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Phân tích điện hóa 2023
Phân tích điện hóa 2023
02/2023
Content
2
References
➢ Electroanalytical Methods: Guide to Experiments and
Applications
Fritz Scholz
➢ Electrochemical Methods: Fundamentals and Applications
Allen J. Bard, Larry R. Faulkner
3
Categories
Electroanalytical methods
Hydrodynamic
voltammetry
Electrochemical Synthesis
Organics, inorganics, materials, polymers
Electrochemical analysis
• Measure the Potential of reaction or process
E = const + k log C (potentiometry)
• Measure the Rate of a redox reaction; Current (I) = k C (voltammetry)
5
Applications
8
Definition
9
Definition
10
Definition
13
Electrochemical Cells
Galvanic Cells
14
Electrochemical Cells
Galvanic Cells
A galvanic cell (also called a voltaic cell) uses a
spontaneous chemical reaction to generate
electricity. To accomplish this, one reagent must be
oxidized and another must be reduced. The two
cannot be in contact, or electrons would flow directly
from the reducing agent to the oxidizing agent.
Instead, oxidizing and reducing agents are
physically separated, and electrons are forced to
flow through a wire to go from one reactant to the
other. 15
Electrochemical Cells
Galvanic Cells
1. Metals
2. Solution (ion migration)
3. Electrode reactions (at interfaces)
17
Electrochemical Cells
Galvanic Cells
Conduction in a Cell
In the silver and copper electrodes, as well as in the external
conductor, electrons are the charge carriers, moving from the copper
electrode through the external conductor to the silver electrode.
19
Electrochemical Cells
Galvanic Cells
Conduction in a Cell
Cathode Anode
Denoted by a positive Denoted by a negative
sign since electrons are sign since electrons are
consumed here liberated here
A reduction reaction An oxidation reaction
occurs in the cathode of occurs here
an electrochemical cell
Electrons move into the Electrons move out of
cathode the anode
20
Potentiometry
Galvanic Cells
Electrochemical reaction
21
Electrochemical Cells
Galvanic Cells
22
Potentiometry
Reduction Oxidation
2+ – 2+ –
Cu ( aq ) + 2 e → Cu( s) Zn ( s ) → Zn ( aq ) + 2e
Cu 2+(aq ) + Zn ( s ) ↔
→ Zn 2+(aq ) + Cu (s )
➢ Zn (the reducing agent) is being oxidized (its oxidation number is going from 0 to +2)
➢ Cu2+ (the oxidizing agent) is being reduced (its oxidation number is going from +2 to 0)
23
Electrochemical Cells
➢ Electrochemistry
➢ Electroanalytical chemistry
➢ Galvanic Cells (Components of Electrochemical Cells, Conduction)
24
Electrochemical Cells
Electrolytic Cells
25
Electrochemical Cells
Galvanic Cells
26
Electrochemical Cells
Galvanic Cells
Salt bridge
- Acts to isolate two halves of
electrochemical cell while allowing
migration of ions and current flow
- Usually consists of a tube filled with KNO3
or others
- Separate species to prevent direct
chemical reactions
27
Potentiometry
Galvanic Cells
Salt bridge
Daniell Cell without salt bridge
Carefully merge
Liquid-liquid interface
two solutions.
Make CuSO4 more
dense than ZnSO4.
Sheath Cu
electrode in glass.
28
Electrochemical Cells
Line Notation
29
Electrochemical Cells
Line Notation
30
Electrochemical Cells
Line Notation
32
Electrochemical Cells
Standard Potentials
33
Electrochemical Cells
Standard Potentials
34
Electrochemical Cells
Standard Potentials
A reaction is spontaneous if ΔG
is negative and E is positive.
ΔG and ΔE refer to the free
energy change and potential
when the activities of reactants
and products are unity.
ΔG = -nFE
35
Electrochemical Cells
Nernst Equation
2
36
Electrochemical Cells
Nernst Equation for a Complete Reaction
The measured voltage is the difference between the potentials of the two electrodes:
E = ECathode - EAnode
37
Electrochemical Cells
Nernst Equation for a Complete Reaction
Step 1 Write reduction half-reactions for both half-cells and find E° for each.
Multiply the half-reactions as necessary so that they both contain the same number of
electrons. When you multiply a reaction, you do not multiply E°.
Step 2 Write a Nernst equation for the right half-cell, which is attached to the positive
terminal of the potentiometer. This is ECathode
Step 3 Write a Nernst equation for the left half-cell, which is attached to the negative terminal
of the potentiometer. This is EAnode
Step 4 Find the net cell voltage by subtraction: E = ECathode - EAnode
Step 5 Write the net cell reaction by subtracting the left half-reaction from the right
halfreaction. (Subtraction is equivalent to reversing the left half-reaction and adding.)
38
Electrochemical Cells
Nernst Equation for a Complete Reaction
Find the voltage of the cell if the right half-cell contains 0.50 M AgNO3(aq) and the left half-cell
contains 0.010 M Cd(NO3)2(aq). Write the net cell reaction and state in which direction electrons
flow.
39
Electrochemical Cells
Nernst Equation for a Complete Reaction
40
Electrochemical Cells
Nernst Equation for a Complete Reaction
41
Electrochemical Cells
Nernst Equation for a Complete Reaction
42
Electrochemical Cells
Nernst Equation for a Complete Reaction
43
Electrochemical Cells
LIQUID JUNCTION POTENTIALS
The interface between electrochemical solution and
the salt bridge (liquid-liquid interface)
→ could develop as junction potential
➢ Electrochemistry
➢ Electroanalytical chemistry
➢ Galvanic Cells
➢ Line Notation
➢ Nernst Equation
➢ Liquid junction potentials
45
Potentiometry
The Standard Electrode Potential
46
Potentiometry
Standard Hydrogen Electrode - SHE
The SHE consists of platinum wire that is connected to a Pt
surface in contact with an aqueous solution containing 1 M
H+ in equilibrium with H2 gas at a pressure of 1 atm. In the
molecular view, the Pt surface catalyzes the oxidation of
hydrogen molecules to protons or the reduction of protons
to hydrogen gas.
The convention is to select a particular electrode and
assign its standard reduction potential the value of 0.0000V.
This electrode is the Standard Hydrogen Electrode.
48
Potentiometry
Standard Hydrogen Electrode - SHE
49
Potentiometry
Standard Hydrogen Electrode - SHE
51
Potentiometry
Đo hiệu thế giữa hai điện cực nhúng vào một dung dịch nhất
định
➢ Điện cực so sánh có thế không đổi (Reference electrode: maintains a fixed
potential)
➢ Điện cực chỉ thị có thế thay đổi theo bản chất và nồng độ của ion cần xác
định (Indicator electrode: responds to analyte activity)
Từ thế E thay đổi có thể suy ra hoạt độ hoặc nồng độ của ion
cần xác định dựa trên phương tr.nh Nernst.
Hệ hoạt động với cường độ d.ng gần như bằng 0 (i~0), không có phản ứng điện hóa
xảy ra, thành phần dung dịch không đổi. 52
Potentiometry
53
Potentiometry
The Standard Electrode Potential
Disadvantage ???
54
Potentiometry
The Standard Electrode Potential
55
Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES
56
Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES
Tinh thế điện cực so sánh vs SHE khi nồng độ KCl 3M? 57
Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES
58
Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES
59
Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES
First, we prepared the autopipettor tip with gel by mixing 1.4g agarose, 100 ml water and 5.0g KNO3, and heat the
solution to boiling with constant stirring
60
Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES
61
Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES
Finally, we filled the autopipettor tip with 3.0 M KCl solution, and inserted the wire into the tip.
We used the parafilm to both prevent the evaporation of the KCl solution and stablised the silver
wire.
62
Potentiometry
SATURATED CALOMEL ELECTRODES - SCE
63
Potentiometry
CALOMEL ELECTRODES
Temperature dependent!
64
Potentiometry
Example
The potential for an Fe3+/Fe2+ half-cell is +0.750 V relative to the standard hydrogen electrode.
What is its potential when using a saturated calomel electrode or a saturated silver/silver
chloride electrode?
We can use the same equation to calculate the potential when using a saturated calomel electrode
65
Potentiometry
Example
The potential for an Fe3+/Fe2+ half-cell is +0.750 V relative to the standard hydrogen electrode.
What is its potential when using a saturated calomel electrode or a saturated silver/silver
chloride electrode?
66
Potentiometry
The Reference Electrode
Yêu cầu của điện cực so sánh
➢ Thế tuân theo phương trình Nernst và trở lại thế ban đầu khi chịu một
dòng điện rất nhỏ. Phản ứng điện cực hoàn toàn thuận nghịch
68
Potentiometry
INDICATOR ELECTRODES
69
Potentiometry
INDICATOR ELECTRODES - Electrodes of the first kind
A pure metal electrode : in direct equilibrium with its cation in the solution
𝟎. 𝟎𝟓𝟗𝟐 𝟏
𝑬𝒊𝒏𝒅 = 𝑬𝟎 − 𝒍𝒐𝒈 𝒏+
𝒏 𝑴
70
Potentiometry
INDICATOR ELECTRODES - Electrodes of the first kind
K is a constant that includes the standard-state potential for the Mn+/M redox couple, the
potential of the reference electrode, and the junction potential
71
Potentiometry
INDICATOR ELECTRODES - Electrodes of the first kind
If we place a copper electrode in a solution containing Cu2+, the electrode’s potential due to the
reaction: 𝟐+ −
𝑪𝒖 𝒂𝒒 + 𝟐𝒆 ↔ 𝐂𝐮 (𝒔൯
is determined by the activity of Cu2+
If copper is the indicator electrode in a potentiometric electrochemical cell that also includes a
saturated calomel reference electrode
then we can use the cell potential to determine an unknown activity of Cu2+ in the indicator
electrode’s half-cell
𝟎. 𝟎𝟓𝟗𝟏𝟔 𝟏
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒊𝒏𝒅 − 𝑬𝑺𝑪𝑬 + 𝑬𝒋 = +𝟎. 𝟑𝟒𝟏𝟗 𝑽 − 𝒍𝒐𝒈 − 𝟎. 𝟐𝟒𝟒𝟒 𝑽 + 𝑬𝒋 72
𝟐 𝒂𝑪𝒖𝟐+
Potentiometry
Indicator electrodes
Problems
• Electrode of the first kind is not very popular because...
➢ Metallic indicator electrodes are not very selective and respond not only to their own cations
but also to other more easily reduced cations.
➢ Many metal electrodes can be used only in neutral or basic solutions because they dissolve
in the presence of acids
➢ Easily oxidized, can be used only when analyte solutions are deaerated to remove oxygen
➢ Certain hard metals (Fe, Cr, Co, Ni) do not provide reproducible potentials
• Limited electrodes are: Ag/Ag+ and Hg/Hg2+ in neutral solutions and Cu/Cu2+, Zn/Zn2+, Cd/Cd2+,
Bi/Bi3+, Tl/Tl+, and Pb/Pb2+ in deaerated solutions.
73
Potentiometry
INDICATOR ELECTRODES - Electrodes of the second kind
➢ Dùng để xác định các anion Xn-.
➢ Dùng một kim loại M làm điện cực. Kim loại này tạo hợp chất ít tan hoặc tạo phức bền với anion X.
74
Potentiometry
INDICATOR ELECTRODES - Electrodes of the second kind
If we saturate the indicator electrode’s half-cell with AgI, the solubility reaction
75
Potentiometry
INDICATOR ELECTRODES - Electrodes of the second kind
where Ksp, AgI is the solubility product for AgI
we find that the potential of the silver electrode is a function of the activity of I-. If we
incorporate this electrode into a potentiometric electrochemical cell with a saturated calomel
electrode
where K is a constant that includes the standard-state potential for the Ag+/ Ag redox couple, the
solubility product for AgI, the reference electrode’s potential, and the junction potential
76
Potentiometry
INDICATOR ELECTRODES - Electrodes of the second kind
Mercury : indicator electrode of second kind for the EDTA anion Y4-. When a small amount of
HgY 2- is added to a solution containing Y4-, the half-reaction of a Hg electrode
77
Potentiometry
INDICATOR ELECTRODES - redox electrodes
A Redox electrode will measure the ratio of oxidized species to reduced species in a solution
where both are present. The indicator electrode will measure the electron movement and to do
this, it must be chemically inert and an excellent electron conductor.
78
Potentiometry
Membrane electrodes
79
Potentiometry
pH Electrode
What is pH? Potential Hydrogen or Power of Hydrogen
H3O+ + OH- ↔ 2H2O
[HCl] 0.1 M and [CH3COOH] 0.1 M ???? CH3COOH + H2O ↔ CH3COO- + H3O+
pH = -log[aH+]
80
Potentiometry
pH Electrode
81
Potentiometry
pH Electrode
82
Potentiometry
pH Electrode
83
Potentiometry
pH Electrode
84
Potentiometry
pH Electrode
85
Potentiometry
pH Electrode
86
Potentiometry
pH Electrode
87
Potentiometry
pH Electrode
88
Potentiometry
pH Electrode
89
Potentiometry
pH Electrode
Temperature effects
➢ Electrode
➢ Calibration
➢ Buffers
➢ Samples
90
Potentiometry
pH Electrode
Temperature effects
91
Potentiometry
pH Electrode
92
Potentiometry
pH Electrode
pH Calibration
93
Potentiometry
pH Electrode
pH Calibration
Bracket your process pH
➢ Cardinal Rules for pH Calibration
Always have your calibration buffers “bracket” your process
pH measurement of interest.
-Example; Process pH of 8.2 should utilize 7 and 10
buffers
➢ Never calibrate with two buffers more than 3 pH units apart
94
Potentiometry
pH Electrode
pH Calibration
96
Potentiometry
pH Electrode
Electrode Care and Maintenance
When do you need to clean your electrode?
➢ Check slope range
Ideal range: 95 % - 102 %
Cleaning range: 92% - 95%
Replacement range: below 92%
➢ Check response times in buffers
Electrode stability within 30 seconds
➢ Check precision of electrode by reading buffers as samples
➢ Check for any drift of electrode in pH buffer
97
Potentiometry
pH Electrode
Electrode Care and Maintenance
➢ General electrode bulb cleaning
Soak in Cleaning Solution for 30 minutes
Replace electrode fill solution
Soak in storage solution for at least 2 hours
➢ Electrode junction cleaning
Soak in 0.1M KCl for 15 minutes at 70 oC
Replace electrode fill solution
Soak in electrode storage solution for 2 hours
➢ Check junction by suspending in air for ten minutes
98
Observe KCl crystal formation
Potentiometry
pH Electrode
Keys to Accuracy
➢ Always use fresh buffers
Check bottle expiration and date opened
➢ Fresh buffer for each calibration
➢ Replace the fill solution in the electrode every week
Fill solution concentration is maintained
KCl crystallization is prevented
➢ Make sure to use the correct fill solution
99
Potentiometry
pH Electrode
Keys to Accuracy
➢ Use insulation between stir plate and sample container to minimize heat transfer
100
Potentiometry
pH Electrode
Troubleshooting pH Problems
➢ Common measurement problems
▪Readings not reproducible
▪Slow response
▪Noisy response
▪Drifty response
▪Inaccurate
➢ Troubleshooting Sequence Meter
▪ Buffers
▪ Reference electrode
▪ pH electrode
▪ Sample
101
▪ Technique
Potentiometry
pH Electrode
Electrode Check
➢ Check Slope Range (102% -95%)
➢ Check response time in buffers (stable reading in 30 seconds)
➢ Verify mV readings are in the correct range for each buffer
pH 4.01 is +178 mV +/-30 mV
pH 7.00 is 0 mV +/-30 mV
pH 10.01 is -178 mV +/-30 mV
IF the Electrode Check FAILS:
➢ Check for air bubbles near bulb
➢ Verify correct filling solution is being used
➢ Check for salt crystal formation inside electrode
➢ Check junction is open by suspending in air for 10 minutes and KCl crystal formation should
occur
➢ Use Junction cleaning procedures
➢ Re-check instruction manual for electrode conditioning procedures 102
Potentiometry
pH Electrode
Alkaline error
• Exhibited at pH > 9
• Electrodes respond to H+ and alkali
cations
• C,D,E and F: measured value is < true
value
• Electrode also responds to other
cations
• Higher pH at lower [Na+]
103
Potentiometry
pH Electrode
Acid error
104
Potentiometry
pH Electrode
105
Potentiometry
pH Electrode
106
Potentiometry
pH Electrode
Cleaning Electrodes
General Cleaning: Soak the electrode in 1:10 dilution of reagent in a 0.1 to 0.5% liquid
detergent solution in hot water with vigorous stirring for 15 minutes. Place junction
under warm, running tap water for 15 seconds. Drain/refill the reference chamber. Soak
the electrode in storage solution for at least 10 minutes
Salt Deposits: Dissolve the deposit by immersing the electrode in 0.1 M HCl for five
minutes, followed by immersion in 0.1 M NaOH for five minutes, and thorough rinsing
with distilled water
Air Bubbles: If air bubbles appear in the electrode (especially with microelectrode
and narrow test tube electrodes), open up the fill hole, grab the cable of the probe
about 18" from the connection to the electrode, and spin in a circular motion over
your head (like a helicopter) for about a minute. The centrifugal force should force
108
the air bubble to the fill hole/top of the electrode
Potentiometry
pH Electrode
Cleaning Electrodes
General
Soak in 0.1M HCl or 0.1M HNO3 for half an hour. For refillable electrodes. Drain and refill the
Electrode Filling Solution. Soak the electrode in Filling or Storage Solution for 1 hour.
Inorganic
Soak in 0.1M tetrasodium EDTA solution 15 minutes. Drain and refill the Electrode Filling
Solution. Soak the electrode in Filling or Storage Solution for 1 hour.
Protein
Soak in 1% pepsin in 0.1M HCl for 15 minutes. Drain and refill the Electrode Filling Solution.
Soak the electrode in Filling or Storage Solution for 1 hour.
Grease and Oil
Rinse with mild detergent or methanol solution. Drain and refill the Electrode Filling Solution.
Soak the electrode in Filling or Storage Solution for 1 hour.
109
Potentiometry
pH Electrode
110
Potentiometry
pH Electrode
111
Potentiometry
pH Electrode
112
Potentiometry
Membrane electrodes
➢ Glass electrode
➢ Crystalline-Membrance electrode
➢ Liquid membrance electrode
113
Potentiometry
Membrane electrodes
Crystalline-Membrane electrode
114
Potentiometry
Membrane electrodes
Crystalline-Membrane electrode
115
Potentiometry
Membrane electrodes
Crystalline-Membrane electrode
Ag2S 116
Potentiometry
Membrane electrodes
Crystalline-Membrane electrode
119
Potentiometry
Membrane electrodes
Crystalline-Membrane electrode
120
Potentiometry
Membrane electrodes
Crystalline-Membrane electrode
122
Potentiometry
Membrane electrodes
Gas sensing electrode
123
Potentiometry
DIRECT POTENTIOMETRY
➢ A rapid and convinient method of detecting the activity of cations and anions
➢ The technique used in this method is a comparison of the potential developed by the
indicator electrode when it is immersed in the solution with that when it is immersed in
standard solution of the analyte
124
Potentiometry
125
Potentiometry
POTENTIOMETRIC MEASUREMENT
➢ Calibration Method
➢ Standard Addition Method
126
Potentiometry
POTENTIOMETRIC MEASUREMENT
➢ Calibration Method
➢ Standard Addition Method
127
Potentiometry
128
Potentiometry
POTENTIOMETRIC TITRATION
➢ Involves measurement of the potential of a suitable indicator electrode as a function of
titrant volume
➢ Provides MORE RELIABLE data than the usual titration method
➢ Useful with colored/turbid solutions
➢ May be automated
➢ More time consuming
129
Potentiometry
POTENTIOMETRIC TITRATION
131
Potentiometry
POTENTIOMETRIC TITRATION
132
Potentiometry
POTENTIOMETRIC TITRATION
➢ Thế của điện cực chỉ thị tỉ lệ với logarit hoạt độ của
chất phân tich (lga).
➢ Trong qua trinh chuẩn độ, hoạt độ giảm dần, lga thay
đổi chậm theo thế E đo được.
➢ Gần đến điểm tương đương, hoạt độ tiến đến 0, lga
và thế E biến thiên mạnh
➢ Nếu ΔE la độ biến thiên của thế ứng với thể tích thêm
vào thì ΔE/ ΔV biến thiên chậm khi còn xa điểm tương
đương, tăng rất nhanh khi đến gần điểm tương đương,
qua một cực đại ở điểm tương đương, sau đo giảm dần.
133
Potentiometry
POTENTIOMETRIC TITRATION
It is used when the endpoints are very difficult to determine either when:
➢ Very diluted solution.
➢ Coloured and turbid solution.
➢ Absence of a suitable indicator.
134
Potentiometry
POTENTIOMETRIC TITRATION
135