Lecture 08

Steady-state Voltammetry
ENCH800029

Muhammad Ibadurrohman, Ph.D (DIC)

Room R-401, Department of Chemical Engineering
Faculty of Engineering, Universitas Indonesia
Email: ibad@che.ui.ac.id
Types of States in Electrochemical Cells

• Equilibrium state: No concentrations change with time in an equilibrium experiment and there
are no fluxes of any kind.

• Steady state: No pertinent concentrations change with time when an experiment is in a steady
state. Fluxes do occur, but their densities do not change with time within the space of interest.

• Periodic state: Concentrations change with time, as do fluxes. However, all important
concentrations and fluxes return to their original values after integer multiples of a specific time
interval, the period.

• Transient state: Concentrations and fluxes change nonperiodically with time in transient studies.
Voltammetry

• The word “voltammetry” was used to describe the

measurement (-metry) of the interdependence of
electrode potential (measured in volt-s) and cell
current (in -am-peres)

• One of most important means of chemical

analysis:
• Kinetics of electron transfer

• Thermodynamic properties

• Transport behaviour
Voltammetry

Typical arrangements:
• One electrode of interest (WE)

• Excessive support electrolyte

• Area of WE is from 10-6 to 10-4 m2

• Current density is lower than 100 Am-2

• Electrode potential is from -2.5 V to +2.5 V

• The duration of half-cycle is short (0.1 – 60 s)

• Volume of solution is 100 ml or less

• Dilute electroreactant concentration (0.1 mM – 10 mM)

Voltammetry
Voltammetric Techniques
Voltammetric Techniques
Potential-step Voltammetry
Potential-step Voltammetry

𝐹𝑒 3+ + 𝑒 − → 𝐹𝑒 2+

𝜕 𝜕 2
𝐹𝑒 3+ = 𝐷 2 𝐹𝑒 3+
𝜕𝑡 𝜕𝑥

𝑖𝑐 = −𝑛𝐹𝐴𝑘𝑟𝑑 𝐹𝑒 3+

𝑛𝐹𝐴𝑘𝑟𝑑 𝐹𝑒 3+ 𝐷
𝑖 =
𝜋𝑡
Linear-sweep Voltammetry

For a reversible electrochemical reaction the CV recorded has certain well defined characteristics :
• The positions of peak voltage do not alter as a function of voltage scan rate
• The ratio of the peak currents is equal to one
• The peak currents are proportional to the square root of the scan rate
Cyclic Voltammetry
𝐸

𝐸𝑟

𝑡𝑟 2𝑡𝑟

𝐸0

(a) Ideal voltammetry: unique 𝐼-𝐸 one-to-one correlation

(b) Moderately large scan rate: slight depart between forward
and reverse scan
𝑣 = scan rate 𝑡𝑟 = reversal time
(c) Large scan rate: distinguishable forward and reverse scan
Cyclic Voltammetry
𝐸

𝐸𝑟

𝑡𝑟 2𝑡𝑟

𝐸0

𝑣 = scan rate 𝑡𝑟 = reversal time

Cyclic Voltammetry
Cyclic Voltammetry
 Cyclic Voltammetry

• Oxygen Region is found at positive potentials. During

the positive sweep prior to O2 evolution a hydrated Pt
oxide monolayer is formed (anodic current)

• Double-layer Region is a region where only low currents

(positive anodic for the positive sweep and negative for
the negative sweep) can be found (only capacitive
processes)

• Hydrogen Region is found at negative potentials

Rodriguez et al. (2000). J. Chem. Edu. Vol. 77 No. 9

 Cyclic Voltammetry

• Hydrogen Region:
• The reduction of H+ and the adsorption of H atoms:
𝐻 + 𝑎𝑞 + 𝑒 − + site → 𝐻 𝑎𝑑

• Adsorption of H2 molecules:
2𝐻 + → 𝐻2 𝑎𝑑

• Desorption of H2 gas:
𝐻2 𝑎𝑑 → 𝐻2 𝑔

Rodriguez et al. (2000). J. Chem. Edu. Vol. 77 No. 9

Cyclic Voltammetry (Ethanol Electrooxidation)

Simoes et al. (2007). J. Power Sources 167 (2007) 1–10

 Cyclic Voltammetry (Ethanol Electrooxidation)
Simoes et al. (2007). J. Power Sources 167 (2007) 1–10
7. 2M + C2H5OH → M—CH2CO—M + H+ + e-
8. M—CH2(CHOH)—M + M → M--CH2—M + M-CO + 2H+ + e-
9. M—CH3CO → M—CH2CO—M + H+ + e-
10. M—CH2CO—M + M → M--CH2—M + M-CO
11. M--CH2—M + M-CO + M--OH → CO2 + 3M + 2H+ + 2e-
1. Adsorption of ethanol
M + C2H5OH → M—CH(CH3)OH + H+ + e-
2. Dehydrogenation of ethanol (formation of acetaldehyde)
M—CH(CH3)OH → M + CH3CHO + H+ + e-
3. Re-adsorption of acetaldehyde
M + CH3CHO → M—CH3CO + H+ + e-
4. Reaction between adsorbed acetaldehyde and adsorbed
hydroxyl producing acetic acid
M + H2O → M--OH + H+ + e-
M—CH3CO + M—OH → CH3COOH + 2M + H+ + e-
5 & 6. Another path of acetic acid formation (less probable)
2M + C2H5OH → M—C((CH3)OH)—M + 2H+ + 2e-
M—C((CH3)OH)—M + M—OH → CH3COOH + 3M