Print version. Lecture #31 Coordination Chemistry: Case Studies: EDTA, detergents. (Stumm & Morgan, Chapt.6: pg ) Benjamin; Chapter

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1 Updated: 11 April 2018 Print version Lecture #31 Coordination Chemistry: Case Studies: EDTA, detergents (Stumm & Morgan, Chapt.6: pg ) Benjamin; Chapter David Reckhow CEE 680 #31 1

2 EDTA Complexation M +n + Y -4 = MY n-4 K = [MY n-4 ]/[M +n ][Y -4 ] Metal Log K Metal Log K K (+I) 0.8 Pb (+II) Na (+I) 1.66 Sn (+II) 18.3 Li (+I) 2.79 Ni (+II) Ba (+II) 7.86 Cu (+II) Mg (+II) 8.79 Hg (+II) 21.7 Ca (+II) Al (+III) 16.3 Cr (+II) 13.6 Cr (+III) 23.4 Mn (+II) Mn (+III) 25.3 Fe (+II) Fe (+III) 25.1 David Reckhow CEE 680 #31 2

3 EDTA Protonation Acidic groups Carboxylic groups pk 1 = 0.0 pk 2 = 1.5 pk 3 = 2.0 pk 4 = 2.66 Amine groups 4 pk 5 = 6.16 pk 6 = Y α 6 n= 0 6 n 4 H n Y α 6 = 1/{[H ] 6 /K 1 K 2 K 3 K 4 K 5 K 6 + [H+] 5 /K 2 K 3 K 4 K 5 K 6 + [H+] 4 /K 3 K 4 K 5 K 6 + [H+] 3 /K 4 K 5 K 6 + [H+] 2 /K 5 K 6 + [H+]/K 6 + 1} Major ligand form: Y -4 [ ] David Reckhow CEE 680 #31 3

4 EDTA: Alpha diagram α 1 α 4 α 5 α 6 =Y -4 /C T 0.7 α α 2 α α ph David Reckhow CEE 680 #31 4

5 Titration of a model fresh water with EDTA Fixed ph = 8.10 Total concentrations Ca T = 3.7 x 10-4 M Mg T = 1.6 x 10-4 M K T = 6 x 10-5 M Na T = 2.8 x 10-4 M Fe(III) T = 5 x 10-7 M Cu T = 5 x 10-8 M Hg T = 10-9 M Zn T = 1.5 x 10-7 M Ni T = 5 x 10-9 M Pb T = 10-9 M [CO 3 ] T = 10-3 M [SO 4 ] T = 10-4 M Cl T = 2 x 10-4 M Me:EDTA speciation EDTA speciation Metal speciation Figure 6.10 from: Morel & Hering, 1993 David Reckhow CEE 680 #31 5

6 O S N Titration of a model fresh water with cysteine Same concentrations as in previous EDTA figure Except no Cu Me: Cysteine speciation Metal speciation Cysteine speciation Figure 6.12 from: Morel & Hering, 1993 David Reckhow CEE 680 #31 6

7 Complexation Problems Metal-Simple Monodentate Ligand Example: Al-F system Can be solved graphically Metal-Multidentate Ligand (1:1 complex) Must consider Ligand protonation Example: Cu-NTA system Can be solved algebraically Metal-Multi-ligand system Example: Pb-OH-CO 3 -citrate system Best to use computer solution (MINEQL) David Reckhow CEE 680 #31 7

8 Surfactants Anionics 65% Cationics 7% Nonionics 28% From: Schwarzenbach et al., 1993, pg. 38 David Reckhow CEE 680 #31 8

9 See: Knud-Hansen Paper Powdered Detergents Component Examples Anionic surfactants Alkylbenzene sulfonates Fatty alcohol sulfates Fatty alcohol ether sulfates Alpha-olefln sulfonates Nonionic surfactants Alkyl and nonylphenyl poly(ethylene glycol) ethers Suds-controlling agents Soaps, silicon oils, paraffins Foam boosters Fatty acid monoothanol amides Chelaters (builders) Sodium tripolyphosphate Ion exchange Zeolite 4A, poly(acrylic acids) Alkalies Sodium carbonate Cobuilders Sodium citrate Sodium Nitrilotriacetate NTA Bleaching agents Sodium perborate Bleach activators Tetraacetylethylenediamine Bleach stabilizers Ethylenediaminetetraacetate Fabric softeners Quaternary ammonium compounds Antiredeposition agents Cellulose ethers Enzymes Proteases, amylases Optical brighteners Stilbene derivatives Anticorrosion agents Sodium silicate Fragrances Dyes and blueing Agents Formulation aids Fillers and water David Reckhow CEE 680 #31 Sodium sulfate 9 Typical Formulation

10 Liquid Detergents Component Anionic surfactants Nonionic surfactants Suds-controlling agents Foam boosters Enzymes Builders Formulation aids Optical brighteners Stabilizers Fabric softeners Fragrances Dyes Water Examples Alkylbenzene sulfonates Fatty alcohol ether sulfates Soaps poly(ethylene glycol) ethers, Soaps Soaps Fatty acid alkanolamides Proteases Potassium diphosphate sodium tripolyphosphate sodium citrate sodium silicate Xylene sulfonates, ethanol, propylene glycol Stilbene derivatives Triethanolamine Quaternary ammonium salts David Reckhow CEE 680 #31 10

11 To next lecture David Reckhow CEE 680 #31 11

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