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CIVE 350 Water Chemistry

Pascal E. Saikaly

Department of Civil and Environmental Engineering American University of Beirut

Outline Water Chemistry

• Introduction

• Physical properties of water

• Chemical reactions

• Acid/Base, Precipitation/Dissolution, Complexation, Oxidation/Reduction

• Chemical units

• Stoichiometry

• Chemical equilibrium

• Precipitation reactions

• Acid-Base reactions

• The carbonate system

• Solubility of gases in water

Water chemsitry

Almost every pollution problem that we face has a chemical basis (e.g. greenhouse effect, ozone depletion, toxic wastes, groundwater contamination, disinfection, softening, air pollution, and acid rain). A knowledge of the fundamentals of water chemistry is essential to the understanding of processes governing water quality and wastewater treatment.

Physical Properties of Water

Density: mass per unit volume (Kg/m 3 )

of Water • Density : mass per unit volume (Kg/m 3 ) • Specific gravity S

Specific gravity

S

=

ρ

ρ

0

ρ=

M

V

The subscript denotes the density of water at 3.98 o C, 1,000 Kg/m 3 .

A measure of friction is viscosity (higher friction: harder to pump liquid)

A measure of friction is viscosity (higher friction: harder to pump liquid)

Dynamic viscosity or absolute viscosity, μ, has dimensions of mass per unit length per time, with units Pa . S.

Kinematic viscosity (m 2 /s)

μ

ρ

ν=

Physical properties of water at 1 atm

Physical properties of water at 1 atm

Chemical Reactions

Important types of chemical reactions in environmental engineering

Acid/Base (e.g. dissociation of bicarbonate)

HCO 3 -

Acid/Base (e.g. dissociation of bicarbonate) HCO 3 - H + + CO 3 2 - •

H + + CO 3 2-

Precipitation/dissolution

CaCO 3 (s)

CO 3 2 - • Precipitation/dissolution CaCO 3 (s) Ca 2 + + CO 3 2

Ca 2+ + CO 3 2-

Ion-association or complexationCaCO 3 (s) Ca 2 + + CO 3 2 - Fe 3 + + OH

Fe 3+ + OH -

2 - Ion-association or complexation Fe 3 + + OH - FeOH 2 + Redox reactions:

FeOH 2+

Redox reactions: Oxidation/Reduction (valence changes and transfer of electrons) Fe Fe 2 + + 2e - (Oxidation, loss (valence changes and transfer of electrons) Fe Fe 2+ + 2e - (Oxidation, loss of electrons)

Fe Fe 2 + + 2e - (Oxidation, loss of electrons) 2H + + 2e -

2H + + 2e -

H 2 (g)

(Reduction, gain of electrons)

Chemical Units

Methods of expressing concentration of a given material in aqueous solution

One mole of a substance contains: 6.023 X 10 23 molecules.

Number of moles = mass/molecular weight (g)/(g/mole) = mass/molecular weight (g)/(g/mole)

Molarity, M (mol/L): The number of moles of a specific species per liter of solution. The number of moles of a specific species per liter of solution.

1-molar solution (1 M) is 1 mole/L

Molarity is related to mg/L by mg/L = molarity X molecular weight X 10 3 mg/L = (moles/L) X (g/mole) X (10 3 mg/g)

Molality, m (mol/Kg): The number of moles of a specific species per Kg of solvent.

Chemical units

Normality, N (equivalents/L): The number of equivalent weights of acid, base, or redox-active species per liter of solution.

Normality =

Mass of substance per liter

Equivalent weight

Equivalent weight =

where,

Molecular weight

n

or

Normality = Molarity × n

1. For Acid/Base rxn

n = number of protons (H + ) or hydroxyl ions (OH - ) that react in an acid-base

reaction

2.

For Redox rxn

n

= number e - transferred per mole of species

3.

For precipitation rxn

n

= the valance of the element in question (see table next page)

4.

For compounds

n

= number of hydrogen ions that would be required to replace the cation

Typical valences of elements and compounds in water

Typical valences of elements and compounds in water

Example 1

Find the normality of the following solutions

A) 155 mg Ca 3 (PO 4 ) 2 /liter given that Ca 3 (PO 4 ) 2 participates in the dissolution rxn

Ca 3 (PO 4 ) 2

participates in the dissolution rxn Ca 3 (PO 4 ) 2 3Ca 2 + + 2PO

3Ca 2+ + 2PO 4 3-

B) 49 mg H 3 PO 4 /L with respect the rxn

H 3 PO 4

49 mg H 3 PO 4 /L with respect the rxn H 3 PO 4 2H

2H + + HPO 4 2-

C) 45 mg CO 3 2- /L with respect the rxn

CO 3 2- + H 2 O

2 - /L with respect the rxn CO 3 2 - + H 2 O HCO

HCO 3 - + OH -

D) Equivalent weight of O 2 for the reduction rxn

O 2 + 4H + +4e -

Equivalent weight of O 2 for the reduction rxn O 2 + 4H + +4e -

2H 2 O

Example 1

A) n = 6. Each Ca 3 (PO 4 ) 2 forms 6 + and 6 – charges. MW of Ca 3 (PO 4 ) 2 is 310 g/mole. Equivalent weight = (310 g/mole)/(6 eg/mole) = 51.67 g/eg or 51.67 mg/meq Normality = (155 mg/L)/(51.67 mg/meq) = 3 meq/L

B) n = 2. Equivalent weight = (98 g/mole)/ (2 eq/mole) = 49 g/eq or 49 mg/meq Normality = (49 mg/L)/(49 mg/meq) = 1 meq/L

C) n =1. Equivalent weight = (60 g/mole)/(1 eq/mole) = 60 g/eq or 60 mg/meq Normality = (45 mg/L)/(60 mg/meq) = 0.75 meq/L

D) n = 4. Equivalent weight = (32 g/mole)/(4 eq/mole) = 8 g/eq

E) n = 2. Equivalent weight = ( 40.08 g/mole)/(2 eq/mole) = 20.04 g/eq

Example 2

Find the weight of sodium bicarbonate, NaHCO 3 , necessary to make a 1 M solution. Find the normality of the solution.

NaHCO 3 HCO 3 HCO 3 - + H 2 O

solution. NaHCO 3 HCO 3 HCO 3 - + H 2 O - Na + +

-

solution. NaHCO 3 HCO 3 HCO 3 - + H 2 O - Na + +

Na + + HCO 3 H + + CO 3 2- H 2 CO 3 + OH -

-

3 HCO 3 HCO 3 - + H 2 O - Na + + HCO 3

Example 2

The molecular weight of NaHCO 3 is 84. using the equation mg/L = molarity X molecular weight X 10 3 = (1 mole/L)(84 g/mole)(10 3 mg/g) = 84,000 HCO 3 - is able to give or accept only one proton; therefore n = 1. Equivalent weight = (84 g/mole)/(1 eq/mole) = 84 g/eq or 84 mg/meq Normality = (84,000 mg/L)/(84 mg/meq) = 1000 meq/L or 1 eq/L

Stoichiometry

Chemical reaction

Qualitative information: Which chemicals are interacting to produce which end products

Quantitative: Principle of conservation of mass

Stoichiometry: The balancing of equations so that the same number of each kind of atom appears on each side of the equation and the subsequent calculations, which can be used to determine amounts of each compound involved.

Atomic weight of an atom is the mass of the atom measured in atomic mass units.

Molecular weight of a molecule is the simply the sum of the atomic weights of all the constituent atoms (e.g. CH 4 , atomic weight of C is 12 and atomic weight of H is 1. Therefore, the MW of methane = 12 + 4(1) = 16 g/mole).

Stoichiometry

Various ways to express the oxidation of methane

CH 4

1 molecule

of methane

or, 1 mole of methane or , 16 g of methane

+

+ 2O 2

methane or, 1 mole of methane or , 16 g of methane + + 2O 2

CO 2

2 molecules of oxygen

1 molecule of carbon dioxide or , 16 g of methane + + 2O 2 CO 2 2 molecules of oxygen

+ 2 mole of oxygen

1 mole of

carbon dioxide1 molecule of carbon dioxide + 2 mole of oxygen 1 mole of + 64 g

+

64 g of oxygen

44 g of carbon dioxide + 2 mole of oxygen 1 mole of carbon dioxide + 64 g of oxygen +

+ 2H 2 O

+ 2 molecules of water

+ 2 moles of water

+

36 g of water

The mass is conserved in the last expression ( 80 g = 80 g)

Example 3

Consider a 1.67 X 10 -3 M glucose solution that is completely oxidized to CO 2 and H 2 O. Find the mg/L of oxygen required to complete the reaction.

C 6 H 12 O 6 + 6O2

180 g

192g

the reaction. C 6 H 1 2 O 6 + 6O2 180 g 192g 6CO 2

6CO 2 + 6H 2 O

264g

108 g

It takes 192 g of oxygen to oxidize 180 g of glucose

mg/L = molarity X molecular weight X 10 3 = (1.67 X 10 -3 M )(180 g/mole)(10 3 mg/g) = 301 mg/L So the oxygen requirement would be

Chemical Equilibrium

Different approaches may be used in predicting aqueous chemistry speciation (i.e. concentration of products & reactants)

Chemical kinetics: The rate at which a reaction proceeds toward equilibrium

Chemical equilibrium: tell you what the chemistry will be at equilibrium, but not the kinetic rate at which the system

reaches the equilibrium state.

method for obtaining chemical speciation.

This is the most widely used

Most chemical reactions are, to some extent, reversible, proceeding in both directions at once. When products are being formed on the right at the same rate as they are being formed on the left, the reaction is said to have reached equilibrium .

aA + bB

the reaction is said to have reached equilibrium . aA + bB cC + dD The

cC + dD

The small letters a, b, c, and d are coefficients corresponding to the number of molecules or ions

Chemical Equilibrium

aA + bB

At equilibrium we can write

K =

Chemical Equilibrium aA + bB At equilibrium we can write K = cC + dD [C]

cC + dD

[C]

c [D]

d

[A]

a [B]

b

where the [ ] represents the concentration of the substance at equilibrium, expressed in moles per liter (molarity). DO NOT USE mg/L.

K is the equilibrium constant

K: Dissociation constant or ionization constant K s : Solubility product K H : Henry’s constant; equilibrium constant describing the concentration of gas in the water in equilibrium with the concentration of gas in the air.

X

pX

=

pX

logX

10

=−

Precipitation Reactions

All solids are to some degree soluble, although some are much more than others (e.g. NaCl is very soluble, whereas AgCl are very insoluble).

A generalized equation describing the equilibrium condition in which a solid is dissociating into its ionic components (dissolution) at the same rate that ionic compounds are recombining into the solid form (precipitation)

Solid aA + bB a b [A] [B] K =
Solid
aA + bB
a
b
[A]
[B]
K =

[solid]

As long as there is still solid present at equilibrium, its effect can be incorporated into the equilibrium constant

K

s

= [A]

a

[B]

b

K s values are often reported as pK s

pK

s

= −logK

s

Selected solubility product constants at 25 o C

Selected solubility product constants at 25 o C Solid a A + b B • If

Solid

Selected solubility product constants at 25 o C Solid a A + b B • If

aA + bB

If we place solid in water, for every a moles of A that dissolves, b moles of B will dissolve until equilibrium is reached.

When precipitating ions, it is possible to have a higher concentration of ions in solution than dictated by the solubility product. This is called a supersaturated solution.

concentration of ions in solution than dictated by the solubility product. This is called a supersaturated

Solubility product constants at 25 o C

S olubility product constants at 25 o C

Example 4

How many mg/L of PO 4 3- would be in solution at equilibrium with AlPO 4 (s)?

AlPO 4 (s)

solution at equilibrium with AlPO 4 (s)? AlPO 4 (s) Al 3 + + PO 4

Al 3+ + PO 4 3-

pK s for aluminum phosphate is 20 (see table in previous slides)

K

s

=

10

20

=

[Al

3 +

][PO

4

3

]

For every mole of AlPO 4 (s) that dissolves, one mole of Al 3+ and one mole of PO 4 3- are released into solution. At equilibrium, the molar concentration of Al 3+ and PO 4 3- in solution will be equal.

3 + [Al K
3 +
[Al
K

]

s

=

[PO

4

= 10

20

3

]

= X

2

=

X

Solving for X, we find PO 4 3- = 10 -10 moles per liter

mg/L = molarity X molecular weight X 10 3 = (10 -10 moles/L)(95 g/mole)(10 3 mg/g) = 9.5 X 10 -6

Example 5

If 50 mg of CO 3 2- and 50 mg of Ca 2+ are present in 1 L of water, what will be the final (equilibrium) concentration of Ca 2+ ?

CaCO 3 (s)

(equilibrium) concentration of Ca 2 + ? CaCO 3 (s) Ca 2 + + CO 3

Ca 2+ + CO 3 2-

Molecular weight of Ca 2+ is 40.08 and CO 3 2- is 60.01, resulting in initial molar concentration of 1.25 X 10 -3 moles/L and 8.33 X 10 -4 moles/L for Ca 2+ and CO 3 2- , respectively.

K

s

=

10

pK

s

=

10

8.305

=

[Ca

2 +

][CO

3

2

]

For every mole of Ca 2+ that is removed from solution, one mole of

CO 3 2- is removed from solution. If the amount removed is given by

Z, then

8.305

9

3

4

10

=

4.95

×

10

=

[1.25

×

10

Z][8.33

10

Z]

×

6

3

2

1.04

×

10

(2.08

×

10

)Z

+

Z

=

0

b ±

− b ± b 2 − 4ac

b

2

4ac

 
 

2a

×

10

3

±

±

4.34

×

10

6

4(1.04

×

10

6

)

Z =

2.08

=

2

=

8.28

×

10

4

Example 5

So that the final Ca 2+ concentration is

[Ca 2+ ] = 1.25 X 10 -3 – 8.28 X 10 -4 = 4.22 X 10 -4 M

or,

mg/L = molarity X molecular weight X 10 3 = (4.22 X 10 -4 moles/L)(40 g/mole)(10 3 mg/g) = 16.9 mg/L

Acid-Base Reaction

In 1923, Bronsted and Lowry suggested a new concept

of acid and base behavior. They proposed that an acid is any substance that can donate a proton to another substance.

HNO 3 (aq) + H 2 O(l)

HNO 3 (aq)

substance. HNO 3 (aq) + H 2 O(l) HNO 3 (aq) H 3 O + (aq)

H 3 O + (aq) + NO 3 - (aq)

H + (aq) + (aq)

+ NO 3 - (aq)

And a base is a substance that can accept a proton from any other substance.

NH 3 (aq) + H 2 O(l)

NH 4 + (aq) + OH - (aq) 4 + (aq) + OH - (aq)

If a compound is stronger acid than water, then water will act as a base. If a compound is a strong base than water, then water will act as an acid. The acid/base chemistry centers on water and it is important to know how strong an acid water is

H 2 O(l) + H + (aq) + OH - (aq) − [H ][OH ]
H 2 O(l)
+
H + (aq) + OH - (aq)
[H
][OH
]
K
=

[H O]

2

Acid-Base Reaction

Since water dissociates only slightly, the molar concentration after ionization is not changed enough to be a of significance, so [H 2 O] is essentially constant and can be included in the equilibrium constant

[H

+

][OH

]

=

K

w

= 1 ×

10

14

at 25

o

C

where K w is the dissociation constant of water (pK w = 14). temperature dependent.

K w is

A solution is said to be acidic if [H + ] is greater than [OH - ], neutral if

equal, and basic if [H + ] is less than [OH - ]. Neutral solution , then [H + ] = [OH - ] = 10 -7 M.

A convenient expression of the hydrogen ion (proton) is pH.

pH

=−

log[H

+

]

where

[H

+

]

=

10

pH

Acid-Base Reaction

Therefore, a neutral solution at 25 o C has a pH of 7, an acidic solution has a pH < 7, and a basic solution has a pH > 7.

Strong acids

< 7, and a basic solution has a pH > 7. Strong acids Note the use

Note the use of single arrow to signify that, for practical purposes, we may assume that the reaction proceeds completely to the right.

Acid-Base Reaction

Selected weak acid dissociation constants at 25 o C

Selected weak acid dissociation constants at 25 o C Weak acids are acids that do not

Weak acids are acids that do not completely dissociate in water. An equilibrium exists between the dissociated ions and undissociated compound. The reaction of a week acid is

HA(aq)

+ − [H ][A
+
[H
][A

H + (aq) + A - (aq)

]

pK

a

=−

logK

a

K

a

=

[HA]

Example 6

If 100 mg of H 2 SO 4 (MW = 98) is added to 1L of water, what is the final pH?

100mg

1L H2O

 

 

1

98g/mole

H 2 SO 4 (aq)

  1   = 1.02 × 10      
1 
=
1.02
×
10
 
10
3 mg/g
2H + + SO 4 2-

3

mole/L

Therefore 2 X (1.02 X 10 -3 )M H + is produced. The pH is:

pH = -log(2.04 X 10 -3 ) = 2.69.

Example 7

If 15 mg/L HOCl (hypochlorous acid) is added to a potable water for disinfection and the final pH is 7.0, what percent of the HOCl is not dissociated ? Assume the temperature of water is 25 o C.

pK a = 7.54

HOCl(aq) H + (aq) + OCl - (aq) − 7.54 − 8 K 10 =
HOCl(aq)
H + (aq) + OCl - (aq)
7.54
8
K
10
=
2.88
× 10
a =
+
[H
][OCL ]
=
K a
[HOCL]
7
[10
][OCL ]
8
2.88
×
10
=

[HOCL]

Solving for the HOCL concentration [HOCl] = 3.47[OCl - ]

Example 7

Since the fraction of HOCl that has not dissociated plus the OCl - that was formed by the dissociation must, by the law of conservation of mass, equal 100% of the original HOCL added [HOCl] + [OCl - ] = 100%

then

3.47[OCl - ] + [OCl - ] = 100% [OCl - ] = 23.37% [HOCl] = 77.6%

The Carbonate System

Buffer solution: A solution which resists large changes in pH when an acid or base are added. Atmospheric carbon dioxide, CO 2 (g), produces a natural buffer through the following reactions:

CO 2 (g)

natural buffer through the following reactions: CO 2 (g) CO 2 (aq) + H 2 O

CO 2 (aq) + H 2 O

following reactions: CO 2 (g) CO 2 (aq) + H 2 O H 2 CO 3

H 2 CO 3

CO 2 (g) CO 2 (aq) + H 2 O H 2 CO 3 H +

H + + HCO 3 -

2-

2 (aq) + H 2 O H 2 CO 3 H + + HCO 3 -

2H + + CO 3

where H 2 CO 3 HCO 3 - CO

2-

3

= carbonic acid = bicarbonate ion = carbonate ion = carbon dioxide gas

CO 2 (g)

CO 2 (aq) = aqueous carbon dioxide

Aqueous CO 2 (aq) is formed when atmospheric CO 2 (g) dissolves in water; we can find its concentration in fresh water using Henry’s law Where K H = Henry’s law constant (mol/L . atm); P CO2 = partial pressure of CO 2 in the atmosphere

[CO

2

]

aq

= K

H

P

CO

2

The Carbonate System

The carbonate system is the most important buffer system in water and wastewater treatment. Also, it is the most important acid-base system in natural waters because it largely controls its pH.

CO 2 (g)

Any change in the system components to the right of CO 2 causes the CO 2 either to be released from solution or to dissolve. Le Chatelier’s Principle: A system at equilibrium, when subjected to a perturbation, responds in a way that tends to minimize its effect.

responds in a way that tends to minimize its effect. CO 2 (aq) + H 2

CO 2 (aq) + H 2 O

that tends to minimize its effect. CO 2 (aq) + H 2 O H 2 CO

H 2 CO 3

minimize its effect. CO 2 (aq) + H 2 O H 2 CO 3 H +

H + + HCO 3 -

2 (aq) + H 2 O H 2 CO 3 H + + HCO 3 -

2H + + CO 3

2-

Examine the character of the buffer system in resisting a change in pH assuming 4 cases (system exposed to atmosphere, system is open)

Case I:

increasing H + concentration) Case II: Base is added to the system (base consumes H + ) Case III: CO 2 is bubbled into the carbonate system Case IV: carbonate buffer is stripped of CO 2

Acid is added to the system (it unbalances the system by

Behavior of carbonate buffer system with the addition of acids and bases or the addition or removal of CO 2

of acids and bases or the addition or removal of CO 2 Case I and II

Case I and II are common in natural

settings when

a reaction

proceeds over

a relatively

long period

when a reaction proceeds over a relatively long period The pH will change more dramatically because

The pH will change more

dramatically

because the atmosphere is no longer a source or sink of CO 2

the atmosphere is no longer a source or sink of CO 2 Case III and IV

Case III and IV are not common in natural settings. They are used in water treatment to adjust the pH

The Carbonate System

In natural waters in equilibrium with atmospheric CO

CO 3 2- in solution is quite small in comparison to the HCO 3 - in solution. The presence of Ca 2+ in the form of limestone rock or other naturally

occurring sources of calcium results in the formation of calcium carbonate CaCO 3 , which is very insoluble. As a consequence it precipitates from solution

2

, the amount of

CaCO 3 (s)

insoluble. As a consequence it precipitates from solution 2 , the amount of CaCO 3 (s)

Ca 2+ + CO 3 2-

The Carbonate System

Alkalinity: is the sum of all titratable bases down to about pH of 4.5. It is found experimentally by determining how much acid it takes to lower

the pH of water to 4.5.

contributions to alkalinity are the carbonate species and any free H + or

OH - .

carbonate species is

In most waters the only significant

The total H + that can be taken up by a water containing primarily

Alkalinity

=

[HCO

3

]

+

2[CO

3

2

]

+

[OH

]

[H

+

]

In most natural water situations (pH 6 to 8), the OH - and H + are negligible such that

Alkalinity

=

[HCO

3

]

+

2[CO

2

3

]

Note that [CO 3 2 - ] is multiplied by two because it can accept two protons.

H 2 CO HCO 3 -

3

because it can accept two protons. H 2 CO HCO 3 - 3 H + +

H + + HCO 3 - H + + CO 3 2-

pK a1 = 6.35 pK a2 = 10.33

pC-pH diagram for carbonate system

H 2 CO 3 HCO 3 - pK a1 pK a2 < 4.5 > 12.3
H 2 CO 3
HCO 3
-
pK a1
pK a2
< 4.5
> 12.3
OH -
H +
CO 3 2-

Below pH of 4.5, essentially all the carbonate species are present as H 2 CO 3 , and the alkalinity is negative (due to H + ).

1.
1.

2. At pH of 8.3 most of the carbonate species are present as HCO 3 - , and the alkalinity equals HCO 3 - .

Titration curve for a hydroxide-carbonate mixture

Titration curve for a hydroxide-carbonate mixture Source: Sawyer, McCarty, and Parkin, 1994 The figure shows the

Source:

Sawyer,

McCarty, and Parkin,

1994

The figure shows the change of species described above as the pH is lowered by the addition of acid to a water containing alkalinity. At about pH 8.3 the carbonate is essentially all converted to bicarbonate

The Carbonate System

By convention, alkalinity is not expressed in molarity units, but rather in mg/L as CaCO 3 .

mg/L as CaCO

3

= (mg/L as species)

EW

  EW

CaCO

3

species

The alkalinity is then found by adding all the carbonate species and the hydroxide, and then subtracting the hydrogen ion. When using the units “mg/L as CaCO 3 ” the terms are added directly. The multiple of two CO 3 2- has already been accounted for in the conversion.

Example 8

A water contains 100.00 mg/L CO 3 2- and 75.0 mg/L HCO 3 - at a pH of 10. Calculate the alkalinity exactly at 25 o C. Approximate the alkalinity by ignoring [OH - ] and [H + ].

The equivalent weight are:

CO 3 2- :

MW = 60, n = 2, EW = 30

HCO 3 - :

MW = 61, n = 1, EW = 61

H + :

MW =

1, n = 1, EW =

1

OH - :

MW = 17, n = 1, EW = 17

pH = 10; therefore [H + ] = 10 -10 M. mg/L = (10 -10 mole/L)(1 g/mole)(10 3 mg/g) = 10 -7 [OH - ] = K w /[H + ] = 10 -14 /10 -10 = 10 -4 moles/L mg/L = (10 -4 mole/L)(17 g/mole)(10 3 mg/g) = 1.7

Example 8

mg/L as CaCO3 is found using the equation

EW

CaCO

3

mg/L as CaCO

(mg/L as species)

3

=

EW

species

The equivalent weight of CaCO 3 = MW/n where n = 2 EW CaCO 3 = 100/2 = 50

CO 3 2- = 100.0(50/30) = 167

HCO 3 - = 75.0(50/61)

H +

= 10 -7 (50/1)

OH - = 1.7(50/17)

= 61 = 5 X 10 -6 = 5.0

The exact alkalinity (in mg/L) is found by Alkalinity = 61 + 167 + 5.0 – (5 X 10 -6 ) = 233 mg/L as CaCO 3

Solubility of Gases in Water

When air comes in contact with water, some of it dissolves into the water.

The relationship between the equilibrium concentration of gas dissolved in solution and the partial pressure of the gas defined by Henry’s law:

[gas] = K

P

H

g

where

[gas]

K H

= concentration of dissolved gas (mol/L) = Henry’s law constant (mol/L . atm)

P g = the partial pressure of the gas in air (atm)

P g is simply the volumetric concentration times the atmospheric

pressure.

atmosphere, so at 1 atm: P g would be 0.21 X 1 atm = 0.21 atm.

For example, oxygen makes up about 21 percent of the

Henry’s law constant varies both with temperature (solubility decreases as temperature increases) and with concentration of other dissolved gases and solids (the solubility decreases as other dissolved material in the liquid increases).

Solubility of Gases in Water

Because atmospheric pressure varies with altitude, P g will change as well

(Thomson and Mueller, 1987)

Where

P

=

P

0

1.15

×

10

4

H

P

= atmospheric pressure at altitude H (atm)

H

= altitude (m)

P 0 = atmospheric pressure at altitude H (atm)

Example 9

By volume, the concentration of oxygen in air is about 21 percent. Find the equilibrium concentration of O 2 in water (in mol/L and mg/L) at 25 o C and 1 atm of pressure. Recalculate it for Denver at an altitude of 1,525 m.

P g = 0.21 X 1 atm = 0.21 atm. At 25 o C, K H for O 2 = 0.0012630 mol/L . Atm

[O 2 ] = K H P g = 0.0012630 X 0.21 = 2.65 X 10 -4 mol/L

In Denver, at 1,525 m, atmospheric pressure can be estimated using the equation

P

=

P

0

1.15

×

10

4

H

=

1 - 1.15

×

10

-4

×

1,525

=

0.825 atm

P g = 0.21 X 0.825 atm = 0.17325 atm. [O 2 ] = K H P g = 0.0012630 X 0.17325 = 2.19 X 10 -4 mol/L

Alkalinity vs. Alkaline

Buffer solution: A solution which resists large changes in pH when an acid or base are added.

Alkalinity serves as a measure of buffering capacity.

The greater the alkalinity, the greater the buffering capacity.

Alkaline water: water that has a pH greater than 7. High alkalinity water: water with high buffering capacity.

An alkaline water may or may not have a high buffering capacity. Likewise, a water with high alkalinity may or may not have a high pH.