Dissolution of species in water

(Nazaroff & Alvarez-Cohen, Section 3.B.2)

dissolution

air In the environment, water is often in contact with air, and chemicals are exchanged between water and air. An equilibrium is reached in the absence of perturbing processes. water

PA [A]
volatilization

At equilibrium, a fixed ratio is established between the concentration [A] of substance A in the water and its partial pressure PA in the air:

[A] = K H PA
or, in reverse,

PA = H [A]
This is known as Henrys Law, and H = 1/KH is called Henrys Law constant. It varies from species to species and is also a function of temperature.

Species Ammonia Benzene Benzopyrene Carbon dioxide Carbon monoxide Chloroform Ethylbenzene Formaldehyde Hydrogen sulfide Methane Naphthalene Nitric acid Nitrogen Oxygen Phenol Sulfur dioxide Tetrachloroethylene Toluene Trichloroethane Trichloroethylene

Formula NH3 C6H6 C20H12 CO2 CO CHCl3 C8H10 HCHO H2S CH4 C10H8 HNO3 N2 O2 C6H6O SO2 C2Cl4 C7H8 C2H3Cl3 C2HCl3

KH (M/atm) 62 0.18 2040 0.034 0.0010 0.31 0.11 6300 0.115 0.0015 2.2 2.1 x 105 0.00067 0.001384 2200 1.24 0.083 0.15 0.055 0.11

H (atm/M) 0.0161 5.6 4.9 x 10-4 29 1000 3.2 9.1 1.6 x 10-4 8.7 670 0.45 4.8 x 10-6 1500 720 4.5 x 10-4 0.81 12 6.7 18 9.1

Temperature 25oC 20oC 20oC 25oC 20oC 20oC 20oC 25oC 20oC 20oC 20oC 25oC 20oC 20oC 20oC 25oC 20oC 20oC 20oC 20oC

(Nazaroff & Alvarez-Cohen, Table 3.B.2, page 96)

Example: Dissolution of oxygen in water

From the previous table, we note that KH for oxygen is 0.00138 M/atm. We also know that oxygen accounts for 21% of air in the atmosphere. Thus,

[O 2 ] = K H PO2 = (0.00138 M/atm)(0.21 1 atm) = 2.90 10 4 M = 2.90 10 4 mol/L

Since the molecular weight of oxygen is 2 x 16 = 32 g/mol, we can convert the preceding number in mg/L:

DO = MWO2 [O 2 ] = (32 g/mol)(2.90 10 4 mol/L) = 0.00928 g/L = 9.28 mg/L

After repeating the procedure for various temperatures, we obtain the following table for the equilibrium level of dissolved oxygen in open water. This quantity is called the Saturated Value of Dissolved Oxygen and is noted DOs.
Temperature (oC) 0 1 2 3 4 5 6 7 8 9 10 11 12 DOs (mg/L) 14.6 14.2 13.8 13.5 13.1 12.8 12.5 12.2 11.9 11.6 11.3 11.1 10.8 Temperature (oC) 13 14 15 16 17 18 19 20 21 22 23 24 25 DOs (mg/L) 10.6 10.4 10.2 10.0 9.7 9.5 9.4 9.2 9.0 8.8 8.7 8.5 8.4

No wonder that active fish prefer cold waters! This is why there is such good fishing in Maine and Alaska.

EPA recommendation for a healthy fish population: DO 5 mg/L For better fish, such as trout and salmon, water must have DO 8 mg/L

Solubility of nonaqueous-phase liquids (NAPL)

(Nazaroff & Alvarez-Cohen, pages 97-98)

Some liquids (ex. petroleum, organic solvents) do not readily mix with water but, once in contact with water, become partially dissolved. Like for Henrys Law in case of water-air contact, an equilibrium is sought for which the concentration of the liquid contaminant dissolved in the water is proportional to the concentration in the pure liquid (fixed). In other words:

C A = K ws (T )

where Kws is the water solubility of constituent A; it varies with temperature T.

Species Benzene Ethylbenzene Tetrachloroethylene (PCE) Trichloroethane (TCA) Solubility (in mg/L) 1,780 152 200 4,400

pH of Pure Water
(Nazaroff & Alvarez-Cohen, Section3.C.2)

In water, there is always a small fraction of its molecules that break into ions:

H2O H+ + OHThe equilibrium constant of this reaction is

K water =

[H + ] [OH ] = 1.83 10 16 mol/L [H 2 O]

Since, the molarity of water is always [H2O] = 55.4 mol/L, we have

[H + ] [OH ] = (1.83 10 16 mol/L) [H 2 O] = (1.83 10 16 mol/L) (55.4 mol/L) = 1.01 10-14 (mol/L)2
Finally, in the absence of any other ion (pure water!), electroneutrality requires:

[H + ] = [OH ] [H + ] = 1.01 10 14 (mol/L) 2 = 1.0 10 7 mol/L pH = log10 [H + ] = 7.0

pH of Natural Water
(Nazaroff & Alvarez-Cohen, Section 3.C.2)

Let is now consider water not in a pure state but as it occurs in nature, that is, in contact with the atmosphere, which contains carbon dioxide (CO2). The reactions and their equilibrium relations are:

CO 2 in the water CO 2 in the air CO 2 in the water + H 2 O H 2 CO 3

H 2 CO 3 H + + HCO 3

[CO 2 ] = K H PCO 2 , K H = 0.034 M/atm [H 2 CO 3 ] = 1.58 10 3 [CO 2 ]

[H + ] [HCO3 ] = 2.834 10 4 M [H 2 CO 3 ] 2 [H + ] [CO 3 ] = 4.68 10 11 M [HCO3 ]

2 HCO3 H + + CO 3

H 2 O H + + OH

[H + ] [OH ] = 10 14 M 2

Then, we close the system of equations with the principle of electroneutrality:

2 [H + ] = [OH ] + [HCO3 ] + 2 [CO3 ]

385 For a partial pressure of CO2 in the atmosphere equal to 350 ppm, we have

[CO 2 ] = (0.034 M/atm) (350 10 6 atm) = 1.19 10 5 M

From the first chemical equilibrium, we deduce:

385

1.31

[H 2 CO 3 ] = (1.58 10 3 )[CO 2 ] = (1.58 10 3 )(1.19 10 5 M ) = 1.88 10 8 M

We solve the remaining simultaneous equations and obtain:
[HCO 3 ] = 2.31 10 6 M 2 [CO 3 ] = 4.67 10 11 M

1.31

2.07

2.42 x 10-6 M 4.67 x 10-11 M 4.13 x 10-9 M 2.42 x 10-6 M 5.62

[OH ] = 4.33 10 M [H ] = 2.31 10 M

+ 6

Thus, the pH of natural (clean) water is

pH = log10 [H + ] = 5.64

Clean, natural water is slightly acidic. And, it is getting increasingly acidic. There is fear that coral in the sea will not survive.

(http://news.bbc.co.uk/2/hi/science/nature/4226917.stm)

An easier example: Ammonia in water

Ammonia (NH3) is often generated on farms as a by-product of animal manure. Because of its nitrogen content, it is a good soil nutrient, but in water, it affects the pH. In water, ammonia forms the ammonium ion (NH4+) via

NH 3 + H 2 O NH + + OH 4

with

[ NH + ][OH ] 4 = 1.70 10 5 M [ NH 3 ]

Between air and water, Henrys Law constant of NH3 is 62 M/atm.

If the concentration of ammonia in the air is 50 ppm, what is the pH of the water? (Assume no CO2 is present.)

Answer: First determine [NH3] in water:

[NH 3 ] = 62 PNH3 = (62 M/atm)(50 10 6 atm) = 3.10 10 3 M [NH + ][OH ] = (1.70 10 5 )[NH 3 ] = 5.27 10 8 M 2 4

Use this in the equilibrium relation:

Finally, apply the constant of dissociation of water and electroneutrality:

[H + ][OH ] = 10 14 [OH ] =

10 14 + [NH 4 ] = 5.27 10 + 6 [H + ] [H + ] 10 14 [H + ]

+ [H + ] + [NH 4 ] = [OH ] [H + ] + 5.27 10 + 6 [H + ] =

[H + ] = 4.36 10 11 pH = log10 (4.36 10 11 ) = 10.4

Ammonia can act as a strong base! Does that mean that we could dump ammonia in lakes that have become acidified by acid rain???

Consider: 1. Equilibrium between water and atmosphere would mean that much of the ammonium in the water would leak as ammonia in the air and be swept away with the wind. The system has a big leak! 2. Ammonia in the air has a pungent odor. So, these lakes would smell bad. 3. Ammonia even at dilute concentrations is highly toxic to aquatic animals, and for this reason it is classified as dangerous for the environment.

Answer: Very bad idea !

So, what would be a better idea to remedy acid lakes?

Answer: Use calcium, or simply rely in the calcium that is naturally there.

CaCO 3 Ca + + + CO 3 CO 3 + H + HCO 3 HCO 3 + H + H 2 CO 3

H 2 CO 3 H 2 O + CO 2 CO 2 in water CO 2 in air

The net effect of limestone is to deliver calcium ions that displace protons, and thus reduce acidity. There is efficiency in this because one Ca++ eliminates two H+s.

But think: - A lake has become too acidic because of some acid input. - It is better to eliminate that acid source than to remediate the lake. - Often, acidity comes from acid precipitation (rain / snow) over the lake. - This atmospheric acidity is primarily in the form of sulfuric acid (H2SO4) and nitric acid (HNO3). - Sulfuric acid is the consequence of burning coal with sulfur content, creating SO2 in the combustion fumes that later turn into H2SO4. - Nitric acid originates from NO2 out of tailpipes of gas and diesel engines. - Solutions therefore consist in Scrubbing the SO2 from fumes before release through the smokestack. Burning low-sulfur coal. Burning some fuel other than coal for electricity Getting electricity from windmills or other non-fuel alternative

- Regulate tailpipe emissions. - Have people drive better cars. - Have people drive less Reduce food shipment by consuming local foods.