ApplicationofCoordinationCompounds

StabilizationofOxidationStates
Co3+(aq) + e- Co2+(aq) E = +1.82 V

4 Co3+(aq) + 2 H2O(l) 4 Co2+(aq) + 4 H+ + O2(g), Ecell = +0.59 V But: Co3+(aq) + NH3(aq) [Co(NH3)6]2+(aq) and [Co(NH3)6]3+(aq) + e- [Co(NH3)6]2+(aq) Kf = 4.5.1033 E = +0.10 V

Photography:FixingaPhotographicFilm
Blackandwhite.
FinelydividedemulsionofAgBr onmodifiedcellulose. PhotonsoxidizeBr toBrandreduceAg+toAg.

Hydroquinone(C6H4(OH)2)developer:
ReactsonlyatthelatentimagesitewheresomeAg+is presentandconvertsallAg+ toAg. Negativeimage.

FixerremovesremainingAgBr.
AgBr(s)+2S2O32(aq)[Ag(S2O3)2]3(aq)+Br(aq)

Printthenegative

Chelates: ComplexesofSpecialInterest
Chelatesgenerallyaremuchmorestablethan complexeswithmonodentateligands. Theincreaseinentropyduringchelationisan importantfactorinthestabilitiesofchelates.
[Ni(NH3)6]2+(aq) + EDTA4-(aq) [NiEDTA]2-(aq) + 6 (NH3)6(aq)

K = 8 x 109

SequesteringMetalCations
tetrasodiumEDTA

 Tosequester ametalioninsolutionmeans totieitupinaformthateffectively removesitfromsolution solution. EDTA(ethylenediaminetetraaceticacid)is commonly l used d t tosequester t metal t li ionsi in solution. Chelationtherapy,usingEDTA,is sometimesusedtotreatheavymetalion poisoning.

AMetalEDTAComplex p

Hexadentate ligand

completely surrounds and isolates the metal ion.

SequesteringMetalCations

SomeLog values:10.6(Ca2+),18.3(Pb2+),24.6(Fe3+).

porphyrin

chlorophyl p y a

(an enzyme that lacks its metal center or prosthetic groups)

Why is CO lethal?

Hemoglobin (Hb) is the main chemical component of red blood cells, carrying oxygen from the lungs to the body tissue transporting oxygen from a region of high tissue, concentration to low concentration. This transportation is accomplished by the formation of the oxygen-hemoglobin complex, oxyhemoglobin (HBO2)
Hb(aq) + O2(g) [HbO2] [Hb] PO2 HbO2 (aq)

K=

In the absence of Hb, , the amount of O2 in blood is low. Because of the formation of the HbO2 complex, the amount of O2 in blood is increased by a factor of 70.
Hb(aq) + O2(g) HbO2 (aq)

LeChateliers principle predicts that in regions of high O2 partial pressure, the Hb-HbO2 equilibrium is shifted to the right, i ht which hi h i is th the case i in th the l lungs In regions g of low O2 p partial p pressure, , the equilibrium q shifts to the left, resulting in a breakup of the HbO2 complex, releasing O2 to the bodys tissues.

What happens if a person breathes CO?

Hb(aq) + CO(g) HbCO (aq)

[HbCO] K(CO)= [Hb] PCO

K(CO) > (KO2 ) Which means that CO binds more tightly to Hb compared to O2 When Hb is exposed p to both O2 and CO, there is competition for the Hb, and the following reaction takes place:
HbO2 (aq) + CO(g) HbCO(aq) + O2 (g)

The relative amounts of HbCO and HbO2 depend p on the partial pressures of CO and O2.
HbO2 (aq) + CO(g) HbCO(aq) + O2 (g)

Since K(CO) > K(O2), K for the competition reaction is >1 In fact at 38oC, the value of K is 210 and so the position of f the th equilibrium ilib i strongly t l f favors th the f formation ti of f th the HbCO complex, with CO displacing O2 from the HbO2 complex . However, the process is reversible - from LeChateliers principle, a large partial pressure of O2 will result in the equilibrium of the competition reaction to favor the HbO2 complex.