Introduction Definitions: Electrochemistry Electrochemical Engineering Challenges Course Content Major Applications History

Electrochemistry Electrochemistry is the branch of chemistry concerned with the interrelation of electrical and chemical effects Deals with The study of chemical changes caused by the passage of a current The production of electrical energy by chemical reactions

Electrochemical Engineering The use of chemical engineering fundamental principles for the study and analysis of electrochemical systems Thermodynamics Transport phenomena kinetics

What is an electrochemical system? System characterized by: Strong interactions among solute and with the solvent (ionic species) Passage of a current Potential Electrical energy transformed into chemical energy or vice versa e.g., batteries, fuel cells, etc
4

Challenges No much cover on other courses Chemistry Thermodynamics Physical chemistry Electrochemical systems are different Break any myths about electrochemical systems

Course Content Basic concepts Thermodynamics Electrode kinetics Transport mechanisms Modeling Applications

Applications Production of Al and Cl Corrosion Batteries and Fuel Cells Electroplating Cathodic protection Super capacitors

Major Products based on electrochemical technology

Process or Product (data from National Research Council)
Aluminium Sodium Hydroxide Chlorine Copper Other metals and chemicals Electroplating Batteries Semiconductor Processing

Annual Market ($ billion)

4 3 2 2 2 10 4 1

Total

28

History Discoveries started around 1800 Allesandro Volta (first battery) Michael Faraday (Faradays law) David Grove (1839) discovered the fuel cell Georges Leclanche (1868) constructed the carbon zinc battery

History Hall-Heroult aluminum process (1886) reduced the price from $100/lb to $2/lb Walter Nernst Julius Tafel Great advances in electroplating (1920-1940s)

10

History The formal synthesis of electrochemistry and engineering began in 1950s Norbert Ibl in Switzerland Charles Tobias in US

11

Summary Electrochemistry Electrochemical Engineering What is an electrochemical system? Major applications of electrochemistry

12

Chapter 1: Basic Concepts

Outline
Redox reactions Electrochemical Cells-definition Standard electrode Standard cell potential Electrochemical cells
Representation Galvanic cells Electrolytic cells

Nernst equation Faradays law Current and voltage efficiency Ion conduction Transfer numbers
1.13

Redox reactions: Oxidation Oxidation Process by which an element losses electrons (increases its oxidation number) The electrode at which oxidation takes place is called the anode e.g.,

1.14

Redox reactions: Reduction

Reduction
Process by which an element gains electrons (decreases its oxidation number) The electrode at which reduction takes place is called the cathode e.g.,
1.15

Exercise # 1
Classify the following redox reactions, include the electrodes name

1.16

Electrochemical Cells
Consists of:
At least two electrodes where reactions occur Electrolyte, for conduction of ions External conductor, to guarantee continuity of the circuit

1.17

Electrochemical Cells

1.18

Key information
Electrochemical reactions ALWAYS take place on electrodes NOT in the bulk A potential is always measured respect to ANOTHER electrode

1.19

Standard Electrode Potentials The universal reference electrode is hydrogen (SHE) Standard conditions: Temperature 25oC Unit activity coefficient of H+ ions Reaction

E: Electrode potential 0: Standard conditions

1.20

SHE Consists of a Pt wire immersed in a solution of 1 M H+ Hydrogen gas is bubble at 1 atm The Pt wire provides a surface area for the reaction to take place The gas stream keeps the solution saturated at the electrode site

1.21

SHE It is a theoretical electrode It cant be manufactured because it is impossible to have hydrogen ion activity of 1.00 M However, hydrogen electrodes can be manufactured

1.22

Building a H2 Electrode
Making a simple, standard Hydrogen electrode

Begin with a Pyrex test tube

Step 1: Using glassblowing techniques, add a short glass tube to the side of the tube

Step 2: Spot weld (or silver solder) a 1 cm x 1 cm square of platinum foil as a Platinum wire

Step 3: Again, using glassblowing, seal the platinum wire into the base of the test tube

1.23

Meaning of Potential The potential represents the maximum electrical energy available from a cell Its related to the Gibbs free energy of the cell by:

n: number of electrons F: Faraday's constant (96485 C/eq)

1.24

Questions? What should be the sign of the potential E0 for a reaction to be spontaneous? Answer: POSITIVE Positive potentials mean that the reaction is spontaneous Negative potentials mean that the reaction is not spontaneous

1.25

Standard Potentials in Electrochemical Cells Appendix B of the book summarizes the standard electrode potentials Standard electrode potentials can be used to calculate the Standard potential of an electrochemical cell

1.26

Standard cell potential: Calculations 1. Choose the electrode reactions from the standard electrode potentials table 2. Reverse the sense of the reactions according to your system 1. Reverse the sign of your standard potential 3. Balance the number of electrons multiplying by a positive number 4. Add the electrode reactions to obtain overall reaction 5. Add the potentials to obtain the overall potential of the cell
1.27

Standard Cell potential: Calculations You can balance the stoichiometry of the equation by multiplying by any positive constant This operation does not alter the potential of the cell (potential is an intensive quantity, unaffected by the number of electrons)

1.28

Schematic Representation of Electrochemical Cells Include all the phases involved Separate the phases using bars Include information about solvent and concentrations if available e.g.:

1.29

Exercise #2 Calculate the standard potential of the cell What is the anode? What is the cathode?

1.30

Galvanic Cells It is an energy producing cell Also known as: Driving cell Spontaneous cell They are used as batteries (several cells in series) The standard potential is the maximum potential that can be provided by the cell The anode is assigned a negative sign (negative electrode) 1.31

Galvanic Cells: continued The cathode is assigned a positive sign (positive electrode) Sign of current: Positive if it leaves the electrode to the electrolyte Negative if it enters the electrode from the electrolyte

1.32

Exercise #3 Write the reactions, identify positive and negative electrodes, identify cathode and anodes, identify direction of the current, and draw the cell including external circuit and flow of electrons, for the following reaction

1.33

Electrolytic Cells It is an energy consumer cell Also known as: Driven cell Non Spontaneous cell Opposite process of a battery (required energy to operate) The standard potential is the minimum necessary potential required for the cell to operate
1.34

Electrolytic Cells: continued The cathode is assigned a negative sign (negative electrode) The anode is assigned a positive sign (positive electrode) Sign of current: Positive if it leaves the electrode to the electrolyte Negative if it enters the electrode from the electrolyte
1.35

Exercise #4 Write the reactions, overall reaction, calculate the total standard potential of the cell, identify positive and negative electrodes, identify cathode and anodes, identify direction of the current, and draw the cell including external circuit and flow of electrons, for the following reaction:

Cu + Zn 2+

Cu 2+ + Zn
1.36

Hint It is recommended that for every problem that you solve you start by: Writing reactions Calculating open circuit potential (identifying type of cell) Drawing schematic of cell and identifying: Positive and negative electrodes Anode and cathode Direction of the current Direction of electrons This is important to understand your problem and the data that you are given
1.37

Electrolysis of Brine

Membrane: bi-layer membrane made of perfluorocarboxylic and perfluorosulfonic acid-based films

1.38

Summary Where do electrochemical reactions take place? What is oxidation? What is reduction? What is the meaning of potential? Define galvanic and electrolytic cell Calculate the standard potential of a cell Define +,-, cathode, anode, current sign, flow of electrons Draw schematic of electrochemical cell
1.39

Nernst Equation Express relationship between the potential of the cell and the concentration (no standard concentration)

si: stoichiometric coefficient of species i

1.40

Nernst Equation The electrode reaction is written in simplified form as

si : Mi: zi :

positive for products and negative for reactants symbol for the chemical species charge number of the chemical species

1.41

Steps to use Nernst Eq. Write down electrode reactions Determine # of electrons transferred (balance equations) Use Eq. 1 accordingly

1.42

Exercise #6 In a Zn/Cu cell, If the reaction is done in a cell in 5.00 M Zn+2 and 0.30 M Cu+2 at 25oC, what is the cell voltage?

1.43

Faradays Law Relationship between charge passed (Q) and amount of substance oxidized or reduced (m) at an electrode The amount of product formed is directly proportional to the charge passed For a specified quantity of charge passed, the masses of products formed are proportional to the electrochemical equivalent weights of the products
1.44

Faradays Law Eq.

M: atomic or molecular weight I: current, A t: time elapsed, s F: Faradays constant, 96,485 C/equiv or 26.8 Ah/equiv (last one is very useful in battery applications)
1.45

Faradays Law Eq. The product of: (It) is known as total charge passed (Q) If current changes with time, it should be integrated over time to obtain Q

1.46

Deviations from Faradays Law Some causes of deviation from Faradays law are: Consumption of some of the charge by parasitic processes All of the reactants are not consumed The postulated process is not the actual process Some of the material from the sample falls of

1.47

Units and Formula Reminder Power is the product of current by voltage: P=IV (units are W in international system) W = AV W = J/s A = C/s

1.48

Exercise #7 Solve Ex. 2 of the book (Ch2, p26), parts a, b, and c.

1.49

Current efficiency For electrolytic process

1.50

Current efficiency For galvanic process, known as faradays efficiency

1.51

Voltage efficiency For electrolytic process:

For galvanic process:

1.52

Energy efficiency Product of the current and voltage efficiencies:

1.53

Exercise #8 Solve problem 4 of the book (Ch2, p. 27)

1.54

Ion Conduction Conductivity The measure of the materials capability to transfer electrical energy Electrical conductivity (electronic conductivity) is used in metals Ionic conductivity is used in electrolytes (ions transfer the current) Conductivity of metals much higher than ionic conductivity Units: S/cm (Siemens)
1.55

Order of Magnitude of Conductivities In an aqueous system at room temperature: 10-2 S/cm Much lower than metals, order of magnitude for metals is: 105 S/cm

1.56

Ionic Conductivity This Equations assumes complete dissociation of species

ui: ionic mobility, cm2-mol/J-s zi: charge of species, dimensionless Ci: concentration of species, mol/cm3
1.57

Charged particle in electrified model Assumes: Ions are spheres Continuous viscous medium Low Reynolds numbers Uses Stokes law to calculate the drag force Uniform electric field

1.58

Charged particle model continued

r : radius of particle, cm Ef : forced field, V/cm. For calculations assume 1 V/cm e : charge of an electron, 1.6x10-19 C/chg : viscosity, g/cm-s
1.59

Units Reminder

1.60

Procedure to use charge particle model Calculate velocity using Eq. 11. Assume Ef = 1V/cm Check value of Re number

d: ion diameter, cm : density, g/cm3

1.61

Procedure continued Calculate current density

Since the field is proportional to the negative of the potential gradient, the conductivity can be calculated

1.62

Equivalent conductance model Equivalent conductance (, cm2/ohm-equiv) does not change abruptly with concentration Correlated with square root of concentration (Fig. 2.4) Extrapolating to zero gives the equivalent conductance at dilute conditions () Kohlrausch noticed that the difference between having a common ion was approximately constant
1.63

Equivalent conductance model Kohlrausch concluded that the equivalent conductance can be considered the sum of two ionic components acting independently:

Equivalent conductances are given in Appendix C

1.64

Mobility and diffusivity Equivalent ion conductance is related to mobility: At dilute conditions Nernst-Einstein equation relates mobility to diffusivity:

Di: diffusion coefficient of species i, cm2/s

1.65

Calculation of ionic conductivity using ion conductance Get equivalent conductance (Appendix C, CRC, etc) Calculate mobility using Eq. 14 Calculate conductivity using Eq.10 This procedure is not valid at high concentrations (see Fig. 2.6)

1.66

Exercise #9 Calculate the ionic conductivity of a 0.1 N KCl solution using two different methods. Compare your values. The crystal radius of K is 1.33

1.67

Effect of Temperature on ionic conductivity As a general rule ionic conductivity increases with increasing temperature Rule of thumbs:

1.68

Problem What would be the conductivity of KCl at 60 oC?

1.69

Transference number Represents the fraction of current carried by a specified ion in the absence of concentration gradients

1.70

Useful Expression Combining Eqs 18 and 14:

1.71

Transference number The fractional current carried by each species must add up to the total current, then

1.72

Transference number For a binary electrolyte

1.73

Exercise #10 Solve problem 6 of the book, Ch2 (p. 27). The transference number of Cu+2 in a copper sulfate solution in water is 0.44

1.74

Summary Use and understand Nernst equation Calculate theoretical amount of reactants and products using Faradays law Determine current, voltage and energy efficiency Calculate ionic conductivity Calculate transference numbers

1.75

Chapter 2: Thermodynamics of Electrochemical Systems Outline Cell thermodynamics Temperature and Pressure effects Nernst Equation Pourbaix Diagram Equilibrium constant Reversible heat transfer

2.76

Cell Thermodynamics

Meaning of potential

G = n F E
0

n :number of electrons F : Faraday's constant (96485 C/eq) Previously we used the definition of potential
2.77

Cell Thermodynamics Need to relate thermodynamic (reversible) potential to state variables Electrochemical cells are treated at constant T and P Consider closed system (transport of material between system and surrounding is not permitted) at constant T and P to start relationships

2.78

Cell thermodynamics Using first law of thermodynamics (closed system):

U = q w
The work can be associated with Mechanical changes Other sources: magnetic, surface, or electric work
2.79

Cell thermodynamics Mechanical contribution to work

Total work Mechanical Electrical (we)

2.80

Cell thermodynamics For a reversible change at constant temperature, the heat transferred is given by

S: change in entropy

2.81

Cell thermodynamics The canonical state variable for a system operating at constant T and P is the Gibbs free energy:

The enthalpy change is given by:

2.82

Cell thermodynamics Combining Eqs. 1 to 4:

2.83

Cell thermodynamics Substituting Eqs. 6 and 7 into 5 yields:

Reversible work, therefore it is the maximum work that can be obtained from the system

2.84

Cell thermodynamics The maximum electrical energy available in an external circuit is equal to the number of charges multiplied by the maximum potential difference (reversible work):

By using: F in C/ eq and E in V, your work will give you J

2.85

Cell thermodynamics Equating Eqs. 8 and 9:

Equation 10 demonstrates that we can obtain thermodynamics information from electrochemical measurements, and vice measurements, and viceversa

2.86

Cell thermodynamics Because Gibbs free energy is a state function (it does not depend on trajectory) we can manipulate equations mathematically to obtain reversible potentials, e.g.:

2.87

Cell thermodynamics Substituting Eq. 10 into 11:

Dividing by F and simplifying:

Eq. 13 is ALWAYS TRUE

2.88

Thought We said before: You can balance the stoichiometry of the equation by multiplying by any positive constant This operation does not alter the potential of the cell (potential is an intensive quantity, unaffected by the number of electrons)

2.89

Answer to thought Yes it is true because we were multiplying the individual reactions to eliminate the electrons from the total reaction However, Eq. 13 is still true See demonstration on the board

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2.90

Thought What happen when the final reaction involve electrons? 1. Choose the electrode reactions from the standard electrode potentials table 2. Reverse the sense of the reactions according to your system 3. Reverse the sign of your standard potentials 4. Add the potentials using Eq. 13 to obtain the potential of the total reaction
2.91

Cell thermodynamics: conclusions Eq. 13 is always valid If your overall reaction does not involve electrons you dont need to correct the potentials (use procedure explain before) If your final reaction has electrons involved you need to strictly use Eq. 13.

2.92

Standard Potential and Gibbs free energy According to Eq. 10 the standard potential of the cell can be calculated from the Gibbs free energy Gibbs Free energy for a reaction:

Where: s: stoichiometric coefficient (positive for products and negative for reactants G: free energy of formation. Information tabulated see Thermo chemical data handout
2.93

Exercise 1 Solve Problem 2 of the book (Ch 3,p. 46)

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2.94

Temperature Effect We can calculate the reversible electrode potential at other temperature by calculating the Gibbs free energy at a specified T and Using Eq. 10

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2.95

Temperature Effect Consider a reversible process were only mechanical work is permitted, then the first law is

2.96

Temperature Effect The enthalpy is defined by

A differential change in enthalpy is given by

2.97

Temperature Effect The Gibbs free energy is defined by

A differential change in Gibbs free energy is given by

2.98

Temperature Effect Combining Eqs. 14, 16, and 18

Consider a process from state 1 to state 2, we can write Eq. 19 for each state as:

2.99

Temperature Effect At constant pressure Eq. 19 becomes:

Substituting Eq. 10 into Eq. 21 yields:

2.100

Temperature Effect Using Eq. 22 we can calculate the effect of temperature on the reversible potential. Over a small temperature range a constant entropy change of reaction is usually justifiable, then integrating Eq. 22:

2.101

From thermodynamics The enthalpy, entropy, or Gibbs free energy of a reaction is given by:

Where: M: property (H, S or G) s: stoichiometry coefficient (positive for products and negative for reactants)
2.102

Temperature Effect: Important considerations It is very important to include the phases in the calculation, that is, make sure that you read the properties of the compounds at the T physical stage

2.103

Exercise 2 In a fuel cell the overall reaction is given by:

Write the electrode reactions Estimate the standard cell potential Calculate the change in reversible potential with temperature (mV/K) near room temperature What is the reversible potential of the cell at 35 oC.
2.104

Pressure Effect The change in the reversible potential with pressure can also be calculated from Eq. 19 by taking its derivate at constant temperature:

Change of volume in the reaction

2.105

Pressure Effect Substituting Eq. 10 into Eq. 24 yields:

At low pressure the ideal gas assumption is valid, then:

2.106

Pressure Effect Substituting Eq. 26 into Eq. 25 and integrating:

Eq. 27 can be used at low pressures where the ideal gas assumption is valid

2.107

Exercise 3 Calculate the reversible potential of the cell described in Exercise 2 at 3 atm

2.108

Thermodynamics Properties Thermodynamics properties can be obtained by measuring electrochemical potential, e.g., enthalpy can be calculated by

Entropy change of a reaction can be calculated by using Eq. 22

2.109

Nernst Equation Walther Nernst developed an equation that correlates the voltage of the cell with its properties To calculate the reversible potential at conditions different to standard we can use the Eq:

Where a is the activity coefficient of species i

2.110

Nernst Equation As an approximation, we can ignore activity coefficient corrections and use concentrations in place of activities:

2.111

Assumptions when using Nernst Equation Neglects: Activity coefficients Potential that arise from bringing two different liquid phases into contact

2.112

Nernst Equation: Important considerations It cant be used to make T and concentration corrections simultaneously. In such a case: Use Eq. 22 or Eq. 25 to make T and P corrections, respectively Applied Nernst Eq. at the new T or P.

2.113

Nernst Equation: Conventions to activity coefficients Assume activity coefficient of 1 for the following cases: Substances in excess (e.g., solvents) solids

2.114

Pourbaix Diagram Consists of plotting the potential vs pH This type of diagram is useful because it allows identifying phases in equilibrium providing critical information on the behavior of the system It was proposed by Marcel Pourbaix

2.115

Procedure to build Pourbaix Diagram Write down all the equations involved in the system Use Nernst equation Express all reactions as a function of potential, pH, or both Plot Potential vs. pH Eqs. independent of pH are plotted as a horizontal line Eqs. independent of potential are plotted as a vertical line Eqs. dependent on both (pH & potential) are plotted as an oblique line
2.116

Pourbaix diagram other assumptions Typical assumptions Concentrations of ions 10-6 M Gases at 1 atm

2.117

Exercise 4 Build the Pourbaix diagram for the lead-water system (also known as le Plant battery). Take into consideration the following reactions

2.118

Equilibrium Constant When the reversible potential equals zero, means that the driving force for the electrochemical reaction is zero, which represents the stable equilibrium state for the cell

2.119

Equilibrium Constant Since the potential is zero at equilibrium, we can determine the equilibrium constant from the standard open circuit potential:

2.120

Exercise 5 Calculate the equilibrium constant for the Daniell Cell Zn/Zn+2 /Cu+2 /Cu

2.121

Heat Transfer Because the system works at constant T and Pressure, we expect to see some transfer of heat to the medium Heat transfer includes: reversible and irreversible heat (always negative, loss to ambient) The reversible heat is given by

If S>0 the process is endothermic If S<0 the process is exothermic

2.122

Heat Transfer For a reversible process in an open system, the energy balance is given by:

:partial molar quatity (includes mixing energy) Most of the time mixing energy is low compared to energy of reaction, then the change can be calculated based on pure components
2.123

Summary
Meaning of potential (related to Gibbs free energy) For temperature effects use the entropy change (be careful with the physical change stage of the reactants and products) For pressure change use the volume change (include only gases in the change calculation) Use assumptions in Nernst Equation

2.124

Summary
You cant correct for T, P and concentration effects simultaneously
Correct for T and P Correct for concentration effect

Know how to build and interpret Pourbaix diagram Calculate equilibrium constants Calculate heat transfer in open systems Whats the meaning of a positive and negative entropy change?
2.125

Chapter 3: Electrode Kinetics

Outline Interface Role Electric Double Layer Helmholtz model Electrode Kinetics Models Butler-Volmer Equation Tafel Equation Reference Electrodes
3.126

Interface Role Electrode kinetics are governed by the potential difference across a thin (order 10 A) layer adjacent to the electrode surface This layer is called the double-layer Potential difference across the thin layer is about 0.1 V Large magnitude of electric field (106 V/cm)

3.127

Interface Role Large driving force for the electrode reaction Because of the large electric field we will have charge separation in the double layer Electroneutrality condition does not apply in the double layer region

3.128

Interface Role At equilibrium (thermodynamics relationships are used) theres no current applied When current is applied the potential will deviate from equilibrium The difference between the potential and the equilibrium potential is called the overpotential (or surface overpotential)

3.129

Interface Role The surface overpotential is given by:

3.130

Issues with Electrode Kinetics Electrode reactions are heterogeneous. This implies that a conductive surface must be in contact with the electrolyte This arrangement produces a number of issues (we need a clean surface to evaluate pure kinetics): Film formation Changes in electrode microstructure Electrolyte contamination All of them cause variations in current-potential measurements
3.131

Experimental Solutions Careful electrode surface preparation (e.g., polish the surface, in corrosion we need a rough surface instead) Electrolyte purification (e.g., deoxygenation of the electrolyte) Control of mass transport to the electrode surface (mixing)

3.132

Typical Kinetics Experimental Set-ups

1-reference electrode 2-gas in 3-gas out 4-Luggin capillary 5-platinum counter electrode 6-rotating electrode 7-temperature probe 8-pH electrode 9-working electrode.

3.133

Typical Kinetics Experimental Set-ups The electrode rotates to have control of the mass transfer limitations The flow profile is known in this type of systems Classical arrangements: Rotating disk electrode (use for laminar flows) Rotating cylinder electrode (use for turbulent flows)

3.134

More Issues with Electrode Kinetics Accurate measurement of the potential is difficult Because we cant measure an absolute value for the potential, we are forced to use a reference electrode Reference electrodes are chosen based on: reversibility, stability, and convenience (cost) Suitable placement of the reference electrode is another issue (need to correct for ohmic differences)

3.135

Electric Double Layer When we apply a potential to an electrode the charges that accumulate at the surface of the electrode attract opposite charges from the electrolyte We expect to have a distribution of charges in order to balance the charges at the surface with the charges from the electrolyte

3.136

Electric Double Layer There are different models to determine the effect (or to simulate the effect) of the double layer: Helmholtz model Gouy and Chapman model Stern model

3.137

Helmholtz Model It was developed in 1879 Its the simplest model for double layer Two parallel layers of charges are separated by solvent molecules The distance (d) represents the outer Helmholtz plane Fixed distribution of layer (charges)
3.138

Helmholtz Model Double layer model as a simple parallel plate capacitor

C: capacitance per unit area (F/m2 or mF/cm2) D: dielectric constant (or relative permittivity) d: Separation between charges, cm 0: Permittivity of free space, 8.8542x10-14 F/cm
3.139

Helmholtz Model The potential distribution is a linear function between the two layers of charge

Because the distribution of the charges does not change the potential is constant, also C is constant

3.140

Helmholtz Model For water D10, d10 A, then:

3.141

Helmholtz Model Experimental measurements use a NaF solution in a mercury electrode Mercury offers a uniform surface and NaF is not adsorbed Capacitance in the right order of magnitude but it is not constant Only for high concentrations the capacitance tends to be constant 3.142

Fig. Capacitance vs. potential relative to the point of zero charge for a NaF solution on a mercury electrode at 25oC (experimental data)

Gouy-Chapman Model It was developed in 1910 Its analogous to the DebyeHckel theory The thickness of the double layer represents a compromise between electrical forces (tending to maintain the ordering) and thermal forces (tending to make the arrangement random) No fixed charges Significant deviation from electroneutrality occurs on the Debye length
3.143

Gouy-Chapman Model The capacitance is given by

3.144

Gouy-Chapman Model Fig. Capacitance vs. potential relative to the point of zero charge for a NaF solution, calculated using Gouy-Chapman model (Eq. 3) Fig. 5.2 Capacitance vs. potential relative to the point of zero charge for a NaF solution on a mercury electrode at 25oC (experimental data) Its good at potentials near the zero charge region At potentials ore than 0.5 V in either direction the observed flattering of the capacitance is not predicted
3.145

Stern Model
Combines the Helmholtz model and the Gouy-Chapman model Some of the charge is fixed (d region) and some of the charge is diffuse or spread out The total length of the boundary layer is given by the fixed region plus the diffuse region

3.146

Stern Model Because the capacitances are in series the capacitance of the double layer is given by:

3.147

Stern Model The smallest capacitance is the one that governs the behavior of the system: If CH CG-C then CSCG-C Eq. 5 If CH CG-C then CSCH

3.148

Stern Model Assuming that CH is constant The Stern model predicts the experimental data very well Fig. Capacitance of 0.001 M NaF vs. potential relative to the point of zero charge at 25oC. The experimental data (circles) agrees very well with the model (Stern Model, Eq. 4)
3.149

Consequences of the Double-Layer Species outside the Helmholtz region are too distant to react The driving force for the reaction is the potential drop across the Helmholtz region rather than the potential drop across the whole double layer

3.150

Consequences of the Double-Layer Concentration at the bulk is different to the concentration at the surface of the electrode When we study kinetics we need only the intrinsic effect of kinetics (need to eliminate the effect of the double layer) Add a non-reacting supporting electrolyte to the solution This increases the CG-C, then the overall capacitance is approximated by the CH
3.151

Electrode Kinetics In ordinary kinetics we express the progress of a reaction by plotting the reaction coordinate vs. the energy of the species (assuming transition state theory)

3.152

Electrode Kinetics Let us consider one elementary step electrochemical reaction:

Where O+: oxidized species R: reduced species kc: cathodic reaction rate constant ka: anodic reaction rate constant
3.153

Electrode Kinetics A more negative potential (more positive energy) tends to promote reduction At progressively more negative potential, the energy of the oxidized species is increased

3: reduction is favored 1: oxidation is favored 2: equilibrium potential, no net reaction takes place
3.154

Electrode Kinetics Consider the case where we start an experiment at the potential 1 and we reduce it to 2 The activation energy for the first process (Eac1) is higher than for the second process (Eac2)

3.155

Electrode Kinetics We can express the activation energy for the second process as a function of the first process by:

Where is the symmetry factor (transfer coefficient) represents the fraction of energy that has been used to reduce the activation energy of the reaction
3.156

Electrode Kinetics Similarly the activation energy for the anodic process (which increases) can be expressed by:

n: is the number of electrons transferred in the reaction. For elementary steps n is most of the time 1, it is unusual to have more than1 electron involved in an elementary step

3.157

Electrode Kinetics The form of our kinetic expression is the same as that for chemical reactions (using an Arrhenius dependence of temperature):

Where k: is the a constant, cm/s G: is the free energy of activation

3.158

Electrode Kinetics The rate of electrochemical reaction is directly proportional to the current density:

Where r: reaction rate, mol/s cm2 i: current density, A/cm2 (the area is the electrode surface area) c: is the reactant concentration (mol/cm3)
3.159

Electrode Kinetics For the general anodic reaction given in Eq.6 (first order reaction), we substitute Eq. 8 into Eq. 10

We have assumed a reference potential, therefore the subscripts 1 and 2 have been dropped
3.160

Electrode Kinetics We can redefine the reaction constant including the activation energy at our reference potential:

3.161

Electrode Kinetics Similarly for the cathodic reaction:

The net current density (i=ia-ic) is the difference between the anodic and cathodic current densities (Eq. 12-Eq. 13)

3.162

Electrode Kinetics At equilibrium the net current density is zero, but the rates of the anodic and cathodic reaction are not zero. The magnitude of both (ia and ic) are the same and this is called exchange current density (i0)

3.163

Electrode Kinetics If we designate the equilibrium potential as

0

Taking the logarithm of Eq. 15 and rearranging:

3.164

Electrode Kinetics Substituting Eq. 16 into Eq. 14 and using the definition of overpotential:

3.165

Electrode Kinetics Rearranging Eq. 17:

Eq. 18 is a general kinetics expression for the first order Eq.18 elementary step given in Eq. 6 The concentration of the reactants are at the surface of the electrode The cathodic and anodic kinetic constants can be evaluated at equilibrium from the exchange current density: Where the superscript 0 represents equilibrium conditions
3.166

Electrode Kinetics Substituting the kinetic constants into Eq. 18 we obtain:

3.167

Butler-Volmer Equation Redefining the transfer coefficients for the anodic and cathodic components as:

And assuming the concentration at the surface is equal to the concentration at the bulk which will be the case of equilibrium condition, then Eq. 19 becomes:

Eq. 20 is known as the Butler-Volmer Equation

3.168

Butler-Volmer Equation Three variables a, c, and i0 need to be determined to use Butler-Volmer Equation Butler-Volmer equations gives a good representation of experimental data for many systems The exchange current density is a strong function of temperature When the exchange current density is very large, the reactions is said to be reversible

3.169

Butler-Volmer Equation When two reactions take place simultaneously, on the same electrode surface, we can use the ButlerVolmer equation for each of them We will have to determine the individual parameters for both reactions

3.170

Linear form of Butler-Volmer Equations One of the disadvantages of the Butler Volmer equation is that the overpotential cant be expressed implicitly To confront this several approximations have been made Small surface overpotential Large surface overpotential

3.171

Linear form of Butler-Volmer Equations When the overpotential is very small, the exponential term in Eq.20 can be expanded using Maclaurin series, neglecting some of the terms in the series:

3.172

Linear form of Butler-Volmer Equations Eq. 21 is the linear form of the Butler-Volmer Equation The current density is a function of only one parameter (i0 and the transfer coefficients can be defined as one constant) It is used to model systems operating at low current densities Its often used when the overpotential is 10mV or less If the current density does not vary widely (30%), the linear expression can be used even in the high current density
3.173

Tafel Equation If the overpotential is large and positive, the second term in Eq. 20 can be neglected:

If the overpotential is large and negative, the first term in Eq. 20 can be neglected:

3.174

Tafel Equation Eqs. 22 and 23 are known as Tafel equations Taking the logarithm of Eq.22 and rearranging: Where and

The constant B is called the Tafel Slope Use of the Tafel approximation depends on the error that can be tolerated It is general used when the overpotential is at least 50 to 100 mV 3.175 The Tafel slope varies between 30 to 300 mV/decade

Tafel Equation Values of the exchange current density and the transfer coefficient are obtained experimentally Plot overpotential vs. log(i). The slope of the line will give the transfer coefficient, and the intercept will give the exchange current density

3.176

Example 1 Solve problem 3 of chapter 5 in your text book

3.177

Example 2 Solve problem 2 of chapter 5 in your text book

3.178

Reference Electrodes So far we have learned how to estimate kinetic expressions as a function of the overpotential We have also learned that the overpotential is given by:

3.179

Reference Electrodes When using the overpotential equation, we need to make sure that the potential that we measure is only due to the electrochemical reaction One of the ways to accomplish that is by using reference electrodes Before discussing more details about reference electrodes, we will present a discussion in the factors that affect the potential

3.180

Contributions to the Potential in Galvanic Cells The maximum potential that we can measure in a galvanic cell is the equilibrium potential. The equilibrium potential is only obtained when no current (or very small current) flows through the circuit When a current flows through the circuit the potential measure will always be smaller than the equilibrium potential
3.181

Contributions to the Potential in Galvanic Cells The decrease in the potential of the cell is due to several limitations, and this is often called Potential loss, Eloss Therefore, the potential of a cell is defined as:
Where E: equilibrium potential : potential of the cell
3.182

Contributions to the Potential in Galvanic Cells The potential limitations include: Surface overpotential limitations, due to kinetics limitations Concentration overpotential, due to diffusion and convection limitations in the electrolyte (also known as liquid-junction potential) Ohmic drop, due to the mobility limitations (ion interactions) Solid diffusion limitations, due to diffusion limitations in porous electrodes, e.g., electrodes that the ones used in lithium ion batteries
3.183

Contributions to the Potential in Galvanic Cells Accounting for all the limitations the potential loss is given by:

Where:

3.184

Contributions to the Potential in Galvanic Cells In an electrolytic cell the minimum potential that we need to apply for the reaction to take place is the equilibrium potential Therefore the potential in an electrolytic cell is given by:

The potential loss is calculated using Eq. 25.

3.185

Reasons for Using Reference Electrodes Measurement of the potential at equilibrium conditions is relatively easy. All we need to make sure is that the current that flows through the circuit is very small Such determination depends on the use of a counter-electrode having a known reversible potential

3.186

Reasons for Using Reference Electrodes Under load the measurement of the potential respect to a reference electrode becomes more complicated (due to the Eloss). In addition we will have significant reactions at both electrodes Then a simple two electrode approach is not longer satisfactory for making accurate measurements A technique to overcome this problem is to use a third electrode into the electrolyte

3.187

Reasons for Using Reference Electrodes The reference electrode should be place very close to the working electrode In theory it should be placed just outside the electrical double layer However, the electrical field of the electrode can affect the measurement of the overpotential A rule of thumbs suggest to place the reference electrode at least 4diameters (of the reference electrode) away from the working electrode
3.188

Reasons for Using Reference Electrodes An approach to avoid the effect of the reference electrode field on the working electrode is to use a luggin capillary Ohmic drop in the capillary tube is small because the current that flows through it is very small
3.189

Reasons for Using Reference Electrodes Sometimes a second reference electrode is added to measure the ohmic drop between two points in the solution. This approach is known as the four electrode arrangement Another use of reference electrodes is to measure current distributions in a cell having a non uniform current distribution

3.190

Reasons for Using Reference Electrodes Summarizing the reasons for using reference electrodes are: Accurate measurement of surface overpotentials Measurement of ohmic drops in solution Measurement of current distribution

3.191

Types of Reference Electrodes When choosing a reference electrode we have the following criteria Reproducibility Stability Small temperature sensitivity Sometimes a reference electrode of the same type as the working electrode is chosen, this is known as a pseudo reference electrode: Avoids: Contamination problems Liquid junction potential problems The problem with doing this is that sometimes the results are not reproducible and they are more difficult to 3.192 generalize

Types of Reference Electrodes Generally the reference electrode should be chosen that is reversible to one of the ions in solution. However, this is difficult to accomplish all the time The practical approach is to choose a reference electrode that is standard built for some electrolyte conditions

3.193

Types of Reference Electrodes Typical reference electrodes Hydrogen electrode Calomel electrode (SCE) Mercury-Mercuric oxide electrode Mercury-mercurous sulfate electrode Silver-Silver Chloride electrode

3.194

Calomel Electrode It is constructed by covering a pool of mercury with mercurous chloride (calomel) Potassium chloride is the electrolyte for the following reaction:

3.195

Calomel Electrode The equilibrium potential is given by:

Commercial electrodes are commonly prepared with three concentrations of KCl: 0.1 N, 1 N and saturated The calomel electrode is best used in acid solutions Reproducibility is about 2 mV
3.196

Ag/AgCl Electrode It is used when mercury contamination is not allowed KCl is used as the electrolyte. The most common concentration is 4M It is also used in acidic solutions The reaction involved is: The equilibrium potential is given by:
3.197

Mercury/Mercurous electrode It is used in acid solution When chloride contamination is not allowed The reactions if given by:

3.198

Mercury/Mercuric oxide electrode It is used in basic solutions It uses KOH as the electrolyte The reaction is given by:

3.199

Calculation of overpotentials For the calculation of overpotential we need to use Eq.

Because the applied potential is measured respect to a reference electrode, the Equilibrium potential for the reaction needs to be expressed respect to the reference electrode: Ew: equilibrium potential of the working electrode Eref: equilibrium potential of the reference electrode
3.200

Example 3 The deposition of nickel takes place in a typical sulfate bath that contains: NiSO4, H2O, NiCl2 and H3BO4 Typical operating conditions are T=25oC, pH=5 and nickel concentration of 1 M A SCE reports a measurement of -0.67 V. At this conditions the ESCE=0.22V vs. SHE We know that hydrogen will be evolved as a parasitic reaction and we would like to estimate the current efficiency We know that hydrogen generation and nickel deposition can be characterized by Tafel equation according to: and with i in A/cm
2
3.201

Summary At the end of this chapter you must be able to: Use and understand the different expression to express electrode kinetic rates Calculate over potentials Correct surface overpotentials from other loss effects Know the uses and applications of reference electrodes Understand the effect of the double layer on the electrode kinetics (e.g., what do you do experimentally do reduce this effect?)
3.202

Chapter 4: Mass Transport

Outline Fundamental relationships Mass transport boundary layer Concentration Overpotential Limiting Current Density

4.203

Fundamental Relationships A general description of an electrochemical system takes into account: Species fluxes Material conservation (material balance) Current flow Electroneutrality Electro-kinetics Global reactions Hydrodynamics
4.204

Species Flux Using dilute concentration theory (considers only interactions between solute-solvent), the flux of species is given by:

Comparing to general chemical engineering systems the difference in the flux is given by the migration term (potential generated due to the ion interactions)
4.205

Species Flux Where: Ni: flux of species, mol/cm2 s zi: charge number of species i, eq/mol ui: mobility of species i, cm2-mol/Js ci: concentration of species i, mol/cm3 : electrostatic potential, V Di: diffusion coefficient of species i, cm2/s v: fluid velocity, cm/s The flux is perpendicular to the surface area (as usual)
4.206

Current Flow Current will arise from the motion of the charges and is given by:

4.207

Material Balance The material balance is given by:

Where Ri represents a chemical reaction ccurring in solution (mol/cm3). Eq. 3 assumes constant volume
4.208

Electroneutrality Equation Because the electrical forces between charged species are so large, significant charge separation cannot occur. Therefore, in the bulk the electroneutrality assumption is valid:

4.209

Simulations To carry out a simulation of the performance on an electrochemical system, Eqs. 1-4 need to be solved simultaneously We need a description of the flow pattern to account for v in Eq. 1 Eqs. 1 to 4 apply at the bulk, the electrode kinetics is used as boundary conditions for the solution of the differential equations
4.210

Common simplifications If bulk concentrations can be ignored we can demonstrate that the gradient of the current is given by: This Eq. is known as conservation of charge When concentration variations can be neglected we obtained ohms law instead of Eq. 2:

Where k (conductivity) is given by:

4.211

Common simplifications Another important definition is the transport number:

When concentration variations are important, ohms law becomes modified ohms law:

4.212

Common Simplifications When migration is negligible (in excess of a supporting electrolyte), the coefficient of the potential gradient in Eq. 1 is large, then the potential gradient must be small The material balance can be obtained from substituting simplified Eq. 1 into Eq. 3

4.213

Common simplifications (supporting electrolyte) This equation is known as the convective diffusion equation:

The potential distribution can still be obtained by solving the modified ohms law equation

4.214

Mass transport boundary layer For systems where the concentration gradient is significant, one common simplification is to treat the boundary layer region as a region with a linear concentration gradient

This is known as Nernst diffusion layer

4.215

Mass transport boundary layer Nernst approximation for the concentration gradient is expressed as:

Where: c: concentration at the bulk c0: concentration at the surface : thickness of the boundary layer. The thickness of this layer is between 0.05-0.001 cm
4.216

Example 1 Use the transport equations to derive an expression for the current for a copper deposition reaction as a function of the surface and bulk concentration. The electrolyte is composed of copper, water and H2SO4 (added to increase conductivity) Write down expressions for your transport properties

4.217

Consequences of adding supporting electrolytes Reduces ohmic losses Reduces limiting current density Increases the viscosity of the solution and therefore decreases the maximum velocity Reduces the magnitude of the electric field

4.218

Concentration Overpotential Concentration overpotential is associated with the mass transport limitations It results from: The concentration difference between bulk and electrode surface From the potential gradient (see modified Ohms law, second term)

4.219

Concentration Overpotential Assuming that the variations in the ionic conductivity are small (small current densities or a supporting electrolyte is used). The concentration overpotential can be obtained by:

4.220

Concentration Overpotential When the conductivity is large the equation can be approximated with:

This is the concentration overpotential for a cathodic reaction. The concentration overpotential for a cathodic reaction is negative (as well as its surface overpotential)
4.221

Concentration Overpotential For an anodic reaction, the concentration overpotential is positive and can be estimated (for large conductivities) by:

4.222

Limiting current When the current at the surface is equal to zero, the current measured is known as the limiting current For the boundary layer assumption, the current is defined as (we demonstrated this in Example 1):

4.223

Limiting current Then the limiting current for the Nernst diffusion layer is given as:

The limiting current density is a function of the flow pattern. It is up to 100 order of magnitude larger in stirred solutions
4.224

Limiting current The overpotential can be expressed as a function of the limiting current, for example for high conductivities the cathodic concentration overpotential is given by Eq. 6, which can be expressed as:

4.225

Limiting current At currents higher than the limiting current additional reactions takes place After the limiting current the two reactions take place in parallel with the secondary reaction taking over the primary reaction

4.226

Limiting current Supporting electrolytes reduce ohmic losses but tend to reduce the limiting current Supporting electrolytes increase the viscosity of the solution and decreases the mobility of the ions

4.227

Diffusion coefficient The transport equations require the use of the diffusion coefficient. The diffusion coefficient for ionic species can be calculate by using the Nernst-Einstein equation:

For a binary electrolyte the diffusion coefficient becomes:

4.228

Diffusion coefficient Because the ionic diffusion coefficient is related to the mobility, it can be calculated using the equivalent conductances:

4.229

Values of diffusion coefficients of selected ions at infinite dilution in water at 25oC p284

4.230

Estimation of limiting current The limiting current can be estimated from the mass transfer correlations Usually mass transfer limitations are expressed as:

Where km is the mass transfer coefficient (cm/s)

4.231

Estimation of limiting current At the limiting current the surface concentration is zero, therefore, the limiting current is related to the mass transfer coefficient:

The mass transfer coefficient is related to the Sherwood number (Sh) which is a function of the Reynolds (Re) and the Schmidt (Sc) numbers

4.232

Estimation of limiting current The following correlations are used

Where L is the characteristic length, v is the velocity of the fluid, and v is the kinematic viscosity (cm2/s) (v = /)
4.233

Estimation of limiting current Some correlations require the use of the Grashof number (Gr). This number is used when the mass transport is affected by density differences

Where: g: acceleration due to gravity : bulk density 0: surface density, equal to the solvent density
4.234

Estimation of limiting current Correlations for the Sherwood number has been determine for specific geometries where the flow pattern is well known The correlations are summarized in appendix E of the book

4.235

Example 2 For the cathodic deposition of copper from 0.5 M CuSO4 and 0.5 M H2SO4 electrolyte, the kinetic parameters are c=0.5 and i0=1 mA/cm2. If the applied potential is 100 mV respect to a SCE. Calculate: A. The current density for copper deposition expected if only kinetics limitations are involved B. The limiting current density if two plane parallel copper electrodes, 2 cm long are used in a beaker of unstirred electrolyte C. Estimate the thickness of the Nernst diffusion layer
4.236

Summary At the end of this chapter you should be able to: Calculate diffusion coefficients for ionic species Determine limiting current for different geometries Calculate currents when kinetics and mass transport limitations are involved Write down the fundamental equations to model an electrochemical system assuming dilute solution theory
4.237

Chapter 5: Industrial applications of Electrochemical Engineering

Outline Batteries and Fuel cells: Working Principle, types, applications and design aspects Production and refining of metals : Applications in chemical industries Corrosion Prevention

Fuel cells-An introduction Output of conventional batteries are limited. They are polluting. Continuous operation results in fall in efficiency. Output not stable under long durations of operations. Fuel cell An Electrochemical energy conversion device Produces electricity from external fuel and oxidant. Can operate virtually continuously as long as the necessary flows are maintained.

Basic Fuel Cell Concept

Fuel cells-Working principle A fuel cell is an electrochemical device that converts the chemical energy in fuels (e.g. hydrogen, methane, butane or even gasoline and diesel) into electrical energy. It exploits the natural tendency of oxygen and hydrogen to react to form water. The direct reaction is prevented by the electrolyte, which separates the two reactants. Therefore two half-reactions occur at the electrodes: Anode: Fuel (e.g. H2, CO, CH4) is oxidized Cathode: Oxygen is reduced

 The ions are transported to the other electrode through the electrolyte. The fuel cell contains no moving parts and only four active elements: cathode, anode, electrolyte and interconnect; It is a simple and robust system.

A fuel cell uses a chemical reaction to provide an external voltage, as does a battery, but differs from a battery in that the fuel is continually supplied in the form of hydrogen and oxygen gas. It can produce electrical energy at a higher efficiency than just burning the hydrogen to produce heat to drive a generator

Types of Fuels cells The general design of most fuel cells is similar except for the electrolyte. The six main types of fuel cells, as defined by their electrolyte, are Alkaline Fuel Cells, Proton Exchange Membrane Fuel Cells, Phosphoric Acid Fuel Cells, Molten Carbonate Fuel Cells, Direct Methanol Fuel Cells, Solid Oxide Fuel Cells.

Alkaline Fuel Cell Electrolyte is a porous matrix saturated with aqueous alkaline solution (normally KOH) Provides heat, electricity and potable water as outputs. Used in Apollo Mission to moon.

1: Hydrogen 2:Electron flow 3:Charge 4:Oxygen 5:Cathode 6:Electrolyte 7:Anode 8:Water 9:Hydroxyl Ions

Chemical reaction The chemical reaction that occurs at the anode is: 2H2 + 4OH 4H2O + 4 e The reaction at the cathode occurs when the electrons pass around an external circuit and react to form hydroxide ions, OH : O2 + 4e + 2H2O4OH

Types of alkaline Fuel cell

Mobile Electrolyte
-eg. Pure H2 Fuel-Electrolyte pumped through a circuit

Static Electrolyte
- eg. Pure H2 Fuel-But electrolyte is held in a matrix material

Dissolved Fuel Electrolyte

-eg. Hydrazine Fuel

Fuels used in Alkaline Fuel Cells Metal Hydride Ability to be recharged with electrical energy Low operating temperatures (down to -20C); Fast kinetics; Extended shelf life; Absorbs and stores hydrogen within the cell.

Fuels used in Alkaline Fuel Cells Direct borohydride cell A solution of sodium borohydride is used as the fuel. Prevents the conversion of KOH to K2CO3 Cheaper than traditional fuel cells as it does not need platinum electrodes.

Features of Alkaline fuel cell Advantages Cathode reaction faster in alkaline electrolyte, higher performance Byproduct is pure water, can be used for other purposes. Gives out heat which can be used for heating purposes. Disadvantages Expensive removal of CO2 from the cell required.

Features of Alkaline fuel cell Alkaline fuel cells encountered many problems including cost, reliability, ease of use, durability, and safety which were not easily solved. Attempts at solving these problems proved to be uneconomical given the other sources of energy at the time.

PEMFCProton Exchange Membrane Fuel Cell The proton exchange membrane (a.k.a. Polymer Electrolyte membrane) fuel cell uses a polymeric electrolyte. This proton-conducting polymer forms the heart of each cell and electrodes (usually made of porous carbon with catalytic platinum incorporated into them) are bonded to either side of it to form a onepiece membrane-electrode assembly (MEA).

Advantages A quick overview of some key advantages that make PEMs such a promising technology for the automotive markets: Low temperature operation, and hence Quick start up No corrosive liquids involved Will work in any orientation (or zero g for that matter) Thin Membrane-electrode assemblies allow compact cells

Reactions in PEMFC

Molten Carbonate Fuel Cells Operates at high temperature Molten carbonate is used as electrolyte. Produces water and CO2 as byproducts. Delivers high power, of the order 100 MW

Features of MCFC Advantages High efficiency Fuel flexibility Can use a variety of catalysts Suitable for CHP Disadvantages High temperature speeds corrosion and breakdown of cell components Complex electrolyte management Slow start-up

PAFC Phosphoric Acid Fuel Cell Electrolyte used is Phosphoric Acid Not affected by CO in the hydrogen stream Works above a temperature of 400C. If working at 150 to 200 C, expelled water can be converted to steam and used for heating. Combined heat and power efficiency of 80 %. Large weight and size

SOFC Solid oxide fuel cells Solid oxide fuel cells (SOFCs) use a hard, nonporous ceramic compound as the electrolyte. Because the electrolyte is a solid, the cells do not have to be constructed in the plate-like configuration typical of other fuel cell types. SOFCs are expected to be around 50%60% efficient at converting fuel to electricity

SOFC Solid oxide fuel cells

Solid oxide fuel cells (SOFCs) Solid oxide fuel cells operate at very high temperatures around 1,000C (1,830F). High-temperature operation removes the need for precious-metal catalyst, thereby reducing cost. It also allows SOFCs to reform fuels internally, which enables the use of a variety of fuels and reduces the cost associated with adding a reformer to the system. SOFCs are also the most sulfur-resistant fuel cell type; they can tolerate several orders of magnitude more of sulfur than other cell types.

Solid oxide fuel cells (SOFCs) In addition, they are not poisoned by carbon monoxide (CO), which can even be used as fuel. This property allows SOFCs to use gases made from coal. have the distinct advantage of being able to run on biogas (which delivers the most energy per hectare of crops), natural gas, propane, ethanol, diesel or biodiesel and don't require hydrogen,

Fuel Cell Type PEM Fuel Cell

Performance of Fuel Operating Cells System Output Applications Temperature

50 - 100C <1kW 250kW Backup power Portable power Small distributed generation Transportation Auxiliary power Electric utility Large distributed generation Military Space Distributed generation Electric utility Large distributed generation

Solid Oxide FC

650 - 1000C

5kW 3MW

Alkaline Fuel Cell Phosphoric Acid FC

90 - 100C 150 - 200C

10kW 100kW 50kW 1MW <1kW 1MW

Molten Carbonate FC 600 - 700C

Performance analysis of fuel cellcalculation

Efficiency

Fuel cells-Design aspects

1.The maximum energy output from a fuel cell is equal to its Gibbs energy (at Standard conditions) E max =G O=Hf - TS= Hf - Eloss
Correction due to variation in Standard conditions:

aA + bB cC + dD

From Nernst Equation,

Where pi is the partial pressure of the reactants and products.

pc c. pd d G = Go + RT ln pa a. pb b

2.The Electric potential can be calculated from the equation G = n F E cell

Ecell pc c. pd d = Eo + RT ln pa a. pb b

3.The theoretical efficiency of the Fuel cell,max.

max =
H f Eloss H f G nFE = = H f H f

4.The practical fuel cell efficiency,

f = max . v . I
f
v

is the practical fuel cell efficiency

is the voltage efficiencythe current efficiency is I

5.The Overall system efficiency,

O = f . R . C
R

is the Reformer efficiency is the DC/AC converter efficiency

BatteriesElectrochemical cells What is a battery? A battery is an electrochemical cell that converts chemical energy into electrical energy. It comprises of two electrodes: an anode (the positive electrode) and a cathode (the negative electrode), with an electrolyte between them. At each electrode a half-cell electrochemical reaction takes place.

Basic principlesThe Electrochemical series Different metals (and their compounds) have different affinities for electrons. When two dissimilar metals (or their compounds) are put in contact through an electrolyte, there is a tendency for electrons to pass from one material to another. The metal with the smaller affinity for electrons loses electrons to the material with the greater affinity, becoming positively charged. The metal with the greater affinity becomes negatively charged.

Most wants to reduce (gain electrons) Gold Mercury Silver Copper Lead Nickel Cadmium

The Electrochemical Series

Iron Zinc Aluminum Magnesium Sodium Potassium Lithium

Most wants to oxidize (lose electrons)

Types of Batteries

Primary (Nonrechargeable) Batteries

Secondary (Rechargeable) Batteries

Battery Reactions and Chemistry

Discharge
Electrode 1 is an anode: the electrode is oxidised, producing electrons. Electrode 2 is a cathode: the electrode is reduced, consuming electrons. In the fully charged state, there is a surplus of electrons on the anode (thus making it negative) and a deficit on the cathode (thus making it positive). During discharge, electrons therefore flow from the anode to the cathode in the external circuit and a current is produced. Therefore in simple terms batteries work as electron pumps in the external circuit, preferably with only ionic current flowing through the electrolyte.

If the anode were zinc and the cathode were copper the half reactions would proceed as follows: At the anode: Zn Zn2+(aq) + 2e Eo = 0.76V At the cathode: Cu2+(aq) + 2e Cu Eo = 0.34V Thus the total potential for this cell is 1.10 V.

During use as a battery, discharge leads to dissolution of Zn at the anode and the deposition of Cu at the cathode. Such a cell is embodied in the Daniell Cell introduced in 1836. As a practical cell this required two electrolytes (typically zinc sulphate and copper sulphate aqueous solutions) to avoid polarisation. The electrolytes are separated from each other by a salt bridge or a porous membrane, which

Charge When the cell potential is depleted the battery can be recharged. When a current is applied to the cell in the opposite direction the anode becomes the cathode, and vice versa. Thus electrode 2 that was oxidised upon discharge is now reduced and the electrode 1 that was reduced is now oxidised so the electrodes are returned to their former state, ready to be discharged again. This time the anode would be copper and the cathode would be zinc, and the half reactions would proceed as follows: At the anode: Zn2+(aq) + 2e Zn Eo = -0.76V At the cathode: Cu Cu2+(aq) + 2e Eo = -0.34V The minimum potential required for charging will be 1.10 V, as this is the potential of the cell. In reality much higher potentials will be required to overcome the polarisation.

Lead Acid Battery-An automobile industry application

In the charged state, each cell contains electrodes of elemental lead (Pb) and Lead (IV) Oxide (PbO2) in an electrolyte of approximately 33.5% v/v (4.2 Molar) sulfuric acid (H2SO4). In the discharged state both electrodes turn into lead(II) sulfate (PbSO4) and the electrolyte loses its dissolved sulfuric acid and becomes primarily water. Due to the freezing-point depression of water, as the battery discharges and the concentration of sulfuric acid decreases, the electrolyte is more likely to freeze during winter weather. The chemical reactions are (discharged to charged): Anode (oxidation): Cathode (reduction):

Performance characteristics of Batteries The relationship between current, discharge time, and capacity for a lead acid battery is approximated (over a certain range of current values) by Peukert's law: where QP is the capacity when discharged at a rate of 1 amp. I is the current drawn from battery (A). t is the amount of time (in hours) that a battery can sustain. k is a constant around 1.3.

Electrorefining Electro refining of a metal by electrolysis is a way of purification of a metal previously extracted by classical metallurgical or electrochemical processes In electro refining, the anodes consist of unrefined impure metal, and as the current passes through the acidic electrolyte the anodes are corroded into the solution so that the electroplating process deposits refined pure metal onto the cathodes.

Electrorefining In the case of electrorefining of copper, the anode is made of impure copper, while cathode is made of a thin sheet of pure copper. The electrolyte is an aqueous solution of copper sulphate acidified with sulphuric acid. The reactions taking place during electrolysis are,
Anode - oxidation: Cu metal (impure)---> Cu+2 + 2 electrons Cathode - reduction: Cu+2 + 2 electrons ---> Cu metal (pure)

Steps in Electro refining

Steps in Electro refining

Industrial Applications-Copper refining

Electrorefining of copper

Extraction of Aluminium from bauxite-Three stage process

Refining of aluminium (Hoopes process)

Refining of aluminium (Hoopes process) The cell consists of an iron tank lined with carbon at the bottom. A molten alloy of copper, crude aluminium and silicon is used as the anode. It forms the lower most layer in the cell. The middle layer consists of molten mixture of fluorides, of sodium aluminium and barium (cryolite + BaF2). The upper most layer consists of molten aluminium. A set of graphite rods dipping in molten aluminium serve as cathode. On passing current aluminium ions from the fused electrolyte are discharged at cathode and pure aluminium collects as the top layer. Meanwhile, an equivalent quantity of aluminium from crude alloy at the bottom goes into electrolyte in the middle layer.

Performance evaluation in Electrorefining The amount of metal deposited was determined by the weight change (W) observed in the cathode before and after electrolysis. The theoretical amount of metal that can be deposited for the quantity of electricity passed during the experiment was determined Using the Faraday's law: where
Wm is the theoretical amount of metal deposited, the term I t (current time) is the quantity of electricity supplied, n is the number of electrons transferred in the elementary act of the electrode reaction, Am is the atomic weight of the metal and F isthe Faraday constant (96485 Coulombs).

 Current efficiency (eff), which is defined as the ratio of the actual amount of metal deposited to that expected theoretically , was calculated by equation :

 The energy consumption (E) during the electro refining was determined by Eq.(5) using the current efficiency and the applied cell voltage:

where V is the applied cell voltage, eff is current efficiency, and Q is the theoretical charge required for depositing a fixed amount of material according to the Faraday's law.

Electrochemistry of corrosion Corrosion in an aqueous environment and in an atmospheric environment (which also involves thin aqueous layers) is an electrochemical process because corrosion involves the transfer of electrons between a metal surface and an aqueous electrolyte solution. It results from the overwhelming tendency of metals to react electrochemically with oxygen, water, and other substances in the aqueous environment.

Electrochemistry of corrosion
The same metallic surface exposed to an aqueous electrolyte usually possesses sites for an oxidation (or anodic chemical reaction) that produces electrons in the metal, and a reduction (or cathodic reaction) that consumes the electrons produced by the anodic reaction. These "sites" together make up a "corrosion cell". The anodic reaction is the dissolution of the metal to form either soluble ionic products or an insoluble compound of the metal, usually an oxide. Several cathodic reactions are possible depending on what reducible species are present in the solution. Typical reactions are the reduction of dissolved oxygen gas, or the reduction of the solvent (water) to produce hydrogen gas.

Reactions involved in Corrosion

Methods of Corrosion Prevention Change of Materials Change of Environment complete or partial change of materials used either a complete change in environment or a partial alteration by modification of pH etc either organic coatings or electroplating etc. sacrificial coatings, cathodic or anodic protection etc. allowances for general corrosion and control of factors such as temperature, velocity etc.

Barrier Films Electrochemical Techniques

Design

Electrochemical engineering for corrosion control Cathodic protection(CP) is a technique to control thecorrosionof a metal surface by making it work as acathodeof anelectrochemical cell. This is achieved by placing in contact with the metal to be protected another more easily corroded metal to act as the anode of theelectrochemical cell. Cathodic protection systems are most commonly used to protectsteel, water or fuelpipelinesandstorage tanks, steel pierpiles, ships, offshoreoil platformsand onshoreoil wellcasings.

Cathodic Protection is an electrochemical means of corrosion control in which the oxidation reaction in a galvanic cell is concentrated at the anode and suppresses corrosion of the cathode in the same cell. Figure 1shows protection system. The steel pipeline is cathodically protected by its connection to a sacrificial magnesium anode buried in the same soil a simple cathodic

Figure 1shows two of these metals--iron and zinc--separately immersed in a weak mineral acid. The chemical reactions that occur inFigure Fe --> Fe Oxidation reaction 1are: + 2e
2+ -

2H+ + 2e---> H2

Reduction reaction Net reaction Oxidation reaction Reduction reaction Net reaction

2H+ + Fe --> Fe2+ + H2 Zn --> Zn2+ + 2e2H+ + 2e- --> H2 2H+ + Zn --> Zn2+ + H2

Figure 1: Corrosion of zinc and iron in hydrochloric acid

Both metals corrode, and both corrosion (oxidation) reactions are balanced by an equal reduction reaction, which in both cases involves the liberation of hydrogen gas from the acid environments. The two corrosion reactions are independent of each other

When the two metals were immersed in the same acid and electrically connected (Figure 2), the reactions for zinc would then become:
Zn --> Zn2+ + 2e- Oxidation 2H+ + 2e- --> H2 Reduction

The oxidation of the zinc anode inFigure 2is much faster than that inFigure 1. At the same time, most of the corrosion of iron inFigure 1has stopped inFigure 2. As shown schematically, the zinc anode inFigure 1has been

Figure 2: Cathodic protection of iron

Corrosion rate

Where RF = The Electrochemical rate constant, -The density , Aw-Atomic mass, rnumber of reactions per second, As -Surface area, t-time, z-no of electrons, icorr -Current

Exercise # 1 Determine the Nernst reversible potential for a molten carbonate fuel cell. Note that there are two moles of electrons and one mole of CO2 transferred from the cathode to the anode.

Estimate 1.The theoretical efficiency of the fuel cell. 2.The practical efficiency. 3.The Overall system efficiency of the given molten carbonate fuel cell. The system properties are given as follows: Anode Reaction: CH3OH + H2O CO2 + 6H+ + 6eCathode Reaction: 3/2 O2 + 6H+ + 6e- 3H2O Standard operating temperature=950 C Overall: CH3OH(l) + 3/2O2(g) CO2(g) + 2H2O(l) Eocell = 1.21 V. The reformer efficiency=0.61.The converter efficiency=0.36. The voltage efficiency=0.51.The current efficiency=0.56.

Exercise # 2

Exercise # 3 A 100 W, 220 V incandescent lamp is connected in series with an electrolytic cell containing copper sulphate solution. What weight of copper will be deposited by the current flowing for 5 hours? (At. mass of Cu = 63.54).

Exercise # 4 In an industrial elctrorefining process, Aluminium is purified from its ore by passing a current of 0.48 A (with an applied cell voltage of 220 V) with the actual metal deposited as 0.82 g. Determine 1. The theoretical amount of metal that can be deposited for the quantity of electricity passed during the experiment 2. Current efficiency 3. The energy consumption

Exercise # 5 Calculate :a) the mass and number of moles of a zinc battery casing, b) the mass and number of moles of the manganese dioxide in the electrolyte if the battery has a stored energy of 36 kJ/V and a power of 3 Watts. c) Find the time it takes to consume the stored energy if the battery operates at a current of 2 A and the potential (voltage). The thickness of the cell is x=1 mm.Other dimensions, such as length (L) and radius are indicated below. The discharging reaction is

Exercise # 6 2 A copper surface area(100 cm ) is exposed to an acid solution. After 24 hours the loss of copper due to corrosion is 15x10-3 grams. Calculate a. Current density in A/cm2 b. the corrosion rate CR in mm/y and c. the number of reactions per unit time. Aw=63.54 g/mol, =8.96 g/cm3, qe=1.6022x10-19 C/reaction

Exercise # 7 An electrochemical cell shown below is used as a concentration cell in order to measure the current due to the difference in the ionic concentration between the anodic half cell and the cathodic half cell. Determine the corrosion rate in terms of electrons/second and the number of anodic reactions/second if the measured current is

Exercise # 8

Calculate the corrosion rate CR in mm/y and the electrochemical rate constant in g/cm2.s and mol/cm2 s for a low carbon steel plate (1cmx1cmx4cm) immersed in sea water. Given data I=110A, =7.87 g/cm3 and Aw=55.85 g/mol