ATMOSPHERE - WATER INTERACTIONS

Hydrological Cycle Water – a minor

component of the
atmosphere. Also,
only 0.001% of
the total water in
the world is in
cloud or in
atmosphere.

Hydrogeochemical
cycles couple
atmosphere, land
and water

Atmosphere is an important conveyor belt for many pollutants.

Example: China is a major source of pollution in Japan; Canada is affected by
emission from the Northeast USA; PM10 from Punjab to Delhi
 COMPOSITION OF AIR (DRY BASIS)

Source: www.co2.earth
Atmosphere-Surface Water Interactions: Mechanism behind the
Sustenance of Aquatic Life
O2
O2 is vital 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
b) Through photosynthesis by algae in
presence of sunlight.

At any time in steady state condition, there

is an equilibrium partitioning of oxygen
between water and atmosphere.
RAINWATER DROPLET IN THE AIR
CO2

As the droplet passes through

the atmosphere to fall on the NH3 NO2
earth surface, various gases,
liquid and solids that are
either part of the atmosphere
or are suspended in air, tend
to get inside the water Dust SO2
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 (1903, England)
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)

Molar concentration: n P
C 
V RT
Dalton’s Law
that the pressure exerted by a mixture of gases in a fixed volume is equal to the
sum of the pressures that would be exerted by each gas alone in the same volume.

Ptot = pA + pB + …
= (nA + nB + …)RT/V
= (ntot)RT/V
 The atmosphere:
(by volume)
N2 78%
O2 21%
Ar 0.9345%
CO2 0.04%
Other gases Rest

Partial pressure of O2 = pO2 = 0.21*Ptot=0.21*1 atm =0.21 atm

Partial pressure of CO2 = pCO2 = 0.0004*1 atm =0.0004 atm

 Example 1.

Find out the aqueous solubility of oxygen in a fully aerated water at

25 oC in a treatment plant. KH of O2 at 25 oC = 1.26X10-3 M/atm
Solution 1.

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
[1M O2= 32 g/L]
= 8.467 mg/L
 The value of Henry’s Law constant changes inversely with temperature

Thermal
pollution:
Dissolved
oxygen
level
reduces

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

Carbon Dioxide (CO2) makes up approximately 0.0413%

of the Earth’s atmospheric gases now.
– Carbon dioxide concentration in the atmosphere is
regulated by:
• Removal of CO2 from the atmosphere as green plants fix the
CO2 into complex carbohydrates-photosynthesis process
• Exchanges of CO2 between the atmosphere and the oceans
• Dissolution of CO2 in rain water
• Chemical reactions between the rain water and limestone &
magnesium carbonate
CaCO3(s) + H2CO3(aq) = Ca(HCO3)2(aq)
MgCO3(s)+ H2CO3(aq) = Mg(HCO3)2(aq)
CARBON DIOXIDE - WATER INTERACTION NATURAL ACIDITY
Unlike dissolution of oxygen, gases like carbon dioxide,
sulfur oxides or nitrogen oxides after dissolution form CO2
further hydrated species which add acidity to the water.

Carbon dioxide is a natural constituent of

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

When carbon dioxide dissolves in water it H++HCO3-

forms aqueous carbon dioxide which is
popularly known as carbonic acid (H2CO3). H++CO32-

Depending upon the solution pH, the species further dissociates into
hydrogen ion and bicarbonate ion.

Bicarbonate ion can get further dissociated into hydrogen ion and
carbonate ions.
 Carbon dioxide : Natural Acidity (Determination of pH)
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.
Pauling's principle of electroneutrality, 1948
[ 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 407 ppm of carbon dioxide on mole basis.

pCO2  407 *10 6 atm.  10-3.4 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
 Carbon dioxide : Natural Acidity (Determination of pH)
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
10  2
[ H ]  10 11 .2 [ H  ]  10 5.6
[H  ] 
[H  ]
pH   log[ H  ]  5.6

In general, for rainwater containing only CO2 approximately,

[ H  ]2  10 6.3 *10 1.5 * pCO2

[ H  ]  10  6.3 *10 1.5 * pCO 2

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

pH?
2. For a can of carbonated drink,
pCO2= 5 atm. What will be the pH?
 Find out the pH if the atmospheric CO2 concentration is doubled.
Solution.
pCO2= 2*407*10-6 atm. =10-3.4 atm.

[ H  ]  10 6.3 *10 1.5 *10 3.4

pH   log[ H  ]  5.6

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 5.6  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 407 ppm of CO2 as discussed earlier. KH for SO2 is 100.096
M/atm , Ka1=10-1.77 ; Ka2=10-7.21
 Find out the pH of acid rain when the atmosphere has 5 ppb of SO2
along with 407 ppm of CO2 as discussed earlier. KH for SO2 is 100.096
M/atm , Ka1=10-1.77 ; Ka2=10-7.21
Solution. SO2 ( g )  SO2 (aq.) KH =10 0.096 M/atm.
According to Henry’s Law: [ SO2 ]aq  K H pSO2  10 0.096 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, Pauling's principle of electroneutrality, 1948

[ 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 ]

The pH should be less than the rainwater pH with only CO2 present; 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.
 Effect of acid rain

60 years….
pH
 Mathura Refinery – 58 km by road and 46
km (air) from Agra
 Acid rain damaged the shine of the Taj
Mahal
 Sulphur recovery systems are installed at
Refinery now
 The cupolas in Taj trapezium were relocated
 Only battery operated vehicles are allowed
near Taj Mahal
 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 and 682 feet deep. Under the bed,
LAKE NYOS, CAMEROON the volcano is leaking carbon dioxide into the
water and carbonic acid getting formed.
 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 biphasic 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.

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 (Solubility Product
Constant) of calcium carbonate is 10-8.42.
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 (Solubility Product Constant) of calcium carbonate is 10-8.42.

Solution.
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 407 ppm (by volume) gas= 407 * 10-6
atm
109.68[ H  ]2  10 14
10 7.8
* 407 * 10 6
10 18.1
* 407 *10 6
2* 6
 [ H ] 
 
 2*
407 *10 [H ] [H ] [ H  ]2

14 11 .2 21.2

10 10 10
1013.4 [ H  ]2  [ H  ]  
 
  2
[H ] [H ] [H ]
For a test case, lets consider that [H+]=10-7

10 0.6  10 7  10 7  10 4.2  10 7.2

This means that only first term on the LHS and second term in the RHS in
the equation is significant for obtaining an approximate solution.
11 .2
10 [ H  ]3  10 24.6
1013.4 [ H  ]2 
[H  ]
[ H  ]  10 8.2 pH= 8.2
 9.68  2 [ H  ]  10 8.2
2 10 [H ]
[Ca ] 
pCO2 p CO2  407 *10 6 atm
9.68  2
10 [ H ]
[Ca 2 ]  [Ca 2 ]  19.14mg / L
pCO2
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 19.14 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.
 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 CO3 
2-
 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(meq / L)  [ HCO3 ]  2[CO32 ]  [OH  ]  [ H  ]
 10  2.97  2 *103.27  10 4  1010
 Alkalinity (meq / L)  [ HCO3 ]  2[CO32 ]  [OH  ]  [ H  ]
 10  2.97  2 *10 3.27  10  4  10 10  2.246 *10-3

1 eq/L CaCO3 = 100/2=50 g/L of CaCO3 [Molecular weight of CaCO3 is =100]

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