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Reaction Kinetics
Dr.-Eng. Zayed Al-Hamamre
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Content
Overview Faradays Laws Fuel Cell Performance and Irreversibility Electrode Electrolyte Interface Electrochemical Kinetics ButlerVolmer Equation Polarization Losses
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Overview
Electrochemical reactions results in the transfer of electrons between an electrode surface and a chemical species adjacent to the electrode surface (heterogeneous reaction). For an electrochemical reaction to take place, there are several necessary components: 1. Anode and Cathode Electrode: The electrochemical reactions occur on the electrode surfaces. Oxidation occurs at the anode and reduction at the cathode Electrolyte The main function of the electrolyte is to conduct ions from one electrode to the other. It is also serves to physically separate the fuel and the oxidizer and prevent electron short-circuiting between the electrodes.
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3. External Connection between Electrodes for Current Flow: If this connection is broken, the continuous circulation of current cannot flow and the circuit is 3 open.
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Overview
The H2 gas and protons can not exist inside the electrode, while free electrons can not exist in the electrolyte
2eElectrode + H2 + + 2H+ +Electrolyte
The current produced by fuel cell (number of electron per time) depends on the rate of electrochemical reactions.
Q Charge in C, t is time, n No. of electron, dN\dt is the rate of electrochemical reaction Although the anode and cathode reactions are independent, they are clearly coupled to each other by the necessity to balance the overall reaction, so that the electrons produced in the HOR are consumed in the ORR
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Overview
Current produced by the cell is directly proportional to the area of the interface, therefore, current density (current per unit area, A or mA\cm2) is used
Where A is the area Electrochemical reaction rate can be expressed per unit area base:
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Overview
The total charge passed by the flow of an ampere of electrons in one second
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Overview
Faradays constant F represents the charge per mole of equivalent electrons
The equivalent electrons (eq) is very important. Many electrochemical reactions do not exchange 1 mol of electrons for 1 mol of reactant. For the reaction
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
FARADAYS LAWS:
CONSUMPTION AND PRODUCTION OF SPECIES How much mass of a given reactant is required to produce a given amount of current? Conversely, how much current is required to produce a certain amount of product ? The fundamental relationships should be based on conservation of mass and charge The charge transfer per mole of species of interest is nF. In the reaction ,, electrons are transfer per mole of oxygen, thus the charge passing is 4F (coulombs/mole)
n simply permits determination of the relationship between charge passed and reactant consumption (or product generation) of any species chosen.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
FARADAYS LAWS:
CONSUMPTION AND PRODUCTION OF SPECIES Considering water produced as the species of interest, the value of n is 2, and there are 2F coulombs passed per mole of H2O produced. Faradays Laws establish a link between the flow of charge and mass The amount of product formed or reactant consumed is directly proportional to the charge passed. J
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Example
Consider a single hydrogen fuel cell at 4 A current output: Anode oxidation: Cathode reduction: Global reaction: 1. What is the molar rate of H2 consumed for the electrochemical reaction?
2.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Example
3. What is the minimum molar flow rate of air required for the electrochemical reaction?
4.
What is the maximum molar flow rate of air delivered for the electrochemical reaction? There is no maximum of reactant supplied. What is the rate of water generation at the cathode in grams per hour?
5.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrode Electrolyte
Electrode Electrolyte
Electrode Electrolyte
eFermi Level.
Equilibrium
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
What is the physical nature of the activation polarization and how exactly does the charge transfer reaction proceed?
Between an electrode and the electrolyte, there exists a complex structure known as the electrical (charge) double layer. At the electrode surface and in the adjacent electrolyte, a buildup of charge occurs. At the anode, the potential is lower than the surrounding electrolyte, so the there is a buildup of negative charge along the surface of the catalyst and a positive charge in the surrounding electrolyte forming the double-layer structure. 17
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
O2 + 4e + 4H+ 2H2O
The charge double layer at the surface the cathode in an acidic electrolyte fuel 19 cell .
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
The more the charge, the greater is the current. Any collection of charge, at the electrode/electrolyte interface will generate an electrical voltage (activation overvoltage). The overvoltage opposes and reduces the reversible ideal voltage (Voltage lost in driving the chemical reaction that transfers the electrons to or from the electrode). charge double layer needs to be present for a reaction to occur, that more charge is needed if the current is higher, and so the overvoltage is higher if the current is greater.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Capacitance
dielectric constant
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Diffuse charge
The Capacity,
n0 NO. of ions per unit volume in the bulk of the electrolyte , V is the potential drop from the metal to the bulk of the electrolyte. 23
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Equilibrium: Measurements of redox potentials (and voltage potentials) Gives a quantitative estimate of the reaction tendency to proceed (equilibrium) No kinetic information is derived from these measurements Kinetics: Concerned the mechanism by which electron transfer process occur. Need to know if the reactions (electron transfer) will proceed fast enough to make them useful We desire the rate of electron transfer (ET) that occurs at the electrode electrolyte interface for given conditions How can kinetic information about ET processes be derived? Increasing the rates of fuel-cell reactions is central to developing highly efficient 26 commercial fuel cells.
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Basic Kinetic Concepts for Interfacial ET process: Current flow is proportional to reaction flux (rate) Reaction rate is proportional to interface reactant concentration Similar to homogeneous reaction chemical kinetics: constant of proportionality between reaction rate (mol/cm2/s) and reactant concentration c (mol/cm3) is the rate constant k (cm/s) All chemical and electrochemical reactions are activated processes Activation energy barrier that must be overcome for reactions to proceed Energy must be supplied to surmount the activation energy barrier Energy may be supplied thermally or also (for ET processes at electrodes) via application of a potential to the electrodes
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Applying a potential to an electrode generates an electric field at the electrode/electrolyte interface that reduces the magnitude of the activation energy barrier increasing the ET reaction rate, Electrolysis works on this principle An applied potential acts as a driving force for the ET reaction Expect that current should increase with increasing driving force Catalysts act to reduce the magnitude of the activation energy barrier .
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
The reaction is thermodynamically favorable, and the reaction will generate current, a flow of electrons or ions. 29
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
The rate of electrochemical reaction is finite because the energy barrier (activation Energy) impedes the conversion of reactants into products.
For reaction to take place, the activation energy must be over come
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Electrochemical Kinetics
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Electron Transfer and Mass Transport We know that both mass transport (reactants and products) and the electron transfer process itself contribute to kinetics Let us ONLY consider the kinetics of interfacial electron transfer from a classical, macroscopic and phenomenological (non quantum) viewpoint This approach is based on classical Transition State Theory, and results in the ButlerVolmer Equation Transition State Theory Quantitative study of the transition state that molecules pass through during reaction (chemical, electrochemical)
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Transition State Theory
Reaction driving force voltage over potential at the electrode Elementary charge transfer reaction step Fuel /Oxidizer Free energy or enthalpy Partially converted reactants Boltzmann constant
Rate constant
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Electrochemical Kinetics
Eyring and Arrhenius Equations The Eyring equation is valid for many types of dynamic rate processes (gases, liquids, in solution, and on surfaces) Consider the transition state (*) of an activated process
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Activation energy of charge transfer reactions For the H2 2H+ + 2e-, the following series of steps are being followed: 1. Mass transport of H2 onto the electrode H2 (bulk) H2 (near electrode) 2. 3. Absorption of H2 onto the electrode surface H2 (near electrode) + M M H2
M: represents the nonreacting catalyst surface
4.
5.
Separation of the H2 molecules into two individual bond (chemisorbed) Hydrogen atoms on the electrode surface M H2 + M 2MH Transfer of electrons from the chemisorbed hydrogen atoms to the electrode releasing H+ ions into the electrolyte (limiting step) 2 [MH (M + e-) + H+ (near electrode) Mass transport of the H+ away from the electrode 2 [H+ (near electrode) H+ (bulk electrolyte) 38
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
The overall reaction rate will be determined by the slowest step in the series Activation energy 1 increase with the distance from metal surface (stability improves with absorption to the electrode surface). 2 energy is required to bring H+ to the electrode surface to over come the repulsive force (unfavorable for the H+ to be at the surface of electrode)
Free energy 1 2
Free energy H+ Free energy of the Chemisorbed H
G*1
MH
G*2
(M + e-) + H+ Distance from interface
Grxn
The red line represent the min. energy path for the conversion (conversion involves an over come of energy max. (a: activated state)
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Overall rate of reaction:
For the case where the activation energy of the product state lower than the reactants state, then the forward reaction proceeds faster than the backward reaction rate. The unequal rates results in a build up of charge (e- accumulating at the electrode and H+ in the electrolyte) . The charge accumulation continues until the resultant potential across the reaction interface counter balance the free energy difference between reactants and products. (electro-chemical equilibrium)
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Exchange current density Defined as the rate of the forward or reverse reaction under equilibrium conditions. Since
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
At equilibrium: and Where j0 is the exchange current density
The free energy of charge species are sensitive to voltage. Therefore, changing the cell voltage changes the free energy of the charged species taking part in the reaction. The size of the activation barrier can be manipulated by varying the cell potential.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Rate constant, k, varies with applied potential, E, because G* varies with applied potential.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Application of a finite overpotential, = E - ENernst, lowers the activation energy barrier for an electrochemical reaction by a fixed amount, (Symmetry factor, , or the electron transfer coefficient, determines how much of the electrical energy input affects the activation energy barrier of the redox process (0 < < 1)). In the previous figure, the activation barrier of the forward reaction is decreased by while the reverse activation barrier is increased by
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
ButlerVolmer equation Gibbs Free Energy: Interims of the exchange current density: and = overpotential
ButlerVolmer equation
where
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
ButlerVolmer Equation Increasing the exchange current density can be performed by: Increasing the reactant concentration Decreasing the activation barrier Increasing the temperature T Increasing the number of active reaction site (increasing the reaction interface)
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
ButlerVolmer equation, effect of activation overvoltage on fuel cell performance The curve was constructed by calculating the ideal cell potential (Nernst Equation) then subtracting Reaction kinetics inflict an exponential loss on a fuel cell i-V curve (BV equation) The smaller the j0, the greater is this voltage drop. Having a high j0 is critical to have good fuel cell performance
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Electrochemical Kinetics
The current produced by an electrochemical reaction increases exponentially with the activation overvoltage (voltage loss to overcome the activation barrier associate with electrochemical reaction). The equation state that, to obtain more electricity (current) from the fuel cell, a price interims of lost voltage must be paid.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
ButlerVolmer Model of Kinetics (More general expression)
To describe activation polarization losses at a given electrode. The BV model describes an electrochemical process limited by the charge transfer of electrons (ORR, and in most cases the HOR with pure hydrogen). The assumption of the BV kinetic model is that the reaction is rate limited by a single electron transfer step The net current density is
For an anode reaction with For a cathodic reaction with positive , the anodic branch negative , the cathodic branch will exponentially increase, will exponentially increase, >> 0 << 0
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Electrochemical Kinetics
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
If = 1 the additional overpotential at the electrode goes completely toward promoting the reduction reaction If = 0 the additional potential is applied toward promotion of the anodic oxidation reaction.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
ButlerVolmer Model: High-Electrode-Loss Region of ButlerVolmer (Tafel equation)
The overvoltage at the surface of an electrode followed a similar pattern in a great variety of electrochemical reactions. For high polarization one of the branches will dominate, thus the overvoltage value is given by
n
For j > j0
Tafel plots for slow and fast electrochemical reactions
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
ButlerVolmer Model: Low-loss (overpotential) region In the low-loss region and using Taylor series expansion and linearization of the BV equation, then the overvoltage potential can be expressed as:
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
ButlerVolmer Equation with Identical Charge Transfer Coefficientssinh Simplification
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
Apply the Eyring equation to electron transfer (ET) process Consider the transition state (*) of an activated process
Characteristic ET distance (molecular diameter)
Let
then
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
ButlerVolmer Simplifications
A low-overpotential region where kinetics are facile and relatively low losses occur A higher overpotential region, where losses become much more significant A very high current region where mass transport losses dominate At low current density, the activation overpotential required to maintain a net reaction rate in a given direction is small. Beyond a threshold value in current density related to the equilibrium reaction exchange rate of the electrode, the additional polarization required for increasing current is greatly increased.
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Electrochemical Kinetics
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Activation Polarization
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Activation Polarization
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Activation Polarization
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Activation Polarization
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888
Ohmic Polarization
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Concentration Polarization
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Cell Voltage
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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan Tel. +962 6 535 5000 | 22888