Calculation of Keq from Ecell

At equilibrium G = 0 , Ecell = 0 E0cell = RT/nF ln Keq log Keq= nE0cell/0.0592 log Keq= n[redE0cath. - redE0anod.]/0.0592

Calculation of Ksp
Using the following cell with Ecell=0.403V
Cu/CuX2(satd),NaX(0.01M) HCl(0.014M),AgCl/Ag
anode cathode

//

Ecell =

Ercthode 1/2Cl2Cl-

Eranode Cu2+ Cu

0.403

= {E0 Ag+/Ag -0.0592log[Cl-]}

{E0 Cu2+/Cu +0.0295log[Cu2+]}

0.403={0.222-0.0592 log[Cl-]} - {0.337+0.0295 log[Cu2+]} [Cu2+] = 3*10-14 Ksp = [Cu2+][X]2 , [X]=0.01M from cell Ksp =(3*10-14 )(1*10-4) = 3*10-18

Titration curve
Let us use the following cell SCE//Ce4+,Ce3+,Fe3+,Fe2+/Pt
Reference electrode // Analyte electrod/Pt Maybe anode or cathode // Maybe anode or cathode
SCE: (saturated calomel electrode) Hg/Hg2+,KCl (sat,d) , ESCE = 0.241 V Cell reaction is:
SCE Ce4+ 0.1 N

Pt

System Anode or cathode

Ce4+ +Fe2+Ce3+ +Fe3+ = E Ce /Ce or = E Fe /Fe

4+ 3+ 3+

2+

Fe2+ 50mL 0.05N

1- Initial potential [Fe2+]is known, but[Fe3+]unknown, thus Einitial un calculated

2- Addition of 5mL of Ce(lV) [Ce3+] = {(5*0.1)/55} - [Ce4+] equilib.

[Fe2+]={(50*0.05)-(5*0.1)}/55

0.5/55 = [Fe3+]

Negligible amount

+ [Ce4+] equilib. 2/55=

Negligible amount

Either: Esys.=ECe /Ce = E0Ce /Ce -0.0592 log([Ce3+ ]/[Ce4+ ]) , ( ) increase with addition Or =EFe /Fe = E0Fe /Fe -0.0592 log([Fe2+ ]/[Fe3+ ]) , ( ) decrease with addition =0.68 0.0592 log {(2/55) / (0.5/55)} = 0.64 V
4+ 3+ 4+ 3+ 3+ 2+ 3+ 2+

3- At equivalence point: Ce3+/Ce4+= Fe3+/Fe2+ E syst. =(E0Ce+E0Fe) /2 =(1.44+0.68)/2 = 1.06V In general: E eq. = (nAE0A+nBE0B)/nA+nB _ n: number of ( e ) in reduction reaction 4 Addition of 25.1mL of Ce4+
[Ce3+]= {(25*0.1)/75.1} [Fe2+] 2.5/75.1 = [Fe3+] [Ce4+]= {(25.1*0.1)-(50*0.05)}/75.1 + [Fe2+] 0.01/75.1 Esys.=ECe
4+/Ce3+

= 1.44-[0.0592 log {(2.5/75.1)/(0.01/75.1)}]=1.3 V

Titration of Fe2+ with KMnO4

5Fe2+ + MnO4- +8H+5Fe3+ +Mn2+ +4H2O Fe2+Fe3+ +e , Mn7+ +5eMn2+ E eq. = (nAE0A+nBE0B)/nA+nB ={(1*0.68)+(5*1.51)}/(1+5) = 1.37 V Pre equivalence point and post equivalence point as in the last example.

Chemical Indicators
A- True oxidation reduction indicators. Their behavior depend on E sys. at equivalence point In ox. +ne In red. Esys.=E0sys. (0.0592/n)log ([Inred.]/[Inox.]) To observed the color of indicator must be (1/10) ([Inred.]/[Inox.]) (10/1) Esys.=E0sys. (0.0592/n)

B-Specific indicators
Their behavior depend on the selective reaction with one of the participants in the titration such as: 1- Starch: change solution color from colorless to dark-blue complex formation, with iodine in iodometric titration. 3I + S4O6
Colorless _ starch 2-

dark-blue

2+2S O 3 2 3

2-KSCN form a color complex with Fe3+

SCN _

Fe3+

Fe2+

Volhard Back-titration

C- Self-indicators
One of reaction compounds act as indicator.
H+

MnO4- +C2O42- Mn2+ +CO2+H2O

pink 5e colorless OH-

MnO4- +C2O42- MnO2 +CO2+H2O

pink 3e brown