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Ch 9. Thermodynamics of Aerosols. CONTENTS 9.1 Thermodynamics Principles 9.2 Aerosol Liquid Water...
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Transcript of Ch 9. Thermodynamics of Aerosols. CONTENTS 9.1 Thermodynamics Principles 9.2 Aerosol Liquid Water...
CONTENTS9.1 Thermodynamics Principles
9.2 Aerosol Liquid Water Content
9.3 Equilibrium Vapor Pressure Over a Curved Surface: The Kelvin Effect
9.4 Thermodynamics of Atmospheric Aerosol Systems
CONTENTS• 9.1 Thermodynamics Principles
• 9.1.1 Internal Energy and Chemical Potential
• 9.1.2 The Gibbs Free Energy• 9.1.3 Conditions for Chemical Equilibr
ium• 9.1.4 Chemical Potentials of Ideal Ga
ses and Ideal Gas Mixtures• 9.1.5 Chemical Potential of Solutions• 9.1.6 The Equilibrium Constant
Chemical Potential
藉由熱力學觀念討論 Gas-Phase 、 Aqueous Phase 、 Solid Phase 三相平衡SOLID=LIQUID
Chemical Potential =f(T, P, ni)ni:the moles of species i
9.1 Thermodynamics Principles
CONTENTS• 9.2 Aerosol Liquid Water Content
• 9.2.1 Chemical Potential of Water in Atmospheric Particles
• 9.2.2 Temperature Dependence of the DRH
• 9.2.3 Deliquescence of Multicomponent Aerosols
• 9.2.4 Crystallization of Single and Multicomponent Salts
DRH(deliquescence relative humidity)
Low RH aerosol solid
Deliquescence :當 RH 開始增加至 DRH 時,氣膠內特定組成會開始吸收水分,藉以維持其其熱力學平衡關係,因而變為水相。每一物種之DRH並不相同。Crystallization :當 RH 下降時,其水分會揮發形成結晶,但此 RH 與 DRH 並不相同。例如 (NH4)2SO4 , fig 9.4
9.2 Aerosol Liquid Water Content
Deliquescence and Crystallization
Deliquescence當 RH<DRH, , Solid 之 Gibbs free energy 較低,因而致使 (NH4)2SO4以 Solid 存在
當 RH>DRH , Liquid 之 Gibbs free energy 較低,因而致使 (NH4)2SO4以 Liquid 存在
當 RH=DRH ,兩者之 Gibbs free energy 相同,因而致使 Solid 會開始吸收水分Gibbs free energy 變化圖
Crystallization當 RH 下降至 DRH 時,水分並不會在此時揮發。
RH 持續下降,使氣膠成為超飽和溶液。帶其達到臨界超飽和 (Critical Supersaturation) 後,即發生再結晶現象
9.2.1 Chemical Potential of Water in Atmospheric Particles
Water Vapor (atmosphere): the order of grams per m3 of air.
H2O concentration in the aerosol is less than 1 mg/m3 of air
氣膠相內水之濃度變化並不會影響大氣中水蒸氣之濃度 氣膠熱力學模式計算時,可將 ambient RH 視為一常數
9.2.1 Chemical Potential of Water in Atmospheric ParticlesWater Activity
Pw: the water vapor pressure(in atm)
w: the water activity in solution
純水平衡 w=1 , pw=pw0(T, saturation
vapor pressure)
(9.61) 、 (9.62) 可得
)(2)(2 aqg OHOH
)(22 )( aqOHgOH
)61.9(lnln *0
22 wOHwOH RTpRT
)62.9(ln 00*
22 wOHOH pRT
1000
RH
p
p
w
ww
9.2.1 Chemical Potential of Water in Atmospheric ParticlesWater Activity
由於 Pw/Pw0 即為相對濕度 (0~1) 之定義
大氣氣膠中之水活性 (w) 即為相對濕度 (RH)
單一鹽類於 DRH , H2O 於氣相與氣膠相平衡
ws: the water activity of the saturated solution of the salt at T (It can be calculated from thermodynamic arguments )
1000
RH
p
p
w
ww
ws
DRH 100
9.2.2 Temperature Dependence of the DRH
單一鹽類之 DRH 會隨溫度改變 (推導 )、 (應用 )
n: the solubility of S in water(moles of solute/mole of water) (A 、 B 、 C)
Hs: the enthalpy of solution of the salt(data)
)()(2
)(2)(2
aqsaq
aqg
nSnSOH
OHOH
298
298ln
298
11exp298 TC
TB
TA
R
HDRHTDRH s
Temperature Dependence of the DRH
bnSnSOH
aOHOH
aqsaq
aqg
)()(2
)(2)(2 )(
vs HHnH
)67.9(lnln
222 RT
Hn
RT
H
dT
pd
RT
H
dT
pd svww
)68.9(ln
2
0
RT
H
dT
pd vw
(a) 式:水之冷凝熱 (-Hv) 即為水之蒸發熱 (Hv) 之負值
(b) 式:鹽類之溶解熱 (Hs)
The overall enthalpy change
溶液中水蒸氣於此溫度之變化 =>Clausius-Clapeyron equation
純水 時之飽和蒸汽壓:溫度T0wp
298
298ln
298
11exp298 TC
TB
TA
R
HDRHTDRH s
0
000
ln11
ln TTCT
TB
TTA
R
H
TDRH
TDRH s
2
100/ln
RT
Hn
dT
DRHd s
結合 (9.67) 、 (9.68)
代入 DRH 關係式
2
0/ln
RT
Hn
dT
ppd sww
Temperature Dependence of the DRH( 續 )
代入 n=A+BT+CT2 ,積分範圍 T0~T
T0=298 K
9.2.3 Deliquescence of Multicomponent Aerosols
多成分氣膠 (Multicomponent Aerosols)之吸水行為與單一鹽類相同。 KCl-NaCl之 deliquescence growth 、 evaporation 、crystallization 如 fig 9.7 。
Hydroscopic growth and evaporation of a mixed-salt particle
Initial66% mass KCl 34% mass NaCl
混合鹽類之 DRH 較低
DRH
Mixed-salt 72.7%
KCl 84.2%
NaCl 75.3%
推導雙電解質造成之 DRH 改變Gibbs-Duhem equation :用於計算單一電解質加入單一溶質水溶液中之 DRH 改變於溫度 T 、壓力 p ,包含雙電解質 (1,2) 、水(w)
n1、 n2、 nw: the numbers of moles of electrolytes of 1, 2, and water
1、 2、 w: chemical potential
9.2.3 Deliquescence of Multicomponent Aerosols
0dndndn ww2211
9.2.3 Deliquescence of Multicomponent Aerosols
初時假設 electrolyte 1 與固相鹽類 1 平衡,此時並不包含 electrolyte 2 。加入 electrolyte 2 , electrolyte 1 之化學潛能尚未改變,即 d1=0 。 electrolyte 2 和 H2O 之化學潛能 0dlnndlnn ww22
0dlnn
1000dlnm w
w22
1000
mM
n
n 2w
w
2 m2: the molality of electrolyte 2
Mw: the molecular weight of water
推導雙電解質造成之 DRH 改變
9.2.3 Deliquescence of Multicomponent Aerosols
積分 m’2=0~m2
Wexler and Seinfeld(1991)
由上式可知加入 electrolyte 2 後, water activity會減少,因而降低 DRH
得知 ( 實例, NH4NO3 and NH4Cl)
1.DRH 時之水活性最小 (m2=0 ,左右兩項相等 )2. 混合鹽類之 DRH 恆小於單一鹽類之 DRH
2m
0
'2'
2
'22
'22
'2w
w
2w dmdm
md
m
m
1000
M-
0
mln
0mm 2w2w 0
dm
d
2
2
推導雙電解質造成之 DRH 改變
9.2.3 Deliquescence of Multicomponent Aerosols
NH4NO3 and NH4Cl
303 K DRH
NH4Cl(only) 77.4%
NH4NO3(only) 61.8%
兩電解質混合後,潮解點相對濕度會降低,最低達 51% 。
1
23
4 56
7
9.2.3 Deliquescence of Multicomponent Aerosols
NH4NO3 and NH4Cl
1
23
4 5 6
7
Solid Aqueous
1 - NO3-,NH4
+,Cl-
2 NH4Cl NO3-,NH4
+,Cl-
3 - NO3-,NH4
+,Cl-
4 NH4Cl NO3-,NH4
+,Cl-
5 - NO3-,NH4
+,Cl-
6 NH4NO3 NO3-,NH4
+,Cl-
7 NH4ClNH4NO3, RH<DRH*(51%)
不同 RH 時,氣膠內組成變化
9.2.3 Deliquescence of Multicomponent Aerosols
氣膠內組成變化 (RH)
氣膠內組成: 40%NH4NO3 、 60%NH4Cl
RH : 40%~90%(increase)
No evaporation and condensationRH xNH4NO3 xNH4Cl
51%* 0.811 0.189
60% 0.73 0.27
70% 0.42 0.58
71% - -
Eutonic point: 最低 DRH 之相對組成點
如表 9.4
9.2.3 Deliquescence of Multicomponent Aerosols
多於三物種之相轉換圖 ( 如圖 9.9)• Solid:(NH4)2SO4 、 NH4HSO4 、 ((NH4)3H(SO4)2) 、 NH4N
O3 (Solid lines 區分各主導 solid ,為 phase boundary ,線上為共存。 Label : DRH)• Aqueous:H+ 、 NH4
+ 、 HSO4- 、 SO4
2- 、 NO3-
(Dashed lines 說明反應發生方向 )• Total Hydrogen= total moles of protons and bisulfate ions• Total Sulfate=total moles of sulfate and bisulfate ions• Dotted line 乃指反應發生方向 (path lines) ,乃指低於 DRH 之 RH(solid) 減少時之進行方向。如: 1 mole (NH4)2SO4 形成必須消耗 2 moles NH4
+ 、 1mole SO42- ,因而 X 、
Y 會改變。
9.2.3 Deliquescence of Multicomponent Aerosols
X(Ammomia)
Y(Sulfate) DRH Solid
1 1 80% (NH2)4SO4
1 0.3 68% (NH2)4SO4·2NH4NO3
9.2.4 Crystallization of Single and Multicomponent Salts
1. 再結晶過程會有延遲現象。2. 多種鹽類組成之粒狀物會顯示多個再結晶點,如圖 9.7 。 KCl-NaCl 之組成有兩階段蒸發過程: KCl(65%) 、 NaCl(62%)3.Spann and Richardson(1985) :氣膠組成介於 NH4HSO4和 (NH4)2SO4組成, crystallization RH:10%~40% ,於大氣中氣膠並不會呈現固體
CONTENTS• 9.3 Equilibrium Vapor Pressure Over a
Curved Surface: The Kelvin Effect• Aerosol : curved interface(not flat)• The effect of curvature :在此之前所討論之物種蒸汽壓皆於一平面上,此一節將討論物種 A 於氣膠粒狀物表面上之蒸汽壓,其受曲面之影響
• Gibbs free energy•藉由形成單一液滴之 Gibbs free energy變化,引入表面張力相 (Derived)
G=Gdroplet-Gpure vapor (Result)
G for the formation of a single dropSpecies A 、 radius Rp 、 n molecules
NT: total number of vapor initially
After the drop forms: vapor, N1=NT-n
gl 、 gv:the G of a molecules (Liquid and Vapor)
: surface tension
Rp: the radius of curvature
n:the number of molecules in the drop
(gl-gv) (9-13)
at T, dni=0
dg=vdp or dg=(vl-vv)dp
vv>>vl , dg=-vvdp
vv=kT/p
waterpuredrpolet GGG
vTplv gNRnggNG 21 4
24)( pvl RggnG
l
p
v
Rn
3
4 3
2
3
4)(3
4pvl
l
p Rggv
RG
A
A
p
pvl p
dpkTgg
0
0ln
A
Avl p
pkTgg
2
3
4ln3
4p
ll
p RSv
kT
v
RG
k
iiidnVdpSdTdG
1
Gibbs free change for formation of a droplet
Bulk free energy
Surface tension
The behavior of G as a function of Rp
S<1 Both terms are positive G increase with RpS>1 Small Rp:Surface tension term dominatesLarge Rp:Bulk free energy dominates
0Rp
G
9.3 Equilibrium Vapor Pressure Over a Curved Surface: The Kelvin Effect
The Kelvin effect(Derived)
液滴曲面對平衡蒸汽壓之影響於一外凸液面,要拉住一分子之其他液體分子數目比於一平面之液體數目為少,因而可知,與一液滴達到平衡之蒸汽分子所產生之氣壓要比平面液體之蒸汽壓高。
RpRT
Mpp
lAA
2exp0
9.3 Equilibrium Vapor Pressure Over a Curved Surface: The Kelvin Effect
The Kelvin effectGmaximum G* at Rp=Rp*
the equilibrium at this point is metastable S:Saturation ratio(pA/pA
0) :surface tension
orM:the molecular weight of the substance
l:the liquid-phase density
RpRT
Mpp
lAA
2exp0
2
3
4ln3
4p
ll
p RSv
kT
v
RG
0Rp
G
SkT
vR lp ln
2*
kTRp
vpp lAA
2exp0
The Kelvin Effect
Table 9.5 為水與有機物之表面張力。 298 K 時,五種有機物之分子量 (M/) 為水之 3~6 倍,但其表面張力皆為水之 1/3倍。
9.3 Equilibrium Vapor Pressure Over a Curved Surface: The Kelvin Effect
RpRT
Mpp
lAA
2exp0
The Kelvin EffectFig 9.12 為 H2O 、 DOP(typical organic compound) 於不同粒徑時,受 Kelvin effect 影響之大小
9.3 Equilibrium Vapor Pressure Over a Curved Surface: The Kelvin Effect
H2O :於 0.1 m 時,增加2.1% ;於 0.01 m 時增加 23% ,可知約 50 nm 時, Kelvin effect 影響顯著。
較高分子量有機物,如 DOP : <200 nm 時,則需加以考量
成長區
蒸發區
RpRT
Mpp
lAA
2exp0
CONTENTS• 9.4 Thermodynamics of Atmospheric
Aerosol Systems
• 9.4.1 The H2SO4-H2O system• 9.4.2 The Sulfuric Acid-Ammonia-
Water System• 9.4.3 The Ammonia-Nitric Acid-Water
System• 9.4.4 The Ammonia-Nitric Acid-
Sulfuric Acid-Water System• 9.4.5 Other Inorganic Aerosol
Species
9.4.1 The H2SO4-H2O systemH2SO4-hydroscopic, extremely low RH
9.4 Thermodynamics of Atmospheric Aerosol Systems
Dp/Dp0:particle growth factor
Dpoln(pH2SO4/p0H2SO4):Kelvin effect parameter
How to use fig 9.13(1 m H2SO4-H2O droplet)
9.4.1 The H2SO4-H2O system
RH 50%(negligible Kelvin effect)
90%(negligible Kelvin effect)
H2SO4 Conc. 42.5% 18%
Density() 1.32 1.1
B. P. 115 C 100 C
Surface tension() 76 dyn/cm 73 dyn/cm
Normality 11 N 4 N
Mass concentration(xH2SO4) 0.55 g/cm3 of solution 0.2 g/cm3 of solution
Particle growth factor(Dp/Dp0) 1.48 2.12
pure H2SO4 1/1.48=0.68 m 2.12/1.48=1.43 m
Kelvin effect parameter 11.310-4 m 9.210-4 m
ln(pH2SO4/p0H2SO4) 11.310-4/0.68=16.6210-4 9.210-4/1.43= 6.410-4
(pH2SO4/p0H2SO4) 1.0017 1.0006
9.4.1 The H2SO4-H2O systemThe saturation vapor pressure of pure sulfuric acid, p0
H2SO4
p0H2SO4=1.31.010-8 atm(1310 ppb) at 296 K (T dependenc
e)
H2SO4 蒸汽壓於表面之變化,為 H2SO4-H2O 混合物內組成、溫度之函數RH>50% , [H2SO4]<40% by mass , xH2SO4<0.1(T=20 C) , H2
SO4 equilibrium vapor pressure<10-12 mmHg 。[H2SO4]gas<[SO4
2-]aerosol
9.4.1 The H2SO4-H2O systemThe effect on the composition of atmospheric H2SO4-H2O droplets.
Particle size>1 m, negligible Kelvin effect
For smaller particles the H2SO4 mole fraction in the droplet is highly dependent on particle size.
The water concentration increases as the RH increase.
9.4.1 The H2SO4-H2O systemThe composition of atmospheric H2SO4-H2O droplets
The vapor pressure of H2SO4(g) is zero over atmospheric particles
The whole systembisulfate dissociation reaction
Keq(298 K)=1.0110-2(mol/kg)
The molar ratio of HSO4- to SO4
2-
The ratio is proportional to [H+]
[H+],pH,[HSO4-]
4)(42 HSOHSOH g
)(42)(42 aqg SOHSOH
244 SOHHSO
44
24
24
2
,2 /1001.1HSOHSO
SOHSOH
m
mmkgmol
H
HSO
SOH
SO
HSO mm
m
4
24
24
4
2
,99
9.4.2 The Sulfuric Acid-Ammonia-Water SystemT, RH, NH3, H2SO4, determine the aerosol composition
30%, 298 K, 10 g/m3 H2SO4
9.4 Thermodynamics of Atmospheric Aerosol Systems
[NH3]/[H2SO4]
<0.5 H2SO4 dominate
0.5~1.25 NH4HSO4 dominate
1.25~1.5 (NH4)3H(SO4)2 dominate
2 (NH4)2SO4 dominate
>2 NH3, it does not change the aerosol composition
0.5 1 1.25 2[NH3],[H2SO4],H2O , total mass
9.4.2 The Sulfuric Acid-Ammonia-Water System75%, 298 K, 10 g/m3 H2SO4
9.4 Thermodynamics of Atmospheric Aerosol Systems
[NH3]/[H2SO4]
<0.5 H2SO4 dominate
0.5~1. 5 HSO4- dominate
High NH3 SO42- dominate
DRHNH4HSO4 40%
DRH(NH4)3H(SO4)2 69%
DRH(NH4)2SO4 80%
Molar ratio=2, form (NH4)2SO4, loss water
Liquid phaseSolid Phase
9.4 Thermodynamics of Atmospheric Aerosol Systems
9.4.2 The Sulfuric Acid-Ammonia-Water SystemNH3/H2SO4
molar ratio<0.5
Exist primarily as H2SO4 solution
0.5< NH3/H2SO4 molar ratio<1.5
Consist mainly as HSO4-
NH3/H2SO4 molar ratio=2
Consist mainly as (NH4)2SO4
NH3/H2SO4 molar ratio>2
Ammonia also exist in the gas phase
9.4.3 The Ammonia-Nitric Acid-Water System
NH3(g)+HNO3(g)NH4NO3(s)
Condition:high NH3、 high HNO3、 lowSO42-
2 Cases for NH4NO3
Ambient RH<DRHSolid Ambient RH>DRHLiquid
9.4 Thermodynamics of Atmospheric Aerosol Systems
9.4 Thermodynamics of Atmospheric Aerosol Systems
NH3(g)+HNO3(g)NH4NO3(s)
Ambient RH<DRHSolid
Equilibrium condition (chemical potential of ideal gases and solids)
Kp(ppb2): estimated by van’t Hoff equation, shown as fig9.19, it is sensitive to T change
6954.17.723
ln T
DRH
T(K) DRH
298 61.8%
288 67%
3433 NONHHNONH 33
3334
00*
exp HNONHpHNONHNONH ppTK
RT
298ln1.6
242206.84ln
T
TKp
NH3(g)+HNO3(g)NH4NO3(s)
Lower TLower KpLower equilibrium values of the NH3 and HNO3 gas-phase concentrations
Lower T shift the equilibrium of the system toward the aerosol phase, increasing the aerosol mass of NH4NO3(fig 9.20)
9.4 Thermodynamics of Atmospheric Aerosol Systems
9.4 Thermodynamics of Atmospheric Aerosol Systems
NH3(g)+HNO3(g)NH4++NO3
-(9.92)
Ambient RH>DRHLiquid(8~26 M)
Strongly non-idealneed activity coefficient
Equilibrium condition
Estimate K(T)Need “m”Need aerosol water content
Fig 9.21 depicts the results of such a computation.(The product of the mixing ratios of ammonia and nitric acid over solution as a function of RH)
3433 NONHHNONH
33
34344333
00
expNHHNO
NONHNONHNHNOHNONH
pp
mm
RT
3434
2
NONHNONH
33
3434
2
92.9NHHNO
NONHNONH
pp
mmK
TTTK
298298ln151.111
2987.64exp104 17
92.9
9.4 Thermodynamics of Atmospheric Aerosol Systems
Water activity=RH
One needs to relate the tendency of the aerosol components to absorb moisture(RH)
W: the mass of aerosol water(kg of water/m3 of air)
Ci:the aqueous-phase concentration of electrolyte i (moles/m3 of air)
mi,o(aw):the molality(mol/kg) of a single-component aqueous solution of electrolyte i (water activity, aw=RH/100)查表計算
Aerosol water content
(ZSR relationship, Zdanovskii-Stokes-Robinson relationship)
i w
aoi
miC
W,
9.4 Thermodynamics of Atmospheric Aerosol Systems
NH3(g)+HNO3(g)NH4++NO3
-(9.92)Y=1no (NH4)2SO4, 隨 RH 增加,濃度乘積快速減少,可知主要以 aerosol phase 為主。 Water 會使 NH4NO3 溶解,並使其在 aerosol phase 量增加。
33 NHHNOpK
9.4 Thermodynamics of Atmospheric Aerosol Systems
NH3(g)+HNO3(g)NH4++NO3
-(9.92)
Input RH, T, [TN], [TA], 可知 gas phase-aerosol phase 平衡組成[TN]=[HNO3(g)]+[NO3
-]
[TA]=[NH3(g)]+[NH4+]
Kp/(RT)2[TN][TA]: no NH4NO3
[TN][TA]Kp/(RT)2: NH4NO3 formation
Equilibrium Kp/(RT)2=[NH3(g)]e[HNO3
(g)]e[NH4NO3]e=0.5([TA]+[TN]-[([TA]+[TN])2-4([TA][TN]-Kp/(RT)2)]0.5
[NH3(g)]=[TA]-[NH3NO3]e
[HNO3(g)]=[TN]-[NH3NO3]e92.9
2
3434
K
mmK NONHNONH
p
9.4.4 The Ammonia-Nitric Acid- Sulfuric Acid-Water System
Gas Phase: NH3,HNO3,H2SO4,H2O
Solid Phase:NH4HSO4, (NH4)2SO4, NH4NO3, (NH4)SO4·2NH4NO3, (NH4)2SO4 ·3NH4NO3,(NH4)3H(SO4)2
Aqueous Phase:NH4+,H+,HSO4
-,SO42-,NO3
-,H2O
Two observations 1.Sulfuric acid possesses an extremely low vapor pressure( 僅在 aeros
ol) 2.(NH4)2SO4 solid or aqueous is the preferred form of sulfate
Two regime
Fig 9.23
9.4 Thermodynamics of Atmospheric Aerosol Systems
Ammonia SO42- form NH4NO3
Poor [TA]<2[TS] HSO4- No
Rich [TA]>2[TS] SO42- Yes
9.4.4 The Ammonia-Nitric Acid- Sulfuric Acid-Water System
9.4 Thermodynamics of Atmospheric Aerosol Systems
Low [NH3] : SO42- and HSO4
-
As NH3 increase: NH4NO3 become important
Aerosol water content : nonlinear( 與其電解質組成變化有關 )
nonlinear
Low NH3 High NH3
9.4 Thermodynamics of Atmospheric Aerosol Systems
9.4.4 The Ammonia-Nitric Acid- Sulfuric Acid-Water Systemsulfatereplacement by nitrate(HNO3 and NH3 react)
sulfateNO3- , and NH4
+, water, total mass
The reduction of the mass is nonlinear
減少 20 g SO42-/m3(from 30 to 10 g/m3)
Dry aerosol mass 減少 12.9 g/m3
只會增加 10 g NO3-/m3
僅會減少 2.9 g NH4+/m3
9.4.5 Other Inorganic Aerosol Species
加入其他物種 (Cl-、 Na+) 之熱力學計算NaCl(s)+HNO3(g)NaNO3(s)+HCl(g)
2NaCl(s)+H2SO4(s) Na2SO4(s)+2HCl(g)
NaCl(s)+H2SO4(s) NaHSO4(s)+HCl(g)
9.4 Thermodynamics of Atmospheric Aerosol Systems
Suppose a solution contains 6 moles H+/m3, 6 moles Na+/m3, 7 moles Cl-/m3, 5 moles NO3
-/m3
The 4 ions can combine in many ways to form electrolytes: HNO3, HCl, NaNO3, NaCl.
Mass-balance
CH+,m=CHNO3,m+CHCl,m CNa+,m=CNaNO3,m+CNaCl,m
CCl+,m=CHCl,m+CNaCl,m CNO3-,m=CHNO3,m+CNaNO3,m
Result
Y0,k,Y1,k,Y2,k: polynomial coefficients(table)
Aerosol water content
Case CHCl,m CHNO3,m CNaCl,m CNaNO3,m
1 6 0 1 5
2 4 2 3 3
3 1 5 6 0
mHCl
mHCl
mHNO
mHNO
mNaNO
mNaNO
mHCl
mNaCl
ww m
C
m
C
m
C
m
C
mC
,
,
,
,
,
,
,
,
3
3
3
31000
3,3
2,2,1,0, wkwkwkkak aYaYaYYm
Aerosol water content
RPM input: TOTSO4, TOTNH3, TOTNO3
1. 分配 : Temp, gas phase and aerosol phase
TOTSO4 皆為 aqueous phase
2. Composition
1. SO42->2NH4
+: all NH4+(NH4)2SO4 、 H2SO4 、 HNO3
2. 2NH4+>SO4
2-: (NH4)2SO4 、 NH4NO3 、 HNO3
3. Aerosol water content
依個別計算所得之物種莫爾濃度 (in air) 配合大氣相對溼度,計算其相對吸水量,相加後即得氣膠含水量。
i wio
i
am
MW 3
,32
,2,1,00 )( wiwiwiiwi aYaYaYYam
Y’s 為 polynomial coefficients( 如表 )
計算含水率之重要參數 (298.15 K)
(NH4)2SO4
37% R.H.; 29.0 m
HNO3
0% R.H.; 22.6 m
H+/HSO4-
0% R.H.; 30.4 m
NH4NO3
62% R.H.; 28 m
(NH4)2SO4
37% R.H.; 29.0 m
2H+/SO42-
0% R.H.; 30.4 mY
0
1.1065495×102 2.306844303×101 3.0391387536×101 3.983916445×103 1.1065495×102 3.0391387536×101
Y
1
-3.6759197×102 -3.563608869×101 -1.8995055929×102 1.153123266×104 -3.6759197×102 -1.8995058929×102
Y
2
5.0462934×102 -6.210577919×101 9.7428231047×102 -2.13956707×105 5.0462934×102 9.7428231047×102
Y
3
-3.1543839×102 5.510176187×102 -3.1680155761×103 7.926990533×105 -3.1543839×102 -3.1680155761×103
Y
4
6.770824×101 -1.460055286×103 6.1400925314×103 -1.407853405×106 6.770824×101 6.1400925314×103
Y
5
1.894467542×103 -6.9116348199×103 1.351250086×106 -6.9116348119×103
Y
6
-1.220611402×103 4.1631475226×103 -6.770046794×106 4.1631475226×103
Y
7
3.098597737×102 -1.0383424491×103 1.393507324×105 -1.0383424491×103
3,3
2,2,1,00 )( wiwiwiiwi aYaYaYYam