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5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM5152 Dr. A. Franchin [email protected] Gas to particle conversion: condensation and nuclation

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Page 1: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Nucleation and condensationAdvanced Atmospheric Chemistry

CHEM‐5152

Dr. A. Franchin

[email protected]

Gas to particle conversion: condensation and nuclation

Page 2: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Q: what is the smallest possible size for an aerosol particle?

•A:  30 nm•B:  10 nm•C:    3 nm•D:   1 nm

Nucleation: the classical description

∆ 44 ln

3

Vapor Aerosol

Page 3: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Nucleation: the classical description

∆ 44 ln

3

Vapor Aerosol

∆ 44 ln

3 ; ‐2

;

Nucleation: the classical description

Page 4: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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; J;

;

∆ 44 ln

3

Nucleation: the classical description

∆ 44 ln

3

Nucleation: the classical description

Page 5: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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What is the saturation ratio?

What is the saturation ratio?

• The saturation ratio is the maximum amount of vapor at a specific temperature that air can hold in the gas phase

Page 6: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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What is the saturation ratio?

1 1 1

Nucleation: the role of ions

∆ 44 ln

3 81

1 1 1

Page 7: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Nucleation: the role of ions

∆ 44 ln

3 81

1 1 1

ATT!!! This is valid for an Homogeneous vapor. In the atmosphere is much more complicated!

What are the molecules that nucleate in the atmosphere?

Page 8: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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What are the molecules that nucleate in the atmosphere?

Sulfuric acid      H2SO4

Ammonia          NH3

Amines  (dimethylamine shown)           

ELVOCs  (C10H14O12 shown)

How does nucleation look like?

Page 9: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Nucleation: the experimental description

Nucleation: the experimental description

Page 10: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Nucleation: the experimental description

Nucleation: the experimental description

Growth Rates Formation Rates

Page 11: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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1

10

100

1000

Diameter (nm)

08‐Apr‐201707‐Apr‐2017 09‐Apr‐2017 10‐Apr‐201706‐Apr‐201712:00 12:00 12:0012:0012:00

Data from: https://avaa.tdata.fi/web/smart

Nucleation: the experimental description

Where does atmospheric nucleation happen?

Page 12: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Nucleation is not enough. Why do we need growth?

Nucleation is not enough. Why do we need growth?

If particles do not grow they will not able to 1‐ interact with light (direct effect of aerosol on climate)2‐ become cloud condensation nuclei (indirect effect of aerosol on climate)

Page 13: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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What are the phenomena that compete with nucleation?• A. Coagulation

• B. Condensation of condensing vapors on pre‐existing particles

• C. wall losses (in a chamber experiment)

• D. All of the above

The Kelvin effect

Page 14: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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exp4

The Kelvin effect

Remember this?

1 1 1

Page 15: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Remember this?

1 1 ≫ 1

exp ≈1

The Kelvin effect

let sigma be equal to 0.023 N m‐2, as in Tröstl et al., 2016; density = 1400 kg m‐3; monomer molecule mass of 300 amuT = 300 K

It is ~800 times harder to condense molecules on a 10 nm particle than on a flat surfaceIt is ~ 20 times easier to condense molecules on a 200 nm particle than on a 100 nm particle

Page 16: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Connection between Jc and GR

Page 17: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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22

4 3

4

34 33

4

22

2

Page 18: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Extra slides

Page 19: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Instruments: the condensation particle counter (CPC)

Instruments: the differential mobility analyzer (DMA)

Page 20: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Instruments: DMA+CPC = DMPSthe differential mobility particle sizer

The chemical ionization mass spectrometerCI‐APiTOF

Page 21: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Derivation of the link between GR and Jc

0

C = concentration of the diffusing vaporD = vapor diffusion coefficient; [D] = m2s‐1

Steady state

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0

0

0

0

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Boundary conditions:

Fick’s law:

4

4

Page 24: Nucleation and condensation final - CIREScires.colorado.edu/jimenez/CHEM-5152/Lect/Nucleation.pdf5/10/2017 1 Nucleation and condensation Advanced Atmospheric Chemistry CHEM‐5152

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Connection between Jc and GR

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22

4 3

4

34 33

4

22

2