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The folllowing electrochemical cell was constructed, S.C.E. II cell solution I P

ID: 930599 • Letter: T

Question

The folllowing electrochemical cell was constructed, S.C.E. II cell solution I Pt(s) with a cell voltage of 0.353 V. With a total volume of 1 L, the cell solution (pH 6.85) was comprised of 0.0025 M Ce(SO4)2, 0.0010 M CeCl3, and 0.0045 M Na2EDTA.

Please do not answer this if you do not know EXACTLY what you are doing. This is my THIRD time asking this question. Also please answer all parts. Thank you

The folllowing electrochemical cell was constructed, S.C.E. Il cell solution IPt(s) with a cell voltage of 0.353 V. With a total volume of 1 L, the cell solution (pH 6.85) was comprised of 0.0025 M Ce(SO4)2,0.0010 M CeCl3, and 0.0045 M Na2EDTA A) Write the reaction for the right half-cell as a reduction and provide its standard reduction potential (E°). Number 4+ 3 + E" = 1 1.61 B) Calculate the quotient for the uncomplexed ions, (Ce3TCe"], in the cell solution. Number 3+ Ce | | 0.4 = 4+ Ce C) Determine the formatign constant quotient, KCeEDTA)CeEDTA) Number K, (CeEDTA) K CeEDTA -2.5 Incorrect

Explanation / Answer

a.

The reaction for the right half cell as a reduction is:

CeEDTA + e = CeEDTA-                       EoCeEDTA / CeEDTA- = ?       

(EDTA is here the symbol for Y4- , a quadrivalent anion of EDTA)

Eo has to be find in a table or can be calculated.

Theoretical:

Ce4+ + e = Ce3+                                        EoCe4+/Ce3+ = 1.61 V              (1)

CeEDTA + e = CeEDTA-                       EoCeEDTA / CeEDTA- = ?          (2)

From Eq.1 – Eq.2 :

Ce4+ + CeEDTA- = Ce3+ + CeEDTA

For this cell write as usual

Eocell = EoCe4+/Ce3+ - EoCeEDTA / CeEDTA-and

Ecell = Eocell – 0.0592log([Ce3+ ][CeEDTA] / [Ce4+][CeEDTA-])            (3)

If the reaction is at equilibrium Ecell = 0 V and

[Ce3+ ][CeEDTA] / [Ce4+][CeEDTA-] is an equilibrium constant.

K = [Ce3+ ][CeEDTA] / [Ce4+][CeEDTA-] =

    = [Ce3+ ][EDTA][CeEDTA] / [Ce4+][EDTA][CeEDTA-] =

    = Kf,CeEDTA / Kf,CeEDTA-                                                                        (4)

EoCe4+/Ce3+ - EoCeEDTA / CeEDTA- = 0.0592log(Kf,CeEDTA / Kf,CeEDTA-)

From reference tables I found that

logKf,CeEDTA = 24.20    Kf,CeEDTA = 1.585x1024

logKf,CeEDTA- = 15.98     Kf,CeEDTA- = 9.550x1015

K = 1.585x1024 /9.550x1015 = 1.66x108

(If the reaction is not at equilibrium [Ce3+ ][CeEDTA] / [Ce4+][CeEDTA-] is the reaction quotient Q)

At equilibrium, using eq. 3 and 4:

0 = Eocell – 0.0592logK

Eocell = 0.0592logK

         = 0.0592x8.22 =

         = 0.487 V

EoCe4+/Ce3+ - EoCeEDTA / CeEDTA- = 0.49 V

1.61 V- EoCeEDTA / CeEDTA- = 0.49 V

EoCeEDTA / CeEDTA- = 1.12 V

You have to find this value in your book or to use this value, calculated by me.

b.

Your electrochemical cell is not at equilibrium, use eq. (3):

Ecell = Eocell – 0.0592logQ

(If the reaction is not at equilibrium [Ce3+ ][CeEDTA] / [Ce4+][CeEDTA-] is the reaction quotient Q)

Ecell is measured vs SCE, correct the value as referenced to NHE

Ecell = 0.353 + 0.241= 0.594 V vs NHE

Eocell = 0.487 V     (see a.)

0.594 V = 0.487 - 0.0592logQ

logQ = - 0.107/0.0592

          = - 1.807

Q = 0.01558 = 0.0156

Q = ([Ce3+ ][CeEDTA] /([Ce4+][CeEDTA-])) = 0.0156

The initial concentrations used for the preparation of the cell solution were:

CCe3+ = 0.0010M

CCe4+ = 0.0025

CEDTA = 0.0045

The complexes [CeEDTA] and [CeEDTA-] are very stable, thus you may assume with negligible errors that

[CeEDTA] = 0.0025 M

[CeEDTA-] = 0.0010 M

Then:

Q = 0.0156 = ([Ce3+ ] x 0.0025 / ([Ce4+] x 0.0010])) =

                   = 2.5 x ([Ce3+ ]/ [Ce4+])

[Ce3+ ]/ [Ce4+] = 0.00624

c.

Eocell = 0.0592logK   (see a.)

Where K = Kf,CeEDTA / Kf,CeEDTA-    

Eocell = 0.487 V     (see a.)

0.487 = 0.0592 log Kf,CeEDTA / Kf,CeEDTA-

log Kf,CeEDTA / Kf,CeEDTA- = 8.226

Kf,CeEDTA / Kf,CeEDTA- = 108.22 = 1.66 x108