CHAPTER 6

Thermodynamics – II
 Clausius-Clapeyron Equation
The Clausius-Clapeyron equation was initially proposed by a German physics Rudolf Clausius in
1834 and then further developed by French physicist Benoît Clapeyron in 1850. This equation is extremely
useful in characterizing a discontinuous phase transition between two phases of a single constituent.
 Derivation of Clausius-Clapeyron Equation
In order to derive the Clausius-Clapeyron equation, consider a system at equilibrium i.e. the free
energy change for the ongoing process is zero (𝛥𝐺 = 0). However, we know from the principles of
thermodynamics that the variation of free energy with temperature and pressure can be formulated by the
following differential equation.

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 (1)

For typical single-constituent equilibria, we have

𝑃ℎ𝑎𝑠𝑒 𝐼 ⇌ 𝑃ℎ𝑎𝑠𝑒 𝐼𝐼 (2)

Where phase I can be solid, liquid, or gas; whereas phase II can be liquid or vapor depending upon the nature
of the transition whether it is melting, vaporization or sublimation, respectively.
Now consider a system at pressure P and temperature T; and the free energies of phase I and phase
II of the same system are G1 and G2, respectively. Moreover, if we change the temperature from T to T+dT and
pressure from P to P+dP; the free energy changes in phase I and phase II will be dG1 and dG2, respectively.
Mathematically, we can formulate the situation as given below.

𝑑𝐺1 = 𝑉1 𝑑𝑃 − 𝑆1 𝑑𝑇 (3)

𝑑𝐺2 = 𝑉2 𝑑𝑃 − 𝑆2 𝑑𝑇 (4)

Where V1 and S1 represent the molar volume and entropy of phase I, while V2 and S2 represent the molar volume
and entropy of phase II. However, if the phase I and phase II are in equilibrium with each other, we have

𝛥𝐺 = 0 (5)

𝐺2 − 𝐺1 = 0 (6)

Now recalling the fact that G1 and G2 are simply the free energies of the phase I and phase II at temperature T
and pressure P; we can say the same must also be true at temperature T+dT and pressure P+dP i.e.

(𝐺2 + 𝑑𝐺2 ) − (𝐺1 + 𝑑𝐺1 ) = 0 (7)

Copyright © Mandeep Dalal

 290 A Textbook of Physical Chemistry – Volume I

(𝐺2 − 𝐺1 ) + (𝑑𝐺2 − 𝑑𝐺1 ) = 0 (8)

Since 𝐺2 − 𝐺1 = 0 from equation (6), the above equation takes the form

𝑑𝐺2 − 𝑑𝐺1 = 0 (9)

𝑑𝐺2 = 𝑑𝐺1 (10)

After putting the values of 𝑑𝐺1 and 𝑑𝐺2 from equation (3, 4) in equation (10), we get

𝑉2 𝑑𝑃 − 𝑆2 𝑑𝑇 = 𝑉1 𝑑𝑃 − 𝑆1 𝑑𝑇 (11)

or

𝑉2 𝑑𝑃 − 𝑉1 𝑑𝑃 = 𝑆2 𝑑𝑇 − 𝑆1 𝑑𝑇 (12)

(𝑉2 − 𝑉1 )𝑑𝑃 = (𝑆2 − 𝑆1 )𝑑𝑇 (13)

𝛥𝑉. 𝑑𝑃 = 𝛥𝑆. 𝑑𝑇 (14)

𝑑𝑃 𝛥𝑆 (15)
=
𝑑𝑇 𝛥𝑉
Now if the 𝛥𝐻 is the latent heat of phase transformation occurring at temperature, the entropy change is
or

𝛥𝐻 (16)
𝛥𝑆 =
𝑇
After using the value of 𝛥𝑆 from equation (16) into equation (15), we get

𝑑𝑃 𝛥𝐻 (17)
=
𝑑𝑇 𝑇𝛥𝑉
The equation was first developed by Calpeyron in 1834 and therefore is named after him Calpeyron equation.
Now if phase I is solid while phase II is vapor i.e. solid ⇌ melt equilibria, the equation (17) takes the form

𝑑𝑃 𝛥𝑓𝑢𝑠 𝐻 (18)
=
𝑑𝑇 𝑇𝑓 𝛥𝑉

Where 𝛥𝑓𝑢𝑠 𝐻 is the latent heat of fusion and 𝑇𝑓 is the melting point. The term 𝛥𝑉 = 𝑉𝑙 − 𝑉𝑠 i.e. the difference
in the volume of melt and solid phase. Therefore, equation (18) can also be written as

𝑑𝑃 𝛥𝑓𝑢𝑠 𝐻 (19)
=
𝑑𝑇 𝑇𝑓 (𝑉𝑙 − 𝑉𝑠 )

For vaporisation equilibrium i.e. liquid ⇌ vapour,

Buy the complete book with TOC navigation, Copyright © Mandeep Dalal
high resolution images and
no watermark.
 CHAPTER 6 Thermodynamics – II 291

𝑑𝑃 𝛥𝑣𝑎𝑝 𝐻 (20)
=
𝑑𝑇 𝑇𝑏 (𝑉𝑣 − 𝑉𝑙 )

Where 𝛥𝑣𝑎𝑝 𝐻 is the latent heat of vaporization and 𝑇𝑏 is the boiling point. The term 𝛥𝑉 = 𝑉𝑣 − 𝑉𝑙 i.e. the
difference in the volume of vapor and liquid phases. Now since the volume of the liquid is very small in
comparison to the gaseous phase, the term Vl in equation (20) can simply be neglected for simplicity i.e.

𝑑𝑃 𝛥𝑣𝑎𝑝 𝐻 (21)
=
𝑑𝑇 𝑇𝑉𝑣

If the vapor act as an ideal gas i.e. 𝑃𝑉𝑣 = 𝑅𝑇 or 𝑉𝑣 = 𝑅𝑇/𝑃, the above equation can be written as

𝑑𝑃 𝛥𝑣𝑎𝑝 𝐻 (22)
= .𝑃
𝑑𝑇 𝑅𝑇 2
or

1 𝑑𝑃 𝛥𝑣𝑎𝑝 𝐻 (23)
. =
𝑃 𝑑𝑇 𝑅𝑇 2
or

𝑑 𝑙𝑛 𝑃 𝛥𝑣𝑎𝑝 𝐻 (24)
=
𝑑𝑇 𝑅𝑇 2
The above equation is popularly known as the Clausius-Clapeyron equation.
One more popular form of Clausius-Clapeyron Equation is the integrated one which can easily be
derived by using the rearranged form of equation (24) as given below.

𝛥𝑣𝑎𝑝 𝐻 (25)
𝑑 𝑙𝑛 𝑃 = 𝑑𝑇
𝑅𝑇 2
If the temperature changes from T1 to T2 and pressure is varied from P1 to P2, then we can say that
𝑃2 𝑇2 (26)
𝛥𝑣𝑎𝑝 𝐻
∫ 𝑑 𝑙𝑛 𝑃 = ∫ 𝑑𝑇
𝑅𝑇 2
𝑃1 𝑇1

or
𝑇2 (27)
𝑃2 𝛥𝑣𝑎𝑝 𝐻 1
𝑙𝑛 = ∫ 2 𝑑𝑇
𝑃1 𝑅 𝑇
𝑇1

𝑃2 𝛥𝑣𝑎𝑝 𝐻 1 1 (28)
𝑙𝑛 = [ − ]
𝑃1 𝑅 𝑇1 𝑇2

Buy the complete book with TOC navigation, Copyright © Mandeep Dalal
high resolution images and
no watermark.
 292 A Textbook of Physical Chemistry – Volume I

After converting to the common logarithm, we get

𝑃2 𝛥𝑣𝑎𝑝 𝐻 1 1 (29)
2.303 𝑙𝑜𝑔 = [ − ]
𝑃1 𝑅 𝑇1 𝑇2

or

𝑃2 𝛥𝑣𝑎𝑝 𝐻 1 1 (30)
𝑙𝑜𝑔 = [ − ]
𝑃1 2.303 𝑅 𝑇1 𝑇2

Which is the integrated form of Clausius-Clapeyron equation.

 Applications of Clausius-Clapeyron Equation
There are many applications of Clausius-Clapeyron equation ranging from chemistry to meteorology
and climatology as well. Some of the most important applications in chemistry are given below.
i) For transitions between a gas and a condensed phase (liquid or solid), the Clausius-Clapeyron equation can
be given as

𝐿 1 (31)
𝑙𝑛 𝑃 = − ( ) + 𝐶
𝑅 𝑇
Where C represents a constant. The symbol L represents the specific latent heat for a liquid-gas transition
whereas specific latent heat of sublimation for a solid-gas transition. If the latent heat is known, then knowledge
of one point on the coexistence curve determines the rest of the curve. Conversely, as the plot 𝑙𝑛𝑃 vs 1/T is
linear with the zero intercept, the simple linear fitting is used to estimate the latent heat of phase change. The
latent heat of vaporization of any liquid can also be determined if the vapor pressures of the same are known
at two different temperatures.
ii) The boiling point of a liquid at any temperature can be determined if the boiling point at a particular
temperature and latent heat of vaporization of the same are known.
iii) If the latent heat of vaporization and the vapor pressure of a liquid at a particular temperature are known,
the vapor pressure of the same liquid at any other temperature can be known.
iv) One more application of this equation is to check if a phase transition will occur via compression or
expansion in solid ⇌ melt equilibria. To understand this, recall the

𝑑𝑃 𝛥𝑓𝑢𝑠 𝐻 (32)
=
𝑑𝑇 𝑇𝑓 𝛥𝑉

The sign for 𝑑𝑃/𝑑𝑇 can be positive or negative for expansion and compression, respectively.

Buy the complete book with TOC navigation, Copyright © Mandeep Dalal
high resolution images and
no watermark.
 LEGAL NOTICE
This document is an excerpt from the book entitled “A
Textbook of Physical Chemistry – Volume 1 by
Mandeep Dalal”, and is the intellectual property of the
Author/Publisher. The content of this document is
protected by international copyright law and is valid
only for the personal preview of the user who has
originally downloaded it from the publisher’s website
(www.dalalinstitute.com). Any act of copying (including
plagiarizing its language) or sharing this document will
result in severe civil and criminal prosecution to the
maximum extent possible under law.

This is a low resolution version only for preview purpose. If you

want to read the full book, please consider buying.

Buy the complete book with TOC navigation, high resolution

images and no watermark.
D DALAL
INSTITUTE
Home Classes Books Videos Location Contact Us About Us °' Followus: O O O G O

Home

CLASSES BOOKS VIDEOS

NET-JRF, llT-GATE, M.Sc Entrance & Publications Video Lectures

llT-JAM
Are you interested in books (Print and Ebook) Want video lectures in chemistry for CSIR UGC
Want to study chemistry for CSIR UGC - NET published by Dalal Institute? - NET JRF. llT-GATE. M.Sc Entrance, llT-JAM,
JRF, llT-GATE, M.Sc Entrance, llT-JAM, UPSC, READ MORE UPSC, ISRO, II Sc, TIFR, DRDO, BARC, JEST, GRE,
ISRO, II Sc, TIFR, DRDO, BARC, JEST, GRE, Ph.D Ph.D Entrance or any other competitive
Entrance or any other competitive examination where chemistry is a paper?
examination where chemistry is a paper? READ MORE
READ MORE

Home: https://www.dalalinstitute.com/
Classes: https://www.dalalinstitute.com/classes/
Books: https://www.dalalinstitute.com/books/
Videos: https://www.dalalinstitute.com/videos/
Location: https://www.dalalinstitute.com/location/
Contact Us: https://www.dalalinstitute.com/contact-us/
About Us: https://www.dalalinstitute.com/about-us/

Postgraduate Level Classes Undergraduate Level Classes

(NET-JRF & IIT-GATE) (M.Sc Entrance & IIT-JAM)
Admission Admission
Regular Program Distance Learning Regular Program Distance Learning
Test Series Result Test Series Result

A Textbook of Physical Chemistry – Volume 1

“A Textbook of Physical Chemistry – Volume 1 by Mandeep Dalal” is now available globally; including India,
America and most of the European continent. Please ask at your local bookshop or get it online here.

-------- READ
Share this article/info with MORE
your classmates and friends

Join the revolution by becoming a part of our community and get all of the member benefits
like downloading any PDF document for your personal preview.

Sign Up
join the revolution by becoming a part of our community and get all of the member benefits like downloading any PDF document for your personal preview.

Sign Up

Copyright© 2019 Dalal Institute

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