CHAPTER 3

Chemical Dynamics – I
 Effect of Temperature on Reaction Rates
The temperature of the system shows a very marked effect on the overall rate of the reaction. In fact,
it has been observed that the rate of a chemical reaction typically gets doubled with every 10°C rise in the
temperature. However, this ratio may differ considerably and may reach up to 3 for different reactions. Besides,
this ratio also varies as the temperature of the reaction increases gradually. The ratio of rate constant at two
different temperatures is called as “temperature coefficient” of the reaction. Although we can determine the
temperature coefficient between any two temperatures for any chemical reaction, generally it is calculated for
10°C difference.

𝑘 𝑇+10 (1)
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝐶𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 = =2−3
𝑘𝑇

Where 𝑘 𝑇 and 𝑘 𝑇+10 are rate constants at temperature T and T+10, respectively. Now, if once the temperature
coefficient is known, you can determine the relative increase or decrease in the overall reaction-rate by using
the following relation.

𝑅2 𝑘2 𝑇2 −𝑇1 (2)
= = (𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝐶𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡) ∆𝑇𝑡𝑐
𝑅1 𝑘1

Where R2 and R1 are the reaction-rates at temperatures T2 and T1, respectively. The ∆𝑇𝑡𝑐 is the temperature
range for the temperature coefficient.
In order to illustrate the dominance of the effect of temperature change on the reaction rate, consider
a reaction in which the temperature of the system is raised from 310°C to 400°C. Now, if the temperature
coefficient for 10°C temperature-rise is 2, the relative increase in the rate constant or rate will be

𝑅2 𝑘2 400−310 (3)
= = (2) 10
𝑅1 𝑘1

𝑅2 𝑘2 (4)
= = (2)9 = 512
𝑅1 𝑘1

𝑅2 (5)
= 512
𝑅1

Hence, a 90°C rise in temperature increases the rate of reaction 512 times, which is definitely huge. Now the
question arises, why is it so? What did the temperature do that made this happen? In this section, we will
answer these questions.

Copyright © Mandeep Dalal

 114 A Textbook of Physical Chemistry – Volume I

 Fundamentals of Temperature-Rate Correlation

Before we discuss the effect of temperature on the reaction rate, we must understand the cause of a
reaction itself first. The primary requirement for a reaction to occur is the collision between the reacting
molecules. In other words, the reactant molecules must collide with each other to form the product. Therefore,
if we assume that every collision results in the formation of the product, the rate of reaction should simply be
equal to the collision frequency of the reacting system.
For a reaction between A and B, the collision frequency (Z) is the number of collisions between A and
B occurring in the container per unit volume per unit time.

(6)
8𝑘𝐵 𝑇
𝑍 = 𝑛𝐴 𝑛𝐵 𝛩𝐴𝐵 √
𝜋𝜇𝐴𝐵

Where nA and nA are the number densities (in the units of m−3) of particles A and B, respectively. The term ΘAB
is the reaction cross-section (in m2) when particle A with radius rA and B with radius rB collide with each other
i.e. ΘAB = π (σAB)2 = π(rA + rB)2 = π(σA/2 + σB/2)2. kB is the Boltzmann's constant (m2 kg s−2 K−1). T represents
the temperature of the system. The term μAB represents the reduced mass of the reactants A and B i.e. μAB =
mAmB/mA+mB. From equation (6), it follows that when we heat the substance, the particles collide more
frequently and hence increase the collision frequency. Now one may think that this collision frequency would
result in a larger rate of reaction, and therefore, the mystery is solved. However, this isn’t sufficient to
rationalize the experimental observations. For instance, if we increase the temperature from 300 K to 310 K,
the relative increase in the collision frequency (nZ), and hence in reaction rate, from equation (6) can be
determined as given below.

(7)
310
𝑛𝑍 = √ = 1.0165
300

This is only 1.65% increase for a 10° rise in temperature. This is pretty far from the reality i.e. reaction-rate
almost gets double (100% increase). So, the actual mechanism is still behind the scene and must be understood.
At this point we must introduce the concept of activation energy, otherwise, the concept cannot be
discussed further. The collision of reacting molecules would result in the chemical reaction only if they possess
a certain amount of minimum energy i.e. threshold energy. Since every molecule does have some energy, the
energy it needs to reach the threshold is less than the actual threshold energy. The energy required by reactant
molecules to cross the barrier is called the activation energy or the enthalpy of activation for the reaction. A
simple equation can be used to deduce their relationships as given below.

Activation energy = Threshold energy – Energy actually possessed by the molecules

The rate of a chemical reaction is inversely proportional to the magnitude of the activation energy i.e. larger
the activation energy, slower will be the reaction and vice-versa.

Buy the complete book with TOC navigation, Copyright © Mandeep Dalal
high resolution images and
no watermark.
 CHAPTER 3 Chemical Dynamics – I 115

Figure 1. The reaction coordinate diagram for a typical chemical reaction.

Hence, we can say that only effective collisions would result in the chemical reactions, but how can we find
the number of molecules having energy high enough to react with each other. For this, we need to go into the
basics of energy distribution among a large number of particles i.e. Maxwell’s distribution of energies.

Figure 2. The Maxwell-Boltzmann distribution of energies at temperature T.

After marking the activation energy on the Maxwell-Boltzmann distribution curve, the particle with sufficient
energy to react can easily be found from the area under the corresponding curve i.e. dashed area. The undashed
area at a particular temperature is quite large, and therefore, represents the number particle whose collision
would not result in any reaction chemical change. It can be clearly seen that most of the particles don't have

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

enough energy, and hence, are unable to yield the product. The reaction-rate will be very small If there are
very few particles with enough energy at any time.
However, if the temperature is raised, the maxima of the Maxwell-Boltzmann distribution curve shifts
towards higher energy. This makes the number of “efficient particles” to increase and thereby increases the
number of effective collisions too. Consider the Maxwell-Boltzmann energy distributions at temperature T and
T+10.

Figure 3. The Maxwell-Boltzmann distribution of energies at temperature T and T+10°C.

Now although the area under the whole curve remains the same, the dashed area is doubled. Thus,
the primary reason for almost 100% rise in the overall rate of reaction for every 10°C is the 100% increase in
the number of effective collisions.
 The Arrhenius Equation
In 1884, the famous Dutch chemist Jacobus Henricus Van't Hoff realized that his equation (Van't
Hoff equation) could also be used to suggests a formula for the rates of both forward and backward reactions.
In 1889, Svante Arrhenius immediately noticed the importance of this invention and proposed an empirical
equation based on Van't Hoff’s work. This equation is extremely useful in the modeling of the temperature
variation of many chemical reactions. The equation proposed by Arrhenius is

𝑘 = 𝐴 𝑒 −𝐸𝑎/𝑅𝑇 (8)

Where the symbol k, R and T represent rate constant, gas constant and temperature, respectively. A is popularly
known as the pre-exponential factor or Arrhenius constant with the units identical to those of the rate constant
used, and therefore, will vary depending on the order of the reaction. The term Ea represents the activation
energy measured in joule mole−1.

Buy the complete book with TOC navigation, Copyright © Mandeep Dalal
high resolution images and
no watermark.
 CHAPTER 3 Chemical Dynamics – I 117

Another popular form of the Arrhenius equation is

𝑘 = 𝐴 𝑒 −𝐸𝑎/𝑘𝐵 𝑇 (9)

The only difference in the equation (8) and equation (9) is the energy units of Ea; the former one uses energy
per mole, which is more common in chemistry, while the latter form uses energy per molecule directly, which
is common in physics. The different units are accounted for in using either the gas constant, R, or the Boltzmann
constant, kB, as the multiplier of temperature T. If the reaction is first order, A will have the units of s−1 and can
be called as collision frequency or frequency factor.
The physical significance of k is that it represents the number of collisions that result in a reaction
per second; A is the number of collisions (leading to a reaction or not) per second occurring with the proper
orientation to react. The exponential factor is the probability that any given collision will result in a reaction.
It can also be seen that either increasing the temperature or decreasing the activation energy (for example
through the use of catalysts) will result in an increase in the rate of reaction. Taking the natural logarithm of
both side of equation (8), we get

ln 𝑘 = ln 𝐴 + ln 𝑒 −𝐸𝑎/𝑅𝑇 (10)

𝐸𝑎 (11)
ln 𝑘 = ln 𝐴 −
𝑅𝑇
Rearrange the above equation, we get

𝐸𝑎 (12)
ln 𝑘 = − + ln 𝐴
𝑅𝑇
The equation (12) has the same form as the equation of straight line i.e. 𝑦 = 𝑚𝑥 + 𝑐; which means that if we
plot “ln k” vs 1/T, the slope and intercept will yield “−Ea/R” and “ln A”, respectively.

Figure 4. The Arrhenius plot of ln k vs 1/T.

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

In addition to the equation (12), one of the more popular forms of the Arrhenius equation can be derived by
converting it to the common logarithm as given below.

𝐸𝑎 (13)
2.303 log 𝑘 = − + 2.303 log 𝐴
𝑅𝑇
or

𝐸𝑎 (14)
log 𝑘 = − + log 𝐴
2.303 𝑅𝑇
The equation (14) also has the same form as the equation of straight line i.e. 𝑦 = 𝑚𝑥 + 𝑐; which means that if
we plot “log k” vs 1/T, the slope and intercept will yield “−Ea/2.303R” and “log A”, respectively.

Figure 5. The Arrhenius plot of log k vs 1/T.

To obtain the integrated form of the Arrhenius equation, differentiate the equation (12) as given below.

𝑑 ln 𝑘 𝐸𝑎 (15)
=
𝑑𝑇 𝑅𝑇 2
Now integrating the above equation between temperature T1 and T2, we get

𝑘2 𝐸𝑎 1 1 𝑘2 𝐸𝑎 1 1 (16)
ln = [ − ] 𝑜𝑟 log = [ − ]
𝑘1 𝑅 𝑇1 𝑇2 𝑘1 2.303𝑅 𝑇1 𝑇2

The above equation can be used to find the activation energy if rate constants are known at two different
temperatures.

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