ACEE 219

E i
Environmental
t l Chemistry
Ch i t

Week
W k9
April 27, 2010
Innovation Hall 127
ACEE 219 Spring 2010 HDP 1
 Gas/Liquid Equilibrium

http://www.xtolhydro.com/images/degasser.JPG3
http://www.techworld.com/cmsdata/features/3221356/Cloud.jpg

Dissolution of gases Stripping ammonia

http://www.visionequipment.net/images/Wastewater_Treatment_
Plant_Aeration_Tank_Rectangular.jpg http://www.advancedaquarist.com/2009/2/chemistry_album/image003.jpg

Aeration in activated sludge system Carbonate system

ACEE 219 Spring 2010 HDP 2

 Gas--Phase Concentrations
Gas
• Relationship
p between the molar concentration of a g
gas and its p
partial p
pressure
ni P
cG ,i = = i cG ,i : gas - phase concentration of i in moles per unit volume
VG RT ni : number of moles of i in the ggas pphase
VG : gas volume
Pi = RTcG ,i Pi : pressure exerted by i in the gas phase (the partial pressure of i )

• Relationship between the partial pressure of a gas and the total pressure

N N Pi RTcG ,i cG ,i
Ptotal = ∑ Pj = RT ∑ cG , j = N
= N
≡ yi
RT ∑ cG , j ∑c
j =1 j =1
Ptotal
G, j
j =1 j =1

RTc 'G ,i yi ≡
moles of i in gas phase
Pi = yi Ptotal = RTcG ,i = total moles of all species in gas phase
MWi
c 'G ,i : mass concentration of i the gas phase mole fraction of i in the gas phase

ACEE 219 Spring 2010 HDP 3

 Gas/Liquid Equilibrium
CO2 (g)
( )

Absorption Volatilization or stripping

CO2 (aq) = CO2·nH2O

H2O H2O
CO2
H2O H2O
CO2 (aq) H2O

Henry’s law: the solubility of a gas in a liquid is proportional to the pressure

of that gas above the liquid

ACEE 219 Spring 2010 HDP 4

 Henry’s
Henry s Constant

A·nH2O ↔ A(g) + nH2O or A(aq) ↔ A(g)

[A(g)]eq
H=
[A(aq)]eq

A(g) + nH2O ↔ A·nH2O or A(g) ↔ A(aq)

[A(aq)]eq
KH =
[A(g)]eq

KH = 1/H

ACEE 219 Spring 2010 HDP 5

 Henry’s
Henry s Constant
• Different forms of Henry
Henry’s
s constant

M. Benjamin Table 7-1

ACEE 219 Spring 2010 HDP 6

 Henry’s
Henry s Constant
• Different forms of Henry
Henry’s
s constant

LL bar ⋅ LL bar ⋅ LL LL mol of solution

LG mg i mol i mol of gas mol of gas

• ((Example)
p ) Henry’s
y constant for oxygen
yg at 20oC
bar ⋅ LL bar ⋅ LL LL
730 0.023 30
mol mg LG

mol O2 mol solution

2.46 ×10 −5 4.01×10 4
mol solution mol gas

ACEE 219 Spring 2010 HDP 7

 Henry’s
Henry s Constant
Compound H* Compound H*
Nitrogen 1560 Hydrogen sulfide 9.8
Hydrogen 1260 Chloroform 4.0
Carbon monooxide 1050 Sulfur dioxide 0.81
Oxygen 790 Bromoform 0.70
Methane 776 Benzene 0.22
Ozone 107 Hydrogen cyanide 0.040
Carbon dioxide 28.8 Ammonia 0.017
Tetrachloroethylene 20 Acetic acid 0.0013
Trichloroethylene 11
* The unit of the Henry’s constant is bar-liter/mole

• The less polar a molecule is the larger its Henry’s constant tends to be.
• Larger molecules tend to be less volatile than small ones.
M. Benjamin Table 7-2
Henry’s constants of some environmentally important gases

ACEE 219 Spring 2010 HDP 8

 Henry’s
Henry s Constant
• Volatilityy increases dramaticallyy as temperature
p increases ((i.e.,, Henry’s
y
constant increases)
o
• The standard enthalpy of volatilization ( ΔHaq→gas ) of all gases is positive.
• Volatility increases as with increasing ionic strength (i.e., Henry’s constant
increases)

M. Benjamin Fig. 7-2

ACEE 219 Spring 2010 HDP 9

 Example 7
7.3
3
• Determine the concentrations of dissolved oxygen in water and the partial
pressure of oxygen in air at 10oC (H = 588 bar-liter/mole
bar liter/mole @ 10oC)

@ initial @ equilibrium
Air ((0.1 liter)) O2 = 0.21 bar O2 = ?? bar

Water (1.0 liter) O2 = 0.0 mg/L O2 = ?? mg/L

@ initial PO2 ( g )V (0.21bar )(0.1L)

ntot ,O2 = ngas ,O2 = = = 9.04 ×10 − 4 mole
RT initial
(0.082bar − L / mol K )(283 K )
o o

@ equilibrium
q PO2 ( g )Vgas PO2 ( g )Vsolution
ntot ,O2 = ngas ,O2 + nsolution ,O2 = + M. Benjamin Example 7-3
RT H
PO2 ( g ) (0.1L) PO2 ( g ) (1.0 L) PO2 ( g ) = 0.15 bar
−4
9.04 × 10 mole = +
b − L / moll o K )(283o K )
(0.082bar b − L / mole
588bar l PO2 ( g )
[O2 (aq)] = = 8.2 mg / L
H O2
ACEE 219 Spring 2010 HDP 10
 Gas/Liquid Eq.
Eq (Acids)
3.5x10-4 bar CO2
pH
0 2 4 6 8 10 12 14
0

2
n, pC

pCT,CO3
4
[H2CO3*]
entration

6
og Conce

8
[HCO3-]
10
‐lo

12 [OH-] [H+]
[CO32-]
14

ACEE 219 Spring 2010 HDP 11

Gas/Liquid Eq.
Eq (Bases)
1.0 x10-7 bar NH3

pH
0 2 4 6 8 10 12 14
0

2
pCT,NH3
n, pC

4
entration

[NH3]
6
[NH4+]
og Conce

10
‐lo

[OH-] [H+]
12

14

ACEE 219 Spring 2010 HDP 12

Ionizabale Molecules

M. Benjamin Figure 7-5

ACEE 219 Spring 2010 HDP 13

Lecture for the Next Week

Precipitation and Dissolution

- Kinetics
- Equilibrium calculation
- S l bilit off salt
Solubility lt off weak
k acids
id and
dbbases
- Effect of complexation on solubility

ACEE 219 Spring 2010 HDP 14