CHAPTER 1

Quantum Mechanics – I
 Postulates of Quantum Mechanics
In modern quantum theory, the postulates of quantum mechanics are simply the step-to-step
procedure to solve a simple quantum mechanical problem. In other words, it is like the manual that must be
followed to retrieve the information about various states of any quantum mechanical system. We will first
learn about the nature and the significance of these postulates, and then we will apply them to some real
problems like the particle in a one-dimensional box or the harmonic oscillator.
 The First Postulate
All time-independent states of any quantum mechanical system can be described mathematically as
long as the function used is single-valued, continuous and finite.
Explanation: The systems around us can be broadly classified into two categories; the first is classical and the
other one as quantum mechanical. The classical systems simply refer to the systems which are governed by
the classical or the Newtonian mechanics. Now because all the macroscopic objects follow Newton’s laws of
motion, they fall in the category of classical systems; for example, a rotating gym dumbbell, the vibrating
spring of steel, or an athlete running in the playground. Every classical system can possess many states which
belong to a continuous domain, and each state can be described mathematically.

However, if the rotating gym dumbbell is replaced by the rotating diatomic molecule, the system
would not remain classical anymore and would start violating classical laws. The states of such microscopic
systems (here it just means the extremely small) belong to a discontinuous domain and can also be described
mathematically. These mathematical descriptions are labeled as ψ1, ψ2, ψ3 ….. ψn and generally called as the
“wave functions”. The term “wave function” is used because as we go from the macroscopic to the microscopic
world i.e. from classical to the quantum mechanical world, things start behaving like waves rather particle. All
of the states are wave-like; and because every wave we see around us is continuous, single-valued and finite;

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 12 A Textbook of Physical Chemistry – Volume I

only continuous, single-valued and finite expressions can represent those states. For instance, when you drop
a stone in a standstill pond, the waves are generated which travel from the center to the boundary of the pond;
and you don’t see any discontinuity in it.

Hence, if a function is not single-valued, continuous and finite; it will not be able to represent any
wave-like behavior at all. That is why every function that correlates a quantum mechanical state must be single-
valued, continuous and finite; and this function describes the corresponding state completely.
 The Second Postulate
For every physical property like linear momentum or the kinetic energy, a particular operator exists
in quantum mechanics, the nature of which depends upon the classical expression of the same property.
Explanation: In classical mechanics, there are simply straight forward formulas for all physical properties;
like linear momentum can simply be calculated by multiplying the mass with velocity. However, in case of
quantum mechanical systems, the value of a certain physical property for a particular state cannot be calculated
simply by using its classical formula but from an operator. It does sound silly but the classical formulas which
are so well-tested on the scale of time fail in quantum world. For instance, you can use the mv2/2 to calculate
the kinetic energy of a moving particle in classical world by just putting its mass and velocity; but if the mass
of the moving particle is extremely less, you will not get any rational results.
It is also worthy to note it again that though the classical formulas fail to give the value of physical
property, they are still important as they form the basis of the derivations for corresponding quantum
mechanical operators. For instance, the operator for kinetic energy (T) along x-axis can be derived as:

1 (𝑚𝑣)2 𝑝2 (1)
𝐾. 𝐸. (𝑇) = 𝑚𝑣 2 = =
2 2𝑚 2𝑚
Where m and v are mass and the velocity, respectively; and p represents the angular momentum whose squared
operator is:

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 CHAPTER 1 Quantum Mechanics – I 13

−ℎ2 𝜕 2 (2)
𝑝̂𝑥2 =
4𝜋 2 𝜕𝑥 2
Now putting the value of momentum squared from equation (2) into equation (1), we get:

−ℎ2 𝜕 2 (3)
𝑇̂𝑥 =
8𝜋 2 𝑚 𝜕𝑥 2
The expressions of various quantum mechanical operators are given below.

Table 1. Various important physical properties and their corresponding quantum mechanical operators.

Physical property Operator

Name Symbol Symbol Operation

Position x 𝑥̂ Multiplication by x

Position squared x2 𝑥̂ 2 Multiplication by x2

Momentum px 𝑝̂𝑥 ℎ 𝜕
2𝜋𝑖 𝜕𝑥
Momentum squared px2 𝑝̂𝑥2 −ℎ2 𝜕 2
4𝜋 2 𝜕𝑥 2
Kinetic energy 𝑃2 𝑇̂𝑥 −ℎ2 𝜕 2
𝑇=
2𝑚 8𝜋 2 𝑚 𝜕𝑥 2
Potential energy V(x) 𝑉̂ (𝑥) Multiplication by V(x)

Total energy 𝐸 = 𝑇 + 𝑉(𝑥) ̂

𝐻 −ℎ2 𝜕 2
+ 𝑉(𝑥)
8𝜋 2 𝑚 𝜕𝑥 2

For three dimensional systems, the total operator can be obtained by summing the individual
operators along three different axes. For instance, some important three-dimensional operators are:

−ℎ2 𝜕 2 𝜕2 𝜕2 (4)
𝑇̂ = ( + + )
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

ℎ 𝜕 𝜕 𝜕 (5)
𝑝̂ = ( + + )
2𝜋𝑖 𝜕𝑥 𝜕𝑦 𝜕𝑧

−ℎ2 𝜕 2 𝜕2 𝜕2 (6)
̂=
𝐻 ( + + ) + 𝑉(𝑥, 𝑦, 𝑧)
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

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 14 A Textbook of Physical Chemistry – Volume I

 The Third Postulate

If ψ is a well-behaved function for the given state of system and  is a suitable operator for a
particular physical property, then the operation on ψ by the operator  gives the function ψ multiplied by the
value of the physical property which can be constant or variable but always real (R). Mathematically, it can
be shown as:

𝐴̂𝜓 = 𝑅𝜓 (7)

Explanation: The third postulate of quantum mechanics actually connects the first and second postulate of
quantum mechanics. The first postulate talks about the possibility of describing a quantum mechanical state
mathematically, while the second postulate says that the values of all physical properties in the quantum world
are obtained by the operator rather than the simple classical formula. Now the third postulate says that if we
operate the operator (from second postulate) over the wave function (from first postulate), we will get the value
of the corresponding physical property.
However, at this point, a new problem arises as we do not know the exact mathematical description
i.e. the wave function of any quantum mechanical state; and the operators need the absolute mathematical
description of the quantum mechanical state to yield any actual result. Now though we know the expressions
of different operators proposed by the second postulate; the first postulate speaks only about the presence of a
single-valued, continuous and finite mathematical function but does not give actual function itself; and without
the knowledge of actual “wave functions”, the operators are pretty much useless. Therefore, one would think
that there must be some route by which the wave functions are obtained first, which would be used as operand
afterward. However, the procedure to find the exact mathematical descriptions of various quantum mechanical
states is somewhat more synergistic. The “magic mystery” is that all the operators need absolute expression of
the wave function that defines the quantum mechanical state except one, the most famous “Hamiltonian
operator”. The special thing about the Hamiltonian operator is that it does not necessarily need the absolute
form but the symbolic form only to yield the value of its physical property i.e. energy. Nevertheless, in the
process of applying the Hamiltonian operator over the symbolic form of the wave function, the absolute
expression is also obtained. Mathematically,

̂ 𝜓 = 𝐸𝜓
𝐻 (8)

After putting the expression of the Hamiltonian operator in equation (8) and then rearranging, we get:

𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 8𝜋 2 𝑚(𝐸 − 𝑉)𝜓 (9)

+ + + =0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2

The second-order differential equation i.e. equation (9) is the famous Schrodinger wave equation, the
solution of which gives not only the energy but the wave function as well. Now, once the exact expression of
the wave function representing a particular state is known, other operators can be operated over it to find their
values.

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 CHAPTER 1 Quantum Mechanics – I 15

 The Fourth Postulate

If the value of the physical property obtained after multiplying the wave function by the
corresponding operator is constant (postulate 3), the value is called as the eigen-value and is directly
reportable; and the wave function will be labeled as the eigen-function of the operator used.
Explanation: The third postulate said that when the wave function of a particular quantum mechanical state
is multiplied by the operator of an observable quantity, we get a real value multiplied by the wave function
itself; however, the value obtained so can be constant or variable. Mathematically,

The constant value of the observable quantity can be reported directly, and the function is called the
eigenfunction of the operator under consideration.
 The Fifth Postulate
If the value of the physical property obtained after multiplying the wave function by the
corresponding operator is variable i.e. non-eigen, the value can be reported only after averaging it over the
whole configurational space.

∮ 𝜓 ∗ 𝑂̂𝜓 𝑑𝜏 (10)
< 𝑎 > 𝑜𝑟 ā =
∮ 𝜓 ∗ 𝜓 𝑑𝜏

Explanation: As we have seen in the fourth postulate that the value obtained by multiplying the Hermitian
operator with any quantum mechanical state can also be variable in nature. For instance, if we multiply a wave
function simply by position operator, we will get

𝑥̂𝜓 = 𝑥𝜓 (11)

or
𝑥𝜓 (12)
𝑥̂ =
𝜓
Now because “x” is a variable number, it must have reported as an average value before any further rational
argument is made.
Therefore, we can say that the fifth postulate is simply an extension of the fourth postulate; i.e. the
fourth postulate is used to obtain the value of a particular physical property if it is an eigenvalue, however, the
fifth postulate is employed to calculate all non-eigenvalues.

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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