190 A Textbook of Physical Chemistry – Volume I

 Debye-Huckel-Onsager Treatment for Aqueous Solutions and Its

Limitations
It is a well-known fact that the conductance of weak electrolytic solutions increases with the increase
in dilution. This can be easily explained on the basis of Arrhenius's theory of electrolytic dissociation which
says that the magnitude of dissociated electrolyte, and hence the number of charge carriers, increases with the
increase in dilution. However, the problem arises when the strong or true electrolytes show the same trend but
at a much lower scale. We used the word “problem” because even at the higher concentration, the electrolyte
dissociates completely inferring that there is no possibility of further dissociation with dilution. This means
that there should be no increase in the conductance of strong electrolytes with the addition of water.

Figure 14. The typical variation of molar conductance (Λm) with the square root of the concentration (√𝑐)
for strong and weak electrolytes.

The primary reason behind this weird behavior of strong electrolyte is that the conductance of any
electrolytic solution depends not only upon the number of charge carriers but also upon the speed of these
charge carriers. Therefore, if the dilution does not affect the number of charge carriers in strong electrolytes,
it must be affecting the speed of ions to change its conductance. The main factor that is responsible for
governing the ionic mobility is ion-ion interactions. Now since these ion-ion interactions are dependent upon
the interionic distances, they eventually vary with the population density of charge carriers. Higher population
density means smaller interionic distances and therefore stronger ion-ion interactions. On the other hand, the
lesser population density of ions would result in larger interionic separations and hence weaker ion-ion
interactions.
In the case of weak electrolytes, the degree of dissociation is very small at high concentrations
yielding a very low population density of charge carriers. This would result in almost zero ion-ion interactions

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 CHAPTER 4 Electrochemistry – I: Ion-Ion Interactions 191

at high concentrations. Now although the degree of dissociation increases with dilution which in turn also
increases the total number of charge carriers, the population density remains almost unchanged since extra
water has been added for these extra ions. Thus, we can conclude that there are no ion-ion interactions in weak
electrolytes neither at high nor at the low concentration; and hence the rise in conductance with dilution almost
a function dissociation only.
In the case of strong electrolytes, the degree of dissociation is a hundred percent even at high
concentrations yielding a very high population density of charge carriers. This would result in very strong ion-
ion interactions at high concentrations, hindering the speed of various charge carriers. Now when more and
more solvent is added, the total number of charge carriers remains the same but the population density
decreases continuously creating large interionic separations. This would result in a decrease in ion-ion
interaction with increasing dilution, and therefore, the charge carriers would be freer to move in the solution.
Thus, we can conclude that though there is no rise in the number of charge carriers with dilution, the declining
magnitude of ion-ion interaction creates faster ions and larger conductance.
 Factor Affecting the Conductance of Strong Electrolytic Solutions
In 1923, Peter Debye and Erich Huckel proposed an extremely important idea to quantify the
conductance of strong electrolytes in terms of these interionic interactions. In this model, a reference ion is
thought to be suspended in solvent-continuum of dielectric constant ε and is surrounded by oppositely charged
ions. Besides the ion-ion interaction, the viscosity of the solvent also affects the overall speed of the moving
ion. The primary effects which are responsible for controlling the ionic mobility are discussed below.
1. Asymmetry effect or the relaxation effect: In the absence of applied electric field, the ionic atmosphere
of the reference ion remains spherically symmetrical. This means that the electrostatic force of attraction on
the reference ion from all the directions would be the same. However, when the electric field is applied, the
ion starts to move towards the oppositely charged electrode. This, in turn, would destroy the spherical
symmetry of the cloud, and more ions would be left behind creating a net backward pull to the reference ion.
This effect, therefore, would slow down the moving ions and the conductance would be decreased.

Figure 15. The asymmetric or relaxation effect in the conductance of strong electrolytes.

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 192 A Textbook of Physical Chemistry – Volume I

Alternatively, this can also be visualized in terms of cloud-destruction and cloud-building around the reference
ion. In other words, during the movement of ion, the ionic cloud around the reference ion must rebuild itself
to keep things natural. Since this rebuilding is not instantaneous and takes some time called as relaxation time,
the old cloud exerts a backward pull on the reference ion opposing oppressing its speed. All this results in a
diminished magnitude of the conductance.
2. Electrophoretic effect: After the application of the external electric field, the reference ion and ionic could
move in opposite directions. During the course of this movement, the solvent associated with the surrounding
ions also moves in a direction opposite to the central ion. In other words, we can say that the reference ion has
to move against a solvent stream, which makes it somewhat slower than usual. This phenomenon is called as
the electrophoretic effect.

Figure 16. The asymmetric or relaxation effect in the conductance of strong electrolytes.

Since the electrophoretic effect reduces the speed of the ion, the conductance of the electrolytic solution is also
affected considerably.
3. Viscous Effect: In addition to the asymmetric and electrophoretic effects, another type of resistance also
exists which affects the conductance of electrolytic solutions, the “viscous effect”. This is simply the frictional
resistance created by the viscosity of the solvent used. For an ion of given charge and size, the ionic mobility
as well the conductance decrease with the increase in the magnitude of the viscosity of the solvent used. In
other words, less viscous solvents yield higher conductance and vice-versa.
 Mathematical Development of Debye-Huckel-Onsager theory of Strong Electrolytes
It is a well-known fact that the equivalent conductivity (Λ) of an electrolytic solution is correlated to
the ionic mobilities (u) ions involved as

𝛬 = 𝐹(𝑢+ + 𝑢− ) (176)

Where F is the Faraday constant. Now, recall the ionic mobilities of the cation and anion i.e.

0
𝑍+ 𝑒0 𝑒02 𝜔 0 (177)
𝑢+ = 𝑢+ −𝜅( + 𝑢 )
6𝜋𝜂 6𝜀𝑘𝑇 +

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 CHAPTER 4 Electrochemistry – I: Ion-Ion Interactions 193

0
𝑍− 𝑒0 𝑒02 𝜔 0 (178)
𝑢− = 𝑢− −𝜅( + 𝑢 )
6𝜋𝜂 6𝜀𝑘𝑇 −

Where 𝑢+ 0
and 𝑢−
0
are the ionic mobilities of the cation and anions at infinite dilution, respectively. The symbol
ε represents the dielectric constant of the medium whereas η is the coefficient of viscosity. 𝑍+ and 𝑍− are
charge numbers of the cation and anion, respectively. The symbol e0 simply shows the electronic charge. The
symbol κ represents (𝑛𝑖0 is the bulk concentration)

1/2 1 (179)
4𝜋 4𝜋𝑍 2 𝑒02 𝑐 2 𝑁𝐴 1/2
𝜅=( ∑ 𝑛𝑖0 𝑍𝑖2 𝑒02 ) =( ) ( )
𝜀𝑘𝑇 𝜀𝑘𝑇 1000
𝑖

The quantity ω is defined as

𝑍+ 𝑍− 2𝑞 𝑍+ 𝑍− 𝜆+ + 𝜆− (180)
𝜔= 𝑤ℎ𝑒𝑟𝑒 𝑞=
1 + √𝑞 𝑍+ + 𝑍− 𝑍+ 𝜆+ + 𝑍− 𝜆−

After putting the values of 𝑢+ and 𝑢− from equation (177) and (178) in equation (176), we get

0
𝑍+ 𝑒0 𝑒02 𝜔 0 0
𝑍− 𝑒0 𝑒02 𝜔 0 (181)
𝛬 = 𝐹 [𝑢+ −𝜅( + 𝑢+ )] + 𝐹 [𝑢− −𝜅( + 𝑢 )]
6𝜋𝜂 6𝜀𝑘𝑇 6𝜋𝜂 6𝜀𝑘𝑇 −

In the case of symmetrical electrolytes, we can put 𝑍+ = 𝑍− = 𝑍, and therefore 𝑍+ + 𝑍− = 2𝑍. Thus, the
above equation for such cases takes the form

0 0)
𝐹𝑍𝜅𝑒0 𝑒02 𝜔𝑘 0 0
(182)
𝛬 = 𝐹(𝑢+ + 𝑢− −[ + 𝐹(𝑢+ + 𝑢− )]
3𝜋𝜂 6𝜀𝑘𝑇

Since 𝐹(𝑢+
0 0)
+ 𝑢− = 𝛬0 , the equation (182) becomes

𝐹𝑍𝜅𝑒0 𝑒02 𝜔𝑘 0
0
(183)
𝛬 =𝛬 −[ + 𝛬 ]
3𝜋𝜂 6𝜀𝑘𝑇

Now expending above equation further by putting the value of κ from equation (179), we get
1 1 (184)
0
𝐹𝑍𝑒0 8𝜋𝑍 2 𝑒02 𝑁𝐴 2 𝑒02 𝜔 8𝜋𝑍 2 𝑒02 𝑁𝐴 2 0
𝛬 =𝛬 −[ ( ) + ( ) 𝛬 ] √𝑐
3𝜋𝜂 1000𝜀𝑘𝑇 6𝜀𝑘𝑇 1000𝜀𝑘𝑇

Define two constant A and B as

1 1 (185)
𝐹𝑍𝑒0 8𝜋𝑍 2 𝑒02 𝑁𝐴 2 𝑒02 𝜔 8𝜋𝑍 2 𝑒02 𝑁𝐴 2
𝐴= ( ) 𝑎𝑛𝑑 𝐵 = ( )
3𝜋𝜂 1000𝜀𝑘𝑇 6𝜀𝑘𝑇 1000𝜀𝑘𝑇

Therefore, the equation (184) can be simplified as

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 194 A Textbook of Physical Chemistry – Volume I

𝛬 = 𝛬0 − (𝐴 + 𝐵𝛬0 )√𝑐 (186)

or

𝛬 = 𝛬0 − 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡√𝑐 (187)

The equation (184) and equation (186) are the popular forms famous Debye-Huckel-Onsager equation for
electrolyte solutions. The constants A and B can easily be determined from the knowledge of temperature T,
valence type of the electrolyte z, the viscosity of the medium, the dielectric constant and other universal
constants like Avogadro number. From Equation (187), it is obviously a straight line equation which means
the for symmetrical electrolytic solutions, we can plot the conductance vs square root of the concentration for
which the slope will be negative. The intercept after extrapolation gives the value of conductance of such
solutions at infinite dilution.
 Limitations of Debye-Huckel-Onsager Equation
Since the plot of conductance vs square root of the concentration is linear with negative slope and
positive intercept, it seems quite straightforward to study the strong electrolytes. However, it has been observed
that the equation (187) is followed only up low and moderate concentrations.

Figure 17. The comparison of theoretical and experimental conductance as a function of concentration for
some symmetric electrolytes.

It can be clearly seen that the theory and experiment move apart as the concentration increases. This is simply
because some approximation used to derive are Debye-Huckel-Onsager equation are not valid.

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Table of Contents
CHAPTER 1 ................................................................................................................................................ 11
Quantum Mechanics – I ........................................................................................................................ 11
 Postulates of Quantum Mechanics .................................................................................................. 11
 Derivation of Schrodinger Wave Equation...................................................................................... 16
 Max-Born Interpretation of Wave Functions .................................................................................. 21
 The Heisenberg’s Uncertainty Principle.......................................................................................... 24
 Quantum Mechanical Operators and Their Commutation Relations............................................... 29
 Hermitian Operators – Elementary Ideas, Quantum Mechanical Operator for Linear Momentum,
Angular Momentum and Energy as Hermitian Operator ................................................................. 52
 The Average Value of the Square of Hermitian Operators ............................................................. 62
 Commuting Operators and Uncertainty Principle (x & p; E & t) .................................................... 63
 Schrodinger Wave Equation for a Particle in One Dimensional Box.............................................. 65
 Evaluation of Average Position, Average Momentum and Determination of Uncertainty in Position
and Momentum and Hence Heisenberg’s Uncertainty Principle..................................................... 70
 Pictorial Representation of the Wave Equation of a Particle in One Dimensional Box and Its
Influence on the Kinetic Energy of the Particle in Each Successive Quantum Level ..................... 75
 Lowest Energy of the Particle ......................................................................................................... 80
 Problems .......................................................................................................................................... 82
 Bibliography .................................................................................................................................... 83
CHAPTER 2 ................................................................................................................................................ 84
Thermodynamics – I .............................................................................................................................. 84
 Brief Resume of First and Second Law of Thermodynamics .......................................................... 84
 Entropy Changes in Reversible and Irreversible Processes ............................................................. 87
 Variation of Entropy with Temperature, Pressure and Volume ...................................................... 92
 Entropy Concept as a Measure of Unavailable Energy and Criteria for the Spontaneity of Reaction
...........................................................................................................................................................94
 Free Energy, Enthalpy Functions and Their Significance, Criteria for Spontaneity of a Process ... 98
 Partial Molar Quantities (Free Energy, Volume, Heat Concept) ................................................... 104
 Gibb’s-Duhem Equation ................................................................................................................ 108
 Problems ........................................................................................................................................ 111
 Bibliography .................................................................................................................................. 112
CHAPTER 3 .............................................................................................................................................. 113
Chemical Dynamics – I ........................................................................................................................ 113
 Effect of Temperature on Reaction Rates ...................................................................................... 113
 Rate Law for Opposing Reactions of Ist Order and IInd Order..................................................... 119
 Rate Law for Consecutive & Parallel Reactions of Ist Order Reactions ....................................... 127
 Collision Theory of Reaction Rates and Its Limitations ............................................................... 135
 Steric Factor................................................................................................................................... 141
 Activated Complex Theory ........................................................................................................... 143
 Ionic Reactions: Single and Double Sphere Models ..................................................................... 147
 Influence of Solvent and Ionic Strength ........................................................................................ 152
 The Comparison of Collision and Activated Complex Theory ..................................................... 157
 Problems ........................................................................................................................................ 158
 Bibliography .................................................................................................................................. 159
CHAPTER 4 .............................................................................................................................................. 160
Electrochemistry – I: Ion-Ion Interactions ..................................................................................... 160
 The Debye-Huckel Theory of Ion-Ion Interactions ....................................................................... 160
 Potential and Excess Charge Density as a Function of Distance from the Central Ion ................. 168
 Debye-Huckel Reciprocal Length ................................................................................................. 173
 Ionic Cloud and Its Contribution to the Total Potential ................................................................ 176
 Debye-Huckel Limiting Law of Activity Coefficients and Its Limitations ................................... 178
 Ion-Size Effect on Potential ........................................................................................................... 185
 Ion-Size Parameter and the Theoretical Mean - Activity Coefficient in the Case of Ionic Clouds with
Finite-Sized Ions ............................................................................................................................ 187
 Debye-Huckel-Onsager Treatment for Aqueous Solutions and Its Limitations ............................ 190
 Debye-Huckel-Onsager Theory for Non-Aqueous Solutions........................................................ 195
 The Solvent Effect on the Mobility at Infinite Dilution ................................................................ 196
 Equivalent Conductivity (Λ) vs Concentration C1/2 as a Function of the Solvent ......................... 198
 Effect of Ion Association Upon Conductivity (Debye-Huckel-Bjerrum Equation) ...................... 200
 Problems ........................................................................................................................................ 209
 Bibliography .................................................................................................................................. 210
CHAPTER 5 .............................................................................................................................................. 211
Quantum Mechanics – II .................................................................................................................... 211
 Schrodinger Wave Equation for a Particle in a Three Dimensional Box ...................................... 211
  The Concept of Degeneracy Among Energy Levels for a Particle in Three Dimensional Box .... 215
 Schrodinger Wave Equation for a Linear Harmonic Oscillator & Its Solution by Polynomial Method
.........................................................................................................................................................217
 Zero Point Energy of a Particle Possessing Harmonic Motion and Its Consequence ................... 229
 Schrodinger Wave Equation for Three Dimensional Rigid Rotator .............................................. 231
 Energy of Rigid Rotator ................................................................................................................ 241
 Space Quantization ........................................................................................................................ 243
 Schrodinger Wave Equation for Hydrogen Atom: Separation of Variable in Polar Spherical
Coordinates and Its Solution ......................................................................................................... 247
 Principal, Azimuthal and Magnetic Quantum Numbers and the Magnitude of Their Values ....... 268
 Probability Distribution Function .................................................................................................. 276
 Radial Distribution Function ......................................................................................................... 278
 Shape of Atomic Orbitals (s, p & d) .............................................................................................. 281
 Problems ........................................................................................................................................ 287
 Bibliography .................................................................................................................................. 288
CHAPTER 6 .............................................................................................................................................. 289
Thermodynamics – II ........................................................................................................................... 289
 Clausius-Clapeyron Equation ........................................................................................................ 289
 Law of Mass Action and Its Thermodynamic Derivation ............................................................. 293
 Third Law of Thermodynamics (Nernst Heat Theorem, Determination of Absolute Entropy,
Unattainability of Absolute Zero) And Its Limitation ................................................................... 296
 Phase Diagram for Two Completely Miscible Components Systems ........................................... 304
 Eutectic Systems (Calculation of Eutectic Point) .......................................................................... 311
 Systems Forming Solid Compounds AxBy with Congruent and Incongruent Melting Points ....... 321
 Phase Diagram and Thermodynamic Treatment of Solid Solutions.............................................. 332
 Problems ........................................................................................................................................ 342
 Bibliography .................................................................................................................................. 343
CHAPTER 7 .............................................................................................................................................. 344
Chemical Dynamics – II ...................................................................................................................... 344
 Chain Reactions: Hydrogen-Bromine Reaction, Pyrolysis of Acetaldehyde, Decomposition of
Ethane ............................................................................................................................................ 344
 Photochemical Reactions (Hydrogen-Bromine & Hydrogen-Chlorine Reactions) ....................... 352
 General Treatment of Chain Reactions (Ortho-Para Hydrogen Conversion and Hydrogen-Bromine
Reactions) ....................................................................................................................................... 358
  Apparent Activation Energy of Chain Reactions .......................................................................... 362
 Chain Length ................................................................................................................................. 364
 Rice-Herzfeld Mechanism of Organic Molecules Decomposition (Acetaldehyde) ...................... 366
 Branching Chain Reactions and Explosions (H2-O2 Reaction) ..................................................... 368
 Kinetics of (One Intermediate) Enzymatic Reaction: Michaelis-Menten Treatment .................... 371
 Evaluation of Michaelis's Constant for Enzyme-Substrate Binding by Lineweaver-Burk Plot and
Eadie-Hofstee Methods ................................................................................................................. 375
 Competitive and Non-Competitive Inhibition ............................................................................... 378
 Problems ........................................................................................................................................ 388
 Bibliography .................................................................................................................................. 389
CHAPTER 8 .............................................................................................................................................. 390
Electrochemistry – II: Ion Transport in Solutions ....................................................................... 390
 Ionic Movement Under the Influence of an Electric Field ............................................................ 390
 Mobility of Ions ............................................................................................................................. 393
 Ionic Drift Velocity and Its Relation with Current Density .......................................................... 394
 Einstein Relation Between the Absolute Mobility and Diffusion Coefficient .............................. 398
 The Stokes-Einstein Relation ........................................................................................................ 401
 The Nernst-Einstein Equation ....................................................................................................... 403
 Walden’s Rule ............................................................................................................................... 404
 The Rate-Process Approach to Ionic Migration ............................................................................ 406
 The Rate-Process Equation for Equivalent Conductivity .............................................................. 410
 Total Driving Force for Ionic Transport: Nernst-Planck Flux Equation ....................................... 412
 Ionic Drift and Diffusion Potential ................................................................................................ 416
 The Onsager Phenomenological Equations ................................................................................... 418
 The Basic Equation for the Diffusion ............................................................................................ 419
 Planck-Henderson Equation for the Diffusion Potential ............................................................... 422
 Problems ........................................................................................................................................ 425
 Bibliography .................................................................................................................................. 426
INDEX ......................................................................................................................................................... 427