Chapman Cycle. The cycle describes reactions of O 2 and O 3 in stratosphere

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Chapman Cycle The cycle describes reactions of O 2 and O 3 in stratosphere Even though reactions are happening, the concentration of O 3 remains constant This is an example of a dynamic equilibrium or steady state condition (UV light is being consumed)

Ozone Depletion in Antarctica Minimum spring stratospheric ozone concentration over Antarctica:

Why Does Antarctica Get the Worst of It? Dude, it s cold there: Cl-containing molecules condense on Polar Stratospheric Clouds (PSCs) When the sun comes out, PSCs provide surfaces for reactions to occur Polar Stratospheric Clouds

Halogens Group to the left of the noble gases, including F, Cl, Br, I, At: Cl 2 (gas) Br 2 (liquid) I 2 (solid)

A Link Between Atmospheric Halogens and Ozone Depletion Flight through the Antarctic ozone hole, 1987: Fig. 2.15 correlated

The Promise of Chlorofluorocarbons (CFCs) Pros: Inert Non-toxic Cheap Excellent refrigerant : replaced NH 3 & SO 2, which are toxic & corrosive Helped growth in humid, hot American south Uses: Refrigerant Fire suppressant Solvents (for electronics and surgical instruments) Discovered in late 1920 s

Electricity Seasonal uses & sources E 0.6 0.4 summer winter 0.2 0 7-Jan 7-Mar 7-May 7-Jul 7-Oct 7-Dec 8-Feb 8-Apr 8-Jul 8-Sep 8-Nov 9-Jan 9-Mar 9-Jun

Refrigeration 5. Cold HFC gas is sucked up by the compressor, and the cycle repeats 4. Liquid HFC vaporizes (light blue), its temperature dropping to -27 F. This makes the inside of the refrigerator cold (A) 1. Compressor (B) compresses HFC gas. (compressed gas heats up as it is pressurized (orange)) 2. Coils on the back of the refrigerator dissipate HFC gas heat. The HFC gas condenses into HFC liquid (purple) at high pressure 3. High-pressure HFC liquid flows through the expansion valve (C). (a small hole). On one side of the hole is high-pressure HFC liquid. On the other side of the hole is a low-pressure area (the compressor is pumping gas out of that side).

US Population by Region in the 20 th Century The South and West accounted for nearly two-thirds of the U.S. population increase from 1900 to 2000. 120 million 100 80 60 Available on RamCT: U.S. Census Bureau, Census 2000 Special Reports, Series CENSR-4, Demographic Trends in the 20th Century Freons discovered in late 1920 s 28

US Population Growth by Region in the 20 th Century Between 1900 and 2000, the mean center of the U.S. population moved about 324 miles west and 101 miles south. Nine western states and Florida accounted for the ten fastest-growing states from 1900 to 1950 and eight western states plus Florida and Texas were the fastest growing from 1950 to 2000. Available on RamCT: U.S. Census Bureau, Census 2000 Special Reports, Series CENSR-4, Demographic Trends in the 20th Century Air conditioning w/ cheap CFCs helped make this population growth possible.

CFCs: Inertness is a Double Edged Sword Cons: Inert remain intact in atmosphere for a long time survive up 120 years & drift into stratosphere in 5 years React with UV-radiation to form stable radicals in the stratosphere CFCs represent the major source of anthropogenic halogen in the atmosphere with adverse consequences

Ozone Depletion Chemistry Natural: H 2 O à (<240 nm) H + OH (above 50 km) 500 kj/mol Anthropogenic: F Cl C F Cl UV photon λ 220 nm Cl F C + F Cl 2Cl + 2O 3 2ClO + 2O 2 2ClO ClOOCl UV photon ClOOCl ClOO + Cl Cl is both a reactant & a product, it s a catalyst (just like catalytic converter) ClOO Cl + O 2 Adding all the equations together: 2Cl + 2O 3 + 2ClO + ClOOCl + ClOO 2ClO + 2O 2 + ClOOCl + ClOO + Cl + Cl + O 2 Cancelling common terms: 2Cl + 2O 3 + 2ClO + ClOOCl + ClOO 2ClO + 2O 2 + ClOOCl + ClOO + Cl + Cl + O 2 2O 3 3O 2 Natural and Human: NO as another source of radicals

Moving Past CFCs 1987: signing of Montreal Protocol on Substances that Deplete the Ozone Layer Eliminates the production and (eventually) the use of CFCs The protocol is working as intended: -fewer CFCs in atmosphere -lower [Cl ] in atmosphere Economic consequences: -cost of alternatives -developing nations Remember: CFCs can exist for ~100 years in the atmosphere (projected)

Replacements for CFCs A. HCFCs More reactive (decompose in troposphere) but still have ozone-depleting potential B. HFCs Contain no chlorine but are more reactive

Unit 4.1 Summary interaction of light and matter need to understand the relationships between wavelength, frequency and energy need to understand how light can break chemical bonds reactivity of ozone Chapman cycle (establishment of steady state concentrations) production of persistent radicals and their interactions with ozone understand the function of catalysts role of CFCs and related materials in ozone depletion environmental, biological and political effects of ozone depletion