202me472 Oh 3

ME 472 University of Hafr Al Batin
College of Engineering
Department of Mechanical Engineering
Engineering
Corrosion
OH-3
Course Instructor:
Dr. Tajammal Imran.
UHB Main Campus Room #2307,
tajammal@uhb.edu.sa
Engineering Corrosion
ME472
• Thermodynamics of Corrosion
Disclaimer: the contents of this lecture are referenced to various resources including textbook, internet resources and lectures.
The instructor claims no credit except the credit of the time and organization of the content.
Overview of Thermodynamics of Corrosion
• Change Of Gibbs Free Energy, • Measurement of pH
ΔG • Oxygen Electrode and
• Measuring the EMF of a Cell Differential Aeration Cell
• Calculation of EMF • The E.M.F. and Galvanic
• Calculating Half-Cell Potentials Series
– Nernst Equation • Pourbaix Diagrams or pH
• The Hydrogen Electrode diagrams or Stability
Diagrams
• The Standard Hydrogen Scale
02/08/2021 202ME472EngineeringCorrosion_Tajim_HO_2 3
Gibbs Free Energy
• It also known as the Gibbs function, • Gibbs free energy is equal to the
Gibbs energy, or free enthalpy, is a enthalpy of the system minus the
quantity that is used to measure the product of the temperature and
maximum amount of work done in a entropy.
thermodynamic system when the • The equation is given as;
temperature and pressure are kept
constant. G = H – TS
• Gibbs free energy is denoted by the Where,
symbol ‘G’. • G = Gibbs free energy
• Its value is usually expressed in Joules • H = enthalpy
or Kilojoules. • T = temperature
• Gibbs free energy can be defined as the • S = entropy
maximum amount of work that can be
extracted from a closed system.
Change of Gibbs Free Energy
Consider the following reaction at 25°C:
The large negative value of G ° (reactants and products in standard states) indicates a pronounced tendency
for magnesium to react with water and oxygen.
The reaction tendency is less. Or we can say that the corrosion tendency of copper in aerated water is not as
pronounced as that of magnesium.
The free energy is positive, indicating that the reaction has no tendency to go at all; and gold, correspondingly,
does not corrode in aqueous media to form Au(OH)3 .
It should be emphasized that the tendency to corrode is not a measure of reaction rate. A large negative G may or may
not be accompanied by a high corrosion rate, but, when G is positive, it can be stated with certainty that the reaction
will not go at all under the particular conditions described.
Change of Gibbs Free Energy
• Thermodynamics can provide a basis for the understanding of the energy changes
associated with the corrosion reaction.
• It can, in general, predict when corrosion is possible.
• Thermodynamics cannot predict corrosion rates.
• The rate at which the reaction proceeds is governed by kinetics.
• The change in Gibb’s free energy, given by the following equation, provides us a tool with
which to predict if a corrosion reaction is thermodynamically possible:
ΔG = -n F E
Practice Problems
• Predicting the Feasibility of Redox Reaction
Any redox reaction would occur spontaneously if the free energy change (ΔG) is negative. The free energy is related to
cell emf in the following manner:
Where n is the number of electrons involved, F is the Faraday constant and Eo is the cell EMF at standard
conditions.
• ΔGo can be negative if Eo is positive.
• When Eo is positive, the cell reaction is spontaneous and serves as a source of electrical
energy.
• If Eo comes out to be negative then the spontaneous reaction cannot take place.
• The resultant value of Eo for redox reaction is important in predicting the stability of a
metal salt solution when stored in another metal container.
Spontaneous – is a reaction that is considered natural because it is a reaction that occurs by itself without any external action towards it.
Example
Steel is placed in aerated seawater (with a neutral pH). Is corrosion of the steel possible, why?
(Assume valence of 2)
Solution:
Practice Problems
• Predicting the Feasibility of Redox Reaction
Any redox reaction would occur spontaneously if the free energy change (ΔG) is negative. The free energy is related to
cell emf in the following manner:
For example, let us find out whether we can store copper sulphate solution in a nickel vessel or not.
We want to see whether Ni metal will displace copper from copper sulphate solution to give NiSO4 by undergoing oxidation
reaction.
From the above reaction, it is clear oxidation terminal will be Ni electrode.
As the emf comes out to be positive, it implies copper sulphate reacts when placed in a nickel vessel and hence cannot be
stored in it.
Measuring the EMF of a Cell
• The EMF of a cell, as set up in the laboratory or in the field, can be measured using a
voltmeter of high impedance, > 1012  (ohms).
• Alternatively, using a potentiometer, the EMF of the cell can be opposed with a known
EMF until no current flows through a galvanometer in series with the cell.
• At exact balance (i.e., when the EMF of the cell is exactly balanced by the known EMF),
no current flows through the cell, and the reading of the known EMF indicates the
exact EMF of the cell.
• In making these measurements, it is essential that any current that flows in the circuit
is sufficiently small that the cell is not polarized — that is, that the emf of the cell is not
changed because of the current flow.
• For this reason, sensitive galvanometers of high input impedance, at least 1012 , must
be used, so that, if the potentiometer and cell are unbalanced to the extent of 1 V, a
current of only 10-12 A flows.
• Such a current is not sufficient to polarize (temporarily alter the emf of) the cell.
Measuring the EMF of a Cell
Procedure:
1. Set the temperature.
2. Select the cathode from the list.
3. Select the anode from the list.
4. Select concentration of the electrolyte.
5. Record the voltage of the cell.
6. Calculate the Gibbs free energy from the
voltage obtained from experiment.
7. Calculate the Equilibrium constant.
8. Predict the spontaneity of the cell reaction.
E.M.F. of a Cell (Electrode Potential)
• The electromotive force of a cell or • The Nernst equation is often used to
EMF of a cell is the maximum calculate the cell potential of an
potential difference between two electrochemical cell at any given
electrodes of a cell. temperature, pressure, and reactant
• It can also be defined as the net concentration.
voltage between the oxidation and • The equation was introduced by a
reduction half-reactions. German chemist Walther Hermann
• The EMF of a cell is mainly used to Nernst.
determine whether an electrochemical
cell is galvanic or not.
Measuring Electrode Potential: SHE
• In an electrochemical cell, the anode • The standard electrode potential of a
has a negative potential and cathode SHE is assumed to be zero.
has a positive potential. • The electrode potential at standard
• The potential of each individual half conditions such as 25°C
cell cannot be measured. temperature, 1 atm pressure, 1 M
• We can measure only the difference concentration of electrolyte, is called
between the potential of the two the standard electrode potential.
half cells. • It is denoted by the symbol “ E0”.
• The potential of a half cell can be • The electrodes are arranged in the
measured by connecting it with increasing order of their standard
Standard Hydrogen Electrode (SHE). reduction potential and are called
electrochemical series.
How do you calculate electrochemical cell potential?
• At the standard state
• The first step is to determine the cell potential at its standard state — concentrations of 1 mol/L and pressures of 1 atm
at 25°C.
• Non-standard state conditions
• If the conditions are not standard state (concentrations not 1 mol/L, pressures not 1 atm, temperature not 25°C), then
cell potentials is to found using Nernst equation (which involves few extra steps).
The procedure is:

1. Write the oxidation and reduction half-reactions for the cell.
2. Look up the reduction potential, E⁰red, for the reduction half-reaction in a table of
reduction potentials
3. Look up the reduction potential for the reverse of the oxidation half-reaction and
reverse the sign to obtain the oxidation potential. For the oxidation half-reaction,
E⁰ox = -E⁰red
4. Add the two half-cell potentials to get the overall standard cell potential.
E⁰cell = E⁰red + E⁰ox
Calculating Half-Cell Potentials – Nernst Equation
• Nernst equation relates the equilibrium state potential of a half cell with the
standard electrode potential of the half cell, temperature, reaction coefficients
as well as activity of the reacting species.
• For an electrode reaction Mn+ + n e– →M(s)
• The equilibrium state EMF is given by;
• Where EMn+| M is the half cell potential • R is the universal gas constant (8.314 J/K/mole)
• EOMn+| M is the S.E.P. of the half cell • T is the temperature in kelvin
• [ M ] is the molar concentration of the metal • n is the number of electrons involved in the reaction
• [ Mn+ ] is the molar concentration of the metal ion • F is the Faraday’s constant (96500 C/mole)
First at the standard state
Let’s use these steps to find the standard cell potential for an electrochemical cell with the
following cell reaction.
Then, at the non-standard state
If the conditions are not standard state (concentrations not 1 mol/L, pressures
not 1 atm, temperature not 25°C), we must take a few extra steps.
Example
Calculate the cell potential for the following reaction when the pressure of the oxygen gas is 2.50 atm,
the hydrogen ion concentration is 0.10 mol/L, and the bromide ion concentration is 0.25 mol/L.
Example
Calculate the cell potential for the following reaction when the pressure of the oxygen gas is 2.50 atm,
the hydrogen ion concentration is 0.10 mol/L, and the bromide ion concentration is 0.25 mol/L.
Standard Electrode Potential of Zinc
• To determine the potential of a single half cell, a
standard half cell whose potential value is already
known, is needed.
• This standard half cell is then connected with the
unknown half cell (Zinc) to determine the overall
potential.
• This overall potential is the difference between the
potentials of the two half cells.
• The standard hydrogen electrode (SHE) is an example of
such a standard half cell.
• The potential value of SHE is inherently set to zero volts.
• The standard hydrogen electrode is connected with an
unknown half cell and the potential difference is
measured.
• As SHE has zero volts, the measured value will be the
potential difference of the unknown half cell.
• The picture represents the method to find the standard
electrode potential of zinc.
Measuring the pH of a Cell
• pH, is a measure of the concentration of • pH refers to whether there is an excess of
hydrogen ions H+ or cations. H+ (hydrogen) or OH− (hydroxyl) ions
• The term pH was derived from the manner, present.
in which the hydrogen ion concentration is • The H+ ion is acid while the OH− ion is
calculated. alkaline or basic.
• It is the negative logarithm of the hydrogen • The pH may be measured with a meter or
ion (H+) concentration: calculated if certain parameters are
established.
• Water itself dissociates to a small extent
to produce equal quantities of H+ and OH−
where log is a base-10 logarithm and aH+ is the activity
10
ions displayed in the following
(related to concentration) of hydrogen ions. The “p”
stands for the German word for power, potenz, so pH is
equilibrium:
an abbreviation for power of hydrogen.
Nernst equation & pH of a Cell
• Nernst equation describes potential of electrochemical cell as a function of concentrations of ions taking
part in the reaction;
Where Q (or K) is a reaction quotient and ‘n’ is number of electrons exchanged. For constant temperature
expression RT/F has constant value. To simplify calculations, it is often combined with conversion factor
between natural logarithm (denoted here by ln) and decimal logarithm (denoted here by log) to form value of
0.0591 (for 25°C).
Example: Nernst equation & pH of a Cell
A circular copper coupon is rotated in seawater. A gradient in the metal ion concentration is
set up on the disk surface. On periphery of the disk copper ion concentration is 0.001 M.
Near the centre of the disk the copper ion concentration is 10 M. What are the potentials of
anodic and cathodic sites on copper? Where will the metal loss occur? Assume STP.
Solution: In this case we find the standard EMF for the following equation;
• For half reaction of MnO4- in acidic media; MnO4- + 8H+ + 5e- → Mn2+ + 4H2O
• The potential is given by
To be precise we should not use concentrations, but thermodynamic activities of the ions present in the solution.
When applied to the full cell formed from half cells present on inside and outside of glass pH electrode, Nernst equation
takes form:
pH inside of the electrode has constant value, thus it can be included in the potential part of the equation:
http://www.ph-meter.info/pH-Nernst-equation
Example: Calculate the potential of oxygen electrode at pH=14.0
To determine in which direction a reaction will go?
K vs Q
• Sometimes it is necessary to determine in which direction a reaction will progress based on initial activities or
concentrations.
• In these situations, the relationship between the reaction quotient, Qc, and the equilibrium constant, Kc, is essential in
solving for the net change.
• With this relationship, the direction in which a reaction will shift to achieve chemical equilibrium, whether to the left or
the right, can be easily calculated.
• The reaction quotient, Q, expresses the relative ratio of products to reactants at a given instant.
• Using either the initial concentrations or initial activities of all the components of the reaction, the progression of a
reaction can easily be determined.
Given the general chemical reaction: ⇌
Q for this reaction may be expressed as the following equations:
The expressions for K are very similar to those for Q:
Equilibrium Constant & Reaction Quotient
K vs Q
• The reaction quotient Q is given by the same equation as the equilibrium
constant K (concentration of products divided by concentration of reactants)
• The value Q will fluctuate as the system reacts.
• The equilibrium constant K is based on equilibrium concentrations.
Equilibrium Constant & Reaction Quotient
K vs Q
Equilibrium K vs Q: Example
To properly use the relationship between Q and K, you must know how to set it up. Take, for example, the reaction below
and
• If the reaction is started with 4.00M of
CH4, 2.00M C2H2, and 3.00M H2
• The question is in which direction will the
reaction progress to reach equilibrium?
Writing Equilibrium Constant Expression: K
• The equilibrium constant, K, expresses the relationship between products and reactants of
a reaction at equilibrium with respect to a specific unit.
• This equilibrium constant expressions, introduces the calculations involved with both the
concentration and the partial pressure equilibrium constant.
• The numerical value of an equilibrium constant is obtained by letting a single reaction
proceed to equilibrium and then measuring the concentrations of each substance involved
in that reaction.
• The ratio of the product concentrations to reactant concentrations is calculated.
• Because the concentrations are measured at equilibrium, the equilibrium constant remains
the same for a given reaction independent of initial concentrations.
• This knowledge permits to derive a model expression that can serve as a "model" for any
reaction.
• This basic "model" form of an equilibrium constant expression is examined here.
1.Equilibrium Constant of Activities
• The thermodynamically correct equilibrium constant expression relates the activities of all of the species
present in the reaction.
• It is essential that the explanation of the derivation of the equilibrium constant expression starts with
activities so that no misconceptions occur. For the hypothetical reaction:
and the equilibrium constant expression is written as
*The lower-case letters in the balanced equation represent the number of moles of each substance, the upper-case letters
represent the substance itself.
• If K > 1 then equilibrium favours products
• If K < 1 then equilibrium favours the reactants
2. Equilibrium Constant of Concentration
• To avoid the use of activities, and to simplify experimental measurements, the equilibrium constant of
concentration approximates the activities of solutes and gases in dilute solutions with their respective
molarities.
• However, the activities of solids, pure liquids, and solvents are not approximated with their molarities.
Instead these activities are defined to have a value equal to 1 (one).
• The equilibrium constant expression is written as Kc, as in the expression for the reaction:
1. Here, the letters inside the brackets represent the concentration (in molarity) of each substance.
2. Notice the mathematical product of the chemical products raised to the powers of their respective coefficients is the
numerator of the ratio
3. The mathematical product of the reactants raised to the powers of their respective coefficients is the denominator.
4. This is the case for every equilibrium constant.
3. Equilibrium Constant of Pressure
• Gaseous reaction equilibria are often expressed in terms of partial pressures.
• The equilibrium constant of pressure gives the ratio of pressure of products over reactants for a reaction that
is at equilibrium (again, the pressures of all species are raised to the powers of their respective coefficients).
• The equilibrium constant is written as Kp, as shown for the reaction:
Where p can have units of pressure (e.g., atm or bar).
For Practice problems, see this page

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Equilibria/Chemical_Equilibria/The_Equilibrium_Constant
Relationship between G and the K
G is the free energy and K is the equilibrium constant
ΔG° is −32.7 kJ/mol of N2 for the reaction; N2(g)+3H2(g) ⇌2NH3(g)

This calculation was for the reaction under standard conditions—that is, with all gases
present at a partial pressure of 1 atm and a temperature of 25°C.
• Calculate ΔG for the same reaction under the following nonstandard conditions:
PN2 = 2.00 atm, PH2 = 7.00 atm, PNH3 = 0.021 atm, and T = 100°C.
• Does the reaction proceed to the right, as written, or to the left to reach equilibrium?
Solution Strategy:
1. Using the values given and following equation to calculate Q.
2. Determine if Q is >, <, or = to K

3. Substitute the values of ΔG° and Q into above equation to obtain ΔG for the reaction under nonstandard
conditions.
Solution Strategy of Relationship between G and the K
G is the free energy and K is the equilibrium constant
1. The relationship between ΔG° and ΔG under nonstandard conditions is given in the
following equation;
Substituting the partial pressures given, we can calculate Q:
2. Because ΔG° is −, K must be a number greater than 1

3. Substituting the values of ΔG° and Q into Equation
Because ΔG < 0 and Q < K (because Q < 1), the reaction proceeds spontaneously to the right, as written, in order to reach equilibrium.
Oxygen Electrode
• The Oxygen electrode (or Clark electrode)
is an electrode that measures ambient
oxygen concentration in a liquid using a
catalytic platinum surface according to
the net reaction:
O2 + 4 e− + 4 H+ → 2 H2O
• It advances on a bare platinum electrode
by use of a membrane to reduce fouling
and metal plating onto the platinum.
Oxygen Electrode
• This electrode is particularly
• The oxygen electrode can be important to corrosion studies
represented by platinized platinum because of its role in differential
immersed in an electrolyte saturated aeration cells in the mechanism of
with oxygen. crevice corrosion and pitting.
• The equilibrium for such an • This reaction, however, unlike the
electrode is expressed as; hydrogen electrode reaction, is not
strictly reversible under practical
conditions of measurement, and
hence the measured potential may
vary with time and is not
reproducible.
Differential Aeration Cell
• A differential aeration cell causes corrosion of metals as a result of the formation of an oxygen
concentration cell, which is caused by an uneven supply of air on the metal surface.
• This uneven level of oxygen creates anodic and cathodic sites in the corrosion cell.
• A differential aeration cell is also known as an oxygen concentration cell.
Differential Aeration Cell
• For illustration, consider two oxygen electrodes in an aqueous environment: one in
contact with O2 at 1 atm (left) and the other with O2 at 0.2 atm (right).
• The potentials of the left - and right - hand electrodes, respectively, are as follows:
The negative value of EMF indicates that G for (5) is positive, and hence the reaction is not spontaneous as written.
Instead, positive electricity flows spontaneously within the cell from right to left. Therefore, the left - hand electrode, (1) , is
positive (cathode) and the right - hand electrode, (3) , is negative (anode). This expresses the fact formulated earlier that, in
any differential aeration cell, the electrode in contact with lower - pressure oxygen tends to be the anode, and the electrode
in contact with higher - pressure oxygen tends to be the cathode.
Reference Electrodes or Cell
1. Hydrogen Electrode
2. Silver–Silver Chloride Electrode
3. The Calomel Electrode
4. Copper–Copper Sulfate Electrode
• The absolute value of electrode potential
cannot be measured.
• In order to measure the potential difference
across the metal/solution interface, we must
choose one electrode as reference electrode.
• The relative electrode potential can be
obtained by measuring the electrode potential
vs. a standard reference electrode.
• Internationally, a standard hydrogen electrode
(SHE), which potential is defined to be zero, is
used as a standard reference electrode.
Hydrogen Electrode
• The half-cell of the hydrogen reference electrode consists of
platinum foil, which serves as a conductor.
• The platinum foil is in contact with a sulfuric acid solution
that contains H+ cations of unit activity, in equilibrium with
H2 gas, in its standard state of 1 atm.
• The standard hydrogen electrode may be represented as:
• According to the Nernst equation:
The hydrogen electrode potential depends on the hydrogen activity and the partial hydrogen pressure. Under standard
conditions, the hydrogen pressure is one atmosphere; thus, its activity is equal to 1 and, therefore, according to IUPAC
convention, the hydrogen reference electrode potential is zero.
Silver-Silver Chloride Electrode
• This electrode consists of silver chloride covering a
silver-plated platinum wire sealed in a glass tube, as
indicated below.
• When the electrode is immersed in a chloride solution
(such as seawater), the potential reaction is:
Ag + Cl-  AgCl + e-
• The potential of the silver-silver chloride electrode
relative to the hydrogen half-cell is +0.266V.
Calomel Electrode
• In establishing the galvanic series of
metals and alloys in seawater, a saturated
calomel half-cell is used.
• Its name ‘calomel’ is taken from one of its
ingredients, mercurous chloride (Hg2Cl2).
• The potential reaction is
2Hg + 2Cl- Hg2Cl2 + 2e-
• The potential of the saturated calomel
half-cell relative to the hydrogen half-cell
is + 0.246V.
• The cell is illustrated in the figure.
Copper-Copper Sulfate Electrode
• The saturated copper-copper sulfate half-cell is an
equally useful cell for corrosion measurements.
• A sketch of the cell is illustrated.
• When used, it is immersed in seawater where the
porous plug makes the connection to the cell.
• The half-cell potential reaction is Cu  Cu++ + 2e-
and its reverse.
• The potential of the copper-copper sulfate half-
cell, relative to the hydrogen electrode is +0.316 V
Pourbaix (Potential-pH or Stability) Diagrams
• These diagrams represent the stability of a metal as a
function of potential and pH.
• They are analogues to phase equilibrium diagrams,
where the stability of various phases is shown as a
function of temperature and percentage composition of
the metal.
• At a particular combination of pH and potential, a stable
phase can be determined from the Pourbaix diagram.
• The redox potential of the corroding system is plotted
on a vertical axis and the pH on a horizontal axis.
• These diagrams are constructed from calculations based
on Nernst equations and solubility data for metal and its
species, such as Fe, Fe2O3, Fe(OH) 2, Fe3O4, etc., in
equilibrium.
Pourbaix (Potential-pH or Stability) Diagrams
• Eh-pH or Pourbaix diagrams showing reactions and products at electrochemical equilibrium
• Thermodynamic data in the form of potential – pH diagrams is plotted, and which relate the electrochemical
and corrosion behaviour of any metal in water.
There are four regions in the diagram, which are;

1. Oxidizing (acidic)
2. Oxidizing (alkaline)
3. Reducing (acidic)
4. Reducing (alkaline)
The basic diagram for aqueous environment

involves upper and lower, stability limits for
water, represented by the oxygen (universal
oxidizing agent) and hydrogen (universal
reducing agent) reactions.
Stability Limits of Water
The chemical behaviour of water across all
possible values of potential and pH is divided
into three regions.
• In the upper region, water can be oxidized to
produce oxygen
• In the lower region it can be reduced to form
hydrogen gas.
• Water is therefore only thermodynamically
stable between lines (a) and (b).
• E-pH stability diagram of water at 25oC is
shown here.
• Two cathodic reactions takes place at (a) and
at (b)
Advantages of Eh-Ph diagram
From a corrosion engineering perspective,
the importance of Pourbaix diagrams is
their;
• Usefulness in identifying potential – pH • The diagrams are generally
domains where corrosion does not occur constructed using
• the metal itself is the stable phase • equilibrium constants,
• solubility data,
• Finding what the corrosion products may
• a form of the Nernst equation
be which includes a pH term.
• Forecasting what effect environmental
changes may have on corrosion
Example of Iron-Stability diagram
• Areas in the Pourbaix diagram mark
regions where a single species (Fe2+(aq),
Fe3O4(s), etc.) is stable.
• More stable species tend to occupy
larger areas.
• Lines mark places where two species
exist in equilibrium.
a) Pure redox reactions are horizontal lines
- these reactions are not pH-dependent
b) Pure acid-base reactions are vertical
lines - these do not depend on potential
c) Reactions that are both acid-base and
redox have a slope of -0.0592 V/pH
Example of Iron-Stability diagram
Examples of equilibria in the iron Pourbaix diagram (numbered on
the plot):
The water redox lines have special significance on a Pourbaix

diagram for an element such as iron.
• Recall that liquid water is stable only in the region between the
dotted lines.
• Below the H2 line, water is unstable relative to hydrogen gas, and
above the O2 line, water is unstable with respect to oxygen.
• For active metals such as Fe, the region where the pure element is
stable is typically below the H2 line. This means that iron metal is
unstable in contact with water, undergoing reactions:
Case Study & Application
Pourbaix Diagram for Corrosion Protection
Summary: Pourbaix Diagram
The information in the diagrams can be beneficially used to
control corrosion of pure metals in the aqueous
environment
1. By altering the pH and potential to the regions of
immunity and passivation, corrosion can be
controlled.
• For example, on increasing the pH of environment
in moving to slightly alkaline regions, the
corrosion of iron can be controlled.
2. Changing the potential of iron to more negative
values eliminate corrosion; this technique is called
Cathodic protection.
3. Raising the potentials to more positive values
reduces the corrosion by formation of stable films
of oxides on the surface of transition metals.
Homework 2.1
• A galvanic cell consists of (Zn) electrode in (ZnSO4)
solution with (1 mole) concentration. The other is of (Ni)
electrode in (NiSO4) solution with (1 mole) concentration.
The two electrodes are separated with porous partition
to prevent mixing of the two solutions. The two
electrodes are contacted with conductive wire. Find.
a) On which electrode the oxidation reaction will take
place?
b) Which electrode will be the anode?
c) Which electrode will be corroded?
d) What is the EMF for this galvanic cell?
Homework 2.2
Write the reactions of the Anodic half cell (oxidation) and Cathodic half cell
(reduction) for the following electrodes and electrolytes, by using standards
potential values :
a) Zinc and copper electrodes are immersed in dilute (CuSO4).
b) Copper electrode is immersed in water saturated with oxygen.
c) Iron electrode is immersed in water saturated with oxygen.
d) Magnesium electrode is immersed in water saturated with oxygen.
Homework 2.3
A galvanic cell is at 250C and is formed by Zinc electrode with (0.10 mole
ZnSO4) solution. The other electrode is of Nickel with (0.05 mole NiSO4)
solution .The two electrodes are separated with porous wall and
connected with external wire. What is the value of the cell potential, when
the circuit is connected.
Example
Example
Example
Summary and Conclusions
• What is Change Of Gibbs Free Energy, ΔG ?
• How to measure the EMF of a Cell or calculation of EMF?
• What is the Hydrogen Electrode and the Standard Hydrogen
Scale
• How to Calculate Half-Cell Potentials – Nernst Equation
• What is Measurement of pH
• What is Oxygen Electrode and Differential Aeration Cell
• What are Pourbaix Diagrams or pH diagrams or Stability
Diagrams
Homogeneous Reactions
• A homogeneous reaction is one where the states of matter of the products and reactions are all
the same.
• In most cases, the solvent determines the state of matter for the overall reaction. For example,
the synthesis of methanol from a carbon monoxide-hydrogen mixture is a gaseous homogeneous
mixture, which contains two or more substances:
CO(g) + 2H2(g) ⇌ CH3OH(g)
• At equilibrium, the rate of the forward and reverse reaction are equal, which is demonstrated by
the arrows.
• The equilibrium constant, however, gives the ratio of the units (pressure or concentration) of the
products to the reactants when the reaction is at equilibrium.
• The synthesis of ammonia is another example of a gaseous homogeneous mixture:
N2(g)+3H2(g) ⇌ 2NH3(g)
Heterogeneous Reactions
• A heterogeneous reaction is one in which one or more states within the reaction
differ.
• For example, the formation of an aqueous solution of lead iodide creates a
heterogeneous mixture dealing with particles in both the solid and aqueous states:
PbI2(s) ⇌ Pb+2(aq) + 2I−(aq)
• The decomposition of sodium hydrogen carbonate (baking soda) at high elevations
is another example of a heterogeneous mixture, this reaction deals with molecules
in both the solid and gaseous states:
2NaHCO3(s) ⇌ Na2CO3(s) + H2O(g) + CO2(g)
C(s) + O2(g) ⇌ CO2(g)

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ME 472 University of Hafr Al Batin

From the above reaction, it is clear oxidation terminal will be Ni electrode.

The procedure is:

The expressions for K are very similar to those for Q:

and the equilibrium constant expression is written as

Where p can have units of pressure (e.g., atm or bar).

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ΔG° is −32.7 kJ/mol of N2 for the reaction; N2(g)+3H2(g) ⇌2NH3(g)

2. Determine if Q is >, <, or = to K

Substituting the partial pressures given, we can calculate Q:

2. Because ΔG° is −, K must be a number greater than 1

• According to the Nernst equation:

There are four regions in the diagram, which are;

The basic diagram for aqueous environment

The water redox lines have special significance on a Pourbaix

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