+

Lab 2
Alkalinity And Hardness

Instructor: Jeong Eun Ahn

+ Calibrating pH meter

1.

Press the Calibrate button

2.

One at a time, place the pH probe into buffers of pH 4, 7, 10

3.

Wait for pH icon stops flashing. Use arrow and functional keys (Digits, Line
Select) to adjust the number to the value of buffer solution (i.e. 4, 7 or 10)

4.

Repeat step 1, 2 and 3 for two others buffer solutions

5.

Press the Measure Save/Print button

+ 1. Alkalinity
: the quantitative capacity of an aqueous solution to
neutralize an acid
n

Measurement of the waters capability to absorb hydrogen ions/

to neutralize acid without significantly pH change

n

Amount of bases in a solution that can be converted to unchanged species by a

strong acid.

It acts as pH buffer in treatment process for water and wastewater.

Can calculate the amount of alkalinity in water by titrating the sample water with
an acid and using an indicator.

+ 1.1 Titration curve for

the carbonate system

Titration does not tell us the actual types of alkalinity present in the water.

Instead, we can report the amount of alkalinity as calcium carbonate

equivalent, which is the amount of alkalinity in terms of its equivalent
value of calcium carbonate.
12
11
10

Point of
Inflection

pH

8
7
Point of
Inflection

6
5
H+ + OH- H2O

H+ + HCO3-
H2CO3

H+ + CO32- HCO3-

3
2
3.00

2.50

2.00

1.50

1.00

0.50

0.00

mL Acid

-0.50

-1.00

-1.50

-2.00

+ 1.2 Phenolphthalein & Bromocresol green

n

Phenolphthalein and bromocresol green are two common acid/base

indicators.

Phenolphthalein's color change from pink (base) to colorless (acid) occurs

near pH 8-10

Bromocresol green's transition occurs from about pH 4 to 5.5.

As a result, a solution with pH of 6 or 7 produces the acidic color of

phenolphthalein but the alkaline color of Bromocresol green.

1.3 Step1:
+
Vacid,1, end point of titration at pH=8.3
1.
2.

3.
4.

Measure pH of sample with pH meter.

Transfer 25 ml sample to Erlenmeyer flask and add about 3 drops
of phenolphthalein indicator into flask (the pink color will be
developed).
Titrate sample with 0.02 N H2SO4 until color changes from pink
to colorless.
Record the volume used of titrant, Vacid,1. And then continue
to step 2 titration.

1.4 Step 2:
+
Vacid,2, end point of titration at pH=4.5
5.

Add 3 drops bromocresol green indicator into flask (the bluegreen color will be developed)

6.

Titrate the sample with 0.02 N H2SO4 until sample color changes
from blue-green to yellow. At this point, don't shake vigorously;
otherwise the carbon dioxide will be escaped from sample.

7.

Record the volume used of titrant, Vacid,2.

+
diagram for the carbonate system
pH 4.5;
CT [H2CO3]

pH 8.3;
CT [HCO3-]

H2CO3

pKa = 6.3;
[H2CO3] = [HCO3-]

pKa = 10.3;
[HCO3-] = [CO32-]

Modified from: Pederson, O., Colmer, T. D., Sand-Jensen, K. 2013. Underwater photosynthesis of
submerged plants recent advances and methods. Front. Plant Sci. 4(140). doi: 10.3389/fpls.2013.00140

+ 1.5

Alkalinity Species and Calculation

Alkalinity!(in!units!of!

Vacid,1
Vacid,2
N
Vsample

mg

L! CaCO! ) = !

V!"#$,! + V!"#$,! !!N!!50,000

V!"#$%&

= volume of acid added in Step 1 of the titration (mL)

= volume of acid added in Step 2 of the titration (mL)
= Normality of the standard acid (i.e., 0.02)
= sample volume (mL)

+ 1.5.1

Whats the meaning of 50,000 in the

equation of Alkalinity

Actual units for the alkalinity titration are moles or equivalents per volume

(moles/L or eq/L).
n

Converting alkalinity from eq/L to mg/L as CaCO3 takes into that one mole of
carbonate (CO32-) can neutralize 2 moles of acid H+

*CaCO3 -> Ca2+ + CO32- : 1 mole CaCO3 yields 1 mole, or 2 equivalents of Ca2+ and
CO32-

+ 2. Hardness
n

Hardness of water is caused by the presence of multivalent metallic cations

and is largely due to calcium, Ca++, and magnesium, Mg++ ions.

Primarily Hardness is measured as the concentration of Calcium and

Magnesium as mg/L of CaCO3

Total Hardness= Ca2++ Mg2+

Hardness is reported in terms of CaCO3

The simplest way to determine the hardness of water is the lather/froth

test: soap or toothpaste, when agitated, lathers easily in soft water but not
in hard water

+ 2.1 Materials
n

Ammonia buffer Solution(Be careful!)

EBT indicator : When Eriochrome Black-T complexes with Ca2+ and

Mg2+ ions, it produces a PINK-RED solution. The indicator is BLUE when the
it is not complexed with Mg2+ (equation 2) and the solution is basic.

As EDTA is added to hard water during the titration it reacts with the
divalent ions (e.g. Ca2+ and Mg2+) present in the hard water.
Once all the divalent ions in solution have reacted with EDTA, the EDTA reacts
with the Mg2+ ions that are complexed with the Eriochrome Black-T indicator,
thus causing the solution to turn BLUE.
n

EDTA

+ 2.2 Procedure
1.

Transfer 25 ml sample into an Erlenmeyer flask.

2.

Add sufficient (0.5 ~ 2 ml) ammonia buffer solution into sample

to adjust to pH 10.0

3.

Add 2 drops of EBT indicator to sample and the wine red color
will be developed.

4.

Titrate sample with 0.01 M EDTA in burette till color of sample

changes from wine red to blue. The duration of the titration should
not exceed 5 minutes.

5.

Record the volume of titrant, VEDTA.

+ 2.3 Calculation
n

Total Hardness (mg/L as CaCO3)

XCa2++Mg2+=(MolarityEDTA

VEDTA)/Vsample
n XCa2++Mg2+= molar concentration of Ca2+ + Mg2+ (mol/L)
n MolarityEDTA = 0.01 M
n VEDTA = volume of EDTA added to the sample during titration (mL)
n Vsample = volume of the sample (mL)
(mg/L as CaCO3)= (XCa2++Mg2+) MWCaCO31000 mg/g
n MWCaCO3= molecular weight of CaCO3 (g/mol)

Hardness

Calcium Hardness = Magnesium Hardness = 1/2 (Total Hardness)

+ 2.4 Carbonate hardness and

Non-carbonate Hardness
1) When alkalinity (in mg/L as CaCO3) < total hardness (in mg/L as CaCO3)
n

carbonate hardness (CH) = alkalinity

Non-carbonate hardness (NCH) = total hardness - alkalinity

2) When alkalinity (in mg/L as CaCO3) total hardness (in mg/L as CaCO3)
n

carbonate hardness (CH) = total hardness (TH)

Non-carbonate hardness (NCH) = 0

+
1.
2.

3.
4.
5.

6.
7.

Special Caution!!!
Ammonia Buffer Solution and Sulfuric Acid
Protective equipment should be worn when using sulfuric acid!
If sulfuric acid comes into contact with your skin, immediately flush the
affected area gently with lukewarm water for at least 30 uninterrupted
minutes
If sulfuric acid gets into your eyes, immediately flush the eye(s) with water
for at least 30 minutes.
If you inhale sulfuric acid aerosols, seek fresh air and medical attention
immediately.
If ammonia buffer comes into contact with your skin, immediately flush the
affected area gently with plenty of soap and water for at least 15 minutes
while removing contaminated.
If ammonia buffer gets into your eyes, immediately flush the eye(s) with
water for at least 15 minutes.
If you inhale ammonia buffer, give artificial respiration if necessary and
seek fresh air

3. Today

1. Before leaving, please clean up everything!

2. Formal laboratory report (due one week after you conduct the lab),
following the format described in the Laboratory Overview handout. Please
include answers to the following questions in the Discussion section:
n What were the total alkalinity and hardness your sample?
n Based on Table X, what was the predominant carbonate species
responsible for alkalinity in your sample? Please explain how you
came to this conclusion.
n What is the hardness of you sample (in mg/L as CaCO3)? What
hardness category does it fall in?
n Can all the hardness in your sample be attributed to carbonate
hardness?

References
n

Pederson, O., Colmer, T. D., Sand-Jensen, K. 2013. Underwater

photosynthesis of submerged plants recent advances and methods.
Front. Plant Sci. 4(140). doi: 10.3389/fpls.2013.00140

http://homepages.ius.edu/DSPURLOC/c121/week13.htm

http://www.chemicalforums.com/index.php?topic=6057.0