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ECHEM Chapter 9
Defs, Concepts , Q&A
65
Chemistry
Undergraduate 4
11/15/2013

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Term
What happens to the mean free path at high altitudes?
Definition
Becomes larger
Term
Describe the Troposhere
Definition
0 to 10 or 16 km
top layer water freezes at -56C
normal lapse rate
Term
Describe Stratosphere
Definition
Troposphere to 50km
Inverse lapse time
Max [O3] ~10ppm
Max temp -2c
absorbs UV radiation
Term
Define normal lapse time
Definition
temp decreases with increase in altitude
Term
Define inverse lapse time
Definition

temperature increases with increase in altitude

observed in the stratosphere

Term
What is the relationship of increasing altitude and atmospheric pressure?
Definition
Atmospheric pressure decreases logrithmicly
Term
Describe the mesosphere
Definition
50 to 85km
normal lapse time
lacks radiation absorbing species
min temp -92C
Term
Describe Thermosphere
Definition

85 to ~500km

temperature varied

Max temp 1200C

Absorption of highly energetic radiation(UV<100nm,x-ray,cosmic rays)

Term
Define Ionosphere
Definition
50km and up
Term
What is Earth's heating balance?
Definition
1.34x103 watts/m2 hits the thermosphere only half reaches Earth's surface
Term
Define mantle heating
Definition
convection and conduction from Earth's mantle. equivalent to 1% of solar heating
Term
What are the three energy transport mechanisms?
Definition
1)Conduction
2)Convection
3)Radiation
Term
Define conduction
Definition
Interaction of adjacent atoms
Term
Define convection
Definition
movement of whole masses
Term
Define Radiation energy transport mechanism
Definition

Electromagnetic radiation

E/M radiation only means of energy transport in vacuum.

 

Term
What does the Earth have to do to all forms of energy in order to cool the planet?
Definition
Convert it to electromagnetic radiation
Term
What is the average e/m energy that reaches the planet?
Definition
~500nm (Green Visible light)
Term
What is the average e/m energy given off by the planet?
Definition
~10,000 nm (Far IR)
Term
What is the green house effect approx equal to?
Definition
[CO2]
Term
What happens to outgoing IR due to water vapor and CO2?
Definition
It is absorbed and re-radiated with 1/2 going back to the planet resulting in a temp inc.
Term
What happens to UV-Vis and IR due to greenhouse gases?
Definition
Transparent to uv-vis and absorbs IR.
Term
What is the chemical rxn for anaerobic respiration?
Definition
2{CH20}->CH4 +CO2
Term
What is the chemical rxn for aerobic respiration?
Definition
{CH2O}+O2->CO2+H2O
Term
What is the chemical reaction for photosynthesis?
Definition
CO2+H2O+hv->{CH2O}+H2O
Term
What is the chemical reaction for combustion?
Definition

C+O2->CO2 

 

Term
What are the experimental parameters of a photochemical reaction?
Definition
1) Very low concentration of species
2) Very high pressure
3) High energy Radiation
4) No third bodies (No container walls)
Term
What are the seven relaxation mechanisms?
Definition
1) Physical quenching
2) Dissociation
3) Direct reaction
4) Luminescence
5) Intermolecular energy transfer
6) Intramolecular Transfer
7) Photoionization
Term
Define Physical quenching
Definition

Loss of energy to another molecule

O2*+M->O2+M(increased translational energy

This process is followed by dissipation of energy as heat

Term
Define Dissociation
Definition
Excite an electron in a bonding MO to a non bonding MO
O2*->O+O
Term
Define Direct reaction
Definition
Excite molecule reacts directly with another molecule O2*+O3->2O2+O
Term
Define Luminesence
Definition

Excited species returns to ground state and gives of light

NO2*->NO2+hv

The emitting wavelength is equal or lesser an energy than what cause the initial excitation

Term
Define Intermolecular energy transfer
Definition

Efficient energy transfer into a quantum state of another molecule(third body) which then becomes excited

O2*+M->O2+M*

Term
Define Intramolecular Transfer
Definition
Transfer in which an excited species transfers energy with in the molecule
X*Y->XY*
Term
Define Photoionization
Definition

Excited molecule ejects an electron, occurs in ionosphere(50km and up)

N2*->(N2+) + e-

Term
Where do ions exist in the atmosphere?
Definition
In the upper atmosphere 50km and up
Term
What are the significant species found in the ionosphere?
Definition
Cations and anions
Term
What is the most abundant anion in the ionosphere?
Definition
electron
Term
Describe how SKIP occurs.
Definition
Through photoionization, you get reflection of radiowaves if the particles formed are the same wavelength apart as the radiowave. During the day the ionosphere is made through photoionization and night it lifts. The reason for the lifting is because the particles are no longer being made and particles at lower elevation react more rapidly because of their shorter mean free path.
Term
What is the mean free path at sea level?
Definition
1x10-6 cm
Term
What is the mean free path at 500km
Definition
1x106 cm
Term
Describe the Santa Anna winds
Definition
Electron rich winds that are formed by the friction of the winds stripping electrons from dried brush
Term
What is an example of Ions in the troposphere?
Definition
Santa Anna Winds
Term
What are characteristics of free radicals?
Definition
1) Atoms with unpaired electrons
2) Formed by energetic radiation
3) highly reactive
4) Stable (relating to high mean free path)
Term
How would you compare excited atoms to free radicals?
Definition
1) Excited atoms have many ways to relax and don't require a collision
2) Free radicals are dependent on mean free path and have to react with a third body. (Life time increased with increase in mean free path)
Term
Define ozone:
Definition
Molecule with a protective function of absorbing UV in the Stratosphere
Term
Where is good ozone found:
Definition
Stratosphere
Term
Where is bad ozone found?
Definition
Troposphere
Term
How is ozone produced? Two step process
Definition

1) O3+hv(242nm) -> O+O2

2)O+O2+M->O3+M(increased energy)

Term
Why is ozone depletion in the stratosphere a concern?
Definition
Ozone production is very slow because of the long mean free path and the unlikelihood of O + O2 + a third body colliding simultaniously
Term
What are the negative effects of ozone in the troposphere?
Definition

1) Toxic, bind irreversibly to cytochrome c

2) Causes labored breathing and eye irritation

3) Oxidizing agent

4) damages materials

Term
Describe CO2 in the atmosphere
Definition

1) Minor constituent 0.035% or 350ppm

2) Like water vapor, CO2 absorbs IR

3) [CO2] rising ~1ppm/yr

4) Estimated increase in global temperature due to CO2 in 2050 is 1.5-4.5C

Term
What are seasonal trends of CO2?
Definition
1)Increased [C02] in fall/winter when photosynthesis is low and degredation is higher
2)Decreased [CO2] in summer when photosynthesis is at its peak.
Term
What is the phenomenon responsible for the temperature maximum at the boundary of the stratosphere and mesosphere?
Definition
Due to the presence of O3 and the heating effect caused by the absorption of UV Followed by radiation and relaxation
Term
What function does a third body serve in an atmospheric chemical reaction?
Definition
Third bodies absorb excess energy when the molecules form, stabilizing the newly formed molecule
Term
Why does the lower boundary of the ionosphere lift at night?
Definition
In darkness, positive ions created by UV light recombine with free electrons in the lower regions of the ionosphere, the process is rapid at high molecular concentrations, causing the lower limit of the ionosphere to lift at night
Term
Considering the total number of electrons in NO2, why might it be expected that the reaction of a free radical with NO2 is a chain terminating reaction?
Definition

NO2 is chain terminating because,

1) NO2 is a stable free radical present at high concentrations and

2) the odd number of electrons make it chain terminating

Term
Of the species O, HO∙*, NO2*, H3C∙, and N+, which could most readily revert to a non reactive "normal" species in total isolation?
Definition
NO2*, Excited species have a finite lifetime because they can lose energy through radiation w/o having to react with other species.
Term
What is the desinction between the symbols * and ∙ in discussing chemically active species in the atmosphere?
Definition
* means the molecule is in an excited electronic state
∙ means free radical or molecular fragment with unshared electrons
Term
What two chemical species are most generally responsible for the removal of hydroxy radicals from the unpolluted troposphere?
Definition
Methane and carbon monoxide
Term
Describe oxygen exchange among the atmosphere, geosphere, hydrosphere, and biosphere
Definition

1) oxygen consumed by reducing gases of volcanoes 2CO+O2->CO2

2)Oxygen consumed by burning of fossil fuels C+O2->CO2

3)Oxidative weathering of reduced minerals O2+4FeO->2Fe2O3

4)Respiration of plants and animals 5)Photosynthesis

6)Combined oxygen held in sediments Ca2+CO32-->CaCO3

7)Ozone shield absoption of UV radiation from 220-330nm

1)O3+hv->O+O2

2)O2+hv-> O+O

3)O+O2+M->O3+M(increased energy)

Term
How far does high energy wavelength (<100nm) penetrate?
Definition
to approximately an altitude of 200km
Term
How far does UV radiation (200-300nm) penetrate?
Definition
to approximately an altitude of 50km
Term
How far does radiation (wavelength > 330nm) penetrate?
Definition
All the way through to the Earth's surface
Term
Composition of the atmosphere
Definition
78.08% nitrogen
20.95% oxygen
0.934% argon
0.035% CO2
0.005% Noble gases
Varied water content 0.1% to 5.0%
Term
What ultimately happens to the energy absorbed as IR radiation?
Definition
Dissipated as heat and raises the temperature of the whole atmosphere.
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