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Coordination Chemistry
CESE 219
Chemistry for Environmental Engineering
COMPLEX FORMATION
OUTLINE
1. Introduction
Definitions
Complex Stability
2. Hardness
2.1. Hardness Definition
2.2. Hardness Determination
2.3. Hardness Removal (Water Softening)
Extra Topics
3. COD Analysis
READING ASSIGNMENT:
Water Chemistry, V. L. Snoeyink and D. Jenkins: Chapter 5.
Extra Handout for Hardness
PROBLEM SOLVING:
Extra Problem for Hardness Removal
Homework #5
1. Introduction
→ Important in water analysis
(e.g. hardness measurement, COD analysis)
→ Affect the chemistry of metal ions in water
→ Complexes
; central metal ions + ligands = complex
→ Ligands Ligands that attach to a central metal
Ion at only one point → monodentate
Ligands that attach at two or more sites → multidentate
→ Total possible number of attachments to a central atom
Coordination number
Liqand + central metal
→ Naming complexes
a) Ligands are named as
Molecules if neutral
* Note : prefix → Number of Ligands
~ ium if positive
~o if negative
b) central metal
anionic → ate
neutral
No suffixes
cationic
2. Hardness
2.1. Hardness Definition
(1) Introduction
→ Hardness : concentration of divalent metallic cations
→ Problems
react with soap to form precipitates
react with certain anions in water to form scale in pipes, heaters, boilers
(Note : no health problem)
Table 1.
Cations causing hardness Anions
Ca2+ HCO3-
Mg2+ SO42-
Sr2+ Cl-
Fe2+ NO3-
Mn2+ SiO32-
→ Source of Hardness : water contacts with soil and rock (leaching cations)
groundwaters are harder than surface waters
2+ 2+ +
CO2 Cations (Ca , Mg , Na )
Anions (HCO3-, SO42-)
optional
Ca2+ Mg2+
HCO3- SO42- Cl-
(1) Introduction
→ Removal of hardness
Chemical precipitation → most popular
Ion exchange
Reverse osmosis
→ Precipitation softening
- most commonly used large-scale hardness removal process
- dependent on low solubility of CaCO3 and Mg(OH)2
Mg2+ + 2OH- → Mg(OH)2↓ (Magnesium Hydroxide)
Ca2+ + CO32- → CaCO3 ↓ (Calcium Carbonate)
- Lime : Ca(OH)2 → lime softening
Soda Ash : Na2CO3 (+ Ca(OH)2) → lime ?soda ash softening
a) CO2 removal
Ca(OH)2 + CO2 → CaCO3(s)↓ + H2O
- necessary to raise pH sufficiently to precipitate the hardness
- does not remove hardness but increase a lime demand
b) Removal of carbonate calcium hardness with lime
Ca(OH)2 + Ca(HCO3)2 → 2CaCO3(s)↓ + 2H2O
- 1 mole Ca(OH)2
c) Removal of carbonate magnesium hardness with lime
2Ca(OH)2 + Mg(HCO3)2 → 2CaCO3(s)↓ + Mg(OH)2(s)↓ + 2H2O
- 2 mole Ca(OH)2
d) Removal of noncarbonated calcium hardness with soda ash
Na2CO3 + CaSO4 → CaCO3(s)↓ + Na2SO4
or Na2CO3 + CaCl2 → CaCO3(s)↓ + 2NaCl
e) Removal of noncarbonated magnesium hardness with lime and soda ash
Ca(OH)2 + Na2CO3 + MgSO4 → CaCO3(s)↓ + Mg(OH)2(s)↓ + Na2SO4
MgSO4 + Ca(OH)2 → Mg(OH)2(s)↓+ CaSO4
CaSO4 + Na2CO3 → CaCO3(s)↓+ Na2SO4
Softening reactions
(5) Recarbonation
→ stabilization of softened water
→ pH (=8.5) control and to avoid CaCO3 ppt
2- -
CO3 + CO2 + H2O → 2HCO3
(CaCO3 + CO2 + H2O → Ca(HCO3)2)
3. COD Analysis
(1) Introduction
: Chemical Oxygen Demand test
→ means to measure organic strength of domestic and industrial wastes
→ measure the total quantity of oxygen required for oxidation to carbon dioxide and water
→ organic matter is converted to carbon dioxide and water regardless of biological
assimilability
→ generally greater than BOD values
→ inability to differentiate between biologically oxidizable and inert organic matter
→ advantage : short time required for evaluation
→ reliable correlation between COD and BOD
→ more detailed test methods → 환경공학 Ⅰ,Ⅱ 실험
→ dichromate (Cr2O72-) are used as oxidizing agent
Stepwise formation
2+ - +
ⓐ Hg + Cl ↔ HgCl logK1=7.15
ⓑ HgCl- + Cl- ↔ HgCl2 logK2=6.9
-
ⓒ HgCl2 + Cl ↔ HgCl3- logK3=2.0
ⓓ HgCl3- + Cl- ↔ HgCl42- logK4=0.7
Overall formation
Hg2+ + Cl- ↔ HgCl+ logβ1=7.15
Hg2+ + 2Cl-↔ HgCl2 logβ2=14.05
2+ -
Hg + 3Cl ↔ HgCl3- logβ3=16.05
Hg2+ + 4Cl-↔ HgCl42- logβ4=16.75
[ HgCl ]
1 10 7.15
[ Hg 2 ][Cl ]
14.05
[ HgCl 2( aq ) 0 ]
2 10
[ Hg 2 ][Cl ]2
[ HgCl 3 ]
3 1016.05
[ Hg 2 ][Cl ]3
2
16.75 [ HgCl 4 ]
4 10
[ Hg 2 ][Cl ]4