Exercise Alkalinity and Hardness

1. Water hardness detected in surface water is originated from the natural occurring calcium
and magnesium mineral salts dissolved from rocks and soils. What is total hardness and why do
we need to remove total hardness from water?

2. Show that total hardness in surface water can be quantified using the equation below.

Total Hardness, mg/L as CaCO3

= 2.5[Ca2+ , in mg/L as Ca2+ ] + 4.12[Mg2+ , in mg/L as Mg2+ ]

3. Based on the water quality analysis of a Sg. Langat carried out by a privatized water
company, the following parameters were obtained:-

Cation Concentration Anion Concentration

(mg/L) (mg/L)

Ca2+ 77.3 HCO3- 224.5

Mg2+ 59.5 CO32- 21.9

Fe2+ 4.8 SO42- 217.0

Fe3+ 5.5 Cl- 22.0

Na+ 7.1 - -

pH = 8.1

i. Find the total hardness (mg/L as CaCO3)

ii. Determine the cation-anion balance and list down the salts as well as their respective
concentration, in mg/L as CaCO3, involved in carbonate and non-carbonate hardness.
(Ca = 40; Mg = 24.3; Fe = 55.85; Na = 23; S = 32; Cl = 35.5; H = 1; O = 16; C = 12)

4. Do the hardness and alkalinity exercises given in the Slide on Calculation Examples
Solution:

1. Total hardness

2. Total Hardness, mg/L as CaCO3 = 2.5[Ca2+ , in mg/L as Ca2+ ] + 4.12[Mg2+ , in mg/L as Mg2+ ]

Convert Ca2+ and Mg2+ into meq/L

(mg Ca 2+ ) 1 mol Ca 2+
2+ 2 eq 2
[Ca ]   2+
= [Ca 2+ ] meq/L
L 40 g 1 mol Ca 40

(mg Mg 2+ ) 1 mol Mg 2+ 2 eq 2
[Mg 2+ ]   2+
= [Mg 2+ ] meq/L
L 24.3 g 1 mol Mg 24.3

Convert meq/L into mg/L as CaCO3

2 1 mol CaCO 3 100 g
[Ca 2+ ] meq/L   = 2.5[Ca 2+ ] mg/L as CaCO 3
40 2 eq 1 mol CaCO 3

2 1 mol CaCO 3 100 g

[Mg 2+ ] meq/L   = 4.12[Mg 2+ ] mg/L as CaCO 3
24.3 2 eq 1 mol CaCO 3

3. Total hardness = 438.4 mg/L as CaCO3

Cation meq/L Anion meq/L

Ca2+ 3.87 HCO3- 3.68

Mg2+ 4.90 CO32- 0.73

Fe2+ 0.17 SO42- 4.52

Fe3+ 0.30 Cl- 0.62

Na+ 0.31

Total 9.55 Total 9.55

 0.0 3.87 8.77 8.94 9.24 9.55

Ca2+ Mg2+ Fe2+ Fe3+ Na+

HCO3- CO32- SO42- Cl-

0.0 3.68 4.41 8.93 9.55

Carbonate Hardness
Ca(HCO3)2 = 3.68 meq/L = 184 mg/L as CaCO3
CaCO3 = 0.19 meq/L = 9.5 mg/L as CaCO3
MgCO3 = 0.54 meq/L = 27.0 mg/L as CaCO3

Non-carbonate Hardness
MgSO4 = 4.36 meq/L = 218.0 mg/L as CaCO3

• If a water contain 29 mg/L of Ca++ and 16.4 mg/L of Mg++, what is the hardness expressed
in miligrams per liter as CaCO3 ?

mg/L of X as CaCO3 = Concentration of X (mg/L) x (50 mg/L CaCO3/meq)

Equivalent weight X (mg/meq)

= 29 x 50 + 16.4 x 50
20 24.3/2

= 72.5 + 67.5

= 140 mg/L

• If a water contains 175 mg/L of magnesium hardness and 40 mg/L of calcium hardness,
what are the concentrations of Ca++ and Mg++ ions?

Mg++ Concentration = Magnesium hardness / 4.12

= 175 / 4.12

= 42.48 mg/L
 Ca++ Concentration = Calcium hardness / 2.5

= 40 / 2.5

= 16 mg/L

• The alkalinity of a water consists of 12 mg/L of CO=3 and 100 mg/L of HCO-3. Calculate
the alkalinity in miligrams per liter as CaCO3.

mg/L of X as CaCO3 = Concentration of X (mg/L) x (50 mg/L CaCO3/meq)

Equivalent weight X (mg/meq)

= 12 x 50 + 100 x 50
60/2 61

= 20 + 81.97

= 101.97 mg/L

• If a water contains 20 mg/L of CO=3 and 34 mg/L of HCO3, what is the alkalinity as CaCO3?

mg/L of X as CaCO3 = Concentration of X (mg/L) x (50 mg/L CaCO3/meq)

Equivalent weight X (mg/meq)

= 20 x 50 + 34 x 50
60/2 61

= 33.33 + 27.87

= 61.2 mg/L