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4.2 Equilibrios de Reducción y Oxidación (2) - Valoraciones Redox

1) The document discusses several half-cell reactions and reference electrodes used in electrochemistry including the Ag/AgCl reference electrode. 2) Equations are provided relating the standard electrode potential (E0) and the reference electrode potential (ERef) to the concentration of ions involved in the half-cell reactions. 3) Methods for determining the potential during redox titrations and factors that influence the accuracy of the results are described.

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Daniela
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29 views24 pages

4.2 Equilibrios de Reducción y Oxidación (2) - Valoraciones Redox

1) The document discusses several half-cell reactions and reference electrodes used in electrochemistry including the Ag/AgCl reference electrode. 2) Equations are provided relating the standard electrode potential (E0) and the reference electrode potential (ERef) to the concentration of ions involved in the half-cell reactions. 3) Methods for determining the potential during redox titrations and factors that influence the accuracy of the results are described.

Uploaded by

Daniela
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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23/06/2020

•
•
• 𝐸Ind 𝐸Ref
•

𝐸 = 𝐸Ind − 𝐸Ref + 𝐸ul

1
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•
•
•

•
• Ag + /Ag Cu2+ /Cu
•
•

𝐸 = 𝐸Ind − 𝐸Ref + 𝐸ul

Ag |AgCl s | Cl− ||

AgCl s + e− ⇌ Ag s + Cl−
𝐸 0 = +0.2223 V
𝑬(𝐬𝐚𝐭. 𝐊𝐂𝐥) = +𝟎. 𝟏𝟗𝟕 𝐕

𝐸Ref = 𝐸 0 − 0.05916 𝑉 Log Cl−

2
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AgCl s + e− ⇌ Ag s + Cl−
𝑬(𝐬𝐚𝐭. 𝐊𝐂𝐥) = +𝟎. 𝟏𝟗𝟕 𝐕

Hg 2 Cl2 s + 2e− ⇌ Hg l + 2Cl−


𝐸 0 = +0.2682 V
𝑬(𝐬𝐚𝐭. 𝐊𝐂𝐥) = +𝟎. 𝟐𝟒𝟏 𝐕

Hg l |Hg 2 Cl2 sat , KCl (𝑥 M)||

𝐸Ref = 𝐸 0 − 0.05916 𝑉 Log Cl−

3
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•
Ag + /Ag Cu2+ /Cu

M 𝑛+ + 𝑛e− ⇌ M

0 0.05916 𝑉 1
𝐸Ind = 𝐸M 𝑛+ /M − Log
𝑛 M𝑛+

0 2.303
𝐸Ind = 𝐸M 𝑛+ /M − pM 𝑛+
𝑛𝐹
0.05916 𝑉
𝐸=𝐾+ Log M𝑛+
𝑛

4
23/06/2020

AgCl s + e− ⇌ Ag s + Cl−

𝑬𝐑𝐞𝐟
▪ Cl− = 𝑬𝐑𝐞𝐟
▪ 𝑬𝐈𝐧𝐝
▪

𝐸Ind = 𝐸 0 − 0.05916 𝑉 Log Cl−

𝑅𝑇
𝐸Ind = 𝐸 0 + pCl− 𝐸 = 𝐾 − 0.05916 𝑉 Log Cl−
𝐹

10

5
23/06/2020

•
▪
▪

Fe3+ + e− ⇌ Fe2+
0
Fe2+
𝐸Ind = 𝐸 − 0.05916 𝑉 Log 3+
Fe
Ox + 𝑛e− ⇌ Red
0.05916 𝑉 Red
𝐸Ind = 𝐸 0 − Log
𝑛 Ox

0.05916 𝑉 Red
𝐸=𝐾− Log
𝑛 Ox

11

𝑬𝐮𝐥

http://dpuadweb.depauw.edu/harvey_web/eTextProject/AC2.1Files/Chapter11.pdf

12

6
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𝑬𝐫𝐞𝐟

http://dpuadweb.depauw.edu/harvey_web/eTextProject/AC2.1Files/Chapter11.pdf

13

14

7
23/06/2020

Fe2+ m𝑀 KMnO4
2+
Fe H2 SO4 H + = 1.0 𝑀
o′ o′
𝐸ref ECS = 0.241𝑉; 𝐸Fe 3+ /Fe2+ = 0.680 𝑉; 𝐸MnO − /Mn2+ = 1.570 𝑉
4

15

16

8
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17

MnO4− 𝐸+ 𝐸celda MnO4− 𝐸+ 𝐸celda

18

9
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400.0 mL de 𝐅𝐞𝟐+ 3.75 𝐦𝐌 con 𝐊𝐌𝐧𝐎𝟒 0.020 M

19

Tl+ IO3−
HCl

Fe2+ Ce4+
HClO4

20

10
23/06/2020

0.05916 𝑉 𝐑𝐞𝐝𝐮𝐜𝐢𝐝𝐚
𝐸= 𝐸0 − Log
𝑛 𝐎𝐱𝐢𝐝𝐚𝐝𝐚

21

𝐑𝐞𝐝𝐮𝐜𝐢𝐝𝐚 10
≥
𝐎𝐱𝐢𝐝𝐚𝐝𝐚 1

𝐑𝐞𝐝𝐮𝐜𝐢𝐝𝐚 1
≤
𝐎𝐱𝐢𝐝𝐚𝐝𝐚 10

0.05916 𝑉
𝐸 = 𝐸0 ±
𝑛

22

11
23/06/2020

23

o
A mayor diferencia entre 𝐸val
o
y 𝐸analito , mejor valoración.

≥ 0.4 𝑉 para Ind


visual redox.

RV vs ECS = RV vs EEH − E (ECS)


RV vs ECS = 1.088 a 1.206 𝑉 − 0.214 𝑉
RV vs ECS = 0.847 a 0.965 vs ECS

24

12
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▪
∆𝐸/∆𝑉 ∆ ∆𝐸/∆𝑉 ∆𝑉

𝐅𝐞𝟐+ 𝐊𝐌𝐧𝐎𝟒
𝐇𝟐 𝐒𝐎𝟒

25

−14788
𝑥 𝑦=0 =
−988.88
= 14.95 mL = 𝑉eq

26

13
23/06/2020

▪
′ ′
𝑛𝐸 𝑛 𝐸ref −𝐸 0 𝑛 𝐸ref −𝐸 0
−
𝑉∙ 10 0.059167 = 𝑉eq ∙ 10− 0.059167 −𝑉 ∙ 10− 0.059167

𝑦 = 𝑏 𝑥 𝑚
𝑛𝐸
−0.059167
𝑉 ∙ 10

▪ m g
m

27

−5.709
𝑥 𝑦=0 =
−0.3806
= 15.00 mL = 𝑉eq

𝐅𝐞𝟐+ 𝐊𝐌𝐧𝐎𝟒
𝐇𝟐 𝐒𝐎𝟒

28

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𝐈𝟔

𝐈𝟔

29

▪ 𝐊𝐌𝐧𝐎𝟒

pH ≤ 1
MnO4− + 8H + + 5e− → Mn2+ + 4H2 O 𝐸 0 = 1.507 𝑉

MnO4− + 4H + + 3e− → MnO2 (s) + 2H2 O 𝐸 0 = 1.692 𝑉


2 M NaOH
MnO4− + e− → MnO42− 𝐸 0 = 0.56 𝑉

30

15
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31

32

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▪ 𝐂𝐞𝟒+
KMnO4

𝐸 0′ = 1.70 𝑉 en HClO4 1 𝑀
𝐸 0′ = 1.61 𝑉 en HNO3 1 𝑀
Ce4+ + e− → Ce3+
𝐸 0′ = 1.47 𝑉 en HCl 1 𝑀
𝐸 0′ = 1.44 𝑉 en H2 SO4 1 𝑀

33

▪ 𝐂𝐫𝟐 𝐎𝟕𝟐−
Cr2 O72− + 14H + + 6e− → 2Cr 3+ + 7H2 O
𝐸 0′ = 1.00 𝑉 en HCl 1 𝑀
𝐸 0′ = 1.11 𝑉 en H2 SO4 2 𝑀
KMnO4 Ce4+

Fe2+

Cr2 O72−

34

17
23/06/2020

I2 + I − → I3− 𝐾 = 7 × 102
▪ I3−

▪ I3−

I3−

35

I3−

36

18
23/06/2020

I3− KIO3 KI
IO3− + 8I− + 6H + → 3I3− + 3H2 O
I3−

I3− + 2S2 O32− → 3I− + S4 O62−

37

+ I3− + H2 O → + 3I − + 2H +

38

19
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39

40

20
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41

42

21
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KIO3 H2 SO4

I3−
Na2 S2 O3 I3−
Na2 S2 O3

H2 SO4
KIO3 I3− Na2 S2 O3

43

44

22
23/06/2020

H2 O2
H2 SO4 KMnO4

H2 O2

45

^_^

46
46

23
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47

24

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