Chemistry of Natural Water

Important properties of water

Property Effects and Significance

1. Excellent Solvent Transport of nutrients, waste product.
2. High dielectric constant High solubility of ionic substances
3. High surface tension Surface phenomena
4. Transparent to visible radiation Allowing light for photosynthesis at and long
UV
5. High density, heat of evaporation, vertical circulation, heat transfer temperature
latent heat of fusion, heat capacity stabilized at freezing point, etc
than any liquid (except ammonia)

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 Alkalinity and acidity of water
Capacity of water to accept H+ ions: Alkalinity

In natural water systems, the capacity of the water to neutralize OH: Acidity

Highly alkaline water have high pH and generally contains high levels of dissolved
solids.

Knowledge of alkalinity of water is necessary for :

a) Water treatment
b) Use of water in boilers
c) Food processing
d) Municipal water system.

Basic species responsible for alkalinity in water: bicarbonate ions, carbonate ions
& hydroxide ions.

Minor contributors to alkalinity in water: ammonia, conjugate bases of phosphoric,

silicic, boric and organic acid.

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 Alkalinity vs. basicity of water
High basicity is manifested by elevated pH, whereas, high alkalinity is the capacity
to accept protons.

Therefore pH is an intensity factor while alkalinity is a capacity factor.

Let us take an example to understand this difference:

1 mM NaOH, pH = 11. 1 L of this solution will neutralize 1 mmol of acid (monoprotic).

While pH of bicarbonate is 8.34, and 1 L of it will be able to neutralize 0.1 mol of acid.

Therefore alkalinity of bicarbonate is 100 times that of the more basic NaOH solution.

Alkalinity is expressed in mg/L of CaCO3, based on the acid base reaction.

CaCO3 + 2H+
Ca2+ + CO2 + H2O

Equivalent weight of CaCO3 is half its formula weight.

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 Speciation of ions
It refers to changing concentration of varying forms of an ion as the pH of the solution
changes

In the case of a weak (monoprotic acid), pH of the acid would depend on its acid
dissociation constant (pKa) given by Henderson-Haselbalch equation:

pH = pKa log ([AH] /A-])

Note:
For 1 % dissociation of acid, ([AH]/[A-]) = 100 ; pH = pKa -2
For 50 % dissociation of acid, ([AH]/[A-]) = 1 ; pH = pKa
For 99 % dissociation of acid, ([AH]/[A-]) = 0.01 ; pH = pKa +2

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Acid Speciation as a Function of pH

HOCl is a weak acid (chlorination)

Cl2 + H2O HOCl + H+ + Cl

HOCl H+ + OCl Ka = 107.60

pKa = -log Ka = 7.60

HOCl is a better disinfectant than OCl.

When pH is low, [H+] is high, HOCl is the dominant form.

When pH is high, [H+] is low, OCl is the dominant form.

pH is the main parameter that defines the dominant forms.

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Base Speciation as a Function of pH
The presence of ammonia in waste water is due in most part to the hydrolysis
of urea to the ammonium ion. The ionization reaction for the ammonium ion is:

NH3(gas) + H+ NH4+
pKb = - log Kb = 9.40

At typical pH values of domestic waste water. (pH=7-7.5), dominant form of

ammonia is NH4+ .
If ammonia is to be removed by stripping it has to be converted to NH3 form,
which is a gas.

When pH is low, NH4+ is the dominant form.

When pH is high, NH3 is the dominant form.

pH is the main parameter that defines the dominant forms.

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 (alpha) notations
TOT A = sum of the concentrations of all the species in solution that contain a
chemical group A.

TOT OCl = [HOCl] + [OCl]

TOT CO3 = [H2CO3] + [HCO3] + [CO32]

TOT PO4 = [H3PO4] + [H2PO4] + [HPO42] + [PO43]

0 = fraction of TOT A that is in the most protonated form.

i = fraction of TOT A that is in a form that has lost i protons.
0 = [H3PO4]/TOT PO4
1 = [H2PO4]/TOT PO4
2 = [HPO42]/TOT PO4
3 = [PO43]/TOT PO4

i = 1
values of acid/base species depend only on the pH of the solution.
[A] = 1 (TOT A)
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 (alpha) notation for monoprotic acids
For a monoprotic acid, HA, having a value of pKa

Rearrange the Ka expression

By adding a value of 1.0 to each side

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 (alpha) notation for monoprotic acids

Questions: 1. At pH = pKa, what is the relation between [HA] and [A ]?

2. What will be the values of 0 and 1 at pH = pKa = 5?
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 Acid base equilibrium

Background knowledge:
Stronger acids have larger Ka values compared to weak acids. Therefore pKa values
should be negative for strong acids

For example:
pKa of HClO4 = -7; HCl = -3; H2SO4: pKa1 = -3 and pKa2 = 1.99, HNO3 = -1.3

For solving acid-base equilibrium problems, it is assumed that the equilibrium occurs
quickly (and hence kinetic consideration is ignored).

Tools to be used:
1) Equilibrium relationship
2) mass balance
3) charge balance
4) proton condition

Goal: concentration of each species, degree of ionization for each species,

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Exact solution for acid-base

CT,H3A = TOT A , the same meaning with different expressions

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 (alpha) notations

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 Example: 1
Determine the equilibrium pH of a solution made by adding HCl to water to give a
concentration of 0.01 M at 25 oC. (Ignore the activity correction).

Ka of HCl = 103, so complete ionization takes place in water. So H+ = Cl- = 0.01

Exact solution: [H+][OH-] = Kw = 10-14 ; ([H+][Cl-]) /[HCl] = Ka = 103

Mass balance: [HCl] + [Cl-] = CT = 0.01; Charge balance: [H+] = [OH-] + [Cl-]

For a monoprotic acid, [Cl-] = 1 CT

In charge balance: [H+] = Kw/[H+] + 1 CT

CT is known, 1 is a function of [H+] and Ka.

Master equation: [H+]3 + Ka[H+]2 (Ka CT + Kw) [ H+] KaKw = 0

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Chart Detail

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 Example 2
An HCl addition of 10-8 M. In this case, CT,HCl = 10-8 M. Here we cannot ignore the
ionization of water. All the equations developed for the previous case hold here; the
only difference is in CT,HCl. The equation to be solved is again

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 Acid-Base Indicator
An Indicator (In) has the acidic form InA and the basic form InB, which differ in
color. The equilibrium between the two forms may be expressed as

InA InB + H+

The equilibrium constant, Kin may be expressed in terms of concentration as

KIn = {[H+] [InB]}/[InA]

Taking logarithm, this gives

log [H+] = log KIn + log {[InB]/[InA]} or pH = pKIn + log {[InB]/[InA]}

It is difficult to recognize a color when it is present below 10% of the other color.
Acid color: [InA]/[InB] > 10; pH = pKIn + log {1/10} = pKIn 1

Basic color: [InB]/[InA] > 10; pH = pKIn + log {10/1} = pKIn + 1

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