Log concentration vs pH (carbonic acid)

Buffers & Buffering

Is natural water a buffer?

Which is a better buffer and

why?

Rain water, Surface water or

Ground water?
 Natural water: A buffer

Buffering is due to Alkalinity anion of a

weak acid or basic salt
Buffer capacity- Buffer Index: Acid or
base required to change pH by ONE unit
= dCb/dpH = - dCa/dpH
pH = pKa + log (alkalinity/acidity); pKa
= 6.34
pH1=pKa+ log (alkalinity H+) -
log(acidity + H+)
H+ -Buffer Capacity
 Buffer Capacity
Sample S1: 1mM NaHCO3; pH = 8.3 &
Sample S2: NaOH solution of pH 8.3
Alkalinity, A of S1 & S2 by calculation or by titration;
A (eq/L) = OH- + HCO3- + 2CO3= - H+ or
Titrate the sample up to pH 4.5 (at this pH carbonates and
bicarbonates are in H2CO3 form)
S1; Alkalinity = 10-3 = H2CO3 + HCO3- + 2CO3=
Electroneutrality at pH 4.5; Na + + H+ = OH- + HCO3-
+ 2CO3= + Ci-
Cl- = HCl = Na+ = Alkalinity = 10-3 M
S2; H+ = 10-8.3; OH- = 10-5.7 = 2 x 10-6
HCl required to reduce pH to 4.5
Cl- = Na+ + H+ - OH- 34 x 10-6 M = alkalinity
Alk of S1 is 30 times the alk of S2
 Buffer Index ()
Buffer Index/Capacity depends on pH
and CT
= dCb/dpH = - dCa/dpH (Cb & Ca ; M
SB & SA)
Charge Balance:
Cb + H+ = OH- + A-; A- anion of WA or
basic salt
Cb = Kw/H+ + A- - H+
= Kw/H+ - H+ + CTKa/(Ka+H+)
Differentiate Cb with dpH and solve;
 Hardness
Facts about hardness
Hardness in natural waters is mostly due to
soluble salts of calcium and magnesium
Very Hard water in water supplies is scale
forming
Non carbonate hardness (NCH)-
chlorides, sulfates of Ca and Mg
Removed by soda (Na2CO3)
Carbonate hardness (CH)
bicarbonates of Ca & Mg
Removed by adding lime
Hardness Classification of Water

Hardness
Classificat Hardness
ion (meq/L) (mg/LCaCO3
)
Soft <1.5 <75
Moderately
1.5 -3 75 - 150
Hard
Hard 3-6 150 - 300
Very Hard >6 >300
 Softening- Hardness Removal

H2CO3 + Ca(OH)2 = CaCO3 + 2H2O

Ca(HCO3)2 + Ca(OH)2 = 2CaCO3 +2H2O

CH Removal
Mg(HCO3)2 +2Ca(OH)2 = CaCO3+Mg(OH)2+2H2O
HCO3-+Ca(OH)2 = CaCO3 + H2O + OH-; (HCO3> TH)

NCH Removal
CaCl2 + Na2CO3 = CaCO3 + 2Na+ + 2Cl-
MgSO4+Na2CO3+Ca(OH)2=CaCO3+Mg(OH)2+2Na+ + SO4=
Write for CaSO4 and MgCL2
 Hardness due to Iron and
Manganese in GW
Iron and manganese hardness is present in
ground water
Ferrous and manganous salts are soluble and
these can be present in water devoid of
oxygen i.e. anaerobic water
Organics in soil + O2 = CO2 + H2O + other
oxides
GW is devoid of DO
Fe2O3 +3H2O =2Fe(OH)3 = Fe(OH)2 =
Fe(HCO3)2
MnO2 + H20 + CO2 = Mn(HCO3)2
Stable-Corrosive-Scale Forming
Water
Water oversaturated with CaCO3- Scale
Forming
Water Under saturated with CaCO3 Corrosive
Stable Water- neither scale forming nor
corrosive
CaCO3 Ca+2 +CO3= ; Ksp = [Ca][CO3]
[CO3] = Ka2 [HCO3]/[H+] = Ksp/[Ca]
[H+] = [HCO3] [Ca] Ka2/Ksp
-log [H+] = pHs = pKa2 Ksp + p[HCO3] +
p[Ca]
pHs = pHm; Stable water
pHm < pHs; Corrosive Water
pHm > pHs; Scale forming Water
 Calcium Carbonate
Precipitation Potential (CCPP)
Experimentally Measured
Sample is equilibrated with CaCO3
Cai (initial calcium) & Caf (final calcium)
as well as HCO3i & HCO3f are measured &
compared
Caf = Cai; Stable water
Caf < Cai; Scale forming
Caf> Cai; Corrosive water
Change in Ca should stoichiometrically
match with HCO3