simulative study on the sources and sinks of ocs under lightning
DESCRIPTION
Simulative Study on the Sources and Sinks of OCS under lightning. Jie Zhu. Content. The importance of study on OCS, CS 2 , SO 2 /CH 4 Why study on lightning The similarity of natural lightning and spark discharge Some experimental results Mechanism of the reactions - PowerPoint PPT PresentationTRANSCRIPT
Simulative Study on the Sources and Sinks of OCS under lightning
Jie Zhu
Content
1. The importance of study on OCS, CS2, SO2/CH4
2. Why study on lightning
3. The similarity of natural lightning and spark discharge
4. Some experimental results
5. Mechanism of the reactions
6. Global calculation and discussion of practical analysis
About OCS
•The most abundant sulfur gas in the atmosphere
•Long-lived in the atmosphere (about 4 years)
•Contribute to form SO2 and SO3, and sulfate aerosol
About CS2
CS2 oxidation is a very important source of OCS
CS2+O OCS+S
CS2+OH OCS+HS
SO2 and sulfur cycle in the atmosphere
Global Sulfur Emissions
Why study on lightning?
Under UV light : CS2+OH
Lightning flashes are a very normal nature phenomena, they happens 100 times/sec in the earth
Global lighting flashes distribution
What is lightning?
Spark discharge?
Franklin’s famous kite experiment testifies lightning and spark discharge are actually the same thing
Conclusion: Using spark discharge to simulate the lighting and to study the reactions of OCS under lightning is reasonable
Franklin’s Kite Experiment
An easily operated experiment
•Gases studied are filled in the cell
•Spark discharge in the cell
•The reaction products are analyzed by FT-IR spectra technique
The system studied and products analysis• CS2+air system (pCS2=1.33103Pa, pair=1.01 105Pa)
Products: CO2, CO,OCS, N2O
• SO2+CH4+O2 system(pSO2=1.33103Pa, pCH4=1.33103Pa, pO
2 =1.01 105Pa)Products: CO, OCS
• OCS system OCS+O2(pOCS=1.33103Pa, pO2 =1.01 105Pa)
Products: CO2, CO, SO3
OCS+dry air(pOCS=1.33103Pa, pair =1.01 105Pa)
Products: CO2, CO, SO3, N2O OCS+ water saturated air(pOCS=1.33103Pa, pair =1.01 105P
a)
Products: CO2, CO, H2SO4, N2O
Reaction mechanism supposed
e*+O2 e+O+O
e* +H2O e+OH+H
CS2+air system:
e*+CS2e+CS+S
O + CS2 OCS+S
OH + CS2 OCS+S
CS+O2OCS+SO
Reaction mechanism supposed SO2+CH4+O2 system
e*+SO2e+SO+O
e*+CH4e+CH3(CH2 、 CH)+H
CH2+SO2OCS+H2O
CH+SO OCS+H
OCS system
e*+OCSe+CO+S
O+OCSSO+CO
OH+OCSCO2+SH
SO+O2 SO3
SO3+H2O HSO4
Practical Calculations Main points:
• The fraction of reaction of SO2 with CH4 to form OCS is relatively small because of very small reaction rate constant. (This will be discussed in the paper turned up).
• The lightning flash produces reactive species as e*, O and OH. As OH>>O>>e*, we consider OH radicals be the main species to react with OCS, CS2 et al.
• So the key reactions contributing to OCS changing in a lightning flash are: OH
+ CS2 OCS+S, k1, OH+OCSCO2+SH, k2
Practical Calculations
• In a lightning flash,
d[OCS]/dt=k1[CS2][OH]-k2[OCS][OH]
• Using the data of the rate constant, k1=1.85 10 –13cm3s-1, k2= 5.7 10 –14cm3s-1,and the global mean OCS and CS2 concentration to calculate, we get:
d[OCS]/dt < 0
That means lightning flashes destroy OCS in global scale.
References:1. Egorova T, Zubov V, Jagovkina S, et al. Lightning production of N
ox and Ozone. Phys. Chem.Earth.,1999,24(5):473-4792. Simon F, The mass budgets of carbonyl sulfide,dimethyl sulfide, ca
rbon disulfide and hydrogen sulfide, Atmos. Environ.,2000 , 34 :761-769
3. William P, Julian H, The photooxidation of carbon disulfide, The Journal of Physical Chemistry.,1971,75(7):854-860
4. Chin M, Davis DD. Global sources and sinks of OCS and CS2, and their distribution. Global Biogeochemical Cycles, 1993,&:321-337
5. Atkinson R, et al. Rate constants for the reaction of OH radicals with OCS, CS2,and CH3SCH3 over the temperature range 299~430K ,Chem. Phys. Lett., 1978,54:14-18
6. Kuhn U, et at. Carbonyl sulfide exchange on an ecosystem scale: soil represents a dominant sink for atmospheric COS. Atmos. Environ.,1999,33: 995-1008