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Potentiometry-3 (1)

analytical

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6 views

Potentiometry-3 (1)

analytical

Uploaded by

ho2304373
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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Pro. Dr.

Hala Zaazaa 1
B) Indicator electrode
• Indicator electrode is electrode dipped in unknown concentration of ions “
sample” to determine its concentration
• Its potential changes rapidly with the change of concentration of sample to be
determined.
It must give: 1- rapid response
2- Its response must be reproducible.
These electrodes are classified into two classes:
a)Metallic Electrodes b) Ion Selective Electrodes
where redox reaction (electron where charge (ions) exchange
transfer) takes place at electrode takes place at specific membrane
surface, It classified according to type of surface
reaction between standard and sample
 Glass electrode

2
Indicator electrodes for different titrations

1-For Redox Reactions :


• Ind. Electrode : inert electrodes e.g.
platinum or gold.
• The electrode is in the form of coils
or foils or plates  ↑ surface area
 reach equilibrium potential
rapidly.
• Used to determine the potential
during redox titrations.
[ox]
E25oC 
[Red] Potentiometric titration curve of Fe2+ against Ce4+
3
2- For Preciptimetric Reactions:
Electrodes of first type (Mo/M+)

I- Determination of Ag+  Cl-, Br- and CN-

Ag° wire for determination of Ag+

𝑬 = 𝑬𝒐 + 𝟎. 𝟎𝟓𝟗𝟐 𝒍𝒐𝒈[𝑨𝒈+ ]

 Ind. Electrode : Ago/Ag+

Other metal electrodes e.g. copper, lead,


cadmium and mercury are used for
determination of their cations.
4
II- For determination of single halide eg : Cl- titrate with AgNO3

Ind. Electrode: 2nd order (type) electrode


determine conc of Cl- (if alone)
Hgo/Hg2Cl2/Cl- or Ago/AgCl/Cl- E  1/[Cl-]

Silver metal

𝐴𝑔𝐶𝑙(𝑠)

Reference
electrode
III- For determination of mixture of
halide eg :
Cl- ,Br -, I - titrate with AgNO3

Ind. Electrode: 1st order electrode


determine conc of Ag+ presents in
AgNO3 during titration (Ago/Ag+)

E  [Ag+]

6
3-For Complexometry reactions :
- For single metal determination titrate with EDTA
Ind. Electrode: 1st order electrode : Mo/M+
eg: Determination of Cu2+ use Cu0/Cu2+ electrode
E  [Cu2+]

- For mixture of metal eg Cd2+ and Ca2+


titration with EDTA
Ind. Electrode: 2nd order electrode:
Mercury electrode: Hgo/ HgY2- /Y4-
to determine EDTA concentration (in
mixture of metals)
E  1/ [Y4 -]
N.B : Cd2+, Ca2+ mix., drops of HgY2- M solution should be added to it. After
complete reaction of EDTA with metal, excess EDTA will cause sharp
decrease in pot. Indicating end point 7
4- For Acid – Base reactions:-

-Used to determine pH and end point of the titration


-All of them has relation between potential and hydrogen ion
conc.
E  [H+]

Electrodes for pH measurement

Hydrogen gas electrode Glass electrode

8
1-Hydrogen Gas Electrode
1-Type :
Indicator electrode (1st Type)

2-Redox Reaction:
2H+ + 2e Pt black H2

3-Half cell:
Pt.H2/H+ (unknown conc.) //

4-Nernest Equation:
E=E0 + 0.059 log [H+]
n [H2]
As E0=Zero [H2] gas=1
E25=0 + 0.059/1 log [H+]
E25= - 0.059 pH
9
-Disadvantages:
1) difficult to control H2 gas pressure at 1 atm.
2) Pt. needs replating
3) Not used in presence of oxidizing or reducing substances
4) not used in presence of volatile acids as H2S, H2CO3 (bec.it
volatalize when bubbling the H2)
5) not used in presence of catalytic poison (as heavy metals (Hg ,
As) & S as they damage Pt

10
2-Ion Selective Electrode

Glass Electrode
• Consisting of ion selective -membrane,
which separate the test sample from
standard solution inside the
membrane (Containing the ion of
interest at a constant concentration).
Internal Standard solution (H+)
• The composition of the membrane is is constatnt
designed to yield a potential due to Membrane selectively binds to
the ion of interest (via selective the analyte
binding processes). External Standard solution (H+)
is unknown( sample)
• They do not involve redox reactions
11
• Potential is developed on the
membrane due to the presence of
different [H+] inside and outside
the membrane.

• The potential is due to ion


exchange between H+ and one
of the component ions of glass
matrix (e.g Na+).

• The H+ exchange in the form of


H3O+ so the electrode should
be hydrated
12
-Composition of glass electrode internal
reference
electrode
inner solution Ag/AgCl
H3O+

External
reference
Na+ electrode
Ag/AgCl

Salt
bridge 0.1N
H3 O+ HCl
Outer solution

Glass
-Potential: membrane
E = K - 0.059 pH
K = is constant called asymetric potential
(pH of internal solution and liquid junction potential) 13
14
Advantages:
1. It can be used to measure the pH of solution containing
oxidizing or reducing agents.

Disadvantages:
1) can’t be used in presence of dehydrating agents eg: alc., conc.
H2SO4
2) fragile
3) pH response is not accurate in high conc. of electrolytes (need dil.
soln.)
4) it attains equilibrium slowly
5) in pH above 12 inaccurate results due to exchange of Na+ in soln.
with H+ (Alkaline error)

15
Upon potentiometric determination of Ag+ by using standard Cl-
Complete the following:

i) Reference electrode
………………………………………………………..
ii) Indicator electrode its type and its order
………………………………………………………….
iii) E α …………….
iv) Titration curve

16

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