Name: Hayden Robbins

Experiment 2
Alkalinity and pH Measurement

OBJECTIVES
1) To determine alkalinity in water
2) To calibrate and measure pH of water sample

INTRODUCTION
Alkalinity
Alkalinity refers to the capacity of water to neutralize acids. In most uncontaminated natural waters, the
alkalinity is determined by the abundance of four ions: carbonate (CO32-), bicarbonate (OH-), hydroxyl
(OH-), and hydrogen (H+). For many practical engineering purposes, we can define the alkalinity by
this expression:
A = [OH-] + [HCO3-] + 2[CO32-] – [H+]
Where the ionic species are measured in mole per liter and alkalinity is expressed in equivalents per liter
or normal.
In practice, alkalinity is measured by titration: A strong acid (such as hydrochloric) is slowly added to the
water of interest until the pH change to 4.5. The amount of acid added (i.e. the moles of charge
associated with the acid anion) per liter of water sample is the measured alkalinity.
To fully understand alkalinity, we need additional knowledge of acid-base reactions and the carbonate
system.
CO2 + H2O + CaCO3  Ca(HCO3)2  2 HCO3- + Ca2+
CO2 + H2O  H2CO3
H2CO3  HCO3- + H+
HCO3-  CO32- + H+

pH < 4.5 All aqueous carbonate is present as H2CO3

4.5 < pH < 8.3 H2CO3 and HCO3- dominate
8.3 < pH < 12.3 HCO3- and CO32- dominate
pH > 12.3 All aqueous carbonate is present as CO32-

1
 Figure 1 relationship between pH and carbonate species

Table 1 relationship among phenolpthalein alkalinity (P), total alkalinity (T) and anion ions contributing to
hardness
Result Hydroxide Alkalinity Carbonate Alkalinity Bicarbonate Alkalinity
P=0 0 0 T
P < T/2 0 2P T-2P
P = T/2 0 2P 0
P > T/2 2P-T 2(T-P) 0
P=T T 0 0

APPARATUS
1. Magnetic stirrer and magnet bar
2. Glassware

REAGENT
Alkalinity Experiment
1. 0.02 N H2SO4 solution
2. Methyl Orange indicator
3. Phenolphthalein indicator
4. water samples

2
 PROCEDURE

Task 1 Determine Alkalinity in the water samples

1. Pipette 5.00 mL of water sample and add 3 drops of Phenolpthalein indicator.
2. Titrate with 0.02 N H2SO4 solution (pink to colorless)

Phenolpthalein Alkalinity (mg/L as CaCO3) = (A × N × 50 × 1000)/B

Where A = Volume of sulfuric acid use for titration
B = Volume of water sample
N = Sulfuric acid concentration (N)

3. In order to find total alkalinity, add 3 drops of Methy Orange indicator in the same flask and continue
titration with 0.02 N H2SO4 (colorless to orange)

Total Alkalinity (mg/L as CaCO3) = ([A+C] × N × 50 × 1000)/B

Where C = Additional volume of sulfuric acid use for titration
B = Volume of water sample
N = sulfuric acid concentration (N)

Table 3 Table of data for Phenolphthalein alkalinity

Determine hardness of three unidentified water samples
Volume of water use 5.00 mL
Concentration of Sulfuric Acid 0.02 N

Sample H2SO4 H2SO4 read after H2SO4 read A C Phenolphthalein Total Alkalinity
Name Read Titration after Titration H2SO4 volume Additional Alkalinity (mg/L of CaCO3)
before (pink to (colorless to for H2SO4 volume (mg/L of CaCO3)
Titration colorless) orange) Phenolphthalein for Total
Alkalinity Alkalinity
(mL) (mL)

Evian 19.59 19.59 19.59 0.00 0.00 0.00 0.00

Tap 19.59 20.74 20.74 1.15 0.00 230.00 230.00

Arrow 20.74 20.99 20.99 0.25 0.00 50.00 50.00
head
Crystal 20.99 20.99 20.99 0.00 0.00 0.00 0.00
Geyser

3
Graph (bar chart)

Phenolphthalein Alkalinity and Total Alkalinity of Water Samples

250

200
Alkalinity (mg/L of CaCO3)

150
Phenolphtalein
Alkalinity

Total Alkalinity
100

50

0
Evian Tap Arrowhead Crystal Geyser

Water Sample

Table 4 Alkalinity concentration contributed from different anion ions

Sample Hydroxide Alkalinity Carbonate Alkalinity Bicarbonate Alkalinity

(mg/L of CaCO3) (mg/L of CaCO3) (mg/L of CaCO3)

Evian 0.00 0.00 0.00

Tap 230.00 0.00 0.00

Arrowhead 50.00 0.00 0.00

Crystal Geyser 0.00 0.00 0.00

4
Graph (bar chart)

Alkalinity Concentration Contributed from Different Anions

250

200
Alkalinity (mg/L of CaCO3)

150 Hydroxide Alkalinity

Carbonate Alkalinity
Bicarbonate Alkalinity
100

50

0
Evian Crystal Geyser Arrowhead Tap Water
Water Sample

5
After experiment (Discussion)
1. Report all alkalinity values and types for each water sample.
a. For the Evian water sample has a zero value for the hydroxide, carbonate, and
bicarbonate alkalinities. The Tap water sample contains a value of 230 mg/L for the
hydroxide alkalinity, and zero values for the carbonate and bicarbonate alkalinities. The
Arrowhead water sample contains a value of 50 mg/L for the hydroxide alkalinity, and
zero values for the carbonate and bicarbonate alkalinities. For the Crystal Geyser water
sample has a zero value for the hydroxide, carbonate, and bicarbonate alkalinities.
2. Discuss the different of alkalinity species (types) in each sample.
a. The difference of alkalinity species in each sample only ranges by value, instead of types.
Tap water and Arrowhead water both only contain the hydroxide alkalinity where Tap
water’s value is 180 mg/L higher than Arrowhead’s. This proves that the water’s buffering
capacity against pH changes of the hydroxide ions in the Tap water is higher. All of the
other water samples (Evian and Crystal Geyser), produced zero values for all alkalinities.

b.