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Lecture 5

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Lecture 5

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atahseen2010
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Lecture #5

Equilibrium constant from cell potentials


Some of the most important results of electrochemistry are the
relationships among cell potential, free-energy change, and equilibrium
constant. Recall that the free energy change ΔG for a reaction equals the
maximum useful work of the reaction:

ΔG = wmax …….(1)

For a voltaic cell, this work is the electrical work:

Wmax= -nFEcell ……… (2)

Where:

n = The number of moles of electrons transferred in a reaction

‫ﻋﺪد ﻣﻮﻻت اﻻﻟﻜﺘﺮوﻧﺎت اﻟﻤﻨﻘﻮﻟﺔ ﻓﻲ اﻟﺘﻔﺎﻋﻞ اﻟﻜﮭﻮﻛﯿﻤﯿﺎﺋﻲ‬

So; when :

‫ﻋﻨﺪﻣﺎ ﺗﻜﻮن ﻛﻞ ﻣﻦ اﻟﻤﻮاد اﻟﻤﺘﻔﺎﻋﻠﺔ واﻟﻤﻮاد اﻟﻨﺎﺗﺠﺔ ﺑﺤﺎﻟﺘﮭﺎ اﻟﻘﯿﺎﺳﯿﺔ‬

ΔGo = -nFEocell ……..(3)

With this equation, cell potential (E) measurements become an important


source of thermodynamic information. Alternatively, thermodynamic data
can be used to calculate cell potentials.

‫( ﻧﻼﺣﻆ ان ﻗﯿﺎﺳﺎت ﺟﮭﺪ اﻟﺨﻠﯿﺔ ﯾﺼﺒﺢ ﻣﮭﻢ ﺟﺪا ﻓﻲ ﺣﺴﺎب اﻟﻘﯿﻢ اﻟﺜﺮﻣﻮدﯾﻨﺎﻣﯿﻜﯿﺔ‬3) ‫ ﻣﻦ ﺧﻼل ﻣﻌﺎدﻟﺔ‬,

‫وأﯾﻀﺎ ﻓﻲ ﺣﺴﺎب ﺛﺎﺑﺖ اﻟﺘﻮازن ﻟﻠﺘﻔﺎﻋﻞ ﻛﻤﺎ ﻣﺒﯿﻦ ﻓﻲ اﻟﻤﻌﺎدﻻت أدﻧﺎه‬:


The measurement of cell potentials gives you yet another way to obtain
equilibrium constants (K):

…….. (4)

Combining eq.(3) with eq.(4) , we will obtain eq.(5) :

E > 0, ΔG <0 …….Spontaneous reaction


‫وﺑﺎﻟﺘﺎﻟﻲ ﺗﻠﻘﺎﺋﻲ ﻏﯿﺮ اﻟﺘﻔﺎﻋﻞ ﻓﺎن (ﺳﺎﻟﺒﺔ ﻗﯿﻤﺔ) ﺻﻔﺮ ﻣﻦ اﺻﻐﺮ اﻟﺨﻠﯿﺔ ﺟﮭﺪ ﻗﯿﻤﺔ ﻛﺎﻧﺖ أذا أﻣﺎ‬
‫(ﻣﻮﺟﺒﺔ ﻗﯿﻤﺔ ) ﺻﻔﺮ ﻣﻦ اﻛﺒﺮ ﺗﻜﻮن ﻟﻠﺘﻔﺎﻋﻞ اﻟﺤﺮة اﻟﻄﺎﻗﺔ ﻗﯿﻤﺔ ﻓﺎن‬
E<0 , ΔG > 0 ………Non-Spontaneous reaction
‫ ﻓﺄن ﻣﺘﻮازن اﻟﻜﮭﺮوﻛﯿﻤﺎﺋﻲ اﻟﺘﻔﺎﻋﻞ ﻛﻮن ﺣﺎﻟﺔ ﻓﻲ أﻣﺎ‬:
E=0 , ΔG=0 …….. Equilibrium reaction
Concentration Cells :
This is similar to galvanic cells except the anode and cathode are of same metals
in a heterogeneous electrolyte. A pipe in soil, Concentration cells may be set up
by: (a) Variation in the amount of oxygen in soils. (b) Differences in moisture
content of soils. (c) Differences in compositions of the soil. Concentration cells are
commonly observed in underground corroding structures, such as buried pipes or
tanks.

There are three general types of concentration cell corrosion:

1)Metal Ion Concentration Cells In the presence of water, a high concentration of metal ions will
exist under faying surfaces and a low concentration of metal ions will exist adjacent to the
crevice created by the faying surfaces. An electrical potential will exist between the two points.
The area of the metal in contact with the low concentration of metal ions will be cathodic and
will be protected, and the area of metal in contact with the high metal ion concentration will be
anodic and corroded.

2)Oxygen Concentration Cells A water solution in contact with the metal surface will normally
contain dissolved oxygen. An oxygen cell can develop at any point where the oxygen in the air is
not allowed to diffuse uniformly into the solution, thereby creating a difference in oxygen
concentration between two points. Corrosion will occur at the area of low-oxygen concentration
(anode).

3)Active-Passive Cells Metals that depend on a tightly adhering passive film (usually an oxide)
for corrosion protection; e.g., austenitic corrosion-resistant steel, can be corroded by active-
passive cells. The corrosive action usually starts as an oxygen concentration cell; e.g., salt
deposits on the metal surface in the presence of water containing oxygen can create the oxygen
cell. The inequality of dissolved chemicals causes a potential difference, which establishes anode
in the more concentrated region and cathode in the less concentrated region.
Electrode-Solution Interface – Definition and Types of Polarization
Proportionality between current density (i) and reacted mass (m) in an electrochemical reaction
is stated by Faraday’s law.

D = density, g/cm3

Through above relationship, anodic current density in corrosion can be converted to metal loss in
mpy. When electrode reactions take place, the potential will no longer be at equilibrium due to
current flow through an electrochemical cell-causing a change in the electrode potential. This
electrochemical phenomenon is termed POLARIZATION. Polarization of anode – anodic
polarization Polarization of cathode – cathodic polarization Corroding systems are not in
equilibrium-deviation from thermodynamics. Deviation of the potential from its reversible value
is referred to as polarization. A cell or electrode is said to be polarised when there is little or no
change in current with larger changes in potential. An electrode is not in equilibrium when a net
current flow from or to its surface. Polarization can result from either a slow step in an electrode
process or discharge of ions at an electrode surface. Distribution of anions and cations at a metal
– solution interface is shown as electrical double layer (Fig. 8.1).

A compact layer (Helmholtz) closest to metal surface in which charge distribution and hence
potential varies linearly with distance (Fig. 8.2). A more diffuse innter layer (G. C. layer) where
potential changes exponentially.
Mass transport to metal surface involves forces such as convection, diffusion and migration,
depending on presence or absence of electric field and flow conditions. Concentration
polarization is controlled by diffusion gradients (Fick’s law). Activation polarization involves
kinetic factors related to charge transfer, such as activation energy barrier and equilibrium
current density. Transport processes at an electrode – electrolyte interface are illustrated in Fig.
8.3. Consider a solid-solution interface. Diffusion of electro-active ions from bulk to the
interface and interaction at electrode resulting from charge transfer.

Polarization resulting from concentration gradients is termed concentration polarization; while


activation polarization is caused by a slow step in the electrode reaction (electrode reaction
requires activation energy in order to reach the final state)

Examples of activation polarization include:

Hydrogen overvoltage (overpotential)

For this cathodic reaction, there will be deviation from the reversible value to more negative
values and that deviation is the overvoltage.
So Total polarization ηT = ηAct + ηConc + ηresist

When polarization occurs mostly at anodes, corrosion reaction is Anodically

Controlled - Anodic process at electrode is accelerated by moving the potential in the positive
direction.

When polarization occurs mostly at cathodes, it is Cathodically controlled - Cathodic process


accelerated by moving the potential in the negative direction.

Resistance control when electrolyte / electrode resistance is so high that the current is insufficient
to polarise either of the electrodes.
Mixed control refers to the condition where both anode and cathode are polarized. Schematic
illustrations of anodic, cathodic, mixed and resistance controls are given in Fig 8.4.

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