ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY COORDINATION CHEMISTRY (Complexation in Solution) Bruce Herbert Geology & Geophysics http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Sampling the Aqueous Phase Soil Water http://ianrpubs.unl.edu/fieldcrops/g964.htm http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Sampling the Aqueous Phase Soil Water Soil water is classified into three categories: (1) excess soil water or gravitational water, (2) available soil water, and (3) unavailable soil water. http://ianrpubs.unl.edu/fieldcrops/g964.htm http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Sampling the Aqueous Phase Soil Water Retention Curves In unsaturated soils, water is under tension and it takes energy to remove it from the soil. As the water content of a soil decreases from the saturation point, the tension used to hold water increases. The relationship of soil water content and soil water tension is represented in the Figure. Curves like Figure 6 are called water retention or soil water characteristic curves. They are different for each soil because of differences in soil textures and structures. http://ianrpubs.unl.edu/fieldcrops/g964.htm Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Sampling the Aqueous Phase Soils ■ Soil solution is the water and gaseous phase held in interstial pores at various tensions (negative pressures) ■ Soil solution samplers have to use negative pressure (suction) to retrieve soil solution. Different tensions will retrieve different volumes and chemistry of samples ■ Typical instruments: the lysimeters ■ Tension lysimeter ■ Zero-tension lysimeter ■ Vacuum extractor ■ Pan and deep pressure vacuum lysimeters ■ Porous ceramic samplers Pu m p S o lu t io n in ly s im e t e r b arre l P o ro u s Cu p Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Sampling the Aqueous Phase Soils ■ Other methods ■ Column displacement ■ Centrifuge samples to extract solution ■ Characterize saturated pastes. This is the only method if the porous media is dry. ■ Generally, all samplers are porous ceramic or teflon bodies that can hold a tension. ■ Preferably at the tension equal to the soil's field moisture capacity. ■ This creates a suction in the sample which opposes capillary pressure. www.usyd.edu.au/.../ sphysic/waterlab/field.htm Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Using Samplers ■ Samplers need to be installed a year or so before use to equilibrate system. ■ Effects of spatial variability ■ Small size of samplers may not incorporate large heterogeneities ■ Soils with macropores may require both tension and zero-tension lysimeters to sample water in bulk soil and macropores ■ Application of vacuum: volatile components may be lost such as organics or CO2(g). This could change pH or redox ■ pH changes of 0.28 to 0.44 pH units are common due to CO2(g) degassing ■ Ceramic cups can adsorb anions and possibly leach cations. Clean ceramic cups with dilute acid with extensive washings with DI water ■ Teflon cups are less reactive than ceramic www.usyd.edu.au/.../ sphysic/waterlab/field.htm http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Sampling the Aqueous Phase Groundwater ■ Chemistry of water samples reflect the conditions in the groundwater over the entire screened interval. Samples can be taken from depth-integrated or depth-specific wells. ■ Depth-integrated: Useful in identifying regional patterns in GW chemistry, but misses variations over small depth scales. These variations are integrated into one sample. ■ Depth-specific: Useful in studying chemical processes in detail or producing 3D data sets. A B C D A: Depth-integrated well. B: Depth-specific well. C: Nested piezometers for depthspecific sampling. D: Depth-specific sampling using inflated packers to isolate a particular zone. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Groundwater Sampling ■ Sampling is concerned with contamination of the groundwater by drilling operations with drilling fluids, gravel pack or casing materials. It may take a long time for these disturbances to diminish. ■ Drilling mud can often change the cation exchange of the solid matrix, changing the cation distribution in GW. ■ Stagnant water in the well is usually flushed from the well before a sample is taken. Usually 3 or so well volumes are flushed from the well before a sample is taking. Too much flushing is wasteful and may result in drawing water from other formations. ■ When brought to the surface, GW is exposed to different physio-chemical conditions than in the subsurface. Major differences in O2 and CO2 can really affect GW chemistry. ■ O2 can redox of elements; CO2 affects alkalinity, carbonates, pH. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY WHY IS CHEMICAL SPECIATION SO IMPORTANT? ■ The biological availability (bioavailability) of metals and their physiological and toxicological effects depend on the actual species present. ■ Example: CuCO30, Cu(en)20, and Cu2+ all affect the growth of algae differently ■ Example: Methylmercury (CH3Hg+) is readily formed in biological processes, kinetically inert, and readily passes through cell walls. It is far more toxic than inorganic forms. ■ Solubility and mobility depend on speciation. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Effect of free Cu2+ on growth of algae in seawater. Figure 6-20 from Stumm & Morgan http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Common Metal Species Cation Acid Sys tems Alkaline Sys tems Na+ Na+ Na+, NaHCO3°, NaSO 4- Mg2+ Mg2+, MgSO 4°, org Mg2+, MgSO 4°, MgCO3° Al3+ org, AlF2+, AlOH2+ Al(OH)4-, org Si4+ Si(OH)4° Si(OH)4° K+ K+ K+, KSO 4- Ca2+ Ca2+, CaSO 4°, org Ca2+, CaSO 4°, CaHCO3+ Cr3+ CrOH2+ Cr(OH)4- Cr6+ CrO4- CrO4- Mn2+ Mn2+, MnSO 4°, org Mn2+, MnSO 4°, MnCO3°, MnHCO3+, MnB(OH) 4+ Fe2+ Fe2+, FeSO 4°, FeHPO 4+ FeCO3°, Fe2+, FeHCO3+, FeSO 4° Fe3+ FeOH2+, Fe(OH)3°, org Fe(OH)3°, org Ni2+ Ni2+, NiSO 4°, NiHCO3+, org NiCO3°, NiHCO3+, Ni2+, NiB(OH) 4+ Cu2+ org, Cu2+ CuCO3°, org, CuB(OH)4+, Cu[B(OH) 4]4° Zn2+ Zn2+, ZnSO 4°, org ZnHCO3+, ZnCO3°, org, Zn2+, ZnSO 4°, ZnB(OH) 4+ Mo5+ H2MoO4°, HMoO4- HMoO4-, MoO42- Cd2+ Cd2+, CdSO 4°, CdCl+ Cd2+, CdCl+, CdSO 4°, CdHCO3+ Pb2+ Pb2+, org, PbSO 4°, PbHCO3+ PbCO3°, PbHCO3+, org, Pb(CO3)22-, PbOH+ http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY DEFINITIONS Coordination (complex formation) - any combination of cations with molecules or anions containing free pairs of electrons. Bonding may be electrostatic, covalent or a mix. Central atom (nucleus) - the metal cation. Ligand - anion or molecule with which a cation forms complexes. Multidentate ligand - a ligand with more than one possible binding site. Chelation - complex formation with multidentate ligands. Multi- or poly-nuclear complexes - complexes with more than one central atom or nucleus. Aqueous Species Si(OH)4Ў Central Ion Si4+ Al(OH)2+ HCO3- Al3+ H+ or CO32- http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY MULTIDENTATE LIGANDS HO O O O O M O N OH N OH O Oxalate (bidentate) N 2H O M HO O N 2H Ethylendiamine (bidentate) Ethylendiaminetetraacetic acid or EDTA (hexadentate) http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Chelation N H 2 H2N N i N H 2 H2N Polynuclear complexes S 2 - S S b S S b S Sb2S42- O H O H H g 2 + H g H g O H O H Hg3(OH)42+ http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY DEFINITIONS - II Species - refers to the actual form in which a molecule or ion is present in solution. Coordination number - total number of ligands surrounding a metal ion. Ligation number - number of a specific type of ligand surrounding a metal ion. Colloid - suspension of particles composed of several units, whereas in true solution we have hydration of a single molecule, atom or ion. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY FORMS OF OCCURRENCE OF METAL SPECIES 10 Å 100 Å Free metal Inorganic ion Organic ion pairs and complexes, complexes chelates 1000 Å Metals bound to high mol. wt. species Me-lipids Highly dispersed colloids Metals sorbed on colloids FeOOH Mex(OH)y Me- humic acid Fe(OH)3 MeCO3, MeS,etc. on clays FeOOH or Mn(IV) on oxides Cu2+ Cu2(OH)22+ Me-SR Fe3+ PbCO30 Me-OOCR Pb2+ CuCO30 Mn(IV) oxides Na+ AgSH0 Ag2S Al3+ CdCl+ Zn2+ CoOH+ http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Coordination Numbers L L L Me CN = 2 (linear) L Me L L CN = 4 (square planar) L L L L M Me L L L CN = 4 (tetrahedral) e L L L CN = 6 (octahedral) Coordination numbers 2, 4, 6, 8, 9 and 12 are most common for cations. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY STABILITY CONSTANTS MEASURE THE STRENGTH OF COMPLEXATION Stepwise constants MLn-1 + L MLn Cumulative constants M + nL MLn [ MLn ] Kn [ MLn 1 ][ L] [ MLn ] n [ M ][ L]n n = K1·K2·K3···Kn http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY STABILITY CONSTANTS MEASURE THE STRENGTH OF COMPLEXATION For a protonated ligand we have: Stepwise complexation MLn-1 + HL MLn + H+ Cumulative complexation M + nHL MLn + nH+ [ ML ][ H ] * n Kn [ MLn 1 ][ HL ] n [ ML ][ H ] * n n [ M ][ HL ]n The larger the value of the stability constant, the more stable the complex, and the greater the proportion of the complex formed relative to the simple ion. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY STABILITY CONSTANTS FOR POLYNUCLEAR COMPLEXES mM + nL MmLn nm [ M m Ln ] [ M ]m [ L]n mM + nHL MmLn + nH+ * nm n [ M m Ln ][ H ] [ M ]m [ HL ]n If m = 1, the second subscript on nm is omitted and the expression simplifies to the previous expressions for mononuclear complexes. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Titration of H+ and Cu2+ with Ammonia and Tetramine (trien) Figure 6-3 from Stumm & Morgan http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY HYDROLYSIS The waters surrounding a cation may function as acids. The acidity is expected to increase with decreasing ionic radius and increasing ionic charge. For example: Zn(H2O)62+ Zn(H2O)5(OH)+ + H+ Hydrolysis products may range from cationic to anionic. For example: Zn2+ ZnOH+ Zn(OH)20 (ZnO0) Zn(OH)3- (HZnO2-) Zn(OH)42- (ZnO22-) May also get polynuclear species. Kinetics of formation of mononuclear hydrolysis products is rather fast, polynuclear formation may be slow. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY METAL HYDROLYSIS ■ The tendency for a metal ion to hydrolyze will increase with dilution and increasing pH (decreasing [H+]) ■ The fraction of polynuclear products will decrease on dilution ■ Compare Cu2+ + H2O CuOH+ + H+ Mg2+ + H2O MgOH+ + H+ log *K1 = -8.0 log *K1 = -11.4 [ MOH ][ H ] * K1 [ M 2 ] http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY MOH [ MOH ] 2 [ MOH ] [ M ] MOH [ MOH ] [ MOH ][ H ] [ MOH ] * K1 1 [H ] 1 * K1 At infinite dilution, pH 7 so CuOH+ = (1 + 10-7/10-8)-1 = 1/11 = 0.091 MgOH+ = (1 + 10-7/10-11.4)-1 = 1/25119 = 4x10-5 Only salts with p*K1 < (1/2)pKw or p*n < (n/2)pKw will undergo significant hydrolysis upon dilution. Progressive hydrolysis is the reason some salts precipitate upon dilution. This is why it is necessary to add acid when diluting standards. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY POLYNUCLEAR SPECIES DECREASE IN IMPORTANCE WITH DILUTION Consider the dimerization of CuOH+: 2CuOH+ Cu2(OH)22+ log *K22 = 1.5 Assuming we have a system where: CuT = [Cu2+] + [Cu(OH)+] + 2[Cu2(OH)22+] we can write: [Cu2 (OH )22 ] [Cu2 (OH )22 ] * K22 2 2 2 2 [CuOH ] (CuT [Cu ] 2[Cu2 (OH )2 ]) So [Cu2(OH)22+] is clearly dependent on total Cu concentration! http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY HYDROLYSIS OF IRON(III) Example 1: Compute the equilibrium composition of a homogeneous solution to which 10-4 (10-2) M of iron(III) has been added and the pH adjusted in the range 1 to 4.5 with acid or base. The following equilibrium constants are available at I = 3 M (NaClO4) and 25°C: Fe3+ + H2O FeOH2+ + H+ log *K1 = -3.05 Fe3+ + 2H2O Fe(OH)2+ + 2H+ log *2 = -6.31 2Fe3+ + 2H2O Fe2(OH)24+ + 2H+ log *22 = -2.91 FeT = [Fe3+] + [FeOH2+] + [Fe(OH)2+] + 2[Fe2(OH)24+] http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY K1 2 2[ Fe ] 22 FeT [ Fe ]1 2 2 [H ] [H ] [H ] * 3 * 3 * Optional Now we define: 0 = [Fe3+]/FeT; 1= [FeOH2+]/FeT; 2= [Fe(OH)2+]/FeT; and 22= 2[Fe2(OH)24+]/FeT. K1 2 2 FeT0 22 0 1 2 2 [H ] [H ] [H ] * 02 2 FeT * 22 [ H ]2 * * 1 * * K1 2 0 1 2 1 0 [H ] [H ] http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Optional This last equation can be solved for 0 at given values of FeT and pH. The remaining values are obtained from the following equations: 22 0 K1 02 2 FeT * 22 [ H ]2 * 1 [H ] 0 22 * 2 [ H ]2 These equations can then be employed to calculate the speciation diagrams on the next slide. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY FeT = 10-4 M Fe3+ 100 80 Fe(OH) 2+ 60 %Fe 40 FeOH 2+ 20 0 Fe 100 FeT = 10-2 M 3+ Fe2(OH) 24+ 80 Fe(OH) 2 + 60 %Fe 40 20 FeOH 2+ 0 1 2 3 4 pH http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Example 2: Compute the composition of a Fe(III) solution in equilibrium with amorphous ferric hydroxide given the additional equilibrium constants: Fe(OH)3(s) + 3H+ Fe3+ + 3H2O log *Ks0 = 3.96 Fe(OH)3(s) + H2O Fe(OH)4- + H+ log *Ks4 = -18.7 Fe3+ log [Fe3+] = log *Ks0 - 3pH Fe(OH)4log [Fe(OH)4-] = log *Ks4 + pH http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY FeOH+ Fe(OH)3(s) + 3H+ Fe3+ + 3H2O log *Ks0 = 3.96 Fe3+ + H2O FeOH2+ + H+ log *K1 = -3.05 Fe(OH)3(s) + 2H+ FeOH2+ + 2H2O log *Ks1 = 0.91 log [FeOH2+] = log *Ks1 - 2pH Fe(OH)2+ Fe(OH)3(s) + 3H+ Fe3+ + 3H2O Fe3+ + 2H2O Fe(OH)2+ + 2H+ Fe(OH)3(s) + H+ Fe(OH)2+ + H2O log *Ks0 = 3.96 log *2 = -6.31 log *Ks2 = -2.35 log [Fe(OH)2+] = log *Ks2 - pH http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Fe2(OH)24+ 2Fe(OH)3(s) + 6H+ 2Fe3+ + 6H2O 2log *Ks0 = 7.92 2Fe3+ + 2H2O Fe2(OH)24+ + 2H+ log *22 = -2.91 2Fe(OH)3(s) + 4H+ Fe2(OH)24+ + 4H2O log *Ks22 = 5.01 log [Fe2(OH)24+] = log *Ks22 - 4pH These equations can be used to obtain the concentration of each of the Fe(III) species as a function of pH. They can all be summed to give the total solubility. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY 5 0 Fe(OH)3(s) -5 log concentration Fe(OH)4 -10 Fe2(OH) 2 4+ 3+ Fe -15 0 2 - 4 6 Fe(OH)2 2+ + FeOH 8 10 12 14 pH Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Complexation & the HSAB Concept ■ Metal ions can be titrated by ligands in the same way that acids and bases can be titrated. ■ According to the Lewis definition, metal ions are acids because they accept electrons; ligands are bases because they donate electrons. ■ We can use the concepts of hard/soft acid and bases to predict propensity and stability of different complexation reactions. ■ Like complexes like Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Metal Complexation and Toxicity Representative data illustrating the relationship between metal effects and metal ion characteristics. Responses range widely from enzyme inhibition (lactic dehydrogenase, LDH) (22) to toxicity of cultured turbot cells (23) to acute lethality of a crustacean (amphipod) (27) to chronic toxicity of mice (1) and Daphnia magna (8). http://ehpnet1.niehs.nih.gov/docs/1998/Suppl-6/1419-1425newman/abstract.html http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Complexation & the HSAB Concept Ionic potential Ґ If IP < 30 n m-1, then metal cations tend to fo rm solvation co mplexes with water Ґ If 95 > IP > 30 n m-1, then metal cations can repel protons f rom solvating water molecules to fo rm the hydroxide co mplexes. Ґ If IP > 95 n m-1, then repulsion is st rong enough to form the oxy ion spec ies Misono Softness Ґ If Y < 25 n m, then meta l cat ions tend to fo rm elect rostat ic bonds Ґ If 0.25 < Y < 0.32 n m, then the meta l cat ions a re borderline meta ls whose cova lency depends on whethe r spec ific so lvent, ste reoche mical, and elect ronic conf igurationa l facto rs a re p resent Ґ If Y > 0.32 n m, then meta l cat ions tend to fo rm cova lent bonds Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Figure 6-4a from Stumm and Morgan: Predominant pH range for the occurrence of various species for various oxidation states http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Figure 6-4b from Stumm & Morgan: The linear dependence of the first hydrolysis constant on the ratio of the charge to the M-O distance (z/d) for four groups of cations at 25°C. http://environmentalgeochemistry.pbworks.com// Correlation between solubility product of solid oxide/hydroxide and the first hydrolysis constant. ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Figure 6-6 from Stumm & Morgan Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY PEARSON HARD-SOFT ACID-BASE (HSAB) THEORY ■ Hard ions (class A) ■ small ■ highly charged ■ d0 electron configuration ■ electron clouds not easily deformed ■ prefer to form ionic bonds ■ Soft ions (class B) ■ large ■ low charge ■ d10 electron configuration ■ electron clouds easily deformed ■ prefer to form covalent bonds Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Pearson’s Principle - In a competitive situation, hard acids tend to form complexes with hard bases, and soft acids tend to form complexes with soft bases. In other words - metals that tend to bond covalently preferentially form complexes with ligands that tend to bond covalently, and similarly, metals that tend to bond electrostatically preferentially form complexes with ligands that tend to bond electrostatically. Complexation http://environmentalgeochemistry.pbworks.com// Classification of metals and ligands in terms of PearsonХs (1963) ENVIRONMENTAL GEOCHEMISTRY ATHSAB TEXAS A&M UNIVERSITY principle. Hard Borderline Soft Acids Acids Acids H+ Li+ > Na+ > K+ > Rb+ > Cs + 2+ 2+ 2+ 2+ Be > Mg > Ca > Sr > 2+ Ba Al3+ > Ga3+ 3+ 3+ 3+ 3+ Sc > Y ; REE (Lu > La3+); Ce4+; Sn4+ Ti4+ > Ti3+, Zr4+ Hf4+ 6+ 3+ 6+ 5+ Cr > Cr ; Mo > Mo > Mo4+; W6+ > W4+; Nb5+, Ta5+ ; Re7+ > Re6+ > Re4+; V6+ > V5+ 4+ 4+ 3+ 3+ 5+ > V ; Mn ; Fe ; Co ; As ; 5+ Sb Th4+; U6+ > U4+ 6+ 4+ PGE > PGE , etc. (Ru, Ir, Os) Bases Fe2+, Mn2+, Co2+, Ni2+ , Cu2+, Zn2+, Pb2+, Sn2+, 3+ 3+ 3+ As , Sb , Bi Au+ > Ag+ > Cu+ Hg2+ > Cd2+ 2+ 2+ Pt > Pd other PGE2+ Tl3+ > Tl+ Bases Bases F-; H2O, OH-, O2- ; NH 3; NO3-; CO32- > HCO3-; SO42- > HSO4-; 32PO4 > HPO4 > H2PO4 ; carboxylates (i.e., acetate, oxalate, etc.); 22MoO4 ; WO4 Cl- I- > Br-; CN -; CO; S2- > HS- > H2S; organic phosphines (R3P); organic thiols (RP); 2polysulfide (SnS ), thiosulfate (S2O32- ), sulfite (SO32- ); 22HSe , Se , HTe , Te ; AsS2-; SbS2- Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY ION PAIRS VS. COORDINATION COMPLEXES ION PAIRS ■ formed solely by electrostatic attraction ■ ions often separated by coordinated waters ■ short-lived association ■ no definite geometry ■ also called outer-sphere complexes COORDINATION COMPLEXES large covalent component to bonding ligand and metal joined directly longer-lived species definite geometry also called inner-sphere complexes Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY STABILITY CONSTANTS OF ION PAIRS CAN BE ESTIMATED FROM ELECTROSTATIC MODELS For 1:1 pairs (e.g., NaCl0, LiF0, etc.) log K 0 - 1 (I = 0) For 2:2 pairs (e.g., CaSO40, MgCO30, etc.) log K 1.5 - 2.4 (I = 0) For 3:3 pairs (e.g., LaPO40, AlPO40, etc.) log K 2.8 - 4.0 (I = 0) Stability constants for covalently bound coordination complexes cannot be estimated as easily. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY COMPLEX FORMATION AND SOLUBILITY ■ Total solubility of a system is given by: [Me]T = [Me]free + [MemHkLn(OH)i] ■ Solubilities of relatively “insoluble” phases such as: Ag2S (pKs0 = 50); HgS (pKs0 = 52); FeOOH (pKs0 = 38); CuO (pKs0 = 20); Al2O3 (pKs0 = 34) are probably not determined by simple ions and solubility products alone, but by complexes such as: AgHS0, HgS22- or HgS2H-, Fe(OH)+, CuCO30 and Al(OH)4-. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Calculate the concentration of Ag+ in a solution in equilibrium with Ag2S with pH = 13 and ST = 0.1 M (20°C, 1 atm., I = 0.1 M NaClO4). Ks0 = 10-49.7 = [Ag+]2[S2-] At pH = 13, [H2S0] << [HS-] because pK1 = 6.68 and pK2 = 14.0 so ST = [HS-] + [S2-] = 0.1 M 2 [ H ][ S ] 14 K2 10 [ HS ] 2 [ H ][ S ] [ HS ] 1014 [ H ][ S 2 ] 2 0.1 [ S ] 14 10 Complexation http://environmentalgeochemistry.pbworks.com// G 1013[ S 2 ] E 2 2 0.1 [ S ] 11 [ S ] 14 10 NVIRONMENTAL EOCHEMISTRY AT TEXAS A&M UNIVERSITY [S2-] = 9.1x10-3 M [Ag+]2 = 10-49.7/10-2.04 = 10-47.66 [Ag+] = 10-23.85 = 1.41x10-24 M Obviously, in the absence of complexation, the solubility of Ag2S is exceedingly low under these conditions. The concentration obtained corresponds to ~1 Ag ion per liter. What happens if we take 100 mL of such a solution? Do we then have 1/10 of an Ag ion? No, the physical interpretation of concentration does not make sense here. However, an Ag+ ionselective electrode would read [Ag+] = 10-23.85 nevertheless. Complexation http://environmentalgeochemistry.pbworks.com// AT TEXAS A&M UNIVERSITY Estimate the concentration of all species in aENVIRONMENTAL solution of SGTEOCHEMISTRY = 0.02 M and saturated with respect to Ag2S as a function of pH (in other words, calculate a solubility diagram). [Ag]T = [Ag+] + [AgHS0] + [Ag(HS)2-] + 2[Ag2S3H22-] Ks0 = [Ag+]2[S2-], but [S2-] = 2ST so Ks0 = [Ag+]2 2ST [ Ag ] Ag+ + HS- AgHS0 AgHS0 + HS- Ag(HS)2Ag2S(s) + 2HS- Ag2S3H22- Ks0 ST2 log K1 = 13.3 log K2 = 3.87 log Ks3 = -4.82 Complexation http://environmentalgeochemistry.pbworks.com// 0 [ AgHS ] K1 [ Ag ][ HS ] ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY [ AgHS 0 ] K1 [ Ag ]1ST [ AgHS ] K11ST [ Ag ] [ HS ] 1ST 0 [ AgHS ] K11ST 0 [ Ag ( HS )2 ] K2 [ AgHS 0 ][ HS ] Ks0 ST2 [ Ag ( HS )2 ] K2 [ AgHS 0 ][ HS ] [ Ag ( HS ) ] K2 K S 2 2 2 1 T 1 Ks0 ST2 Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY [ Ag2 S3 H 22 ] Ks3 [ HS ]2 [ Ag2 S3 H 22 ] K s 3ST212 [ Ag ]T Ks0 2 2 2 2 1 K1ST1 K2 K1ST1 2 K s 3ST1 ST2 Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY -6 -8 -10 -12 AgHS - Ag(HS) 2 0 Ag 2S3H22- -14 -16 pH = pK 1(H2S) -18 log concentration -20 Ag + -22 -24 0 2 4 6 8 10 12 14 pH Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY -7 3 2 4 -8 Ag 2S3H2 5 2- 1 pH = pK 1(H2S) AgHS 0 log concentration -9 Ag(HS) 2- -10 0 2 4 6 8 10 12 14 pH Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Region 1: AgHS0 and H2S0 are predominant Ag2S(s) + H2S0 2AgHS0 log [AgHS0] = 1/2log [H2S0] + 1/2log K log[ Ag ]T pH 0 H2S Region 2: Ag(HS)2- and H2S0 are predominant Ag2S(s) + 3H2S0 2Ag(HS)2- + 2H+ log [Ag(HS)2-] = 3/2log [H2S0] + 1/2log K + pH log[ Ag ]T pH 1 H 2S Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Region 3: Ag(HS)2- and HS- are predominant Ag2S(s) + 3HS- + H+ 2Ag(HS)2log [Ag(HS)2-] = 3/2log [HS-] + 1/2log K - 1/2pH log[ Ag ]T pH 1 / 2 HS Region 4: Ag2S3H22- and HS- are predominant Ag2S(s) + 2HS- Ag2S3H22log [Ag2S3H22-] = 2log [HS-] + log K log[ Ag ]T pH 0 HS Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Region 5: Ag2S3H22- and S2- are predominant Ag2S(s) + 2S2- + 2H+ Ag2S3H22log [Ag2S3H22-] = 2log [S2-] + log K - 2pH log[ Ag ]T pH 2 S 2 Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY THE CHELATE EFFECT ■ Multidentate ligands are much stronger complex formers than monodentate ligands. ■ Chelates remain stable even at very dilute concentrations, whereas monodentate complexes tend to dissociate. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY WHAT IS THE CAUSE OF THE CHELATE EFFECT? Gro = Hro - TSr0 For many ligands, Hro is about the same in multi- and mono-dentate complexes, but there is a larger entropy increase upon chelation! Cu(H2O)42+ + 4NH30 Cu(NH3)42+ + 4H2O Cu(H2O)42+ + N4 Cu(N4)2+ + 4H2O The second reaction results in a greater increase in Sr0. Complexation http://environmentalgeochemistry.pbworks.com// Figure 6-11 from Stumm and Morgan. EEffect of dilution on degree of UNIVERSITY NVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M complexation. Complexation http://environmentalgeochemistry.pbworks.com// 6-12a from Stumm & ENVIRONMENTAL GFigure EOCHEMISTRY AT TEXAS A&M UNIVERSITY Morgan. Complexing of Fe(III). The degree of complexation is expressed as pFe for various ligands at a concentration of 10-2 M. The complexing effect is highly pH-dependent because of the competing effects of H+ and OH- at low and high pH, respectively. Complexation http://environmentalgeochemistry.pbworks.com// Figure 6-12b from Stumm & Morgan. Chelation of Zn(II). ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY METAL-ION BUFFERS Analogous to pH buffers. Consider: Me + L MeL K [ MeL ] [ Me ] [ L] If we add MeL and L in approximately equal quantities, [Me] will be maintained approximately constant unless a large amount of additional metal or ligand is added. If [MeL] = [L], then pMe = pK! Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Example: Calculate [Ca2+] of a solution with the composition - EDTA = YT = 1.95x10-2 M, CaT = 9.82x10-3 M, pH = 5.13 and I = 0.1 M (20°C). For EDTA, pK1 = 2.0; pK2 = 2.67; pK3 = 6.16; and pK4 = 10.26. [CaY 2 ] 10.6 K 10 CaY 2 4 [Ca ][Y ] [CaHY ] 3.5 K 10 CaHY 2 3 [Ca ][ HY ] (i ) CaT [Ca 2 ] [CaY 2 ] [CaHY ] [Ca 2 ]1 KCaY [Y 4 ] KCaHY K 41[ H ][Y 4 ] 1 [Ca 2 ]Ca Ca [Ca 2 ] CaT Complexation http://environmentalgeochemistry.pbworks.com// GEOCHEMISTRY AT TEXAS 2 ENVIRONMENTAL 3 4 2 A&M UNIVERSITY (ii ) YT [ H 4Y ] [ H 3Y ] [ H 2Y ] [ HY ] [Y ] [CaY ] [CaHY ] 0 [Y 4 ](4* )1 [Ca2 ][Y 4 ]KCaY [Ca2 ][ H ][Y 4 ]K41KCaHY * 4 [H ] [H ] [H ] [H ] 1 K4 K 4 K3 K 4 K3 K 2 K 4 K3 K 2 K1 4 i [H Y ] 4 [Y ] 4 i 0 2 3 4 1 i Equations (i) and (ii) must be solved by trial and error. We know pH so we can calculate 4* directly. We can then assume that [HiY4-i] YT CaT. This permits us to calculate [Y4-] and then solve (i) for [Ca2+]. This approach leads to: [CaY2] = 9.66x10-3 M; [CaHY-] = 1.09x10-4 M; [Ca2+] = 4.12x10-5 M; [Y4-] = 6.05x10-9 M; [H3Y-] = 3.07x10-5 M; [H2Y2-] = 8.8x10-3 M; [HY3-] = Complexation 8.21x10-4 M; [H4Y0] = 2.26x10-8 M. http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY MIXED COMPLEXES Examples: Zn(OH)2Cl22-, Hg(OH)(HS)0, PdCl3Br2-, etc. Generalized complexation reaction: M + mA + nB MAmBn log MAm Bn m n log MAm n log MBm n log S mn mn Log S is a statistical factor. For example, the probability of forming MAB relative to MA2 and MB2 is S = 2 because there are two distinct ways of forming MAB, i.e., A-M-B and B-M-A. The probability of forming MA2B relative to MA3 and MB3 is S = 3. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY In simple cases we can use the following formula: ( m n )! S ! npredominate ! In general, mixed complexes usuallym only under a very restricted set of conditions. Complexation http://environmentalgeochemistry.pbworks.com// Figure 6-15 from ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Stumm and Morgan. Predominance of Hg(II) species as a function of pCl and pH. In seawater, HgCl42predominates. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY COMPETITION FOR LIGANDS ■ The ratio of inorganic to organic substances in most natural waters are usually very high. ■ Does a large excess of, say, Ca2+ or Mg2+, decrease the potential of organic ligands to complex trace metals? ■ Example: Fe3+, Ca2+ and EDTA Fe3+ + Y4- FeYlog KFeY = 25.1 Ca2+ + Y4- CaY2- log KCaY = 10.7 These data suggest that Fe3+ should be complexed by EDTA. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY But, let us combine the two above expressions to get: CaY2- + Fe3+ FeY- + Ca2+ log Kexchange = 14.4 2 2 [Ca ] [CaY ] 14.4 3 [ Fe ] [ FeY ] Thus, the relative importance of the two EDTA complexes depends also on the ratio of calcium to iron in solution. For an exact solution to this problem, we also need to consider the species FeYOH and FeY(OH)2. Complexation http://environmentalgeochemistry.pbworks.com// Figure 6.17a from Stumm & Morgan. Competitive effect of Ca2+ on ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY complexation of Fe(III) with EDTA. Fe(OH)3(s) precipitates at pH > 8.6. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Morgan. Competitive effect of Ca2+ on Figure 6.17b from Stumm & complexation of Fe(III) with EDTA. Complexation http://environmentalgeochemistry.pbworks.com// ENVIRONMENTAL GEOCHEMISTRY AT TEXAS A&M UNIVERSITY Morgan. Competitive effect of Ca2+ on Figure 6.17c from Stumm & complexation of Fe(III) with citrate. Complexation http://environmentalgeochemistry.pbworks.com//