Many chemicals off-gas or leech into indoor environments from sources such as consumer products, furnishings, and building materials. An understanding of the pathways from the sources to human exposure is vital in order to implement control strategies and lower exposure. Objects containing Brominated flame retardants (BFRs), one class of semivolatile organic compounds (SVOCs), burn more slowly during combustion. BFRs, especially polybrominated diphenyl ethers (PBDEs), are used in electronic devices including casings and circuit boards. Heat from internal circuitry increases the BFR vapor pressure and the partition coefficient, enhancing its transport out of the substrate and into the indoor environment. In this work, a computer tower in an office setting provides a case study to examine the emissions of, and exposure to, PBDEs. the case of a computer tower, the cooling fan increases the mass transfer coefficient, further increasing emissions. During computer use, the emission rate of PBDEs from the interior of the case is more than double the emission rate from the exterior of the case due to elevated internal temperatures and higher mass transfer due to the cooling fan. The concentration of PBDEs in the room air increases 40 - 80% for every 5°C increase inside the computer case, depending on the PBDE congener. Such enhanced emissions are a concern since recent studies have shown adverse health effects of PBDEs on human health. The major contributions of this work are: A model was developed that is useful for SVOC emissions for various heat and mass transfer situations, including diffusion through the slab and convective boundary conditions on each side of the slab, which may be simplified if the situation warrants; A systematic propagation of the uncertainties and variability of the model parameters was accomplished by using a Monte Carlo method for the input of the parameters into the model; A polydisperse indoor particle distribution was used as a sink, identifying the size-discretized particle phase PBDE concentration; An exposure assessment showed that the inhalation pathway for PBDEs in the gas and particulate phases is relevant and that the particulate phase exposure is dominant. / text

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The phenyl ring in the crown ether, 13-phenyl-1,4,7,10-tetraoxa-13-azacyclopentadecane (I), was used a site for functionalizing the compound. Electrophilic bromination of the ring with tribromide ion gave a 95% yield of the product substituted in the para position. This product underwent lithium-bromine exchange when reacted with n-butyllithium. The resulting anion was used to prepare PhZPX and PhPX2 derivatives, X p-C6H4NCH2(CH2OCH2)4&12 The oxide of PhZPX was completely characterized by an x-ray diffraction study which showed, in general, that the phosphorus was tetrahedral, the nitrogen planar, and the crown ether ring organized with the oxygen atoms endodentate. Several attemps were made to nitrate or nitrosate the phenyl ring in the parent crown ether. Spectroscopic evidence obtained from the products indicate that the reaction led to mixtures of mono and disubstituted products. / Department of Chemistry

This study has resulted in a crown ether functionalized with both phosphine and phenol groups, 5-diphenylphosphino-1,3-xylyl-18-crown-5. The target molecule was obtained from a six step synthesis. 4-Bromophenol was treated in sequence with formaldehyde, dimethylsulfate, and phosphorus tribromide producing 4-bromo-2,6-bis(bromomethyl)anisole. The main intermediate, 5-diphenylphosphino-1,3-xylyl-18-crown-5, was obtained by treating 4-bromo-2,6-bis(bromomethyl)anisole in sequence with tetraethylene glycol, lithium iodide, and methyldiphenyl phosphonite. The lithium iodide cleaved the anisole-to-methyl group bond, and the methyldiphenyl phosphonite provided the phosphine group for the crown ether following a lithium bromine exchange reaction. The 31P NMR of the phosphine crown ether showed a single signal at 6 -5.9, showing consistency of a single product. The IH NMR of the phosphine crown ether in deuterated chloroform showed signals at 6 3.55-3.7 (crown CH2), 6 4.6 (benzylic CH2), 6 7.1 (d, J = 7.o Hz, crown aromatic CH2), and 6 7.2-7.4 (noncrown aromatic CH2). / Department of Chemistry

The phosphine(III) crown ethers, [4'-(N-phenylaza-15crown-5)]3P (1), [4'-(N-phenylaza-l8-crown-6)]3P (2), [4'-(Naza-18-crown-6)]2-Ph-P (3), and [4'-(benzo-15-crown-5)]3P (4) were synthesized by using an electrophilic bromination of the crown phenyl ring (with a tribromide ion) followed by the preparation of a lithium salt and subsequent reaction of the resulting lithiocrowns with P(III) reagents. The oxide of compound 1 was completely characterized by an X-ray diffraction study, which showed that structurally there is not a significant difference in P-O bond distances and OPC bond angles with [4'-(N-phenylaza-15-crown-5)]-Ph2-P=O. Thespectroscopic data of compound 1 and 2 were compared. It appears that 1 and 2 are similar in P environment; also they are more air sensitive than 3 and 4. In addition, a discussion about compounds 1-4, and a literature review of the preparation of phosphines are included. / Department of Chemistry

Access to abstract permanently restricted to Ball State community only / Access to thesis permanently restricted to Ball State community only / Department of Chemistry

Thesis (doctoral)--Stockholm University, 2004. / Cover title. Includes bibliographical references (p. 59-69).

Thesis (M. Sc.)--Carleton University, 2001. / Includes bibliographical references (p. 79-83). Also available in electronic format on the Internet.

Thesis (Ph.D.)--Ohio University, March, 2010. / Title from PDF t.p. Includes bibliographical references.