INSTITUTO POLITÉCNICO DE BRAGRANÇA

CHEMICAL AND BIOLOGICAL ENGINEERING

GENERAL CHEMISTRY II

Determination of the total hardness of tap water.

Professors: António Manuel Esteves Ribeiro

Maria Filomena Filipe Barreiro

Students: Laires Araújo

Svetlana Vasilyeva

Bragança, May – 2017

SUMMARY

The main goal of this work was to determine the hardness of tap water performed by
complexiometric titration (chelatometry). In this titration, the amount of dissolved minerals
was calculated by the reaction of the EDTA and the indicator Eriochrome T with calcium
and magnesium. The water hardness obtained in this analysis was 210,2 with a standard
deviation of 0,0005.
 CONTENTS

SUMMARY .................................................................................................................................... 2
INTRODUCTION .......................................................................................................................... 4
MATERIALS AND METHODS .................................................................................................... 6
Reagents and Materials ............................................................................................................... 6
Procedures ................................................................................................................................... 6
EXPERIMENTAL RESULTS AND DISCUSSION ..................................................................... 8
CONCLUSION ............................................................................................................................... 9
REFERENCES ............................................................................................................................. 10
APPENDICE................................................................................................................................. 11
 INTRODUCTION

Water hardness is a measure of the amount of calcium and magnesium salts dissolved in
water. There are no health hazards associated with water hardness, however, hard water should
be not used for washing (it reduces effectiveness of detergents) nor in water heaters and kitchen
appliances like coffee makers (that can be destroyed by scale). It is also not good for fish tanks.
In general, there are many applications where ability to easily determine water hardness is very
important.

Water hardness is usually noticed because of difficulty in lathering soap and the formation
of a scum in the bathtub. Ca2+ and Mg2+ form insoluble salts with soaps causing precipitation
of the soap scum. Another effect of hard water is “boiler scale”. When hard water encounters
dissolved carbonates, a precipitate of insoluble calcium carbonate forms. This “scale” can build
up on the inside of water pipes to such a degree that the pipes become almost completely
blocked.

There are two types of hardness: temporary hardness and permanent hardness. Temporary
Hardness is due to the presence of bicarbonates of calcium and magnesium. It can be easily
removed by boiling.Permanent Hardness is due to the presence of chlorides and sulphateh of
calcium and magnesium. This type of hardness cannot be removed by boiling.

The ions involved in water hardness, i.e. Ca 2 (aq) and Mg 2 (aq) , can be determined by
titration with a chelating agent, ethylenediaminetetraacetic acid (EDTA), usually in the form of
disodium salt ( H 2Y 2 ). The titration reaction is:

Ca 2 (aq)  H 2 Y 2 (aq)  CaY 2 (aq)  2H  (aq)

HOOC COOH

N CH2 CH2 N


OOC COO 

EDTA (anionic form)

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 Eriochrome Black T is commonly used as indicator for the above titration. At pH 10
Ca 2 (aq) , ion first complexes with the indicator as CaIn  (aq) which is pink. As the stronger

ligand EDTA is added, the CaIn  (aq) complex is replaced by the CaY 2 (aq) complex which is
blue. The end point of titration is indicated by a sharp colour change from pink to blue. Titration
using Eriochrome Black T as indicator determines total hardness due to Ca 2 (aq) and Mg 2 (aq)
ions.

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 MATERIALS AND METHODS

Reagents and Materials

Materials:

250 mL wide mouth Erlenmeyer (6)

25 mL or
50 mL burette
600 mL precipitation beaker
250 ml precipitation beaker
100 ml precipitation beaker (2)
Flask with distilled water
1 mL graduated pipette
100 mL volumetric pipette
Micro-spatula
Pompette

Reagents:

Sample tap water

EDTA standard solution (Previously prepared)
Buffer NH4 + / NH3 buffer (previously prepared)
Black Eriochrome T (s)

Procedures

In the hotte, 1 mL (using a graduated pipette) of NH4+/NH3 buffer solution was added to

the Erlemeyer in order to adjust the pH value of the solution. Also, a micro-spatula of Eriochrome

black T was added to the solution and stirred until its dissolution.

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 A burette with the standard EDTA solution was prepared as follows:

About 50 ml of EDTA standard solution was poured into a 100 mL beaker labeled

“EDTA”.

The burette was washed by passing it twice with distilled water and then with a small

portion of EDTA (about 5 mL). For the remainder of the burette solution a 250 mL beaker was

used labeled with "EDTA waste".

After washing, the burette was filled completely by adjusting the volume to the mark,

making sure that no air bubbles have accumulated inside it, especially in the tap area. In the

laboratory notebook, the real EDTA concentration (with 4 significant digits) was written down

according to the value which was written on the respective flask.

The titration was executed by pouring EDTA solution into the water sample. When the

titration is approaching the endpoint, EDTA is added one drop at a time, with constant swirling,

until one single drop causes a permanent light blue color that does not fade on swirling. The reading

of the burette was recorded to the nearest volume with two decimal places.

Those steps (preparation of the analyte and titration) were repeated four times.

When the analysis has finished, the burette was empty and the waste was poured into the

"EDTA waste" bottle. HCl solution was used to clean the burette (about 5 mL) before rinsing

thoroughly with water to prevent EDTA to attack the glass.

The burette was disposed in the appropriate holder, inverted, with the tap open. All the

material used was cleaned properly and left on the material tray.

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 EXPERIMENTAL RESULTS AND DISCUSSION

EDTA (standard solution) concentration: 0.01117 N

Tap water (volume of the sample): 100 mL

Volume of burette: 25 mL

Water hardness average: 215,63 mol/L

Standard deviation: 0,0005

Table 1: Obtained results from the practical work.

Titrant Volume Concentration Water

Initial Final of Ca+2 and hardness
Analysis Spent volume
reading V1 reading V2 Mg+2 (N) (ppm)
V=V2-V1
(mL) (mL)
1 0.00 19.30 19.30 0,002156
2 0.00 19.30 19.30 0,002156
210,18
3 0.00 19.35 19.35 0,002161
4 0.00 19.20 19.20 0,002145

The hardness found in this practical work was 210,18 ppm or mg of CaCO3 per liter.
According to the Resolution no. 306/2007, about the quality of water intended for human
consumption, with the aim of protecting human health from the harmful effects resulting from the
possible contamination of water, recommends that the total hardness in calcium carbonate should
be between 150 mg/L and 500 mg/L CaCO3.

Table 2: Classification of the water hardness according to CaCO3 concentration (Associação

Portuguesa de distribuição e drenagem de águas, 2012).

CaCO3 concentration
Classification
g/L ppm
Soft 0 – 0.07 0 – 70
Moderately soft 0.07 – 0.135 70 – 135
Slight hard 0.135 – 0.200 135 – 200
Hard 0.200 – 0.350 200 – 350
Very hard more than 0.350 + 350
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 CONCLUSION

It was observed through this practice that the hardness of the water is related to ion concentration
dissolved, and the ions which have the most interference in this determination are calcium and
magnesium. The quantity of those ions is measured based on the concentration of CaCO3 in the
sample. To classify the hardness of a water sample, it is necessary to compare the concentration of
CaCO3 (found through complexometric titration, for example) to standard values. Although the
sample was collected from a soft water area, the water hardness found was 210,2 mg/L CaCO3.
The sample could be possibly groundwater because it has greater contact with geological
formations, therefore, greater hardness.

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REFERENCES

Camp, Ulrich De La, and Oliver Seely. “Complexometric Ca Determination.” N.p., n.d. Web. 15
Oct. 2013.

“Complexometric Titrations.” CHP. N.p., 2000. Web. 15 Oct. 2013.

Associação Portuguesa de distribuição e drenagem de águas. (2012). FT-QI-10: Dureza total

(descrição sumária), 10–12.

Decreto-Lei no 306/2007. (2007). Decreto-Lei n.o 306/2007 do Ministério Do Ambiente , Do

Ordenamento Do Território E Do Desenvolvimento Regional de 27 de Agosto sobre a regulação
da qualidade da água utilizada para consumo humano. Diário Da República: I Série, (164),
5747–5765.

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APPENDICE

Determination of the concentration of Ca+2 and Mg+2 (N):

1 [EDTA]N × VEDTA 0,01117 × 19,30

[Ca+2 + Mg+2 ]N = = = 0,002156 N
100 100

2 [EDTA]N × VEDTA 0,01117 × 19,30

[Ca+2 + Mg+2 ]N = = = 0,002156 N
100 100
3 [EDTA]N × VEDTA 0,01117 × 19,35
[Ca+2 + Mg+2 ]N = = = 0,002161 N
100 100
4 [EDTA]N × VEDTA 0,01117 × 19,20
[Ca+2 + Mg+2 ]N = = = 0,002145 N
100 100

[CA+2 + Mg+2]N: concentration of Ca and Mg ions (in N);

[EDTA]N: EDTA concentration (in N);

VEDTA: volume of EDTA spent in titration (in mL).

Determination of concentration of CaCO3 in ppm:

mol g
[CaCO3 ] = [Ca+2 + Mg+2 ] × MWCaCO3 = 0,0021 × 100,09 = 0,2101 g/L
L mol
g mg
[CaCO3 ] = 0,2101 × 1000 = 210,18 ppm (mg/L)
L g

[CaCO3]: concentration of CaCO3 (ppm or mg/L);

[CA+2 + Mg+2]: concentration of Ca and Mg ions (mol/L);

MWCaCO3: molecular weight of CaCO3.

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Determination of standard deviation:

∑ni=1|xi - x̅ | 0,00014 + 0,00014 + 0,00004 + 0,00070 + 0,00098

σ = = = 0,000489
n 4
σ – absolute standard deviation;
xi – average concentration value;
x̅ – mean of xi;
n – number of obtained values.

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