) side channel gave a reasonable fit to the data. Ab initio calculations at the G3 level supported a mechanism in which the initial adduct, bent H2SiNO, can ring close to form cyclo-H2SiNO, which is partially collisionally stabilized. In addition, bent H2SiNO can undergo a low barrier isomerization reaction leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are NH2 + SiO. The rate controlling barrier for this latter pathway is only 16 kJ mol-1 below the energy of SiH2 + NO. This is consistent with the kinetic findings. A particular outcome of this work is that, despite the pressure dependence and the effects of the secondary barrier (in the side reaction), the initial encounter of SiH2 with NO occurs at the collision rate. Thus, silylene can be as reactive with odd electron molecules as with many even electron species. Some comparisons are drawn with the reactions of CH2 + NO and SiCl2 + NO
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Time-resolved gas-phase kinetic, quantum chemical and RRKM studies of reactions of silylene with cyclic ethers
Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with oxirane, oxetane, and tetrahydrofuran (THF). The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at four or five temperatures in the range 294-605 K. All three reactions showed pressure dependences characteristic of third-body-assisted association reactions with, surprisingly, SiH2 + oxirane showing the least and SiH2 + THF showing the most pressure dependence. The second-order rate constants obtained by extrapolation to the high-pressure limits at each temperature fitted the Arrhenius equations where the error limits are single standard deviations:
log(k(oxirane)(infinity)/cm(3) molecule(-1) s(-1)) = (-11.03 +/- 0.07) + (5.70 +/- 0.51) kJ mol(-1)/RT In 10 log(k(oxetane)(infinity)/cm(3) molecule(-1) s(-1)) = (-11.17 +/- 0.11) + (9.04 +/- 0.78) kJ mol(-1)/RT In 10 log(k(THF)(infinity)/cm(3) molecule(-1) s(-1)) = (-10.59 +/- 0.10) + (5.76 +/- 0.65) kJ mol(-1)/RT In 10
Binding-energy values of 77, 97, and 92 kJ mol(-1) have been obtained for the donor-acceptor complexes of SiH2 with oxirane, oxetane, and THF, respectively, by means of quantum chemical (ab initio) calculations carried Out at the G3 level. The use of these values to model the pressure dependences of these reactions, via RRKM theory, provided a good fit only in the case of SiH2 + THF. The lack of fit in the other two cases is attributed to further reaction pathways for the association complexes of SiH2 with oxirane and oxetane. The finding of ethene as a product of the SiH2 + oxirane reaction supports a pathway leading to H2Si=O + C2H4 predicted by the theoretical calculations of Apeloig and Sklenak