Alkalinity, Hardness,

& Lime/Soda Ash Softening

BY
Muhammad Fahad Ansari
12IEEM14

General Considerations
1. Its capacity to neutralize acids or its buffering
capacity.
2. 3 major classes of materials
A. Bicarbonates, HCO3- - pH 4.0 pH
8.3
B. Carbonates, CO3- - >pH 8.3 < pH
10
C. Hydroxide, OH- - > pH 10.0

Sanitary Significance
1. Lime/Soda Ash Softening
2. Effects on Coagulant Dosing
3. Total Dissolved Solids compliance
4. Industrial Wastes Discharges
5. Calcium Carbonate Stability

Method of Analysis
1. Phenolphthalein Alkalinity
A. Phenolphthalein indicator

Acrobat Document

B. pH 8.3 endpoint of titration

C. Measures Carbonates and Hydroxide ions
2. Total Alkalinity
A. Bromcresol green or Methyl Orange indicator
B. pH 4.5 endpoint of titration
C. Measures Bicarbonates

Methods of Expressing
1. Phenolphthalein Alkalinity as CaCO3
P. Alk. = ml 0.02N sulfuric acid (1000/ml sample) = mg/L as
CaCO3

2. Total Alkalinity as CaCO3

T. Alk. = ml 0.02N sulfuric acid X (1000/ml sample) = mg/L as
CaCO3

3. Hydroxide, Carbonate, and Bicarbonate Alkalinity as

CaCO3

Alkalinity
Relationships
Titration
Result

OHAlkalinity as
CaCO3

CO3-

HCO3-

Alkalinity as
CaCO3

Alkalinity as
CaCO3

P=0

P<1/2 T

2P

T-2P

P=1/2 T

2P

P>1/2 T

2P T

2(T- P)

P=T

Standard Solutions

General Considerations
1. Saves Time in calculating results
2. Selection of Proper Normality is convenient
* 1 mg/ml or 1000mg solution
* 1/eq.wt., example: Alkalinity as CaCO3 = 0.02 N
3. Preparation of Solution of Proper Normality
* Material of Known purity is weighed &
transferred to
volumetric flask
* Purchase Solutions of known Normality

Preparation of 1N Acid
Solution
* Sulfuric acid used for Alkalinity Test
1 GMW = 98 g pure H2SO4 = 2.016 g H+
1 GMW/2 = 49 g pure H2SO4 = 1.008 g H+
Acid is 96% pure, then 49/0.96 = 51 g = 1.008
g H+
Make 5% stronger = 51 X 1.05 = 53.5 g

Procedure: Weigh about 53g of conc. acid into a small beaker on

Trip balance. Place 500 ml of distilled water in 1-liter graduated cyl
And add the acid to it. Rinse the contents of the beaker into the cyl
With distilled water, and add water to the 1-liter mark. Mix by pouri
Back and forth from the cylinder into a large beaker. Cool to room t

Primary Standard
* Sodium Carbonate is a convenient primary standard
MW = 106 of Na2SO3
1EW or 1N = 53g/L when reacting with H2SO4 to pH 4.5, T. Alk
endpoint
Preparation of 0.02 N Acid or N/50 can be made from 1N based on
ml X N = ml X N
Example: ml X 1.0 = 1000 X 0.02
ml = 20

Alkalinity and
hardness - what is it?
Alkalinity:

a measure of the ability of a

water sample to neutralize strong acid
Expressed as mg CaCO3 per liter or microequivalents
Alkalinities in natural waters usually
range from 20 to 200 mg/L

Hardness:

a measure of the total

concentration of calcium and
magnesium ions
Expressed as mg CaCO3 per liter

Alkalinity and
hardness - how to
sample
Usually collected at
the surface in lakes
(0 to 1m depth)

Keep

the sample
cool (4oC
refrigerated) and
out of direct
sunlight

Alkalinity and hardnesswhy measure?

The

alkalinity of natural waters is usually

due to weak acid anions that can accept
and neutralize protons (mostly bicarbonate
and carbonate in natural waters).
Usually expressed in units of calcium carbonate
(CaCO3)

The

ions, Ca and Mg, that constitute

hardness are necessary for normal plant
and animal growth and survival.
Hardness may affect the tolerance of fish
to toxic metals.

Introduction to
Hardness
* Causes & Sources of Hardness

Cations causing
hardness

Anions

Ca++

HCO3-

Mg++

SO4=

Sr++
Fe++

ClNO3-

Mn++

SiO3=

* Source Rain contact with soil and rock formations

Sanitary Significance
* Reasons to Soften
1. Reduce Soap Consumption
2. Improve Aesthetics of Water
3. Hot Water Heaters last longer
* Reasons not to Soften
1. Expensive Process
2. May be less healthy
3. Competes with health related costs

Method of Analysis
* EDTA Ethylenediaminetertraacetic Acid Method

* EDTA complexes Ca & Mg

* Eriochrome Black T serves as an indicator when

EDTA is in excess of the complexed hardness
ions.
* Color change is from red to blue

Types of Hardness
* Calcium and Magnesium Hardness
* Total Hardness Calcium Hardness = Magnesium Hardness

* Carbonate and Noncarbonate Hardness

* When alkalinity < Total Hardness, CO3 Hardness = T. Alkalinity
* When alkalinity Total hardness, CO3 Hardness = T. Hardness
* CO3 hardness removed by boiling or lime (Temporary Hardness)
* Noncarbonate Hardness (permanent) = T. Hardness CO3
Hardness

* Pseudo-Hardness

* Associated with Na+ which causes soap consumption but not

considered part of hardness.

Effective Lime/Soda Ash

Water Softening
By
Douglas Rittmann, Ph.D., P.E.
Water/Wastewater Consultant
Presented to
CE 5345
On
Sept., 2006

Water Softening
I. Introduction
A. Reasons to Soften
1. Reduce Soap Consumption
2. Improve Aesthetics of Water
3. Hot Water Heaters last longer
B. Reasons not to Soften
1. Expensive Process
2. May be less healthy
3. Competes with health related costs

Water Softening
II. What is Hardness?
A. Hardness Classifications
a. Soft Water = 0 to 70 mg/L
b. Moderate Hardness = 71 to 150 mg/L
c. Hard Water = > 150 mg/L
B. T. Hardness, mg/L, as CaCO3 = (Ca X 2.5) + (Mg X 4.12)
(MW=100) (40 X 2.5 = 100) (24.3 X 4.12 = 100)
C. Carbonate Hardness as CaCO3 = T. Alkalinity as CaCO3
a. Removed by Boiling
b. Removed by Lime
D. Non-Carbonate Hardness = T. Hardness T. Alkalinity
a. Unaffected by boiling
b. Removed by Soda Ash

Water Softening
III. Methods of Softening
A. Lime-Soda Ash Chemistry
1. 1st Stage Treatment (Lime only)
a. Carbon Dioxide Removal (< 8.3 pH)
* CO2 + Ca(OH)2
CaCO3 + H2O
b. Carbonate Hardness Removal
* Ca + 2HCO3 + Ca(OH)2
2CaCO3 + 2H2O(pH 8.3-9.4)
* Mg + 2HCO3 + Ca(OH)2

CaCO3 + Mg + CO3 + 2H2O(pH >10.8)

c. Magnesium Hardness Removal (>pH 10.8)

* Mg + CO3 + Ca(OH)2

CaCO3 + Mg(OH)2

* Mg + SO4 + Ca(OH)2

Ca + SO4 + Mg(OH)2

2. 2nd Stage Treatment (Soda Ash)

* Ca + SO4 + Na2CO3
* Ca + Cl2 + Na2CO3

Na2SO4 + CaCO3

CaCO3 + 2NaCl

IV. Chemical Analyses Interpretations

A. Calcium Alkalinity = Ca Hardness or T. Alkalinity whichever is smaller
B1. Magnesium Alkalinity = Mg. Hardness if T. Alkalinity > or = than total hardness
B2. Magnesium Alkalinity = Total Alkalinity calcium hardness if total alkalinity is > than
calcium hardness but less than total hardness.
C. Sodium alkalinity = total alkalinity total hardness
D. NCH = Total Hardness Total Alkalinity ( If Mg Alkalinity present then no Ca NCH)
Analyses

Water #1

Water #2

Water #3

Total Hardness

300

300

300

Calcium
Hardness

200

200

200

Mg Hardness

100

100

100

Total Alkalinity
Interpretations

150
Water #1

250
Water #2

350
Water #3

Calcium
Alkalinity

150

200

200

Mg. Alkalinity

None

50

100

Sodium
Alkalinity

None

None

50

Ca N.C.
Hardness

50

None

None

Water Softening
V. Theoretical versus Practical
A. Theoretical Solubility of Ca & Mg:
Mg(OH)2 = 9 mg/L Solubility
CaCO3 = 17 mg/L Solubility
Total = ~ 26 mg/L Solubility
B. Practical Minimum Total Hardness = 50 to 80 mg/L
Example: Calculate the hydrated lime (100%), soda ash, and carbon dioxide requirement to
Reduce the hardness of a water with the following analysis to about 50 to 80 mg/L by the excess
Lime-soda ash process.
Analyses: Total Hardness = 280 mg/L as CaCO3
Mg++
= 21 mg/L
Alkalinity
= 170 mg/L as CaCO3
Carbon Dioxide = 6 mg/L
Lime Requirement: Carbon Dioxide = (6) (56) / (44)
= 8
Alkalinity
= (170) (56) / (100) = 95
Mg ++
= (21) (56) / (24.3) = 48
Excess Lime =
= 35
Total CaO required = 186mg/L
Soda Ash Requirement: NCH = 280 170 = 110 mg/L
Soda Ash (Na2CO3) = (110) (106) / (100) = 117 mg/L

Water Softening

Hardness is an important water quality parameter in

determining the suitability of water for domestic and
industrial uses
Hard waters require considerable amounts of soap to produce
foam
Hard waters produce scale in hot-water pipers, heaters and
boilers
Ca2+ + 2HCO3- CaCO3 (s) + CO2 (g) + H2O

Groundwater is generally harder than surface water

Principal cations causing hardness and the major anions
associated with them (in decreasing order of abundance
in natural waters)
Cations: Ca2+, Mg2+, Sr2+, Fe2+, Mn2+
Anions: HCO3-, SO42-, Cl-, NO3-, SiO32-

Water Treatment
Chemistry

Water Softening

29

Water Hardness

Hardness expressed in mg/L as CaCO3

Methods of determination
Calculation (see example)
Hardness (mg/L) as CaCO3 = M2+ (mg/L) x 50 / EW of M2+
EDTA titrimetric method
M2+ + Eriochrome Black T (blue) (M Eriochrome Black T)complex (wine red)

Water softening is needed when hardness is above 150200 mg/L; Hardness 50-80 is acceptable in treated water

Water Treatment
Chemistry

Water Softening

30

Lime-Soda [Ca(OH)2-Na2CO3]
Process:
Recarbonation by bubbling CO2 after
softening

Recarbonation is usually required after

lime-soda process
Why?

To prevent super-saturated CaCO3 (s) and Mg(OH)2

(s) from forming harmful deposits or undesirable
cloudiness in water at a later time
CaCO3 (s) + CO2 + H2O Ca2+ + 2HCO3MgCO3 (s) + CO2 + H2O Ca2+ + 2HCO3 To neutralize excessively high pH caused by Na 2CO3
OH- + CO2 HCO3-

Lime - Soda Ash

Softening
Advantages
potential for significantly reducing total
dissolved solids
removes hardness
lime added to process is removed
precipitates
soluble iron and
manganese (groundwater)
disinfection
aids in coagulation

Lime - Soda Ash

Softening
Disadvantages
large quantities of sludge
sodium remains after adding
soda ash
(however, hardness removed by
soda ash is usually a small
percentage of total hardness)

Water Softening
A. Reasons to Soften
1. Reduce Soap Consumption
2. Improve Aesthetics of Water
3. Hot Water Heaters last longer
B. Reasons not to Soften
1. Expensive Process
2. May be less healthy
3. Competes with health related costs

IV. Chemical Analyses Interpretations

A. Calcium Alkalinity = Ca Hardness or T. Alkalinity whichever is smaller
B1. Magnesium Alkalinity = Mg. Hardness if T. Alkalinity > or = than total hardness
B2. Magnesium Alkalinity = Total Alkalinity calcium hardness if total alkalinity is > than
calcium hardness but less than total hardness.
C. Sodium alkalinity = total alkalinity total hardness
D. NCH = Total Hardness Total Alkalinity ( If Mg Alkalinity present then no Ca NCH)
Analyses

Water #1

Water #2

Water #3

Total Hardness

300

300

300

Calcium
Hardness

200

200

200

Mg Hardness

100

100

100

Total Alkalinity
Interpretations

150
Water #1

250
Water #2

350
Water #3

Calcium
Alkalinity

150

200

200

Mg. Alkalinity

None

50

100

Sodium
Alkalinity

None

None

50

Ca N.C.
Hardness

50

None

None

Water Softening
V. Theoretical versus Practical
A. Theoretical Solubility of Ca & Mg:
Mg(OH)2 = 9 mg/L Solubility
CaCO3 = 17 mg/L Solubility
Total = ~ 26 mg/L Solubility
B. Practical Minimum Total Hardness = 50 to 80 mg/L
Example: Calculate the hydrated lime (100%), soda ash, and carbon dioxide requirement to
Reduce the hardness of a water with the following analysis to about 50 to 80 mg/L by the excess
Lime-soda ash process.
Analyses: Total Hardness = 280 mg/L as CaCO3
Mg++
= 21 mg/L
Alkalinity
= 170 mg/L as CaCO3
Carbon Dioxide = 6 mg/L
Lime Requirement: Carbon Dioxide = (6) (56) / (44)
= 8
Alkalinity
= (170) (56) / (100) = 95
Mg ++
= (21) (56) / (24.3) = 48
Excess Lime =
= 35
Total CaO required = 186mg/L
Soda Ash Requirement: NCH = 280 170 = 110 mg/L
Soda Ash (Na2CO3) = (110) (106) / (100) = 117 mg/L

Pb. Result of chemical analysis of a sample of raw

water is given below:
Ca++=80mg/l
Na+=2.5 m.eq/l
Total alkalinity=80mg/l
Total hardness=120mg/l
SO-4=20mg/l
Cl-=140mg/l
NO3-=5mg/l
Prepare bar chart program of raw water.
Estimate the quantity in kg/day of CaO(90%) and
Soda ash as (95% ) to softener 4 million liters of
this water.

Ion Exchange
Ion exchange is an adsorption phenomenon
where the mechanism of adsorption is
electrostatic. Electrostatic forces hold ions to
charged functional groups on the surface of the
ion exchange resin. The adsorbed ions replace
ions that are on the resin surface on a 1:1 charge
basis. For example:

Applications of ion exchange in water & wastewater

Ca, Mg (hardness removal) exchange with Na or H.
Fe, Mn removal from groundwater.
Recovery of valuable waste products Ag, Au, U
Demineralization (exchange all cations for H all
anions for OH)
Removal of NO3, NH4, PO4 (nutrient removal).

Ion Exchangers (types)

Natural: Proteins, Soils, Lignin, Coal. Metal
oxides, Aluminosilicates (zeolites)
(NaOAl2O3.4SiO2).
Synthetic zeolite gels and most common
-polymeric resins (macroreticular, large pores).