Henry's law, chemical law stating that the amount of a gas that dissolves in a liquid is

proportional to the partial pressure of the gas over the liquid, provided no chemical reaction takes
place between the liquid and the gas. It is named after William Henry (1774–1836), the English
chemist who first reported the relationship.

When a gas is in contact with the surface of a liquid, the amount of the gas which will go into
solution is proportional to the partial pressure of that gas. A simple rationale for Henry's law is that
if the partial pressure of a gas is twice as high, then on the average twice as many molecules will hit
the liquid surface in a given time interval, and on the average twice as many will be captured and go
into solution. For a gas mixture, Henry's law helps to predict the amount of each gas which will go
into solution, but different gases have different solubilities and this also affects the rate. The
constant of proportionality in Henry's law must take this into account. For example, in the gas
exchange processes in respiration, the solubility of carbon dioxide is about 22 times that of oxygen
when they are in contact with the plasma of the human body.

Henry's Law and the Solubility of Gases

Concentration of solutions was taken up as part of molar stoichiometry in other sections. The
concentrations used in this section will all be molar concentrations, because in homogeneous
solutions active mass is the ratio of amount of substance to unit volume. Molar concentration will
be indicated by c, with the solute in parenthesis following the symbol, or by placing the solute
molecule or ion symbol in square brackets. Other concentration units, such as molality, are less
commonly usedin aqueous equilibrium calculations.

Gases dissolve in liquids to form solutions. This dissolution is an equilibrium process for which an
equilibrium constant can be written. For example, the equilibrium between oxygen gas and
dissolved oxygen in water is O2(aq) <--> O2(g). The equilibrium constant for this equilibrium is K =
p(O2)/c(O2). The form of the equilibrium constant shows that the concentration of a solute gas in a
solution is directly proportional to the partial pressure of that gas above the solution. This
statement, known as Henry's law, was first proposed in 1800 by J.W. Henry as an empirical law
well before the development of our modern ideas of chemical equilibrium.

Stating the pressure-concentration ratio as an equation and use of the usual modern symbol for the
Henry's law constant on a concentration basis, K'c, gives the following form of Henry's law:

p = K'cc

In this form p is the partial pressure of the gas, c is its molar concentration, and K'c is the Henry's
law constant on the molar concentration scale. Henry's law is found to be an accurate description of
the behavior of gases dissolving in liquids when concentrations and partial pressures are reasonably
low. As concentrations and partial pressures increase, deviations from Henry's law become
noticeable. This behavior is very similar to the behavior of gases, which are found to deviate from
the ideal gas law as pressures increase and temperatures decrease. For this reason, solutions which
are found to obey Henry's law are sometimes called ideal dilute solutions.
Values of the Henry's law constants for many gases in many different solvents have been measured.
The table below gives a few selected values of Henry's law constants for gases dissolved in water.

Table: Molar Henry's Law Constants for Aqueous Solutions at 25oC

Gas Constant Constant

(Pa/(mol/litre)) (atm/(mol/litre))
He 282.7 x 10+6 2865.
O2 74.68 x 10+6 756.7
N2 155. x 10+6 1600.
H2 121.2 x 10+6 1228.
CO2 2.937 x 10+6 29.76
NH3 5.69 x 10+6 56.9
Values in this table are calculated from tables of molar thermodynamic properties of pure
substances and aqueous solutes

The inverse of the Henry's law constant, multiplied by the partial pressure of the gas above the
solution, is the molar solubility of the gas. Thus oxygen at one atmosphere would have a molar
solubility of (1/756.7)mol/litre or 1.32 mmol/litre.
Example. The amount of oxygen dissolved in air-saturated water under normal atmospheric
conditions at 25oC can be calculated as follows. Normal atmospheric conditions are 20.948 mole per
cent oxygen, which makes the partial pressure of oxygen 0.20948 atm or 20.67 kPa. Using Henry's
law, the concentration of oxygen is 0.20948 atm/(756.7 atm/(mol/litre)) which is 2.768 x 10-4
mol/litre or 0.2768 mmol/litre.

Example. We can estimate the amount of nitrogen that a diver must lose from his bloodstream
(about 5 litres) in rising from a depth of 100 m to the surface in order to avoid formation of nitrogen
bubbles in his bloodstream, a painful and often fatal condition known as "the bends", as follows.

The density of water is about 1 kg/litre or 1000 kg/litre. A column of water 100 m high would have
a mass of 100000 kg/m2 of its base which would exert an additional force of 980665 N/m2 or
980665 Pa. (The total pressure would be 980.665 kPa plus 101.325 kPa or 1081.990 kPa.) The
pressure change of 980665 Pa would produce a concentration change of 980665/(155,000,000) =
6.33 mmol/litre. The amount of nitrogen which must be lost is then (5)(6.33) = 31.65 mmol or, at
room temperature and pressure, somewhat over 750 mL of nitrogen. This is enough nitrogen gas to
create massive bubbles in the bloodstream. A depth of 100 m is considered a deep dive;
considerable decompression time will be required in order to reach the surface safely.

The value of the Henry's law constant is found to be temperature dependent. The value generally
increases with increasing temperature. As a consequence, the solubility of gases generally
decreases with increasing temperature. One example of this can be seen when water is heated on
a stove. The gas bubbles which appear on the sides of the pan well below the boiling point of water
are bubbles of air, which is evolved when water which was air-saturated at lower temperatures is
heated and the amount of air which it can contain (the molar solubility of air) decreases. Addition of
boiled or distilled water to a fish tank will cause the fish to die of suffocation unless the water has
been allowed to reaerate before addition.

The decrease in solubility of gases with increasing temperature is an example of the operation of Le
Chatelier's principle. The heat or enthalpy change of the dissolution reaction of most gases is
negative, which is to say the reaction is exothermic. As a consequence, increasing the temperature
leads to gas evolution.

“The pressure of the gas above a solution is proportional to the

concentration of the gas in the solution.”

Oxygen transfer
Factors affecting Co*-Co

Henry's law

Co* equals the concentration of oxygen in gas liquid interface which is equal to the
saturation concentration of oxygen in the reactor.

The value of Co* is determined by the partial pressure of oxygen in the gas phase (P o) and
on Henry's Law and on the medium's Henry's constant for oxygen (H o):

Ho is Henry's constant for oxygen.

The value of a medium's Henry's constant for oxygen is dependent on the concentration
of salts and sugars and on temperature.

For example, Henry's constant for water at 25 oC and 35oC is:

Temperature Henry's constant (atm.mg-1.l)

o
C
25 0.0258
35 0.0299

Note that Henry's constant increases with temperature and thus the solubility of oxygen
also decreases with temperature.
Henry's law is only valid if the partial pressure of the gas is not greater than 1 atm. Even
so, Henry's law can be used to estimate oxygen solubilities at solute partial pressures
greater than 1 atm.

Bubble Gas Transfer

1. Unbroken Surface
2. Bubbles
3. Dynamic Equilibrium

Unbroken Surface
When disequilibrium conditions (determined by Henry's Law) exist for a gas between its
gaseous phase and aqueous concentration, gas transfer occurs. The concentration
gradient drives a gas flux according to the equation:

with the gas invading if P>C/H and evading for the opposite conditions. Clearly the
system will tend towards equilibrium as determined by Henry's Law for each gas. Thus
one gas can be invading while a second gas is evading. Probably the best introductory
discussion on the thin film model, of which all other models of gas transfer (except
surface renewal) are based is provided in Liss, 1973.

Bubbles
Due to the La Place pressure (a result of surface tension on a curved surface), and
hydrostatic pressure (from the weight of the water), the bubble's internal pressure is
greater than atmospheric. As a result, bubbles in a system in Henry's Law equilibrium
will invade gas. Thus in the presence of bubbles, equilibrium occurs at a slight
supersaturation.The effect of surface tension on residence time is only important for
bubbles smaller than 100 micrometers.

The time evolution of a bubble is described by a series of coupled differential equations

that describing the time variation of bubble pressure, radius, depth, and molar content as
the bubble rises. From this, the flux (or gas transfer) of the bubble can be calculated at
any time. The equation describing the mass transfer is
The other equations are in Leifer and Patro (2002) and the system of equations can be
solved numerically. An example of model output is shown in the following figure.

Time evolution of molar content, radius and depth of a 500 micrometer clean bubble from 22 m.

As CH4 outflows the bubble shrinks, increasing the La Place pressure; however, as the
bubble rises the hydrostatic pressure decreases. The situation is complicated further by
the presence of oxygen (O2) and (N2) in the water which inflow simultaneously. The 500
micrometer bubble shown dissolved and thus after ~25 seconds, the air that had just
inflowed the bubble was forced to outflow by the more rapidly outflowing methane.
When a bubble dissolves, the total gas transfered becomes purely dependant upon the
initial gas composition and the solubility coefficient. Diffusivity only affects how long it
takes the bubble to dissolve. In this case, that happeded after ~200 s and after rising only
~5 meters.

Another effect of the finite bubble volume (other than the possibility of dissolution) is
that the flux tends towards zero as the bubble equilibrates; however, since the hydrostatic
pressure continues to decrease as the bubble rises, a gas that initially outflowed may
inflow at shallower depths.

Let us first consider gases with an atmospheric source.

Dynamic Equilibrium
Because of the overpressure, gases outflow the bubble even under conditions where the
net flux through the air-water interface is zero. As a result, the concentration of the gases
in the bubble build towards a supersaturation equilibrium concentration. This
concentration is determined by the effects of bubble "pumping" or invasion of the water
due to bubble gas outflow and evasion (loss) through the air-water interface due to non-
bubble gas exchange. Thus the system approaches a "dynamic" equilibrium where
invasion and evasion balance. There are many complexities in the bubble contribution.
At dynamic equilibrium, large bubbles outflow gas (gas invasion) while small bubbles
inflow gas (gas evasion). The transition size between inflowing large bubbles and
outflowing small bubbles depends upon all the many factors that affect the fate of a
bubble including the bubble depth-size distribution, as well as factors that affect the
bubble parameterizations like surfactants and temperature. Since the bubble gas
exchange rate varies between gases (i.e., diffusivity) a bubble may have a net inflow of
one gas and outflow of another. In other words, the transition radius between inflowing
and outflowing bubbles is gas dependant.

If the air-water exchange rate was infinitely fast, dynamic equilibrium would be the
same as the normal equilibrium determined by Henry's Law (solubility). Instead, the gas
concentration builds up to a supersaturation where the gas flux from the bubbles into the
water is equivalent to loss through the interface. The concept of dynamic equilibrium is
important for several reasons:

 The asymmetery in the gas exchange rate for invasion and evasion in the presence
of bubbles arises because the gas transfer rate is referenced to Henry's Law
equilibrium rather than the dynamic equilibrium .
 Many processes require a net flux of gas into (or out of) the water. Aeration of
water in a sewage treatment plant or fish pond, are two examples. By considering
the mechanisms responsible for creating dynamic equilibrium, greater efficiency
can be achieved.
 In the ocean (or any large body of water), not only is there loss at the air-water
interface, but there is also loss (diffusion) to the bulk ocean. For bubble plumes
from breaking waves, the source is dispersed, thus loss is primarily due to vertical
diffusion (up into the air and down within the mixed layer.

The discussion of dynamic equilibrium naturally leads into another complexity of bubble
gas transfer, local saturation.

Local saturation
Not only does bubble-mediated gas transfer lead to local supersaturation (Dynamic
equilibrium), but the local saturation causes a feedback effect, decreasing the gas transfer
rate. This is simply because by increasing the concentration, C, in the bubble plume, the
driving force decreases.

Hydrocarbon seeps represent a line source of gases that due to the hydrostatic pressure
are significantly above saturation (as determined by the atmospheric composition). As a
result, there is a continuous flux of gas into the ocean. This gas then primarily diffuses
laterally, i.e., similar to the previous discussion. And as above, the water concentration
becomes locally elevated relative to the bulk ocean, which decreases gas outflow. This
has the effect of allowing the bubble to retain more of its methane to a shallower depth.
In a sense, one can consider the hydrocarbon gases in the bubble the same as the air
gases for the purposes of this discussion.

Let us now consider gases with an oceanic source. These include many trace gases, and
for the case of hydrocarbon seep bubbles, air.

Oceanic source gases

For gases with an oceanic source, e.g., dimethyl sulfide, or in some regions, carbon
dioxide, the dynamic equilibrium is below saturation. As mentioned above, not only do
the bubbles outflow air due to the overpressure, but bubbles inflow gases that are below
the concentration in the bubble. Thus dynamic equilibrium involves a subsaturation
rather than a supersaturation. In this case, bubbles remove gas from the water (stripping)
which at dynamic equilibrium is balanced by bubble injection of the gas and diffusion
across the interface.

For hydrocarbon seeps, this means the removal of air gases from the water. The inflow of
air into the rising seep bubbles from the plume water is replaced by diffusion from the
surrounding bulk water.

The bubble concepts just discussed can also be presented in Mac computer animation or
Wintel computer animation form from numerical model output.