Chapter 14 Chemistry of Natural Waters

Water
What are the significant physical/chemical properties of water?

Significant Properties
Intra-molecular bonding? Heat capacity? Polarity? Solubility of gases CO2 and O2? Density as function (temperature?) Presence of indigenous material? Transparency?

Stratification of a water body produced by solar radiation (Fig. 14.2)

Water Surface 1 Epilimnion

Depth(m)
3 4 5 5

Thermocline
Hypolimnion

10

15

20

Temperature (oC)

Transparency
Sunlight can penetrate into water at considerable depths. About 90% of the radiation above 750 nm is absorbed by the time sunlight has penetrated to 1 meter in water. Transparency of water is an important property to consider for chemicals in water such as oil-derived hydrocarbons and pesticides susceptible to degradation by sunlight (i.e. photolysis).
Red

Blue

Salinity
Salinity - 0.5 3.0 % or 3.5% salt, as a result of its solvating capacity. Water dissolves ionic compounds through iondipole interactions. The Venice system which categorizes waters, according to salinity zones. Seawater (>3.0%), estuaries (0.05 3.0%), and freshwater (<.05%)

Solubility of gases in water

Solubility of gases is subject to Henrys Law. [X] = KHPX Oxygen and carbon dioxide are the two most important gases dissolved in water - bar none! KH(CO2) = 3.4x10-2mol L-1atm-1 KH(O2) = 1.3 x10-3 mol L-1atm-1 CO2 provides H2CO3, which serves as a buffering, pH effect on the aquatic environment, and O2, which the aquatic organisms must have to survive. Solubility of these gases is a function of temperature, partial pressure in the atmosphere, and salinity , e.g. In 0oC fresh water at saturation has 2 mg/L more dissolved oxygen than does seawater (3.5% salt). Why is this?

Dissolved Oxygen in Natural waters

Solubility of oxygen is a function of temperature. [Henrys Law] KH = 1.3 x10-3 mol L-1atm-1 Therefore, thermal pollution is a problem Problem. Confirm by calculation the value of 8.7 mg/L for the solubility of oxygen in water. [O2] = KHPO2 = 1.3 x10-3 mol L-1atm-1 X 0.21 atm = 2.7 x10-4 mole/liter 2.7 x10-4 mole/liter X 32.0 grams/mole = 8.7 x103grams/liter = 8.7 mg/liter

Solubility of carbon dioxide

CO2 (g) in the atmosphere is in equilibrium with the water system, in accordance with Henrys law. CO2 (g) ---> CO2 (l) [CO2 (l)] = KHP CO2
(g)

= 3.4x10-2mol L-1atm-1PCO2

PCO2 = 350 ppm = 3.50 x10-4atm. Therefore, [H2CO3] =1.2x10-5

pH of Water without CaCO3

[H2CO3] =1.2x10-5 CO2 (l) + H2O -> H2CO3 -> H+ + HCO3Ka1 = 4.5 x10-7 HCO3- ---> CO32- + H+ Ka2 = 4.7 x10-11 [Dont consider the second step of the diprotic acid, factor 104] pH of water in equilibrium with CO2(g) H2CO3 --> H+ + HCO3Ka1 = 4.5 x10-7 1.2x10-5 -x x x 4.5 x10-7 = [x][x]/[1.2x10-5 -x] x2 = 5.4 x 10-12 x = 2.3 x 10-6 pH = 5.63

Natural waters (acid-base chemistry of the carbonate system)

Acid-base chemistry of natural water systems is dominated by the carbonate ion, CO32 The carbonate ion is the anion of a weak acid, HCO3-, and this makes it a moderately strong base.

Understand this problem from two directions:

CO2 (g) in the atmosphere is in equilibrium with the water system, in accordance with Henrys law. CO2 (g) ---> CO2 (l) [CO2 (g)] = KHP CO2 (g) = 3.4x10-2mol L-1atm-1PCO2 PCO2 = 350 ppm = 3.50 x10-4atm. [H2CO3] =1.2x10-5 CO2 (l) + H2O -> H2CO3 -> H+ + HCO3Ka1 = 4.5 x10-7 pH = 5.6 HCO3- ---> CO32- + H+ Ka2 = 4.7 x10-11 [Dont consider the second step of the diprotic acid, factor 104]

CaCO3 --> Ca2+ + CO32- Ksp = 4.6 x10-9 s = solubility of Ca2+ s2 = 4.5 x10-9 s = [CO32-] = 6.8 x10-5 moles/liter but, CO32- is the anion of a weak acid, thus CO32- + H2O ---> HCO3- + OHK = [HCO3-][OH-]/[CO32-] K = Kw/Ka2 = 1 x10-14/4.7x10-11 = 2.1x10-4 Therefore, CaCO3 + H2O --> Ca2+ + HCO3- + OHK = K x Ksp = 2.1x10-4 x 4.6x10-9 = 9.7x10-13 S = [OH-] = [ Ca2+] = 9.9 x10-5 m/liter compared to 6.8 x10-5 moles/liter when we considered solubility without hydrolysis.Also, gives us a pH = 10

CaCO3(s) is in equilibrium with Ca2+ and CO32-

CaCO3(s) is in equilibrium with Ca2+ and CO32 For the more adventurous, what we have here is coupled equilibria with two interdependent variables; solubility and degree ionization; i.e. s and x, respectively. CaCO3 --> Ca2+ + CO32S S-x CO32- + H2O ---> HCO3- + OHS -x x x 2.1x10-4 = [x][x]/[S-x] and 4.6 x10-9 = [S][S-x] when you change one, you affect the other. Two equations, two unknowns, but both quadratic equations. Set-up an iterative approach, starting with S = 6.78x10-5.

Comparing the iterative method to the approximation method.

Approximation method: S = 6.8x10-5 and [OH-] = 9.9x10-5 pOH = 4.00 pH = 10.0 Iterative method S = 1.25x10-4 and [OH-] = 8.8x10-5 pOH = 4.05 pH = 9.95

Now consider the total system

CaCO3 +CO2 (l) + H2O --> Ca2+ +2 HCO3 K = 1.5x10-6 = [Ca2+ ][ HCO3- ]2 /PCO2 [S][2S]2/0.00035 = 1.5x10-6 S = 5.1 x10-4 M = [Ca2+] and the amount of CO2 dissolved. This is 35 times the amount of CO2 [1.2x10-5 moles/liter] that would dissolve without the presence of CaCO3 and five times the calcium concentration calculated without the involvement of carbon dioxide [1.25x10-4 moles/liter]. This is a synergistic effect.

 The bicarbonate ion can act as either a base or an acid HCO3- --> H+ + CO32Ka = 4.7 x10-11 HCO3- + H2O -----> H2CO3 + OH- Kb = 2.2 x10-8 {Consider only the base reaction because of magnitude difference in Ks} [HCO3-] = 1.02x10-3 moles/l from previous slide, and [H2CO3] = 1.2x10-5 from Henrys law calculation. Therefore: 2.2x10-8 = [OH-][1.2x10-5 ]/[1.02x10-3 - [OH-]] - {neglect addend} solving for [OH-] = 1.9 x10-6 and pH =8.27. Thus, river and lake water at 25oC whose pH is determined by saturation with CO2 and CaCO3 should be slightly alkaline with a pH of about 8.3.

The pH of River and Lake Water Saturated with CO2 and CaCO3

Carbonate system in water

Remember that you have two equilibria taking place, and the extent is dependent upon pH.

Calculating the fraction of each species present in water.

In the equations listed below, the fraction of each species present in the carbonate system is shown.

Expressing the fractions as functions of [H+] and equilibria constants; Ka1 and Ka2
Converting the fractions to expressions of [H+], and Ka1 and Ka2. Note the variance in [H+] dependence . As system becomes acidic, what would you expect to happen?

Concentrations of species in carbonate system as function of pH

The points to note here are (1) the variance in the concs. , and (2) which specie is dominate at specific pH values.

Carbonate system in water

Organic Compounds in Water

Humic substances
Humic substances are the most abundant polymers in nature They are brown, acidic material, formed by oxidation and condensation among polyphenols. Structures will vary in different areas of the country. Polymers form from the breakdown of plant material.

Carbon Cycle
Figure 14.9. Increase in substances rich in organic carbon can increase demand on dissolved oxygen significant implications on aquatic organisms.

Inorganic aqueous wastes

Ammonia - problem in both sewage and waste water treatment because of its toxicity. Nitrification - microbial oxidation of ammonia, nitrate ion is the final product. In soil, final oxidation products are nitrous oxide and nitrogen.

NO3(nitrate dissolved in water) Nitrification

OXIDATION AND REDUCTION

Figure 14.1
Denitrification N2, N2O (atmosphere)

NO2(nitrite dissolved in water)

NH3 (NH4OH) Nitrogen fixation (ammonia dissolved in water)

PHOTOSYNTHESIS

aminoacids

RESPIRATION

Proteins (animals and plants

Estuary and Oceanic systems

Omit pages 327 332 Also, Note Henrys Law is given as H = P/S (solubility) We have used it as S = H*P, note units