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Chapter 5.

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

4. Hydrolysis of Metal Ions

5. Complexes with Inorganic Ligands

6. Complexes with Organic Ligands

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

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Chapter 5. Coordination Chemistry

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

e.g) Fe(CN)64- (hexa cyano ferrate)

hexa cyano ferrate

# of Ligands negative Ligands anionic complex

→ Ligand + Central metal ions ⇒ complex

K ; (complex formation) stability constant


Large K → stable complex

→ A - metal ions ; Alkali metal (Na+/K+)


Alkaline earth metals (Mg2+/Ca2+, Al3+, Si4+)
Coordinate with ligands containing oxygen as electron donor

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Chapter 5. Coordination Chemistry

→ B ? metal ions; Ag+, Zn2+, Hg2+, Pb2+, Sn2+


Coordinate with ligands containing S, P, or N as donor atoms

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-

→ Degree of Hardness (measured in terms of CaCO3)


Table 2.
mg/L (CaCO3) Degree of hardness
0 ~ 75 Soft
75 ~ 150 Moderately hard
150 ~ 300 Hard Softening
300> Very hard required
(Note: Generally finished water 50~150, 80~100 hardness is desirable (for aesthertic and
corrosion control))

→ Source of Hardness : water contacts with soil and rock (leaching cations)
groundwaters are harder than surface waters

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Chapter 5. Coordination Chemistry

(2) Type of Hardness


→ Total hardness
= sum of the calcium and magnesium ion concentration
(Note: concentrations of other divalent cations are very low compared Ca and Mg)
→ Two ways divalent cations
anions associated with cations
→ Based on divalent cations
Calcium Hardness (CaH) : hardness attributable to Ca2+
Magnesium Hardness (MgH) : hardness attributable to Mg2+
Total hardness = CaH + MgH
→ Based on anions associated
Carbonate hardness (CH)
- portion of the total hardness chemically equivalent to the carbonate and bicarbonate
alkalinities
- the amount of Ca2+ and Mg2+ ions that can be removed as insoluble carbonates
(eg. CaCO3) by boiling the water
- ¡temporary hardness¡
Non carbonate hardness (NCH)
- portion of the total hardness in excess of the carbonate and bicarbonate alkalinities
- the amount of Ca2+ and Mg2+ ions remaining in solution after boiling
- ¡permanent hardness¡

(3) Equivalence diagram (bar diagram)

2+ 2+ +
CO2 Cations (Ca , Mg , Na )
Anions (HCO3-, SO42-)

optional

a) Alkalinity < total hardness

Ca2+ Mg2+
HCO3- SO42- Cl-

Alkalinity (at natural pHs)


Carbonate hardness = alkalinity (the rest of hardness = noncarbonated hardness)

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Chapter 5. Coordination Chemistry

b) Alkalinity > hardness


Ca2+ Mg2+ Na+
- -
HCO3 Cl
Carbonate hardness = total hardness
(no noncarbonated hardness)

2.2. Hardness Determination


; determined by titration against EDTA
(ethylene ? diamine - tetra acetic acid) → complex formation

(1) complex formation


→ central metal ions + ligands ⇔ complex
K ; stability constant or complex formation constant
Large K ; more stable complex formation
→ Ligands
Monodentate : Ligands that attach to a central metal ion at only one point
Multidentate : Ligands that attach at two or more site (chelating agent)

(2) complex formation between Ca2+, Mg2+ and EDTA


→ chelating agent EDTA has six bonding sites
4 acetate groups
2 nitrogen atom

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Chapter 5. Coordination Chemistry

→ Ca2+ + EDTA 4- ⇔ (EDTA-Ca) 2- K = 10+10.7


Mg2+ + EDTA4- ⇔ (EDTA-Mg) 2- K = 10+8.7
; EDTA combines first with the Ca2+, then Mg2+

(3) Hardness determination


→ difficult to detect the end point of EDTA titration (no color change ~ colorless)
; indicators are needed
→ total hardness determination
- Eriochrome Black T (EBT) is used as an indicator
[H-EBT]2- + Mg2+ ⇔ [Mg-EBT]- + H+ K = 10 7
Bule Red
- Stability constant
[Ca-EDTA]2- > [Mg-EDTA]2- > [Mg-EBT]-
- The stronger complexing agent decomposes the existing complex and with draws the metal
ion into a complex with itself
- EDTA (at pH=10) EDTA

Ca2+, (Mg-EBT)- (EDTA-Ca)2-, (EDTA-Mg)2-,

(red) (H-EBT)-, (bule)

EDTA first reacts with Ca2+ to form (EDTA-Ca)2- complex


Then breaks up Mg-EBT complex and forms (EDTA-Mg)2- complex
Color change (red → blue)
2+
→ Ca hardness determination
- murexide is used as an indicator (ammonium purpurate)
2+ 2+
[Murexide] + Ca ⇔ [Ca-Murexide]
Purple Pink
- color change from pink to purple when Ca-murexide is broken
; end point of EDTA titration (at pH =12)
2+
→ Mg hardness determination
TH ? CaH = MgH
Note : Ca(OH)2, Mg(OH)2 formation during hardness measurement

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Chapter 5. Coordination Chemistry

2.3. Water Softening

(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

(2) Softening reactions


→ lime ? soda Ash precipitation 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

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Chapter 5. Coordination Chemistry

Softening reactions

meq dose meq sludge


Demand reaction Ca(OH)2 Na2CO3 CaCO3 Mg(OH)2
CO2 Ca(OH)2 + CO2 → CaCO3(s)↓ + H2O 1 0 1 0
CaCH Ca(OH)2 + Ca(HCO3)2 → 2CaCO3(s)↓ + 2H2O 1 0 2 0
MgCH 2Ca(OH)2 + Mg(HCO3)2 → 2 0 2 1
2CaCO3(s)↓ + Mg(OH)2(s)↓ + 2H2O
CaNCH Na2CO3 + CaSO4 → CaCO3(s)↓ + Na2SO4 0 1 1 0
MgNCH Ca(OH)2 + Na2CO3 + MgSO4 → 1 1 1 1
CaCO3(s)↓ + Mg(OH)2(s)↓ + Na2SO4
*
Neg Alk Na(HCO)3 + Ca(OH)2 → CaCO3(s)↓ + NaOH 1 0 1 0
* The negative alkalinity is the alkalinity in excess needed to be neutralized before precipitation

(3) Lime and soda ash requirement


→ based stoichiometry of softening (type of hardness) reactions

(4) Caustic soda softening


- Advantage : less sludge production
- Disadvantage : expensive, hazard

CO2 + 2NaOH → Na2CO3 + H2O


Ca(HCO3)2 + 2 NaOH → CaCO3(s)↓ + Na2CO3 + 2H2O
Mg(HCO3)2 + 4 NaOH → Mg(OH)2(s)↓ + 2Na2CO3 + 2H2O

CaSO4 + 2NaOH → Ca(OH)2 + Na2SO4


MgSO4 + 2NaOH → Mg(OH)2 + Na2SO4
; solubility diagram of Ca(OH)2 and Mg(OH)2

(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)

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Chapter 5. Coordination Chemistry

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Chapter 5. Coordination Chemistry

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

(2) Complex formation between Hg2+ and Cl-


: chloromercury(Ⅱ) complex
: inorganic interference during COD test
→ inorganic ions are also oxidized by Cr2O72-(K2Cr2O7)
→ error in measurement
→ chloride (Cl-) ions are the most serious problem
Cr2O72+ + 14H+ + 6Cl- ↔ 2Cr3+ + 3Cl2(aq) + 7H2O
→ prevented by complexation with Hg2+ (HgSO4)
→ reduce free chloride ions

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

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Chapter 5. Coordination Chemistry

Example 5-1 Complex formation during COD test

Step #1 [Hg2+], [Cl-], [HgCl+], [HgCl20], [HgCl3-], [HgCl42-]


 six unknowns → six equation required
(Note : not acid-base reaction → No H+, OH-
But general frame work should be followed)
Step #2
ⓐ Mass balance (0.4g HgSO4 in 60mL total sample)
CT,Hg = 2.24¡ 10-2M = [Hg2+]+[HgCl+]+[HgCl20]+[HgCl3-]+[HgCl42-]
CT,Cl = 9.39¡ 10-3M = [Cl-]+[HgCl+]+2[HgCl20]+3[HgCl3-]+4[HgCl42-]
ⓑ Complex formation reactions

[ 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

 total of six equations


-
Step #3 Solve for Cl and other complexes
2+
Exact solution → eliminate [Hg ] from mass balance
-
→ solve for [Cl ] using equation
Approximate solution
→ three trial/error method
CT,Hg=[Hg2+] ①
2+
=[Hg ]+[HgCl20] ②
=[Hg2+]+[HgCl20]+ [HgCl+] ③
Answer
→ [Cl-]=3¡ 10-8M
[HgCl20]=1.6¡ 10-3
→ majority of Cl- ions are complexed with Hg2+

CESE 219 Chemistry for Environmental Engineering S.K. Hong 11

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