EXPERIMENT 2 : Determgcnation of Water Hardness by Atomic absorption

spectroscopy (AAS)

INTRODUCTION

Water hardness is defined as the total concentration of alkaline earth metal ions in water.

Because the concentrations of Ca2+ and Mg2+ are usually much higher than those of other

alkaline earth ions, hardness can be equated to [Ca2+] + [Mg2+]. Individual hardness refers

to the individual concentration of each alkaline earth ion. Hardness is commonly expressed as

the equivalent number of milligrams of CaCO3 per liter.

Thus, if [Ca2+] + [Mg2+] = 1 mM, we would say that the hardness is 100 mg CaCO3 per

liter (because 1 mmol CaCO3 = 100 mg CaCO3). Water whose hardness is more than 60 mg

per liter is considered to be "hard". Sometimes, hard water is considered "bad". For example,

it causes the formation of scale in a water boiler or heater, and it consumes soap that would

otherwise be useful for cleaning. However, it is not believed that "hard" water is unhealthy.

Hardness can be determined by many methods such as EDTA titration, and atomic absorption

and emission spectrophotometry. In this experiment, flame atomic absorption

spectrophotometry (AAS) to determine the concentrations of Ca2+ and Mg2+ in tap water,

mineral water and in three unknown samples.

PROCEDURE

1. Seven 50 ml of Ca standard solutions of 0.1, 0.2, 0.5, 1.0, 1.5, 3.0 and 5.0 ppm by

dilution of the 100 ppm Ca stock solution by using deionized water was prepared.

2. Seven 50 ml of Mg standard solutions of 0.1, 0.2, 0.5, 1.0, 1.5, 3.0 and 5.0 ppm by

dilution of the 100 ppm Mg stock solution by using deionized water was prepared.

3. The spectrophometer was set up as described in the operating instructions.

4. The emission intensity of the standards, tap water, mineral water and the unknown

samples are measure.

DATA

1. Instrument:

1. Type of instrument: Atomic Absorption Spectrometry (AAS)

2. Brand of instrument: Agilent Technologies

3. Method file name: (attach the method file with the report)

4. Scanning parameters :

i. Wavelength : 202.6nm
ii. Slid width : 1.0nm
iii. Lamp current : 4.0mA
2. Emission data:

i. Wavelength for Mg measurement: 202.6nm

Sample name [Mg2+] [Ca2+] Intensity Intensity

Standard 2 0.2 0.2 0.0195 0.0464

Standard 3 0.5 0.5 0.0368 0.0455

Standard 4 1 1.0 0.0658 0.0991

Standard 5 1.5 1.5 0.0929 0.1389

Standard 6 3.0 3.0 0.1665 0.2838

Standard 7 5.0 5.0 0.2994 0.4686

Tap H2O 1.02 7.11 0.0655 0.6564

Mineral H2O 2.64 14.50 0.1584 1.3265

Unknown 2 1.736 1.987 0.1065 0.1917

1. Plot the intensity versus concentration of standard solutions. Obtain the slope of the

calibration curve.

Graph 1 : Calcium

The slope of the calibration curve is 0.0907

Graph 2 : Magnesium

The slope of the calibration curve is 0.0571

unknown samples using the slope of the calibration curve.

Calcium

1) Tap water
From graph 1,
y = 0.0907x + 0.0115
Intensity of Ca in tap water, y = 0.6564

Therefore,
0.6564−0.0115
concentration of Ca in tap water, x = = 7.11mg/L
0.0907
7.11−7.09
% of error = | | x 100% = 0.28%
7.09

2) Mineral water
From graph 1,
y = 0.0907x + 0.0115
Intensity of Ca in mineral water, y = 1.3265

Therefore,
1.3265−0.0115
concentration of Ca in mineral water, x = = 14.50 mg/L
0.0907
14.50−14.46
% of error = | | x 100% = 0.28%
14.46

3) Unknown 2
From graph 1,
y = 0.0907x + 0.0115
Intensity of Ca in unknown 2, y = 0.1917

Therefore,
0.1917−0.0115
concentration of Ca in unknown 2 , x = = 1.987 mg/L
0.0907
1.987−1.985
% of error = | | x 100% = 0.10%
1.985
Magnesium

1) Tap water

From graph 2,
y = 0.0571x + 0.0074
Intensity of Mg in tap water, y = 0.0655

Therefore,
0.0655−0.0074
concentration of Mg in tap water, x = = 1.02 mg/L
0.0571
1.02−1.03
% of error = | | x 100% = 0.97%
1.03

2) Mineral water

From graph 2,
y = 0.0571x + 0.0074
Intensity of Mg in mineral water, y = 0.1584

Therefore,
0.1584−0.0074
concentration of Mg in mineral water, x = = 2.64 mg/L
0.0571
2.64−2.65
% of error = | | x 100% = 0.38%
2.65

3) Unknown 2

From graph 2,
y = 0.0571x + 0.0074
Intensity of Mg in unknown 2, y = 0.1065

Therefore,
0.1065−0.0074
concentration of Mg in mineral water, x = = 1.736 mg/L
0.0571
1.736−1.747
% of error = | | x 100% = 0.63%
1.747
3. Calculate the hardness of the water samples.

Water hardness (mg/L) = Ca (mg/L) x 2.497 + Mg (mg/L) x 4.118

Tap water

Water hardness = 7.11 (2.497) + 1.02 (4.118) = 21.954 ppm

Mineral water

Water hardness = 14.50 (2.497) + 2.64 (4.118) = 47.078 ppm

Unknown 2

Water hardness = 1.987 (2.497) + 1.736 (4.118) = 12.110 ppm

Hard water is a water that contains minerals such as calcium and magnesium. Soft water is
treated water that contains only sodium ions. Based on the result of the hardness of the water
samples, mineral water is the hardest between the tap water and the unknown. The mineral
water is classified as slightly hard water in this experiment, whereas, tap water and unknown
are both classifies as soft water. The difference in hardness between tap water and mineral
water is because of the higher level of concentration of magnesium and calcium ions in the
water.

For emission spectrometry, there are 2 type of sources which is plasma and flame.
A plasma is a hot, partially ionized gas that contains an abundant concentration of cations and
electrons. The plasmas used in atomic emission are formed by ionizing a flowing stream of
argon gas, producing argon ions and electrons. A plasma’s high temperature results from
resistive heating as the electrons and argon ions move through the gas. Because plasmas
operate at much higher temperatures than flames, they provide better atomization and a
higher population of excited states. As compared to flames, inert atmosphere in plasma
results in exclusion of oxides. Next is uniform temperature which results in precise
determinations. It is well adapted to multichannel analysis. It is also has minimum chemical
and spectral interferences except for higher possibility of spectral line interference due to
exceedingly large number of emission lines (because of high temperature).

Lastly, there are a few possible interferences encountered while conducting the experiment.
In calculation part, there are deviation in values of calculated concentration of magnesium
and calcium in the three type of water from the theoretical values. This deviation caused by
systematic error. This error might be encountered while preparing the standard solutions
which the pipet used is poorly calibrated and measuring volume by reading a
meniscus (parallax). This error can be avoided by place eyes at the level of the appropriate
measurement marking when measuring the level of a liquid in a graduated cylinder.

CONCLUSION

In conclusion, the water samples obtained from the experiment have different hardness.
Mineral water is the hardest followed by tap water and unknown. More filtered and cleaned
water will be softer and will contain the least amount of Ca2+ ad Mg2+ ions.