ENVE 208

ENVIRONMENTAL CHEMISTRY LABORATORY

ACIDITY, ALKALINITY AND THE CARBONATE SYSTEM
Definition
Capacity of water to neutralize strong acids (≈pH=4.5).
Operational Definition:
It can be defined as the amount of acid required to lower
the pH to 4.5.
Where does it come from?
Ideally all strong bases and the salts of weak acids contribute
to alkalinity.
Any water sample that has a pH higher than 4.5 can be said to contain alkalinity
Different forms of Alkalinity
In natural waters predominant forms:
OH- , CO3= , HCO3-
Bicarbonates represent the major form of alkalinity
In soil, CO2 comes from:
1. The atmosphere
◦ CO2 + CaCO3 + H2O ↔ Ca(HCO3)2 2. Biological oxidation of organic matter (aerobic or
Ca2+ + 2HCO3- anaerobic)
In surface waters,
◦ Algae remove carbon dioxide & therefore shift the equilibrium towards
CO3= and OH- where pH 9-10 can be observed in natural environments
Importance of Alkalinity
Why is it important?
During water treatment - in coagulation: for coagulants to be effective, pH
buffering is done by alkalinity of the raw water
Water softening: chemically treated waters contain CO3 and excess OH-
Wastewater treatment: alkalinity information is required during
biological treatment & also chemical precipitation, sludge
treatment processes
Importance of Alkalinity
Why is it important?
Acidic water→corrosive
pH is important for efficiency and control of treatment processes
Measurement
• Volumetric measure
• Titration with 0.02 N H2SO4
• Findings are in terms of equivalents of CaCO3
Alkalinity measurement
Assume a water sample with pH>8.3: two step titration
pH Reactions Alkalinity
Caustic alkalinity
+ -
Until 10 ~ 11 H + OH ↔ H2O Vp
(hydroxide)

H+ + CO32- ↔ HCO3-
Carbonate alkalinity
Until 8.3 Phenolphthalein end point

Vmo
Total alkalinity
+ -
Until 4.5 H + HCO3 ↔ H2CO3 Methyl orange end point

Vp= Volume of acid/titrant used until phenolphthalein end point

Vmo= Volume of acid/titrant used from phenolphthalein to methyl orange end point

Phenolphthalein pink → Methyl orange orange → red

pH>8.3 pH<8.3 pH>4.5 pH<4.5
During alkalinity titration…

We are adding ACID, therefore we are moving towards the left

Total Alkalinity
Alkalinity (eq/l)= [HCO3-] + 2[CO3=] + [OH-] – [H+]
Total Alkalinity
The amount of acid required to react with the hydroxide, carbonate and
bicarbonate represent the total alkalinity.
Total alkalinity is calculated as:
V Total H 2 SO4 (mL)x N H 2 SO4 x50,000
Total. Alk. (mg / L as CaCO3 ) =
mLsample

Vtotal = Vp + Vmo
Phenolphthalein Alkalinity
Phenolphthalein Alkalinity
The alkalinity measured to the phenolphthalein end point.
V p (mL)x N H 2 SO4 x50,000
Phenol. Alk. (mg / L as CaCO3 ) =
mLsample

Vp = Volume of acid/titrant required to react until

the phenolphthalein end point
Hydroxide and Carbonate Alkalinity
Hydroxide Alkalinity
Samples containing only hydroxide alkalinity have a high pH, usually well
above 10. Titration is essentially complete at the phenolphthalein end point.
In this case hydroxide alkalinity is equal to the phenolphthalein alkalinity.
Carbonate Alkalinity
Samples containing only carbonate alkalinity have a pH of between 8.3 and
10. The titration to the phenolphthalein end point is exactly equal to one half
of the total titration. In this case carbonate alkalinity is equal to the total
alkalinity.
Other forms of Alkalinity
Bicarbonate Alkalinity
Samples containing only bicarbonate alkalinity have a pH of 8.3 or less. In this
case bicarbonate alkalinity is equal to the total alkalinity.
Hydroxide-Carbonate Alkalinity
Samples containing hydroxide and carbonate alkalinity have a high pH,
usually well above 10. The titration from the phenolphthalein to methyl
orange end point represents one half of the carbonate alkalinity.
Therefore Vp>Vmo
Calculations
Hydroxide-Carbonate Alkalinity
Carbonate alkalinity may be calculated as follows:

2 *Vmo(ml)x N H 2 SO4 x50,000

Carbonate Alkalinity =
(mg / L as CaCO ) ml.sample
3
Vmo = Volume of acid/titrant required to react from the phenolphthalein end point to
methyl orange end point
Hydroxide Alk.(mg/l as CaCO3)= Total Alk - Carbonate Alk.
Calculations (cont’d)
Carbonate-Bicarbonate Alkalinity
Samples containing carbonate and bicarbonate alkalinity have a pH above 8.3
and usually less than 11. The titration to the phenolphthalein end point
represents one - half of the carbonate alkalinity. Therefore Vmo>Vp

2xVp x N H 2 SO4 x50,000

Carbonate Alkalinity =
(mg / L as CaCO ) ml.sample
3

Bicarbonate Alk. = Total Alk. - Carbonate Alk.

Various forms of Alkalinity
Graphical representation of titration of samples containing various forms of
alkalinity

Methly orange end point

Ion concentrations
Calculation of the Ion Concentrations
•If Vp = Vmo → There is only carbonate present in the system
Reactions taking place are:
CO3= + H+ ↔ HCO3 as Vp
HCO3- + H+ ↔ H2CO3 as Vmo
[CO3=] = Carbonate ion concentration= Vp * N * V-1
Ion concentrations (cont’d)
Calculation of the Ion Concentrations
•If Vp = 0 → No carbonate, no hydroxide, only bicarbonate present
[HCO3-] = Vmo * N * V-1
•If Vmo = 0 → No bicarbonate, no carbonate, only hydroxide present
[OH-] = Vp * N * V-1
•If Vp > Vmo→ No bicarbonate, hydroxide and carbonate present
[CO3=] = Vmo * N * V-1
[OH-] =(Vp - Vmo) * N * V-1
Ion concentrations (cont’d)
Calculation of the Ion Concentrations
•If Vmo > Vp → No hydroxide, carbonate and bicarbonate present
[CO3=] = Vp * N * V-1
[HCO3-] = (Vmo - Vp) * N * V-1

These equations directly give molarity!

Because Vp is defined as the mL of acid required to titrate CO3= according to:
WHY? H+ + CO32-  HCO3-
So 1 mol H+ added for each mole CO32-
Therefore:
Acid added in eq/L = conc. of CO32- in moles/L
 Alkalinity calculations _ recap
LET US SCRUTINIZE FURTHER THE DIFFERENCE BETWEEN CONCENTRATION & ALKALINITY CALCULATION:
• If Vp > Vmo→ No bicarbonate, hydroxide and carbonate present
• The concentration of species responsible for alkalinity are calculated as:
[CO3=] = Vmo * N * V-1
[OH-] =(Vp - Vmo) * N * V-1
[HCO3-] = 0
• However, when we are calculating alkalinity associated with each specie (i.e., acid buffering capacities of species), then:
CO3= alkalinity = 2 * Vmo * N * V-1
OH- alkalinity = (Vp - Vmo) * N * V-1
TOTAL alkalinity = CO3= alkalinity + OH- alkalinity
TOTAL alkalinity = {2 * Vmo + (Vp - Vmo) } * N * V-1
TOTAL alkalinity = (Vp + Vmo) * N * V-1
Carbonate system (reminder)
Relationship of the
pC-pH Diagram to
the titration curve
for the carbonate
system at 25 oC.
ACIDITY: definition
Acidity is the measure of the capacity of a water to neutralize strong bases.
Where does it come from?
 Ideally all strong acid and weak acids including carbonic acid in natural
waters.
Predominant forms of acidity: H+, H2CO3, HCO3- Remember
how the
H+, H2CO3, HCO3- , CO3 2-, OH- species
contribute to
acidity ACD & ALK
Sources of acidity

From atmosphere & as a result of biological oxidation of organic matter (aerobic &
anaerobic)  concentration of CO2 in groundwaters, it can not escape!

If CaCO3 and/or MgCO3 present they neutralize CO2 to form HCO3- , Ca2+ , Mg2+
CO2 + CaCO3 (s) +H2O  Ca2+ +2 HCO3-

CO2 acidity
Sources of acidity (cont’d)

 from industrial wastes (metallurgy), certain natural waters, drainage from

abandoned mines (containing sulfuric acid)

bacteria
salts of heavy
2S + 3O2 +2H2O  4H+ +2 SO42- OR metals (Fe(III), + H2O ↔ Fe(OH)3+ 3H+
Al(III))

mineral acidity
 Importance of Acidity
 Acidic waters are corrosive (CO2 or mineral acidity, i.e. H+)
 Water softening: CO2 is a concern during lime-soda ash process
 Biological processes require chemical pH adjustment (around pH 6-9): The
amount of chemicals needed to adjust the pH
 Buffering of natural water bodies, for their response to external events
such as:
Untreated acidic industrial wastewater discharge contain significant mineral
acidity (e.g. Electroplating baths can have pH such as 2)
 Drainage from abandoned mines
 If S0 (sulphur), S2- (sulfide) or FeS2 (pyrite) is present & sulfur-oxidizing bacteria is also
present, then acid mine drainage will ocur,e.g.:
2S(s) + 3O2 + 2H2O  4H+ + 2SO42-
Titration curve
Titration curve is prepared when controlled volumes of a titrant is added into a known
volume of solution. The titrant volume is recorded at frequent intervals during which the
solution property is measured.
Titration curve for acidity measurement is prepared when a sample containing an unknown
amount of acidity is titrated with strong base. The pH of the solution is measured at certain
intervals at which volume of titrant is also recorded.

Where the indicator has to be used

Acidity pH Range
End point cannot be observed practically
HCO3-+OH- ↔ CO3 2-

Practically measurable total acidity

H2CO3+OH- ↔ HCO3-

= phenolphthalein acidity
Strong base addition

Vp
End point of strong
acid titration =
mineral acidity
H++OH-↔H2O

Vmo
(methyl orange)
titrant
During acidity titration…

We are adding BASE, therefore we are moving towards the right

Titration curve – Acidity experiment

pH=8.3
OH- + H2CO3 ↔ HCO3-

pH=4.5
OH- + H+ ↔ H2O

High pH Low pH