IslamicUniversityofGazaEnvironmentalEngineeringDepartment

Water Treatment WaterTreatment

Ca(Soap)
2 (s)
(soapscum)
Thisincreasetheamountofsoapneededfor
washing
causescalingonpipesandhotboilers.
cause valves to stick due to the formation of causevalvestostickduetotheformationof
calciumcarbonatecrystals
leavestainsonplumbingfixtures
2
p g
6.HardnessandSofteninginwaterTreatment
Figure 6.1:
3
Figure6.1:
Scalingduetocalcium andmagnesium
precipitation
6.HardnessandSofting inwaterTreatment
B. Hardnessisdefinedasthesumofthedivalent
metalcations(inconsistentunits)existingin
watersuchas:
2 2 2 2
Ca
2+
,Mg
2+
,Fe
2+
,Mn
2+
Practically most hardness is due to Ca
2+
Mg
2+
PracticallymosthardnessisduetoCa
2+
,Mg
2+
ions(thepredominantmineralsinnaturalwaters)
C Total Hardness = Ca
2+
hardness+ Mg
2+
hardness C. Total Hardness=Ca
2+
hardness+Mg
2+
hardness
wheretheconcentrationofeachionisin
consistent units such as mg/L as Ca CO or consistentunitssuchasmg/LasCaCO
3
,or
meq/L.
4
6.HardnessandSofteninginwaterTreatment
D Hard water classification D.Hardwaterclassification
Description Hardness range
(mg/ L as CaCO
3
)
Soft 0 - 75
Moderately hard 75 - 100
Hard 100 - 300 Hard 100 300
Very hard > 300
5
6.HardnessandSofteninginwaterTreatment
E Formation of Hardness E.FormationofHardness
Precipitation
Topsoil
CO +H O H CO3
Subsoil
CO
2
+ H
2
O H
2
CO3
Limestone
CaCO
3(s)
+ H
2
CO
3
Ca(HCO
3
)
2
M CO H CO M (HCO ) MgCO
3(s)
+ H
2
CO
3
Mg(HCO
3
)
2
6
6.HardnessandSofteninginwaterTreatment
F.CarbonateandnoncarbonateHardness
CarbonateHardness(CH)
Ca
2+
,Mg
2+
associatedwithHCO
3

,CO
3
2
Oft ll d "t h d " b Oftencalled"temporaryhardness"because
heatingthewaterwillremoveit.Whenthe
waterisheated,theinsolublecarbonateswill ,
precipitateandtendtoformbottomdepositsin
waterheaters.
Non Carbonate Hardness ( NCH) NonCarbonateHardness(NCH)
Ca
2+
,Mg
2+
associatedwithotherions,Cl

,NO
3

,
SO
4
2
NCH=TH CH
7
6.HardnessandSofteninginwaterTreatment
F.HardnessUnits
TotalHardness=(Ca
2+
+Mg
2+
)
Thehardnessunitisthesameasthatconsistentunit usedforbothoftheabove
ions.Themostusedunitsare:
( )
CaCO of EW
species as mg/L CaCO as mg/L
3
= ( )
species of EW
species as mg/L CaCO as mg/L
3
=
Where,
EW=equivalentweight
S i I R di l C d Species=IonorRadicalorCompound
Radical:suchasCO
3
2
,SO
4
2
Compounds: such as CO CaSO
8
Compounds:suchasCO
2
,CaSO
4
6.HardnessandSofteninginwaterTreatment

Ch El t i l
MW
EW =
For radicals and
compounds

Valance
MW
EW =
Charge Electrical
compounds
Forions
Valance
MW=molecularweightoftheSpecies
Example3.1: a) FindtheEWofMg
2+
thathasaconcentrationof10mg/Las
h b) d h f ) f d f
2
/ theioninwater.b) FindtheEWofCaCO
3
c) findconcentrationofMg
2+
asmg/L
CaCO
3
.
a) Finding the EW for Mg
2+
:

mmole
mg
24.3 MW =

mole
g
24.3 MW =
eq 2 meq 2
a) FindingtheEWforMg :

mole
eq 2
(n) Valance =
mmole
meq 2
(n) Valance =
]
meq/mmole 2
1
[ .
mmole
mg 24.3
EW =

meq
mg
12.15 EW =

V l
MW
EW =
9
meq/mmole 2 mmole
meq
Valance
6.HardnessandSofteninginwaterTreatment
b) Finding the EW for CaCO
3
:

mmole
mg
100 MW =

mole
g
100 MW =
b) FindingtheEWforCaCO
3
:
mmole
mole

mole
eq 2
(n) charge Electrical =

mmole
meq 2
charge Electrical =

Charge Electrical
MW
EW =
mole
]
meq/mmole 2
1
[ .
mmole
mg 100
EW =

meq
mg
50 EW =
Charge Electrical
meq/mmole 2 mmole
meq
D) FindingtheMg
2+
concentrationasCaCO
3
:
( )
CaCO of EW
i /L C CO /L
3
2+
( )
species of EW
species as mg/L CaCO as mg/L
3
3
=
3
CaCO as mg/L 1.15 4
( )
mg/meq 1215
mg/meq 50
2 Mg as mg/L 10 CaCO as mg/L in ) (Mg2
3
+ = +
Mg
2+
conc.
10
3
g
mg/meq 12.15
Ground
Water Water
RapidMixing Flocculation
Sedimentation
Recarbonation
Distribution Disinfection
Storage
Filtration
Figure6.2:SofteningTreatmentPlantSinglestage
softening softening
11
6.HardnessandSofteninginwaterTreatment
6.2 Relation between Alkalinity and hardness: y
A.DefinitionofAlkalinity
Alkalinity is a very important parameter in water chemistry and Alkalinityisaveryimportantparameterinwaterchemistryand
relatedverycloselytohardnessandsofteningprocess.The
followingequationisusedtomeasurethealkalinityinwater:
Alk li it (HCO ) (CO
2
) (OH ) (H
+
) - Alkalinity=(HCO
3

)+(CO
3
2
)+(OH

) (H
+
)
Wheretheconcentrationsareinmeq/Lormg/LasCaCO
3
Usually the (OH

) and (H
+
) are negligible. Usuallythe(OH )and(H )arenegligible.
Therelationbetweenthealkalinityspecies isgivenbythefollowingthree
equations:

[HCO3-]
] ][CO [H
10
2
3
10.33 -
+
=
| | | | OH H 10
-14 +
- =
| |
pH
10 H
+
=
,
,
12
Wheretheconcentrationsaremoles/Linthesethreeequations
VariousFormsofalkalinityandCO
2
relativetopHinwaterat25
o
C.
13
6.HardnessandSofteninginwaterTreatment
l
A sample of water having a pH of 7 2 has the
Example6.1:
AsampleofwaterhavingapHof7.2hasthe
followingconcentrationsofions
Ca
2+
40 mg/L Ca 40mg/L
Mg
2+
10mg/L
Na
+
11.8mg/L
K
+
7.0 mg/L K 7.0mg/L
HCO
3

110mg/L
SO
4
2
67.2mg/L
Cl

11mg/L g/
Constructabarchartoftheionsintermofmg/LCaCO
3
CalculatetheTH,CH,NCH,Alkalinity
14
6.HardnessandSofteninginwaterTreatment
Example 6 1: Example6.1:
Ion Conc.
mg/L
M.W.
mg/mmol
(n(
Eq. Wt.
mg/meq
Conc.
meq/L
Conc.
mg/L as mg/L mg/mmol mg/meq meq/L mg/L as
CaCO
3
Ca
2+
40.0 40.1 2 20.05 1.995 99.8
Mg
2+
10.0 24.3 2 12.15 .823 41.2
Na
+
11.8 23.0 1 23.0 .51 25.7
K
+
7 0 39 1 1 39 1 179 8 95 K
+
7.0 39.1 1 39.1 .179 8.95
HCO
3
-
110.0 61.0 1 61.0 1.80 90.2
SO
4
2-
67 2 96 1 2 48 05 1 40 69 9 SO
4
67.2 96.1 2 48.05 1.40 69.9
Cl
-
11.0 35.5 1 35.5 .031 15.5

15
6.HardnessandSofteninginwaterTreatment
Check The ionic balance: Check The ionic balance:
E(cations) = E(anions)
175.6=175.6mg/LasCaCO
3
O.K
3 51 3 23 /L O K 3.51=3.23meq/LO.K
Note: (errorintherangeof10%isaccepted)
Note:onecheckisenough(eitheras{mg/LasCaCO3}oras{meq/L} )
TotalHardness =E (Ca
2+
)+(Mg
2+
)=99.8+41.2
TH=141mg/LasCaCO
33
orTH=1.995+0.823=2.818meq/L
16
6.HardnessandSofteninginwaterTreatment
Alkalinity=(HCO
3

)+(CO
3
2
)+(OH

) (H
+
)
a. SincepH=7.2
[H
+
]=10
pH
=10
7.2
mole/L=10
7.2
g/L

g/eq 1
/L H g 10
eq/L
-7.2 +
=
| | | |
14
| |
72 14
( ) eq/L 10 H
-7.2
=
+
| |
68
| | | | OH H 10
-14 +
- =
| | OH 0 1 10
-7.2 -14
- =
=
b.
| | g/L 10 * 17 mole/L 10 OH
-6.8 -6.8
= =

g/eq 17
/L OH g 10 * 17
eq/L
-6.8
= ( ) eq/L 10 OH
-6.8 -
=
| | mole/L 10 OH
-6.8
=

C. (HCO
3

) =1.80meq/L=1.80*10
3
eq/L fromthisexamplecalculations
asinthetable.
g/L as HCO
3

= EW * eq/L = (61 g/eq) * 1.80 *10

] =(109.8*10
3
g/L)/(61g/mole)=1.80*10
3
mole/L
17
6.HardnessandSofteninginwaterTreatment
d Find the carbonate concentration:

[HCO3-]
] ][CO [H
10
2
3
10.33 -
+
=
10 x 1.8
] x[CO 10
10
3 -
2
3
-7.2
10.33 -

=
d. Findthecarbonateconcentration:
[CO
3
2
]=1.33x10
6
mole/L=79.8x10
6
g/L
/L g 10 * 79.8
eq/L
-6
=
CO
2
in
=2.66x10
6
eq/L
g/eq 30
eq/L =
CO
3
in
q/
3 6 6 8 7 2 3
/ Alkalinity=(1.80x10
3
)+(2.66x10
6
)+10
6.8
10
7.2
=1.801x10
3
eq/L
Alkalinity=1.801x10
3
x1000x50=90.1mg/LasCaCO
3
Note:itisclearthatthemosteffectiveformofalkalinityisbicarbonate,
thisisalwaystruewhenthepHis8.3orless.
18
6.HardnessandSofteninginwaterTreatment
Carbonate Hardness CarbonateHardness
theportionofthehardnessassociatedwithcarbonateorbicarbonate
Alkalinity=90.1mg/LasCaCO
3
TH =141mg/LasCaCO
3
CH =90.2mg/LasCaCO
3
NoncarbonateHardness:
NCH =TH CH
=141 90.1=50.9mg/LasCaCO
3
19
6.HardnessandSofteninginwaterTreatment
Construct the bar chart of the ions in term of mg/L CaCO
3
Constructthebarchartoftheionsintermofmg/LCaCO
3
99 8 141 166 7 175 6 0 0
TH
Na
+
99.8 141 166.7 175.6
Ca
2+
Mg
2+
K
+
HCO
3

SO
4
2
Cl

0.0
90.2 160.1 0.0 175.6
CH NCH
CaSO
4
MgSO
4
Na
2
SO
4
NaCl
KCl
Note: thechemicalsatthelowerlineof thebargraphiscalledthehypothetical
combination ofpositiveandnegativeionsinthewatersample
20
6.HardnessandSofteninginwaterTreatment
6.3Softeningdefinition: g
a) Softening isthechemicalprocessesinwhichhardness
causingions(Ca
2+
,Mg
2+
)areremovedfromwaterether
completely or partially completelyorpartially.
b) Softeningmaybeachiviedbychemicalprecipitationusing
theLime SodaAsh methodorbyionexchange.
c) Inthechemicalprecipitationmethodtheobjectiveisto
produceCaCO
3
andMg(OH)
2
:
Ca
2+
+ CO
3
2
2CaCO
3( )
Ca +CO
3
2CaCO
3(s)
Mg
2+
+2OH

Mg(OH)
2(s)
These two reactions are achieved by the Thesetworeactionsareachievedbythe
additionofLime[Ca(OH)
2
]andSodaash[
Na
2
CO
3
] as will be shown
21
Na
2
CO
3
]aswillbeshown.
6.HardnessandSofteninginwaterTreatment
f) Acommonwatertreatmentgoalistoprovidea ) g p
waterwithahardnessintherangeof75to120mg/L
asCaCO
3
g) ToprecipitateCaCO
3
andMg(OH)
2
weneedtoraisethepHto10.3by
theadditionofLime[Ca(OH)
2
].TheadditionoftheOH
ill t HCO

t CO
2
willconvertHCO
3

toCO
3
2
h) ToprecipitateMg(OH)
2
weneedtoraisethepHto11bytheaddition
f Soda ash [ Na CO ] This will add the CO
2
ion ofSodaash[Na
2
CO
3
].ThiswilladdtheCO
3
2
ion
neededtoreactwiththeremainingCa
2+
i) Some of theadded lime [Ca(OH) ] is consumed to i) Someoftheaddedlime[Ca(OH)
2
]isconsumedto
removeCO
2
whichisnecessarytoraisethepH.
22
6.HardnessandSofteninginwaterTreatment
6.4ChemistryofLime SodaAshSoftening
softeningreactions
Neutralizationofcarbonicacid
[ToraisethepHweneedfirsttoneutralizeanyacidinthewater]
CO
2
+Ca(OH)
2
CaCO
3(s)
+H
2
O
PrecipitationofCHduetocalcium:
[ToraisethepHto10.3alltheHCO
3

isconvertedtoCO
3
2
]
Ca
2+
+2HCO
3

+Ca(OH)
2
2CaCO
3(s)
+2H
2
O
Precipitation of CH due to magnesium PrecipitationofCHduetomagnesium
[ToraisethepHto11addmorelime]
Mg
2+
+2HCO
3

+Ca(OH)
2
Mg
2+
+CO
3
2
+CaCO
3(s)
+2H
2
O
Mg
2+
+ CO
2
+ Ca(OH) MgOH + CaCO Mg
2+
+CO
3
2
+Ca(OH)
2
MgOH
2(s)
+CaCO
3(s)
23
6.HardnessandSofteninginwaterTreatment
6.4ChemistryofLime SodaAshSoftening
RemovalofNCHduetocalcium
Ca
2+
+SO
4
2
+ Na
2
CO
3
CaCO
3(s)
+2Na
+
+SO
4
2
Ca
2+
+2Cl
1
+ Na
2
CO
3
CaCO
3(s)
+2Na
+
+2Cl
1
RemovalofNCHduetomagnesium
Mg
2+
+ Ca(OH)
2
MgOH
2( )
+ Ca
2+
Mg +Ca(OH)
2
MgOH
2(s)
+Ca
Ca
2+
+Na
2
CO
3
CaCO
3(s)
+2Na
+
24
6.HardnessandSofteninginwaterTreatment
6.4ChemistryofLime SodaAshSoftening
f l Softeningprocesslimitations:
1. LimeSodasofteningcannotproduceawatercompletelyfreeofhardness
becauseofthesolubilityofCaCO
3
andMg(OH)
2
,limitationsofmixing
andreactiontime.
2. Thus,theminimumcalciumhardness thatcanbeachievedis
30mg/LasCaCO
3
,theminimumMagnesiumhardness thatcanbeachieved
3
is 10mg/LasCaCO
3
,thisgivesaminimumhardnessof40mg/LasCaCO
3
.
3. However,normallythewateristreatedtogiveahardnessintherangeof75to
120 mg/L as CaCO
3
. 120 mg/LasCaCO
3
.
4. AnExcesslimebeyondthestoichiometric amountisusuallyaddedto
removeMg
2+
hardness .Theminimumexcesslimeisusually20mg/L
as CaCO maximum excess lime is 62 5 mg/L as CaCO (1 25 meq/L) asCaCO
3
,maximumexcesslimeis62.5mg/LasCaCO
3
(1.25meq/L).
5. Mg
2+
inexcessof40mg/LasCaCO
3
isnotdesiredasitformsscalein
waterheaters.Mg
2+
isexpensivetoremove,soweonlyremoveMg
2+
i f 40 /L C CO
25
inexcessof40mg/LasCaCO
3
.
6.HardnessandSofteninginwaterTreatment
6.4ChemistryofLime SodaAshSoftening
h l Chemicalsrequirements:
Accordingtothesofteningchemicalreactions:
Lime is added at the ratio of 1:1 for each carbonate hardness Limeisaddedattheratioof1:1foreachcarbonatehardness
compoundexceptforMg(HCO
3
)theratiois 2:1[i.e.2limefor
each1Mg(HCO
3
)].
Limeisalsoaddedattheratioof1:1foreachMagnesiumNCH g
compoundsuchasMgSO
4
Sodaashisaddedattheratioof1:1foreachMagnesiumor
CalciumNCHcompoundsuchasMgSO
4
,andCaSO
4
. p g
4
,
4
CO
2
neededis1:1ratiowiththeexcesslimeadded,and1:1
ratiowithCaCO
3
remainingaftersoftening,2:1ratiowith
Mg(OH)
2
remainingaftersoftening. g( )
2
g g
Theunitsofthechemicalsareeitherinmeq/Lormg/LCaCO
3
Example6.2illustratesthechemicalrequirements
calculations.
26
calculations.
6.HardnessandSofteninginwaterTreatment
6.5ExcessLimeSofteningexample
Example:6.2
A i h h i i h i i h b l i b f d h Awaterwiththeioniccharacteristicsshownbelowistobesoftenedtothe
minimumpossiblehardnessbylimesodaashexcesslimeprocess.Calculate
therequiredchemicalquantitiesinmeq/L.Drawabardiagramofthesoftened
water. AssumethataresidualofCaCO
3
of0.60 meq/LandaresidualofMg(OH)
2
of0.20meq/Lwillremaininthesoftenedwater.
7.4 3.4 6.4
Na
2+
CO
2
Ca
2+
HCO
3

Mg
2+
0 0
4.9 7.4
0 6
SO
4
2
0.0 0.6
27
6.HardnessandSofteninginwaterTreatment
Example 6 2 continued Example:6.2..continued
Solution:
Li 0 6 3 4 2(4 9 3 4) (6 4 4 9) li Lime =0.6+3.4+2(4.93.4)+(6.44.9)+excesslime
=8.5+1.25=9.75meq/L
SodaAsh =6.44.9=1.5meq/L(toremoveNCH,MgSO
4
2
)
Na
+
:
TheadditionofsodaashaddstothewateranequalamountofNa
+
.
Sinceweadded1.5meq/Lsodaash,thiswilladd1.5meq/LNa
+
Theoriginalconcentrationexistingintherawwateris1.0meq/L .
TotalNa
+
=1+1.5=2.5meq/LNa
+
.
28
6.HardnessandSofteninginwaterTreatment
Example 6 2 continued Example:6.2..continued
3 3 0 6 0 8 0 0
CO
3
2
Mg
2+
Na
2+
Ca
2+
3.3 0.6
SO
4
2
0.8 0.0
HO

0.6 0.8 3.3