Name: Naraga, Joe Marie B.
Date Performed: 10/23/2019
Padaboc, Frenzes Dianne Marie N. Group No. 6
Roque, Eugenio S. III
Experiment No. 4
Total Hardness of Surface Waters
I. Background
The main characteristic of natural mineral water are the trace minerals and mineral salts that
it contains. It must be obtained directly from underground sources protected from pollution risks,
and which are highly regulated. Natural mineral water must also be packaged close to its source,
and cannot be subjected to most treatments, except for carbonation, or removal of iron and/or
magnesium (Jukes, 1999). These minerals cause the induction of the total harness of water.
Water hardness is the amount of dissolved variety of substances like polyvalent metallic
ions, predominantly calcium and magnesium cations, although other cations (e.g. aluminum,
barium, iron, manganese, strontium and zinc) also contribute (World Health Organization, 2010).
The hardness of water is commonly expressed as milligrams of calcium carbonate equivalent per
liter. General guidelines for classification of waters are: 0 to 60 mg/L (milligrams per liter) as
calcium carbonate is classified as soft; 61 to 120 mg/L as moderately hard; 121 to 180 mg/L as
hard; and more than 180 mg/L as very hard (U.S. Geological Survey, N.D.).
Complexometric titrations are often used for determination of water hardness, which is
important for brewing, distillation, and general cleaning operations in all processing facilities
(Eumann and Schaeberle, 2016 as cited by Heymann, 2017). But hard water can have some
benefits, too. Humans need minerals to stay healthy, and it states that drinking-water may be a
contributor of calcium and magnesium in the diet and could be important for those who are
marginal for calcium and magnesium intake (USGS, N.D.).
WebMD (N.D.) states that EDTA is a chemical that binds and holds on to (chelates) minerals
and metals such as chromium, iron, lead, mercury, copper, aluminum, nickel, zinc, calcium, cobalt,
manganese, and magnesium. When they are bound, they can't have any effects on the body and they
are removed from the body. Water hardness can be readily determined by titration with EDTA
(ethylenediaminetetraacetic acid). This reagent is a weak acid that can lose four H (in bold) on
complete neutralization; its structural formula is:
The four acid oxygen sites and the two nitrogen atoms have unshared electron pairs, which
can form bonds to a metal ion forming a complex ion or coordination compound. The complex is
quite stable, and the conditions of its formation can ordinarily be controlled so that it is selective
for a particular metal ion. In a titration to determine the concentration of a metal ion, the added
EDTA combines quantitatively with the cation to form the complex. The endpoint occurs when
essentially all of the cation has reacted.
This experiment, Total Hardness of Surface Water, aims to determine the total hardness
(total calcium and magnesium ion concentration); determine the Calcium and Magnesium content;
and, learn how to titrate with EDTA solution.
II. Results
Weight of pure CaCO3: 0.2544 g (0.250584g corrected)
% Purity of CaCO3: 98.5%
Total Volume of standard CaCO3 solution: 250 mL
Table 1. Standardization of EDTA solution
Trials 1 2 3
Volume of standard 25 mL 25 mL 25 mL
CaCO3 solution
(mL)
Final reading 28.7 mL 27.7 mL 27.4 mL
EDTA
Initial reading 0.8 mL 0.2 mL 0 mL
EDTA
Net volume EDTA 27.9 mL 27.5 mL 27.4 mL
Molarity of EDTA 0.00897 M 0.009105 M 0.0091378 M
Titer 0.9 0.911 0.91
mgCaCO3/mL mgCaCO3/mL mgCaCO3/mL
EDTA EDTA EDTA
Average Titer: 0.907 mgCaCO3/ mL EDTA
Average Molarity: 0.00907 M
Sample Source: Refresh Mineral Water
Ca content as CaCO3: 25.00 mg/L
Mg content as MgCO3: 35 mg/L
Table 2. Determination of the Total Hardness of Water
Trials 1 2 3
Volume of Water 50 mL 50 mL 50 mL
Sample
Volume of EDTA
Final Volume 15.2 mL 15.1 mL 30.1 mL
Initial Reading 0 0 15.1 mL
Net Volume 15.2 mL 15.1 mL 15. 0 mL
Total Hardness 275.98 mgCaCO3/L 274.16 mgCaCO3/L 272.34 mgCaCO3/L
Table 3. Determination of Total Calcium Hardness in Water
Trials 1 2 3
Volume of Water 50 mL 50 mL 50 mL
Sample
Volume of EDTA
Final Volume 34.2 mL 23.2 mL 7.1 mL
Initial Reading 30.1 mL 19.5 mL 3.9 mL
Net Volume 4.1 mL 3.7 mL 3.2 mL
Calcium Hardness 74. 45 mgCaCO3/L 67.18 mgCaCO3/L 58.10 mgCaCO3/L
Table 4. Determination of Total Magnesium Hardness in Water
Trials Total Hardness Ca content Mg content
1 275.98 mgCaCO3/L 74. 45 mgCaCO3/L 201.53 mgMgCO3/L
2 274.16 mgCaCO3/L 67.18 mgCaCO3/L 206.98 mgMgCO3/L
3 272.34 mgCaCO3/L 58.10 mgCaCO3/L 214.24 mgMgCO3/L
Average 274.16 mgCaCO3/L 66.58 mgCaCO3/L 207.58 mgMgCO3/L
Figure 1 & 2. Preparation of 0.01 EDTA solution
Figure 3 & 4. Preparation of 1000 ppm CaCO3 solution
Figure 5 & 6. Standardization of 0.01 M EDTA solution
Figure 6 & 7. Determination of Total Hardness in Water
Figure 8. Determination of Calcium Hardness in Water
III. Discussion
Standardization of EDTA solution
The EDTA solution can then be used to determine the hardness of an unknown water
sample. Since both EDTA and Ca2+ are colorless, it is necessary to use a special indicator to detect
the end point of the titration. The indicator most often used is called Eriochrome Black T, which
forms a very stable wine-red complex, MgIn– , with the magnesium ion. A tiny amount of this
complex will be present in the solution during the titration. As EDTA is added, it will complex
free Ca2+ and Mg2+ ions, leaving the MgIn– complex alone until essentially all of the calcium
and magnesium have been converted to chelates. At this point EDTA concentration will increase
sufficiently to displace Mg2+ from the indicator complex; the indicator reverts to its uncombined
form, which is sky blue, establishing the end point of the titration (ReadCivil, 2019).
In this part of the experiment, in the standardization of EDTA solution, Calcium carbonate
(CaCO3) was used as standard solution to determine the molarity of the EDTA solution. The
average molarity of EDTA was 0.00907 M EDTA. Ideally, the molarity of EDTA solution must
be 0.01 M and the experimental value, the data is approximately the same as the theoretical value.
Determination of the Total Hardness of Water
The concentration of Ca+ and Mg+ cations dissolved in water is described as the hardness of
water. Complexometric titrations are particularly useful for the determination of a mixture of
different metal ions in solution. The particular standard used in the titration is EDTA
(ethylenediaminetetraacetic acid) with has the ability to potentially donate its six lone pairs of
electrons for the formation of coordinate covalent bonds to metal ions. Titration is performed in a
pH = 10 solution by adding buffer. Ammonium buffer encourage the complexation of the Ca and
Mg ions. The indicator used in this experiment is eriochrome black T in order to determine the end
point. This indicator reacts with Mg and Ca ions as it complexes turning from red-wine color to
cobalt blue. The indicator’s effectiveness (EBT) increases when the pH of the sampled water is 10
by adding the ammonium buffer. Also ammonium buffer aids in preventing the precipitation of
the metal ions (Maghayreh, 2015).
In the experiment, the average amount of EDTA solution that was titrated was 15.1 mL,
thus, showing that the total hardness of Refresh Mineral water, the sample used, was 274.16
mgCaCO3/L. In interpreting the data, the hardness of the sampled water falls in the category of
Very hard as its Calcium carbonate content in ppm was more than 180 mg/L.
Determination of the Calcium Hardness of Water
In the complexometric titration of EDTA in determining the Calcium content, the addition
of NaOH precipitates the Mg ions leaving only Ca ions. Hence the EDTA would only complex
with Calcium ions and with this, its content will be determined. The indicator Murexide, a type of
complexometric indicator in a complexometric titration, was used as it reacts with Calcium content
of the water sample. It changes its color from pink to violet.
In this experiment, the average content of CaCO3 that was determined is 66.58 mgCaCO3/L.
Since the Magnesium ion was removed in the water sample by adding buffer, the content of
Magnesium Hardness can be determined by subtracting the Calcium Hardness to the Total
hardness and average Magnesium Hardness of the sampled water was 207.58 mgMgCO3/L.
IV. Calculation
Determining the molarity of EDTA
Trial 1
1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 1 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 25 𝑚𝐿
0.250584 𝑔 𝐶𝑎𝐶𝑂3 × 100.09 𝑔 𝐶𝑎𝐶𝑂 × ×
3 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 250 𝑚𝐿
𝑀𝐸𝐷𝑇𝐴 = = 𝟎. 𝟎𝟎𝟖𝟗𝟕 𝑴
0.0279 𝐿
Trial 2
1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 1 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 25 𝑚𝐿
0.250584 𝑔 𝐶𝑎𝐶𝑂3 × 100.09 𝑔 𝐶𝑎𝐶𝑂 × ×
3 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 250 𝑚𝐿
𝑀𝐸𝐷𝑇𝐴 = = 𝟎. 𝟎𝟎𝟗𝟏𝟏 𝑴
0.0275 𝐿
Trial 3
1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 1 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 25 𝑚𝐿
0.250584 𝑔 𝐶𝑎𝐶𝑂3 × 100.09 𝑔 𝐶𝑎𝐶𝑂 × ×
3 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 250 𝑚𝐿
𝑀𝐸𝐷𝑇𝐴 = = 𝟎. 𝟎𝟎𝟗𝟏𝟒 𝑴
0.0274 𝐿
Calculating the Titer
Trial 1
0.00897 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 100.09 𝑔 𝐶𝑎𝐶𝑂3 1000 𝑚𝑔 1𝐿
𝑇𝑖𝑡𝑒𝑟𝐸𝐷𝑇𝐴 = ( )×( )×( )×( )×( ) = 𝟎. 𝟗𝟎𝟎∗
1 𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 1𝑔 1000 𝑚𝐿
Trial 2
0.009105 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 100.09 𝑔 𝐶𝑎𝐶𝑂3 1000 𝑚𝑔 1𝐿
𝑇𝑖𝑡𝑒𝑟𝐸𝐷𝑇𝐴 = ( )×( )×( )×( )×( ) = 𝟎. 𝟗𝟏𝟏∗
1 𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 1𝑔 1000 𝑚𝐿
Trial 3
0.009137 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 100.09 𝑔 𝐶𝑎𝐶𝑂3 1000 𝑚𝑔 1𝐿
𝑇𝑖𝑡𝑒𝑟𝐸𝐷𝑇𝐴 = ( )×( )×( )×( )×( ) = 𝟎. 𝟗𝟏𝟒∗
1 𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 1𝑔 1000 𝑚𝐿
Note: * = mgCaCo3/mL EDTA
Calculation for the Total Hardness
Trial 1
0.00907 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100.09 𝑔 𝐶𝑎𝐶𝑂3 1000 𝑚𝑔
( ) × 15.2 𝑚𝐿 × (𝑀𝑜𝑙𝑎𝑟 𝑅𝑎𝑡𝑖𝑜) × ×
1000 𝑚𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 𝑔
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 𝟐𝟕𝟓. 𝟗𝟖∗∗
0.050 𝐿
Trial 2
0.00907 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100.09 𝑔 𝐶𝑎𝐶𝑂3 1000 𝑚𝑔
( ) × 15.1 𝑚𝐿 × (𝑀𝑜𝑙𝑎𝑟 𝑅𝑎𝑡𝑖𝑜) × ×
1000 𝑚𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 𝑔
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 𝟐𝟕𝟒. 𝟏𝟔∗∗
0.050 𝐿
Trial 3
0.00907 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100.09 𝑔 𝐶𝑎𝐶𝑂3 1000 𝑚𝑔
( ) × 15.0 𝑚𝐿 × (𝑀𝑜𝑙𝑎𝑟 𝑅𝑎𝑡𝑖𝑜) × ×
1000 𝑚𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 𝑔
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 𝟐𝟕𝟐. 𝟑𝟒∗∗
0.050 𝐿
Note: ** = mg CaCO3/L
1 𝑚𝑜𝑙 𝐶𝑎 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3
(𝑀𝑜𝑙𝑎𝑟 𝑅𝑎𝑡𝑖𝑜) = ×
1 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎
Calculation of Calcium Hardness
Trial 1
0.00907 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100.09 𝑔 𝐶𝑎𝐶𝑜3 1000 𝑚𝑔
( ) × 4.1 𝑚𝐿 × (𝑀𝑜𝑙𝑎𝑟 𝑅𝑎𝑡𝑖𝑜) × ×
1000 𝑚𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑜3 𝑔
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 𝟕𝟒. 𝟒𝟒∗∗
0.050 𝐿
Trial 2
0.00907 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100.09 𝑔 𝐶𝑎𝐶𝑜3 1000 𝑚𝑔
( ) × 3.7 𝑚𝐿 × (𝑀𝑜𝑙𝑎𝑟 𝑅𝑎𝑡𝑖𝑜) × ×
1000 𝑚𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑜3 𝑔
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 𝟔𝟕. 𝟏𝟖∗∗
0.050 𝐿
Trial 3
0.00907 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100.09 𝑔 𝐶𝑎𝐶𝑜3 1000 𝑚𝑔
( ) × 3.2 𝑚𝐿 × (𝑀𝑜𝑙𝑎𝑟 𝑅𝑎𝑡𝑖𝑜) × ×
1000 𝑚𝐿 𝐸𝐷𝑇𝐴 1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑜3 𝑔
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 𝟓𝟖. 𝟏𝟎∗∗
0.050 𝐿
Note: ** = mg CaCO3/L
V. Conclusion
Water hardness is due to the presence of calcium ions, and to a lesser extent, magnesium,
iron, and manganese (Huang & Miskelly, 2016). Dissolved calcium (Ca++) and magnesium
(Mg++) are the only two divalent cations found at appreciable levels in most waters. In natural
water, both calcium and magnesium primarily exist bound to bicarbonate, sulfate or chloride
(Diggs & Parker, 2009). This experiment determined the total hardness of the water sample,
Refresh Mineral Water, and its calcium and magnesium hardness. Mineral water comes from
underground reservoirs. Unlike regular drinking water, mineral water does not undergo chemical
processing. As the name suggests, mineral water contains high quantities of minerals,
especially magnesium, calcium, and sodium (Marengo & Eske, 2019).
In the experiment that was conducted, different groups have different water sample thus it
depicts different total hardness, calcium hardness and magnesium hardness. But the experimental
value of total hardness of water is somewhat far from the value it indicated in its packaging. The
total hardness or its total dissolved solids is 390.00 mg/L and in the experiment, its value was 274.
16 mg/L. It may because of some errors in conducting the experiment.
VI. References
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Maghayreh, A. M. (2015). “Determination Of Hardness of water. Jordan University of
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