ATMOSPHERE - WATER INTERACTIONS

CONTENTS:

1. Reactions and partitioning at gas-water interface; Henry’s Law

2. Environmental implications
3. A few example problems
Atmosphere-Surface Water Interactions: Mechanism behind the
Sustenance of Aquatic Life O2

O2 is central to the sustenance of life

of aerobic life-forms.
Similarly, aquatic ecosystem
depends on the oxygen dissolved
in the water
Oxygen enters the surface water and
oceans in two different pathways: a)
Diffusion from atmosphere to water
and b) Through photosynthesis by
algae in presence of sunlight.

At any time in steady state

condition, there is an equilibrium
partitioning of oxygen between the
water and the atmosphere.
Atmosphere-Surface Water Interactions: CO2

RAINWATER DROPLET IN THE AIR

NH3 NO2
As the droplet passes through
the atmosphere to fall on the
earth surface, various gases,
liquid and solids that are
either part of the atmosphere Dust SO2
or are suspended in air, tend
to get inside the water
droplet. Aerosols Organic
acids

Many of the species establish a quick equilibrium, thus imbibing

impurities even before the rain water reaches the earth surface.
Gas-Water Partitioning: Henry’s Law
Gas molecules strike the water surface, some
becomes dissolved. Some of the dissolved
molecules also strike the surface, and escape in pA
the gas phase.
At dynamic equilibrium, the rate of dissolution
into water equals the rate of escape into gas [A]aq
phase.
Sealed vessel: liquid
The equilibrium situation is described by Henry’s
and gas phase.
law
The Statement: The amount of volatile species (gas) dissolved in a solution is
directly proportional to the partial pressure of the gas above the solution.
For any species A, [ A]aq  p A [ A]aq  K H p A
[ A]aq M
KH  unit :
pA atm.
KH is called the Henry’s law constant
Partial Pressure and Molar Concentration
Ideal Gas Law: pV  nRT R = 0.0820578 L.atm/(K.mol)
n P
Molar concentration: C 
V RT
• Partial pressure of each gas in a gas mixture, such as the atmosphere, is
the portion of the total pressure that a particular gas would exert
Dalton’s Law
Ptot = pA + pB + …
= (nA + nB + …)RT/V
= (ntot)RT/V

Partial pressure of CO2 = pCO2 = 0.000400*1 atm

Example 1.

Find out the DO in aerated water at 25 deg C in a treatment plant. KH of

O2 at 25 deg C = 1.26X10-3 M/atm

Partial pressure of oxygen in the atmosphere = 0.21 atm.

Aqueous concentration of oxygen = KH*pO2

= 1.26 X10-3 M/atm. * 0.21 atm.
=0.0002646 M
= 8.467 mg/L [1M O2= 32 g/L]

Is KH or Henry’s law constant is really a constant?

• Why is DO content of water lower in the summer
The value of Henry’s Law constant changes inversely with temperature.

Implication: In the summer, the rivers and lakes shall have less dissolved
oxygen as compared to the dissolved oxygen concentration in winter
 Carbon dioxide -Water Interaction: Natural Acidity

CO2
The acidity imposed by carbon
dioxide is referred as natural
acidity. CO2 (aq.)

Depending upon the solution pH,

H++HCO3-
the carbonic acid (dissolved CO2)
further dissociates into hydrogen H++CO32-
ion and bicarbonate ion.

Bicarbonate ion can get further dissociated into

hydrogen ion and carbonate ions.
Carbon dioxide : Natural Acidity (cont’d)
CO2 ( g )  CO2 (aq.) KH =10 -1.5 M/atm.
According to Henry’s Law: [CO2 ]aq  K H pCO2  101.5 pCO2

CO2 (aq.)  H   HCO3 Ka1 =10 -6.3

[ H  ][ HCO3 ]
K a1   10 6.3
[CO2 ]( aq.)
K a1[CO2 ]( aq.) 106.3 * K H pCO2 107.8 pCO2
[ HCO3 ]  
 

[H ] [H ] [H  ]

HCO3  H   CO32 Ka2 =10 -10.3

[ H  ][CO32 ] 10.3
Ka2   10
[ HCO3 ]
10.3
2 K [ HCO 
3 ]
10 *10 7.8 pCO2 10 18.1 pCO2
[CO3 ]  a2

  2

[H ] [H ] [ H  ]2
Carbon dioxide : Natural Acidity (cont’d)
Charge Balance: The sum of the equivalent concentration of cations is
equal to the sum of equivalent concentration of anions.

[ H  ]  [ HCO3 ]  2[CO32 ]  [OH  ]

Because for divalent ions,

equivalent conc. = 2 X molar conc.

107.8 pCO2 1018.1 pCO2 1014

[H  ]  
 2*  
[H ] [ H  ]2 [H ]
In atmosphere, there is 370 ppm of carbon dioxide on mole basis.
pCO2  370 *106 atm.
11.2 21.5 14
10 10 10
[H  ]  
 2*  2  
[H ] [H ] [H ]
Comparing 1st and 3rd term on the right hand side, 3rd term is at least 600
times smaller than 1st term. So, it can be neglected
 11.2 21.5
10 10
[H  ]  
 2*  2
[H ] [H ]
For trial, if the pH is 6 or [H+]=10-6, then left hand side and first term in the right
hand side are dimensionally similar, whereas the last term is about 2000 times
smaller than the other two terms. Hence, the last term can be neglected.
11.2
[H  ] 
10  2
[ H ]  10 11.2 [ H  ]  105.6
[H  ]
pH   log[ H  ]  5.6

In general, for rainwater containing only CO2 approximately,

[ H  ]2  106.3 *101.5 * pCO2

 Find out the pH if the atmospheric CO2 concentration is doubled.

pCO2= 2*370*10-6 atm. =10-3.13

[ H  ]  106.3 *101.5 *103.13

pH   log[ H  ]  5.47

This means that rise in atmospheric CO2 concentration does not change
the acidity of rain water by a significant amount

pH?
For a can of carbonated drink,

pCO2= 5 atm.
[ H  ]  106.3 *101.5 * 5

pH   log[ H  ]  3.56
 • If CO2 is the only species, that affects the rainwater’s acidity,
its natural pH is 5.6

• When additional acidic species are present at

appreciable levels due to man-made activities, pH
of rainwater becomes lower than 5.7  ACID
RAIN

• Major contributors to acid rain : H2SO3, H2SO4 and

HNO3
Find out the pH of acid rain when the atmosphere has 5 ppb of SO2
along with 370 ppm of CO2 as discussed earlier. KH for SO2 is 100.096
M/atm , Ka1=10-1.77 ; Ka2=10-7.21
SO ( g )  SO (aq.)
2 2
KH =10 0.096 M/atm.
According to Henry’s Law: [SO2 ]aq  K H pSO2  100.096 pSO2

SO2 (aq.)  H   HSO3 Ka1 =10 -1.77

[ H  ][ HSO3 ]
K a1   10 1.77
[ SO2 ]( aq.)
K a1[ SO2 ]( aq.) 101.77 * K H pSO2 101.674 pSO2
[ HSO3 ]  
 

[H ] [H ] [H  ]

101.674 pSO2 10 9.97

pSO2 = 5*10-9 atm. [ HSO3 ]  
[H  ] [H  ]
 HSO3  H   SO32 K a 2  10 7.21
[ H  ][ SO32 ]  7.21
Ka2   10
[ HSO3 ]

 7.21 9.97 17.18

K [ HSO ] 10 * 10 10
[SO32 ]  a 2  3   2

[H ] [H ] [ H  ]2
Imposing electro-neutrality condition,

[ H  ]  [ HCO3 ]  [ HSO3 ]  2[CO32 ]  2[ SO32 ]  [OH  ]

11.2 9.97 21.5 17.18 14

10 10 10 10 10
[H  ]  
 
 2*  2  2*  2  
[H ] [H ] [H ] [H ] [H ]

With an initial guess of pH =5, third, fourth and fifth terms on the RHS
are found to be negligible compared to the other terms in the equation.
Therefore, considering only significant terms, the previous equation can be
approximated as,
11.2 9.97
10 10
[H  ]  

[H ] [H  ]

[ H  ]2  1011.2  109.97  109.96

[ H  ]  104.98

pH   log[ H  ]  4.98

We observe that the presence of trace amount SO2 can significantly

alter the pH of the rainwater, the acid causing potential being more
than carbon dioxide. NOx have the same effect as SOx for imparting
acidity to rainwater.
60 years….
pH
 CASE STUDY: LAKE NYOS DISASTER

On August 21, 1986, more than 1700 people and numerous wild life were
killed by a silent and mysterious killer, CO2 gas

It is a lake in the volcano crater, 1.2 miles X 0.75

miles in area, but 682 feet deep. Under the bed,
LAKE NYOS, CAMEROON the volcano is leaking carbon dioxide into the
water. This changes the water into carbonic acid.
 About 230
High partial pressure of CO2, High m deep,
conc. of bicarbonate and low pH Pressure is
about 25
atm

Volcanic gases containing CO2 from the underlying

magma seeps into the bottom of lake

Due to such a high partial pressure of carbon dioxide, the pH was

substantially low, HCO3- concentration was pretty high.
Carbon dioxide gas is heavier than atmosphere, unless there is a strong
dispersion forces such as high wind, it tend to sit at the bottom of the
atmosphere, causing asphyxiation / unconsciousness
http://www.geogonline.org.uk/g1_nyos.htm
REMEDIATION EFFORTS

The method is simple, consisting of a vertical

pipe between the lake bottom and the
surface. A small pump raises the water in the
pipe up to a level where it starts releasing
the gas from the diphasic fluid. At this point
there is a pressure gradient which causes the
water to rise to the surface and erupt like a
fountain. Therefore, once it has primed the
gas lift, the pump is not needed, and the
process becomes self-powered. Isothermal
expansion of gas bubbles drives the flow of
the gas-liquid mixture as long as dissolved
gas is available for ex-solution and expansion.

http://mhalb.pagesperso-
orange.fr/nyos/2006/index2006.htm
http://www.geo.arizona.edu/geo5xx/geos577/
projects/kayzar/html/lake_nyos_disaster.html
http://www.okeanosgroup.com/blog/aquatic-architecture-2/how-to-transform-a-poisonous-
explosive-lake-into-electricity/
Other Applications/ Phenomena Linked with Gas –Water Interaction
 SOIL-WATER INTERACTION

Precipitation
CO2 + H2O  H+ + HCO3-

Topsoil

Subsoil

Limestone CaCO3(s) + H+  Ca2++HCO3-

MgCO3(s) + H+  Mg2++HCO3-

Result: Mobilization of different ions in the groundwater from the

minerals constituting the topsoil and subsoil
EXAMPLE:
Rainwater falls on a soil surface and is under open atmosphere in
contact with soil containing abundant amount of limestone (calcium
carbonate). What will be the pH in this case? Ksp of calcium
carbonate is 10-8.42.
There is abundant quantity of calcium carbonate and it is sparingly soluble
in water. So, the aqueous system is always in equilibrium with solid calcium
carbonate. It is also in equilibrium with the air.
CO2
So, the relevant reactions are: The situation is :

CO2 ( g )  CO2 (aq.) KH =10 -1.5 M/atm. CO2 (aq.)

CO2 (aq.)  H   HCO3 Ka1 =10 -6.3
  2 H++HCO3- H++CO32-
HCO  H  CO
3 3 Ka2 =10 -10.3
Also, Ca2++CO32-
CaCO3  Ca 2  CO32 KSP =10 -8.42
CaCO3
The electro-neutrality condition is now different from before. We have a
divalent calcium ion.
2[Ca 2 ]  [ H  ]  [OH  ]  [ HCO3 ]  2[CO32 ]
From CO2 equilibrium,
10.3
2 K [ HCO 
3 ]
10 *10 7.8 pCO2 10 18.1 pCO2
[CO3 ]  a2

  2

[H ] [H ] [ H  ]2
From solubility of calcium carbonate,
K sp K sp [ H  ]2 10 8.42[ H  ]2 109.68[ H  ]2
[Ca 2 ]  2
  
[CO ] 3 1018.1 pCO2 10 18.1
pCO2 pCO2
Hence,

10 9.68  2
[H ] 10 14
107.8 pCO2 10 18.1 pCO2
2*  [H  ]  
 
 2*
pCO2 [H ] [H ] [ H  ]2
 pCO2= pressure exerted by 370 ppm (by volume) gas= 370 * 10-6
atm
109.68[ H  ]2  10 14
10 7.8
* 370 *10 6
10 18.1
* 370 *10 6
2* 6
 [ H ]   
 2*
370 *10 [H ] [H ] [ H  ]2

14 11.23 21.23

10 10 10
1013.41[ H  ]2  [ H  ]    

[ H ] [ H ] [ H  ]2
For a test case, lets consider that [H+]=10-7

10 0.59  10 7  10 7  10 4.23  10 7.23

This means that only first term and second term in the equation is
significant for obtaining an approximate solution.
11.23
10 [ H  ]3  1024.64
1013.41[ H  ]2 
[H  ]
[ H  ]  108.21 pH= 8.21
 9.68  2 [ H  ]  108.21
2 10 [H ]
[Ca ] 
pCO2 pCO2  360 *106 atm
9.68 8.21 2
2 10 [10 ] 4
[Ca ]  6
 5.05 *10 M [Ca2 ]  20mg / L
360 *10
This eventually means that the rainwater which has a pH of 5.6, when
comes in contact with a limestone deposit on the surface, the whole
chemistry changes because of the dissolution of limestone into the water.
The water turns alkaline with pH of 8.2 and with calcium being dissolved at
a concentration of about 20 mg/L.
Soil contains multitude of different minerals. The rainwater when comes
in contact with soil , dissolves many metal cations , also anions, into the
water and the pH also rises so that the natural waters, surface as well as
underground, normally have a pH in the envelope of 6.5 to 8.5. Also, the
surface- and groundwater contains minerals many of which are
physiologically significant.
 ALKALINITY
Alkalinity is a measure of the acid buffering capacity of water. In other
words, it measures the water’s capability to consume hydrogen ion
without making any change in the pH of the system.

What happens then to H+ ions added to the system?

The H+ ions would react with the components in water mainly, HCO3-,
CO32- and OH- according to the following reactions and would get
consumed and will be unavailable for lowering the pH.
H   CO32  HCO3 H   HCO3  CO2 (aq.) H   OH   H 2O

This means that presence of these ions provide some buffer capacity for the
system, so that the pH does not change even if acid is added to the system.

The summation of all these H+ buffering ions is called acid buffering ability or
alkalinity .
Alkalinity (meq / L)  [ HCO3 ]  2[CO32 ]  [OH  ]  [ H  ]
EXAMPLE

A sample of water at pH 10 has 32 mg/L of CO32-. Find the alkalinity of

the water in the following units: M as well as mg/L as CaCO3.
SOLUTION Estimate all the acid buffering ions.

pH =10 [ H  ]  1010 pOH = 4 [OH  ]  104

3
32 *10 g/L
32 mg/L of CO32-   0.53 *103 M  103.27 M
60 g / mole
HCO3  H   CO32 Ka2 =10 -10.3
[ H  ][CO32 ] 10.3
Ka2   10
[ HCO3 ]
 2 10 3.27
[ H ][ CO ] 10 *10
[ HCO3 ]  3
  10  2.97

Ka2 1010.3
Alkalinity ( M / L)  [ HCO3 ]  2[CO32 ]  [OH  ]  [ H  ]
 102.97  2 *103.27  104  1010
 Alkalinity ( M / L)  [ HCO3 ]  2[CO32 ]  [OH  ]  [ H  ]
 102.97  2 *103.27  104  1010  2.246 *10-3

Alkalinity (meq / L)  ( HCO3 )  2(CO32 )  (OH  )  ( H  )

 102.97  103.27  104  1010 meq/L  1.71 *10-3 meq / L

1 eq/L CaCO3 = 50 g/L of CaCO3

Alkalinity = 2.246*10-3*50 g/L =112.3 mg/L as CaCO3