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1. How oxygen dissolves
Water,
as a polar molecule, induces an accumulation of
electron density
(dipole
moment) at one end of non-polar gas
molecules such as oxygen (O2
) and carbon dioxide (CO2 ). In animation, observe a polar
water molecule approaching a nonpolar O2 molecule. The electron
cloud of O2 is normally distributed symmetrically between
the bonded O2 atoms. When the negative end of the H2O molecule
approaches the oxygen molecule, the electron cloud of the O2
moves away to reduce the negative-to-negative repulsion. A dipole (a
molecule with positive and negative charges separated by a distance)
results in the nonpolar O2 molecule and causes O2
and H2O to become weakly attracted to each other. This intermolecular
attraction between the oppositely charged poles of nearby molecules
is termed a dipole- dipole force. The creation of these forces explains
the mechanism by which gases dissolve in water.
2. The
effects of pressure on
oxygen solubility
Because
dipole-
induced dipole forces are very weak, the quantity of nonpolar gases
(such as O2) that will dissolve in a given volume of water
is strongly affected by temperature and pressure.
Henry's Law describes
the effect of pressure on the solubility of a gas in a liquid. The law
states that the amount of gas that dissolves in a given volume of solvent
at a specified temperature (usually 25°C for water) is proportional
to the partial pressure of the gas above the liquid. When gas under
pressure contacts a liquid, the pressure tends to force gas molecules
into solution. At a given pressure the number of gas molecules that
will enter into solution rises until equilibrium is reached. By definition, at equilibrium, the number of gas molecules
entering and leaving the solutions is balanced and the concentration
of the gas in solution remains constant. If the partial pressure of
a gas increases, more gas enters into solution. If partial pressure
drops, gas comes out of solution and reaches a new equilibrium. This
can be illustrated by opening a can or bottle of soda pop. (See note
under 3.)
At sea
level total atmospheric
pressure is 760 mm Hg. This means that the gravity-induced
weight of the atmosphere generates enough force to move a sufficient
volume of mercury (Hg) 760 mm up a tube. At sea level approximately
20.8 percent of this air is oxygen gas (O2). The partial
pressure of oxygen at sea level is 158 mm Hg (760 mm Hg x 0.208 =
158.08
mm Hg). Oxygen has a Henry's Law constant of 1.7 x 10-6 molal/mm Hg
when dissolved in water at 25°C. Molality of O2 =
(1.7 x 10-6 molal/mm Hg) (158.08 ) = 2.687 x 10-4 m.
From the above value the number of milligrams per liter of oxygen that
will dissolve in 25°C water can be calculated. 2.687 x 10-4 moles/kg
x 32g/mole x 1000 mg/g = 8.6 mg/liter 3. The
effects of temperature on solubility - Le Chatelier's Principle.
Pour cold
water into a glass. After the animation you can observe the oxygen bubbles
that formed inside the glass of water that had been poured cold and
warmed up over time. Next, open two cans of soda pop, one warm and one
cold. It is easily observed that more gas is released if the can is
warm than when it is cold. Both of demonstrations illustrate that the
temperature of a solvent (recall that water is the "universal solvent")
affects the solubility of gases.
Gases that
dissolve in solvents usually release
heat as they dissolve in an exothermic
process. This process continues until saturation is reached. At this
point gas will still dissolve, but will be balanced by the gas that
leaves solution. If heat is added to a solution, gas is released in
this endothermic reaction:
At equilibrium,
as many molecules come out of solution as dissolve in a given time period.
Le Chatelier's
principle states that a change in any of the factors determining equilibrium
will cause the system to adjust in order to reduce or counteract the
effect of the change. Le Chatelier's principle predicts that the solubility
of a gas will increase as a system loses heat and decrease as it gains
heat.
4. O2
supersaturation
Due to
the effects of hydrostatic pressure
on gases in solution, water can
become supersaturated (exceed 100% saturation) with oxygen and other
gases. The attractive forces that hold excess oxygen in solution are
similar to the dipole-induced dipole forces discussed earlier, but a
smaller number of water molecules are available to induce dipoles in
oxygen molecules. This leads to weaker attraction of oxygen molecules
when water is supersaturated with oxygen.
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