环境化学专题知识省公共课一等奖全国赛课获奖课件.pptx

二、光化学二、光化学photochemistry反应基础反应基础 1、光子、光子photon能量能量l l爱因斯坦爱因斯坦爱因斯坦爱因斯坦-普朗克（普朗克（普朗克（普朗克（Einstein-PlanckEinstein-Planck）关系式：）关系式：）关系式：）关系式：=h=hc/(J)(J)E=N0 h=N0 hc/(KJ/mol)(KJ/mol)式中式中式中式中h hPlanckPlanck常数，常数，常数，常数，6.621034J.s6.621034J.s；光子频率，光子频率，光子频率，光子频率，HzHz；c c光速，光速，光速，光速，2.998102.998101010cm/scm/s；光子波长，光子波长，光子波长，光子波长，cmcm；N N0 0阿佛加德罗常数，阿佛加德罗常数，阿佛加德罗常数，阿佛加德罗常数，6.02106.02102323/mol/mol。第1页l l伴随波长增加，光子能量减小。伴随波长增加，光子能量减小。波长（波长（波长（波长（nmnm）能量（能量（能量（能量（kJ/molkJ/mol）l l光区域光区域200200300300597.2597.2398.4398.4紫外光紫外光紫外光紫外光400400700700298.9298.9170.8170.8可见光可见光可见光可见光l l5000500059.759.723.923.9红外线红外线红外线红外线不一样波长光能量不一样波长光能量 高能光，能引发光化高能光，能引发光化学反应（光离解）学反应（光离解）低能光，不能引发低能光，不能引发光化学反应光化学反应 l l例例1计算波长为计算波长为200nm紫外光能量。紫外光能量。普通化学鍵键能大于普通化学鍵键能大于普通化学鍵键能大于普通化学鍵键能大于167.44KJ/mol 167.44KJ/mol 第2页2、光化学反应原理、光化学反应原理l l光化学反应光化学反应：由一个原子、分子、自由基或离：由一个原子、分子、自由基或离：由一个原子、分子、自由基或离：由一个原子、分子、自由基或离子吸收一个光子后所引发反应。子吸收一个光子后所引发反应。子吸收一个光子后所引发反应。子吸收一个光子后所引发反应。l l初级过程：初级过程：l引发：引发：引发：引发：A(A(分子分子分子分子)hhA*(A*(激发态分子激发态分子激发态分子激发态分子)l l次级过程：次级过程：l离解：离解：离解：离解：A*A*C+C+l与其它分子反应生成新物种：与其它分子反应生成新物种：与其它分子反应生成新物种：与其它分子反应生成新物种：A*+BA*+BD+D+l与惰性与惰性与惰性与惰性inertia分子碰撞失活分子碰撞失活分子碰撞失活分子碰撞失活(返回基态返回基态返回基态返回基态)：A*+MA*+MA+MA+Ml发光而失活发光而失活发光而失活发光而失活(返回基态返回基态返回基态返回基态)：A*A*A Ahh第3页3、大气中主要吸光物质光离解、大气中主要吸光物质光离解l l吸光物质吸光物质l l高层大气：高层大气：N2、O2、O3（290nm）l l低层大气：低层大气：NO2、SO2等等第4页l l氧和氮光离解氧和氮光离解l l氧氧分分子子键键能能：493.8kJ/mol（240nm以以下下紫外光可引发）：紫外光可引发）：O2h O+Ol l氮氮分分子子键键能能：939.4kJ/mol（127nm，仅仅限于臭氧层以上）：限于臭氧层以上）：N2h N+N当当当当入入入入射射射射波波波波长长长长低低低低于于于于79.6nm 79.6nm(1391kJ/mol)(1391kJ/mol)时时时时，N N2 2将电离成将电离成将电离成将电离成N N2 2。第5页l l臭氧和过氧化物光离解臭氧和过氧化物光离解l l臭氧臭氧臭氧臭氧分子键能：分子键能：分子键能：分子键能：101.2kJ/mol101.2kJ/mol 220 220290nm 290nm 强吸收（强吸收（强吸收（强吸收（254nm254nm最强吸收）最强吸收）最强吸收）最强吸收）290 290320nm 320nm 少许吸收少许吸收少许吸收少许吸收 450 450700nm 700nm 微弱吸收微弱吸收微弱吸收微弱吸收 离解反应：离解反应：离解反应：离解反应：OO3 3hhOO2 2+O+Ol l烷基过氧化物烷基过氧化物烷基过氧化物烷基过氧化物在在在在300300700nm700nm范围有微弱吸收，范围有微弱吸收，范围有微弱吸收，范围有微弱吸收，光离解反应：光离解反应：光离解反应：光离解反应：ROOR ROORh h RO+RORO+RO第6页l lNO2光离解光离解l l键键键键能能能能：300.5 300.5 kJ/molkJ/mol（300300400nm400nm吸吸吸吸光光光光），光光光光离离离离解反应：解反应：解反应：解反应：NONO2 2hhNO+ONO+OOO2 2+O+OMMOO3 3MMNONO2 2是是是是污污污污染染染染大大大大气气气气中中中中最最最最主主主主要要要要吸吸吸吸光光光光物物物物质质质质,在在在在低低低低层层层层大大大大气气气气中中中中能能能能够够够够吸吸吸吸收收收收全全全全部部部部来来来来自自自自太太太太阳紫外光和部分可见光。阳紫外光和部分可见光。阳紫外光和部分可见光。阳紫外光和部分可见光。OO3 3唯一人为起源唯一人为起源唯一人为起源唯一人为起源第7页OXIDIZING NATURE OF THE ATMOSPHERE Earths atmosphere is oxidizing due to presence of O2SO2-SO42-;CH4-CO;CO-CO2;NO2-HNO3 Radicals are oxidizing agents in the atmosphere OH is the cleansing agent of the atmosphere Key to understanding atmospheric oxidant chemistry Understand radical cycling but radical cycle is intimately connected to oxidant chemistry of other trace compounds including O3 Start with O3O3 is important from chemical,climate,and health perspectives第8页ATMOSPHERIC O3 A BRIEF HISTORY 1840:Ozone discovered in 1840 by C.F.Schnbein thought it was made up of oxygen and hydrogen 1848:Systematic measurement attempts curiousity,growing interest in env.,health effects,economy of nature 1861:Odling suggested that ozone was O3 1930:Chemical mechanism for O3 layer postulated 1952:O3 identified as component of chemical smogChristian Frederich Schnbein第9页OZONE AND HEALTH 90%of O3 is in the stratosphere;O3 layer with max 9 ppm Absorption of =200-320 nm(UV-B and UV-C)by strat.O3Source:Stratospheric Ozone,NASA/GSFC第10页OZONE AND STRATOSPHERIC TEMPERATUREOZONE AND STRATOSPHERIC TEMPERATURE Local heating of the stratosphere due to UV absorption by O3 Tropospheric O3 is also an important greenhouse gasSource:Stratospheric Ozone,NASA/GSFCSource:Environmental Science,Cunningham,P.W.and B.W.Saigo,第11页O3O(1D)O(3P)2OHSolar radiation,wavelength 290-320 nmH2OO2,N2O2OZONE AND ATMOSPHERIC CHEMISTRYOZONE AND ATMOSPHERIC CHEMISTRY O3 is the primary source of tropospheric OH OH is atmospheric detergent 第12页LATITUDINAL&TEMPORAL VARIATION OF TOTAL O3 Total O3 in range of 300-400 DU Patterns due to stratospheric circulation Low total O3 at high southern lat in southern spring due to ozone holeDobson units 1 DU=2.69 x 1016 molecules O3 cm-2Source:Stratospheric Ozone,NASA/GSFC第13页STRATOSPHERIC O3 CHEMISTRY第14页THE CHAPMAN MECHANISM FOR STRATOSPHERIC O3 Cycling between O,O2,and O3 Source:Stratospheric Ozone,NASA/GSFC第15页MISSING CHEMISTRY IN CHAPMAN MECHANISM Global O3 production rate=5 times destruction rate Imbalance suggests overest.of prodn.or underest.of loss O3 production well constrained by good spectroscopic data Implies missing chemical sinks for Ox Reactions of radicals with O and/or O3 But radicals will also be consumed by reaction measuredcalculatedSource:Stratospheric Ozone,NASA/GSFC第16页CATALYTIC OX DESTRUCTION IN THE STRATOSPHERE Radical chain reactions X+O3 XO+O2 XO+O X+O2 Net:O+O3 2O2 X in the stratosphere H,OH,NO,Cl HOx,NOx,and Clx HOx=H+OH+HO2 NOx=NO+NO2 Clx=Cl+ClO Reservoirs tie up active radicals e.g.ClO+NO2 ClONO2 Stratospheric Clx precursorsSource:Stratospheric Ozone,NASA/GSFC第17页Column O3(DU)ANTARCTIC TOTAL OZONE DECREASE Depletion of total column O3 starting in mid-to late-70s during SH spring Gas-phase chemistry predicted smaller decreases¬ over AntarcticaO3Source:Stratospheric Ozone,NASA/GSFCSource:Farmann et al.,Nature,v.315,May 1985第18页 ALTITUDE DEPENDENCE OF ANTARCTIC O3 DECREASE Strong depletion between 12 and 20 km Gas phase chemistry predicted decrease near 40 kmSource:Stratospheric Ozone,NASA/GSFC第19页 TEMPORAL DEPENDENCE OF ANTARCTIC O3 DECREASE Depletion begins around Sep 1.&minimum is reached around Oct 1Source:NOAA/CMDL第20页 REACTIONS ON POLAR STRATOSPHERIC CLOUDS Conversion of inactive Cl to active Cl and removal of NOxSource:Stratospheric Ozone,NASA/GSFC第21页ROLE OF METEOROLOGY Low temps.PSC formation release of active Cl and removal of NOxStrong vortexIsolates air from mid-lats.prevents high O3 air influxFigure shows strong polar vortex旋涡(as shown by size of wind vectors)&low polar temps.(as shown by colors)at various altitudes in the southern hemisphere stratosphereSource:Stratospheric Ozone,NASA/GSFC第22页NORTHERN vs SOUTHERN HEMISPHERE O3 TRENDS Vortex not as strong and temps.not as low in NHSource:Stratospheric Ozone,NASA/GSFC第23页PROJECTED CHANGES IN STRATOSPHERIC Clx Montreal Protocol and subsequent amendments will have signifcant impacts on projected Clx loading of stratosphere(ppb)Source:Stratospheric Ozone,NASA/GSFC第24页 WMO 1998 Scientific Assessment of Ozone Depletion Ozone depletion in 2050 would be at least 50%at midlatitudes in the Northern Hemisphere and 70%at midlatitudes in the Southern Hemisphere,about 10 times larger than today Surface UV-B radiation in 2050 would at least double at midlatitudes in the Northern Hemisphere and quadruple at midlatitudes in the Southern Hemisphere compared with an unperturbed atmosphere.This compares to the current increases of 5%and 8%in the Northern and Southern Hemispheres,respectively,since 1980 ESTIMATED IMPACTS OF Clx CONTROLS第25页TROPOSPHERIC O3 CHEMISTRYSource:EPA第26页 Tropospheric O3 generally less than 100 ppb away from urban areasTROPOSPHERIC O3Source:Wang et al.,1998第27页l lOO3 3 chemical production in stratosphere followed chemical production in stratosphere followed by downward transport to the troposphere by downward transport to the troposphereO2O(3P)Solar radiation,(240 nm)O3O2Solar radiation(CO2+O3 Catalytic role of NOx(NO+NO2)in recycling HO2 to OH Coupling between OH and HO2(HOx)via NOCO OXIDATION CYCLE O3 PRODUCTIONCO2O3第29页NO or O3 OHHO2COO2Net:CO+O3-CO2+O2 Chemical O3 destruction Coupling between OH and HO2(HOx)via O3CO OXIDATION CYCLE O3 DESTRUCTIONCO2O32O2第30页1.O3+hv O2+O(1D)2.2.O(1D)+M O+M3.3.H2O+O(1D)2OH4.4.RH+OH RO2+H2O5.5.RO2+NO RO+NO26.6.RO+O2 RCHO+HO27.7.HO2+NO OH+NO28.8.HO2+HO2 H2O2+O29.9.OH+NO2+M HNO3+MSCHEMATIC OF HYDROCARBON CHEMISRYO2Net rxns 1-7:RH+4O2 RCHO+2O3+H2OSource:Introduction to Atmospheric Chemistry,Jacob,D.J.,1999can produce more O3第31页ROLE OF NOROLE OF NOX X IN O IN O3 3 CHEMICAL PRODUCTION CHEMICAL PRODUCTIONl lCycling of HOCycling of HOx x(OH+HO(OH+HO2 2)by NO)by NOx x vs.radical vs.radical termination reactionstermination reactionsl lToo little NOToo little NOx x:Radical termination(e.g.HO:Radical termination(e.g.HO2 2+HO+HO2 2)rather than radical cycling(e.g.HOrather than radical cycling(e.g.HO2 2+NO)leading to +NO)leading to OO3 3 chemical destruction chemical destructionl lToo much NOToo much NOx x:Radical termination by alternate:Radical termination by alternate route(e.g.OH+NOroute(e.g.OH+NO2 2)as well as short-term O)as well as short-term O3 3 destruction by NO+Odestruction by NO+O3 3-NO-NO2 2 =implications for =implications for OO3 3 peak downwind of strong NO peak downwind of strong NOX X sources sources第32页NOx-AND HYDROCARBON-LIMITED REGIMESNOx limitedHydrocarbon limitedComplications:Natural emissions of hydrocarbons are importantTransport of pollutants into and out of regionSource:Introduction to Atmospheric Chemistry,Jacob,D.J.,1999第33页l lQuestions:Questions:l lNONOx x or HC emission controls or combination or HC emission controls or combinationl lDegree of emission controlsDegree of emission controlsl lUncertaintiesUncertaintiesl lReliability of emission inventoriesReliability of emission inventories清单清单(e.g.(e.g.natural hydrocarbon inventories)natural hydrocarbon inventories)l lReliability of air quality models(e.g.local vs Reliability of air quality models(e.g.local vs transported NOtransported NOx x/HC/O/HC/O3 3)ISSUES IN O3 POLLUTION CONTROL第34页1998 MEASURED SURFACE OZONE CONCENTRATIONS2nd highest daily max 1-hr(ppb)65 65-124125-16465-84205-404Source:1998 EPA National Trends Report11815316936141155167165-2044th highest daily max 8-hr(ppb)50 ppbv and 10-20%of crops in areas with growing-season mean O3 50 ppbv Potentially large impact in future years:Year 2100 IPCC scenario from HARVARD model gives 50%of population in areas with max.monthly-mean O3 85 ppbv,and 50%of crops in areas with growing season mean O3 70 ppbv第36页ATMOSPHERIC AEROSOLS AND ACID RAINATMOSPHERIC AEROSOLS AND ACID RAINCombustion generated Aerosols and acid rain can effect natural&managed ecosystems第37页l l硝酸和烷基硝酸酯光离解硝酸和烷基硝酸酯光离解l lRO-NORO-NO2 2键键键键 能能能能：199.4kJ/mol199.4kJ/mol（吸吸吸吸 收收收收 120120335nm335nm）：）：）：）：硝酸：硝酸：硝酸：硝酸：HNOHNO3 3（HONOHONO2 2）hhHO+NOHO+NO2 2 烷基硝酸酯：烷基硝酸酯：烷基硝酸酯：烷基硝酸酯：RONORONO2 2hh RO+NORO+NO2 2对对对对于于于于300nm300nm以以以以上上上上光光光光吸吸吸吸收收收收速速速速度度度度很很很很小小小小 第38页l l亚硝酸和烷基亚硝酸酯光离解亚硝酸和烷基亚硝酸酯光离解l lHO-NOHO-NO键能：键能：键能：键能：201.1kJ/mol201.1kJ/moll lH-ONOH-ONO键能：键能：键能：键能：324.0kJ/mol324.0kJ/moll lHNOHNO2 2对对对对200200400nm400nm光有吸收，发生光离解：光有吸收，发生光离解：光有吸收，发生光离解：光有吸收，发生光离解：HONOhHO+NOHNO2hH+NO2RONOh NO+RO仅仅仅仅次次次次于于于于NONO2 2光光光光离离离离解解解解最最最最主主主主要要要要光光光光离离离离解解解解初级反应。初级反应。初级反应。初级反应。第39页l l醛光离解醛光离解（CH2O和和CH3CHO）l lH-CHO键键 能能：365.5kJ/mol（吸吸 收收 240360nm），光离解反应：），光离解反应：l甲醛甲醛H2COhH+HCO H2COhH2+COl乙醛乙醛CH3CHOhH+CH3CO CH3CHOhCH3+HCO CH3CHOhCH4+CO第40页l l卤代烃光离解卤代烃光离解l l卤代甲烷光解：卤代甲烷光解：CH3XhCH3+X式中式中X代表代表Cl,Br,I,F。键键键键 强强强强 次次次次 序序序序：CHCH3 3 F F CHCH3 3 HHCHCH3 3ClClCHCH3 3BrBrCHCH3 3I I第41页l lSO2光吸收光吸收l lSO2键键能能：545.1 kJ/mol（200nm），吸吸收收三个波段：三个波段：l l340340400nm400nm（极弱）（极弱）（极弱）（极弱）l l240240330nm330nm（较强）（较强）（较强）（较强）l l280280240nm240nm（很强）（很强）（很强）（很强）l lSO2不能光离解，只能形成激发态分子：不能光离解，只能形成激发态分子：SO2hSO2 活活活活性性性性粒粒粒粒子子子子：HOHO、RORO、RORO2 2、H H、HCOHCO、CHCH3 3、CHCH3 3COCO等等等等自自自自由由由由基基基基被被被被称称称称为为为为大大大大气气气气中中中中“活活活活性性性性粒粒粒粒子子子子”，它它它它们们们们性性性性质质质质尤尤尤尤其其其其活活活活泼泼泼泼，能能能能够够够够引引引引发发发发一一一一系系系系列列列列反反反反应应应应，参参参参加加加加很很很很多多多多污污污污染染染染物物物物化化化化学学学学转转转转化化化化过过过过程程程程，造造造造成成成成生生生生成成成成各各各各种种种种各各各各样二次污染物。样二次污染物。样二次污染物。样二次污染物。第42页三、大气中主要自由基起源三、大气中主要自由基起源 l l键断裂与自由基（键断裂与自由基（free radical）形成：）形成：l l不对称裂解形成正、负离子；不对称裂解形成正、负离子；不对称裂解形成正、负离子；不对称裂解形成正、负离子；l l对称裂解形成自由基。对称裂解形成自由基。对称裂解形成自由基。对称裂解形成自由基。l l自由基自由基含有强烈夺取电子倾向和结协力。含有强烈夺取电子倾向和结协力。l l自由基自由基含有很强氧化能力和化学活性。含有很强氧化能力和化学活性。第43页l l1、HO起源起源HOH2OO+O2O3315nmHNO2400nmH2O2370nmNOHO2O2H+HCOHCHO313nmHOHO基形成路径基形成路径基形成路径基形成路径（1 1）HONOHONOHOHONONO（400nm400nm）（2 2）H H2 2OO2 22HO2HO（300nm300nm）（3 3）OOH H2 2OO2HO2HO（OO来自来自来自来自OO3 3光离解）光离解）光离解）光离解）（4 4）HOHO2 2NONOHOHONONO2 2（HOHO2 2来自来自来自来自HCHOHCHO光离解，光离解，光离解，光离解，产生产生产生产生H H与与与与OO2 2作用）作用）作用）作用）HO基基形成路径形成路径 第44页l l大气中大气中HO浓度测算浓度测算：l l用用用用数数数数学学学学模模模模拟拟拟拟算算算算出出出出大大大大气气气气中中中中HOHO基基基基全全全全球球球球平平平平均均均均浓浓浓浓度度度度约约约约为为为为7107105 5个分子个分子个分子个分子/cm/cm3 3；l l用用用用激激激激光光光光共共共共振振振振荧荧荧荧光光光光光光光光谱谱谱谱法法法法测测测测定定定定HOHO基基基基浓浓浓浓度度度度范范范范围围围围为为为为3 35105104 4个分子个分子个分子个分子/cm/cm3 3，l l浓浓浓浓度度度度数数数数值值值值随随随随纬纬纬纬度度度度、高高高高度度度度及及及及地地地地域域域域不不不不一一一一样样样样而而而而改改改改变变变变，与季节相关。与季节相关。与季节相关。与季节相关。第45页HOHO在对流层中随高度和纬度分布在对流层中随高度和纬度分布在对流层中随高度和纬度分布在对流层中随高度和纬度分布HOHO最最最最高高高高浓浓浓浓度度度度出出出出现现现现在在在在热热热热带带带带（温温温温度度度度高高高高，太太太太阳阳阳阳辐辐辐辐射射射射强强强强）；在在在在两两两两半半半半球球球球间分布不对称。间分布不对称。间分布不对称。间分布不对称。HOHO和和和和HOHO2 2自由基日改变曲线自由基日改变曲线自由基日改变曲线自由基日改变曲线光光光光化化化化学学学学生生生生成成成成产产产产率率率率白白白白天天天天高高高高于于于于夜夜夜夜间间间间，峰值出现在阳光最强时间。峰值出现在阳光最强时间。峰值出现在阳光最强时间。峰值出现在阳光最强时间。夏季高于冬季。夏季高于冬季。夏季高于冬季。夏季高于冬季。第46页2、HO2起源起源l l由由CH2O、CH3ONO以及以及H2O2形成：形成：（1 1）HCHOHCHOH H HCOHCO （313nm313nm）H H OO2 2HOHO2 2 HCOHCO OO2 2HOHO2 2 COCO （2 2）CHCH3 3ONOONONONO CHCH3 3OO （300300 400nm 400nm）CHCH3 3OO OO2 2HOHO2 2 CHCH2 2OO （3 3）H H2 2OO2 22 2HO HO （370nm370nm）2 2HO HO 2H2H2 2OO2 22 2HOHO2 2 2H2H2 2OO 2 2HO HO 2CO2CO2CO2CO2 22 2H H 2 2H H OO2 22 2HOHO2 2 第47页3、CH3、CH3O、RO2起源起源l lCH3：CH3CHOh CH3+HCO CH3COCH3h CH3+CH3CO l lCH3O：CH3ONOhCH3O +NOl lCH3O2 和和RO2：CH3+O2 CH3O2 R O2RO2 第48页四、氮氧化物转化四、氮氧化物转化transforml l1、NOx光化学反应光化学反应l lNO(nitric oxide)NO(nitric oxide)、NONO2 2(nitrogen dioxide)(nitrogen dioxide)与与与与OO3 3(ozone)(ozone)之间存在着化学循环之间存在着化学循环之间存在着化学循环之间存在着化学循环chemical cyclingchemical cycling是是是是大气光化学过程基础。大气光化学过程基础。大气光化学过程基础。大气光化学过程基础。l l当阳光照射到含有当阳光照射到含有当阳光照射到含有当阳光照射到含有NONO和和和和NONO2 2空气时，反应：空气时，反应：空气时，反应：空气时，反应：NO NO2 2hhNO+ONO+O O O2 2+O+OMMOO3 3MM O O3 3NONONONO2 2+O+O2 2 第49页2、NOx气相转化气相转化l lN2O 光解光解photolysis：N2OhN2+O 去除去除elimination：N2O ON2+O2 N2O ONO+NO 第50页2、NOx气相转化气相转化l lNO NONO O O3 3 NONO2 2+O+O2 2 HO+NO HO+NO HONO HONO RO+NO RO+NO RONORONO RO RO2 2+NO +NO RO+NO RO+NO2 2 HO HO2 2+NO +NO HO+NOHO+NO2 2 RCOO RCOO2 2+NO +NO RO+CO+NO RO+CO+NO2 2 第51页l lNO2 HO+NOHO+NO2 2 HNO HNO3 3 O O3 3+NO+NO2 2 NO NO3 3+O+O2 2 l lNONO3 3能够和能够和能够和能够和NONO反应或光解作用再生成反应或光解作用再生成反应或光解作用再生成反应或光解作用再生成NONO2 2，或者，或者，或者，或者再与再与再与再与NONO2 2深入反应生成深入反应生成深入反应生成深入反应生成N N2 2OO5 5。l lN N2 2OO5 5与与与与H H2 2OO作用形成作用形成作用形成作用形成HNOHNO3 3。PAN（过过氧氧乙乙酰酰基基硝硝酸酸酯酯 peroxy acetyl nitrate）CHCH3 3CO+OCO+O2 2 CH CH3 3COOCOO2 2 CH CH3 3COOCOO2 2NONO2 2 CH CH3 3COOCOO2 2NONO2 2 PANPAN含含含含 有有有有 热热热热 不不不不 稳稳稳稳 定定定定 性性性性，遇遇遇遇 热热热热 会会会会 分分分分 解解解解 回回回回 到到到到CHCH3 3COOCOO2 2和和和和NONO2 2。第52页3、NOx液相转化液相转化l lNOx可溶于大气水中，组成一个液相平衡体可溶于大气水中，组成一个液相平衡体系。系。l lNOxNOx液相平衡液相平衡液相平衡液相平衡 NO(g)NO(g)NO(aq)NO(aq)aquatic NO NO2 2(g)(g)NO NO2 2(aq)(aq)2NO2NO2 2(aq)(aq)N N2 2OO4 4 NO(aq)+NO NO(aq)+NO2 2(aq)(aq)N N2 2OO8 8(aq)(aq)l l对于对于对于对于NO-NONO-NO2 2体系，存在液相平衡：体系，存在液相平衡：体系，存在液相平衡：体系，存在液相平衡：2 NO 2 NO2 2(g)+H(g)+H2 2O O 2H 2H+NO+NO2 2-+NO+NO3 3-NO(g)+NO NO(g)+NO2 2(g)+H(g)+H2 2O O 2H 2H+2NO+2NO2 2-第53页l lNH3和和HNO3液相平衡液相平衡aquatic balance aquatic balance NHNH3 3(g)+H(g)+H2 2O O NH NH3 3 H H2 2OO NH NH3 3 H H2 2O O NH NH4 4+OH+OH-HNO HNO3 3(g)+H(g)+H2 2O O HNO HNO3 3 H H2 2OO HNO HNO3 3 H H2 2O O H H+NO+NO3 3-第54页