CE 3131

CE 3131
Environmental Analysis
y

Lab 5 Hardness
Lab 5. Hardness

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 Water Hardness

H d
Hardness: d
degree off mineral
i l content
t t (in
(i contrast
t t with
ith soft
ft water).
t ) Hard
H d water
t
minerals primarily consist of calcium (Ca2+), and magnesium (Mg2+) metal cations, and
p
sometimes other dissolved compounds such as bicarbonates and sulfates.

Total hardness = Ca++ + Mg++ + ion>++ as CaCO3 mg/l

Hardness mg/l as CaCO3

Soft 0 – 60
Moderately Hard 61 – 120
Hard 121 – 180
Very Hard 181 - 350
Brackish Above 350

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 Water Hardness
- For purposes of water supply calculations, substances are expressed as CaCO3
equivalent even.
The conversion can be expressed as :

EW of CaCO3
Subs tan ce (mg / L) 
EW of subs tan ce

Why this equation? (mole concept and charge)

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 Hardness

Determine:
(1) Total hardness
(2) Carbonate hardness
(3) Non-carbonate hardness

Results of Chemical Analysis:

Ca2+ = 80 mg/1
Mg2+ = 24.4 mg/1
Alkalinity (HCO3)- = 150 mg/L as CaCO3
SO4- = 144 mg/1
Na+ =11.5 mg/1
Cl- = 17.8 mg/1

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 Hardness
Results of Chemical Analysis:
Ca2+ = 80 mg/1
Mg2+ = 24.4 mg/1
Na+ =11.5
=11 5 mg/1
Alkalinity (HCO3)- = 150 mg/1 as CaCO3
SO4- = 144 mg/1
EW of CaCO3
Cl- = 17.8 mg/1 Subs tan ce (mg / L) 
EW of subs tan ce

Only the divalent Cations, Ca2+ and Mg2+, cause hardness:

MW EW EW of CaCO3 Conc. mg/L as CaCO3
mg/L
g/
Ca2+ 40 40/2=20 50 80 80*50/20=200
Mg2+ 24.2 24.2/2=12.2 50 24.4 24.4*50/12.2=100
T t l 300 mg/L
Total 300 /L

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Substance Factor Substance Factor Substance Factor
Al+++ 5.56 HCO3¯ 0.82 (alkalinity) SO4 - - 1.04
Al2( SO4)3 0.88 K+ 1.28 Zn+ + 1.54
AlCl3 1.13 KCl 0.67
Al(OH)2 1 92
1.92 K2CO3 0 72
0.72
Subs tan ce mg / L
Ba++ 0.73 Mg++ 4.10  EW of CaCO3
EW of subs tan ce
Ba(OH
( )2
) 0.59 MgCl2
g 1.05
EW of CaCO3
BaSO4 0.43 MgCO3 1.19 EW of subs tan ce
Ca++ 2.50 Mg(HCO3)2 0.68
CaCO3 1.00 MgO 2.48
Ca(HCO3)2 0.62 Mg(OH)2 1.71
CaO 1 79
1.79 Mg(NO3)2 0 67
0.67
Ca(OH)2 1.35 MgSO4 0.83

Multiply the mg/l of the substances listed below by the corresponding factors to
obtain mg/l as CaCO3. For example, 70 mg/l of Mg++ would be (70) (4.10) = 287
mg/l as CaCO3.
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 Hardness

(1) Total hardness = 300 mg/1 as CaCO3 Alkalinity (HCO3)- = 150 mg/1 as CaCO3

Carbonate and Non-Carbonate hardness:

Case I: When alkalinity < total hardness: carbonate hardness (mg/l) = alkalinity (mg/l)

Case II: When alkalinity >= total hardness: carbonate hardness (mg/l) = total hardness

(mg/l)

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 Hardness

(1) Total hardness = 300 mg/1

/1 as C
CaCO3
CO3 Alk li i (HCO3)- = 150
Alkalinity 1 0 mg/1
/1 as C
CaCO3
CO3

Carbonate and Non-Carbonate hardness:

Case I: When alkalinity < total hardness: carbonate hardness (mg/l) = alkalinity (mg/l)

Case II: When alkalinity >= total hardness: carbonate hardness (mg/l) = total hardness

(mg/l)

Alkalinity < total hardness

Carbonate hardness = alkalinity = 150 mg/l as CaCO3
(2) C
Carbonate
b t hhardness
d = 150 mg/l
/l as C
CaCO3
CO3
Non-Carbonate hardness (NCH) = total hardness – carbonate hardness
g as CaCO3
NCH = 300 - 150 = 150 mg/l
(3) Non-carbonate hardness = 150 mg/l as CaCO3
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 Lab Procedure
Sample
Creek Water (Alkalinity)

•Dilute 25 mL of sample to 50 mL using distilled water in an beaker.
•Add 1‐2 mL buffer solution. **Titration should be completed within 5 minutes of the 
addition of this buffer
addition of this buffer.
•Add 1‐2 drops of indicator solution (Eriochrome Black T or Calmagite: Red).
•Add standard EDTA solution drop wise, with continuous stirring, until the color change 
endpoint is reached (Blue).
•Record the amount of EDTA titrant used.

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 Lab Theory
- The quantity of “hardness ions” will be determined by titration.
- Add an indicator (Calmagite). Initially, the indicator will form a complex
with the cations. When complexed it is red in color.
-Add EDTA. In its ionized form, it is able to form soluble complexes with
calcium and magnesium cations, preferentially than Black T(as the EDTA
is added dropwise to the sample, it replaces the Calmagite and forms more
stable complexes with calcium and magnesium)
- When the indicator is released by the metal ions, it has a distinct blue
color.
color
- Therefore, the endpoint of the titration is marked by the color change form
ed to b
red blue.
ue

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 Background Reaction
(1) Plenty of Ca2+ (Mg2+) in
water.
Ca2+
Ca2
C 2
Ca2+

Ca2+
Ca2+

Ca2+
o Ca2+

Ca2+ Ca2+

Ca2+
Ca2+

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 Background Reaction
(1) Plenty of Ca2+ (Mg2+) in
water.
Ca2+ CMG
Ca2
C 2
Ca2+ (2) Adding small amount of
indicators (calmagite, CMG).
Ca2+ - Making Ca2+/CMG complex, of
Ca2+
which color is red.
Ca2+ - This is starting point.
o Ca2+

Ca2+ CMG Ca2+

Ca2+
Ca2+

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 Background Reaction
(1) Plenty of Ca2+ (Mg2+) in
water.
Ca2+ CMG
Ca2
C 2
Ca2+ (2) Adding small amount of
indicators (calmagite, CMG).
Ca2+ - Making Ca2+/CMG complex, of
Ca2+ EDTA
which color is red.
Ca2+ - This is starting point.
o Ca2+
(3) Titration with EDTA chemical.
- Making Ca2+/EDTA.
Ca2+ CMG Ca2+

Ca2+ EDTA
Ca2+

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 Background Reaction
(1) Plenty of Ca2+ (Mg2+) in
water.
Ca2+ CMG
Ca2
C 2 EDTA
Ca2+ (2) Adding small amount of
indicators (calmagite, CMG).
Ca2+ EDTA - Making Ca2+/CMG complex, of
Ca2+ EDTA
which color is red.
Ca2+ EDTA - This is starting point.
o Ca2+ EDTA
(3) Titration with EDTA chemical.
- Making Ca2+/EDTA.
Ca2+ CMG Ca2+ EDTA - Adding EDTA more over time.
- After this, ???

Ca2+ EDTA
Ca2+ EDTA

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 Background Reaction
(1) Plenty of Ca2+ (Mg2+) in
CMG
water.
Ca2+ EDTA
Ca2
C 2 EDTA
Ca2+ (2) Adding small amount of
indicators (calmagite, CMG).
Ca2+ EDTA - Making Ca2+/CMG complex, of
Ca2+ EDTA
which color is red.
Ca2+ EDTA - This is starting point.
o Ca2+ EDTA
(3) Titration with EDTA chemical.
- Making Ca2+/EDTA.
Ca2+ EDTA Ca2+ EDTA - Adding EDTA more over time.
- Competition for Ca2+:
CMG
EDTA>>CMG
Ca2+ EDTA
- CMG is present (no complex),
Ca2+ EDTA which is blue.
-Titration ending point.

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 Calculation
Sample
Creek Water (Alkalinity)

From given/measured ionic species (all concentrations are mg/L as CaCO3):

TH (total hardness) = (Ca2+) + (Mg2+)

CH (carbonate hardness) = lesser of TH and alkalinity

CH (carbonate hardness)  lesser of TH and alkalinity

NCH (noncarbonate hardness) = TH – CH

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