Do Hydroxyl Radical−Water Clusters, OH(H2O)n, n = 1−5, Exist in the Atmosphere?

It has been speculated that the presence of OH(H2O)n clusters in the troposphere could have significant effects on the solar absorption balance and the reactivity of the hydroxyl radical. We have used the G3 and G3B3 model chemistries to model the structures and predict the frequencies of hydroxyl radical/water clusters containing one to five water molecules. The reaction between hydroxyl radical clusters and methane was examined as a function of water cluster size to gain an understanding of how cluster size affects the hydroxyl radical reactivity.

Thermodynamics of the Hydroxyl Radical Addition to Isoprene

Oxidation of isoprene by the hydroxyl radical leads to tropospheric ozone formation. Consequently, a more complete understanding of this reaction could lead to better models of regional air quality, a better understanding of aerosol formation, and a better understanding of reaction kinetics and dynamics. The most common first step in the oxidation of isoprene is the formation of an adduct, with the hydroxyl radical adding to one of four unsaturated carbon atoms in isoprene. In this paper, we discuss how the initial conformations of isoprene, s-trans and s-gauche, influences the pathways to adduct formation. We explore the formation of pre-reactive complexes at low and high temperatures, which are often invoked to explain the negative temperature dependence of this reaction’s kinetics. We show that at higher temperatures the free energy surface indicates that a pre-reactive complex is unlikely, while at low temperatures the complex exists on two reaction pathways. The theoretical results show that at low temperatures all eight pathways possess negative reaction barriers, and reaction energies that range from −36.7 to −23.0 kcal·mol−1. At temperatures in the lower atmosphere, all eight pathways possess positive reaction barriers that range from 3.8 to 6.0 kcal·mol−1 and reaction energies that range from −28.8 to −14.4 kcal·mol−1.

Synthesis of Macrocyclic Polymers Formed via Intramolecular Radical Trap-Assisted Atom Transfer Radical Coupling

The synthesis of cyclic polystyrene (Pst) with an alkoxyamine functionality has been accomplished by intramolecular radical coupling in the presence of a nitroso radical trap Linear alpha,omega-dibrominated polystyrene, produced by the atom transfer radical polymerization (ATRP) of styrene using a dibrominated initiator, was subjected to chain-end activation via the atom transfer radical coupling (ATRC) process under pseudodilute conditions in the presence of 2-methyl-2-nitrosopropane (MNP). This radical trap-assisted, intramolecular ATRC (RTA-ATRC) produced cyclic polymers in greater than 90% yields possessing < G > values in the 0.8-0.9 range as determined by gel permeation chromatography (GPC). Thermal-induced opening of the cycles, made possible by the incorporated alkoxyamine, resulted in a return to the original apparent molecular weight, further supporting the formation of cyclic polymers in the RTA-ATRC reaction. Liquid chromatography-mass spectrometry (LC-MS) provided direct confirmation of the cyclic architecture and the incorporation of the nitroso group into the macrocycle RTA-ATRC cyclizations carried out with faster rates of polymer addition into the redox active solution and/or in the presence of a much larger excess of MNP (up to a 250:1 ratio of MNP:C-Br chain end) still yielded cyclic polymers that contained alkoxyamine functionality.

Examining the Justification for Residential Recycling

Municipalities in the United States have for the past two decades initiated two policies to reduce residential solid waste generation by increasing recycling. The first policy, implemented in over 4,000 municipalities in the United States, requires households to pay a fee for each unit of garbage presented at the curb for collection. The second policy, initiated in 8,875 municipalities, subsidizes household recycling efforts by providing free curbside collection of certain recyclable materials. Both initiatives serve as examples of incentive-based environmental policies favored by many economists. But before economists can celebrate this wide-spread adoption of incentive-based environmental policies, further examination reveals that potentially inefficient command and control policies have been more instrumental in promoting recycling than might be commonly known. This article examines the empirical lessons gained from studying twenty years of solid waste policy in the United States and argues for the replacement of several state recycling mandates with a system of state and/or national landfill taxes.

Explaining the Growth in Municipal Recycling Programs: The Role of Market and Non-Market Factors

The implementation of thousands of municipal recycling programs in the United States has increased recycling’s portion of solid waste from 10% to 30% over the past decade. But the lack of accurate data has spurred a debate over whether the growth in recycling can be attributed to market or nonmarket factors. To address this issue, this article conducts a benefit-cost analysis of a municipal recycling program. Results suggest recycling is costly. So why, then, does it remain popular? This article suggests that local governments could be responding to households that perceive a benefit from recycling services. These benefits are estimated with a contingent valuation survey.

Optimal Solid Waste Policy with Centralized Recycling Opportunities

Economic models have demonstrated the efficiency of curbside collection taxes. This paper demonstrates that such efficiencies disappear in economies with centralized recycling options - where recyclable materials can be removed from the waste stream either by households or at a centralized recycling facility. In such economies a curbside garbage tax not only fails to encourage the centralized recycler to internalize the external costs of waste disposal, but introduces inefficiencies to the cost-minimizing mix of household and centralized recycling efforts. The optimal waste policy is a tax assessed further downstream at the landfill rather than at the curb.

The Costs of Municipal Curbside Recycling and Waste Collection

This paper estimates cost functions for both municipal solid waste collection and disposal services and curbside recycling programs. Cost data are obtained from a national survey of randomly selected municipalities. Results suggest, perhaps unsurprisingly, that both marginal and average costs of recycling systems exceed those of waste collection and disposal systems. Economies of scale are estimated for all observed quantities of waste collection and disposal. Economies of scale for recycling disappear at high levels of recycling - marginal and average cost curves for recycling take on the usual U-shape. Waste and recycling costs are also estimated as functions of factor costs and program attributes.

One Pot, Two Step Sequence Converting Atom Transfer Radical Polymerization Directly to Radical Trap-Assisted Atom Transfer Radical Coupling

Monobrominated polystyrene (PStBr) chains were prepared using standard atom transfer radical polymerization (ATRP) procedures at 80 °C in THF, with monomer conversions allowed to proceed to approximately 40%. At this time, additional copper catalyst, reducing agent, and ligand were added to the unpurified reaction mixture, and the reaction was allowed to proceed at 50 °C in an atom transfer radical coupling (ATRC) phase. During this phase, polymerization continued to occur as well as coupling; expected due to the substantial amount of residual monomer remaining. This was confirmed using gel permeation chromatography (GPC), which showed increases in molecular weight not matching a simple doubling of the PStBr formed during ATRP, and an increase in monomer conversion after the second phase. When the radical trap 2-methyl-2-nitrosopropane (MNP) was added to the ATRC phase, no further monomer conversion occurred and the resulting product showed a doubling of peak molecular weight (Mp), consistent with a radical trap-assisted ATRC (RTA-ATRC) reaction.