Schrödinger's equation

The Schrödinger equation describes the wave properties of an

electron in terms of position, mass, energy.
The simplest form of time independent Schrodinger equation:

H=E
E = Total energy of electron
 = wave function of electron
H = Hamilton operator
In one dimension
Ĥ = −ħ2/2m d2/dx2 + V(x) Where, V(x) = potential energy, (V = − Ze2/4πor)
In three dimensions,
Ĥ = −ħ2/2m (2 ψ/x2 + 2 ψ/y2 + 2ψ/z2) + V(x,y,z)

[−h2/8π2m 2 +V]  = E  2
 Understanding the Schrödinger equation

(Hamiltonian operator) (Eigenfunction) = (Eigenvalue) (Eigenfunction)

H=E
Q1. Show that eax is an Eigen function of the operator d/dx,
and find the corresponding eigenvalue.

Q2. Show that eax² is not an Eigen function of d/dx.

d/dx(eax²) = 2ax (eax²)

This is not an Eigen value even though the same function

occurs on the right, because the function is now multiplied by
a variable factor (2ax), not a constant factor.
3
 Understanding the Schrödinger equation

(Hamiltonian operator) (Eigenfunction) = (Eigenvalue) (Eigenfunction)

H=E
➢ Eigen function is the wave function of an electron corresponding to
the energy E.

➢ Eigen function is different for each eigenvalue.

➢ By solving Schrödinger equation one can find the wave functions

(eigenfunctions) and the corresponding allowed energies
(eigenvalues).

4
 Solutions of Schrödinger equation
[−h2/8π2m 2 +V]  = E 
There are many solutions to the above equation. However, the acceptable
solutions must satisfy following conditions.

1.  must be single valued.



2.  must be continuous.

3.  must be finite.

5
 Solutions of Schrödinger equation
4. First derivative of  w.r.t. its variables must be continuous.

5. Probability of finding particle over the whole space must be unity (Normalization Condition)
+∞
‫׬‬−∞ 𝜓2 𝑑𝜏 = 1 (𝑑𝜏 gives the volume element given by dx, dy and dz)

+∞
If ψ is a complex function, ‫׬‬
−∞
𝜓𝜓 ∗ 𝑑𝜏 = 1

6. Condition of Orthogonality
If ψ1 and ψ2 are two acceptable wave functions, they are orthogonal.
+∞
‫׬‬−∞ 𝜓1𝜓2 𝑑𝜏 = 0

6
 ➢ For an atom several wave functions (1, 2, 3) will satisfy
these conditions and each of these has a corresponding energy
(E1, E2, E3)

➢ The wave function of the electron in the hydrogenic atom is called

an atomic orbital. An orbital is a one-electron wave function.

➢ Each orbital is described uniquely by a set of three quantum

numbers, n, l, ml.

7
 Quantum Numbers
There are four quantum numbers.

Orbital is defined by three quantum numbers (n, l, ml).

An electron is defined by four quantum numbers (n, l, ml, ms).

Principal quantum number (n):

Determines the total energy of an electron.
E = −1/n2 (Z2e4μ/8εₒ2h2)
Or, E = 1/n2 (−13.6) eV
Has value 1, 2, 3, …………∞

8
 Quantum Numbers

Magnetic quantum number (ml):

Describe orientation of orbital in space.
It is the z-component of angular momentum.
(so it never be larger than the ‘l’ value)
It may have +ve z-component or
–ve z-component
So the value ranges from –l, ……0, …….+l
9
 Quantum Numbers

Spin quantum number (ms):

Describes orientation of electron spin in a magnetic field.

The value of ms either +1/2 (in the direction of the field)

or −1/2 (opposed to it).

Arises due to spinning of electron.

10
 Understanding of the Wave Function

ψ does not have any physical significance.

ψ2 or (ψ ψ* ) has a meaningful significance.

It is interpreted as a measure of density of electron at that point

Parallel to the concept of intensity as square of amplitude in light

The Born Interpretation

𝜓2𝑑𝜏 is considered as a measure of probability of finding the

particle in the small volume 𝑑𝜏 (= dx.dy.dz)

11
 Radial and Angular part of wave function 

In 3D,  may be expressed either in Cartesian coordinates

(x,y,z) or in spherical coordinates (r,θ,ϕ).

r = represents the distance from the nucleus.

θ = is the angle from z-axis, it varies from 0-π.
ϕ = is the angle from x-axis, it varies from 0-2π.

(x,y,z) can be converted to (r,θ,ϕ) using:

x = r sinθ cosϕ
y = r sinθ sinϕ
z = r cosθ

12
 Radial and Angular part of wave function 
The Schrödinger equation in spherical polar coordinate is

 may be separated into radial component and two angular

components.

(r,θ,ϕ) = R(r) (θ ) (ϕ)

Combining the two angular components

(r,θ,ϕ) = Rn,l(r) Yl,m(θ,ϕ)

radial
angular
function 13
function
 Radial and Angular part of wave function 
The radial function, Rn,l(r) :

The radial function is determined by the quantum numbers n

and l.

a0 = Bohr radius ~ 0.0529 nm

L = Laguerre polynomials

Rnl(r)  r l
 (Polynomial of degree n-l-1)
 e-r/a0
14
 Radial part of wave function 

Rnl(r)  r l …… 1
 (Polynomial of degree n-l-1) …… 2
 e-r/a0 …… 3

➢ The first factor determines the behavior of the

wave function w.r.t. the distance from the nucleus

➢ the second factor determines the number of

nodes =(n-l-1)

➢ the third ensures that the function goes to 0 as r → 

15
 Radial part of wave function 

Orbital n l R(n,l)
3
1s 1 0  1  2 − 2
2  e
 a0 
3
2s 2 0 1  1  2   − 4
   2 − e
2 2  a0   2
3
2p 2 1 1 1 2 −
   e 4
4 6  a0 
3
3s 3 0 1 1 2
  2  − 6
   6 − 2  +  e
9 3  a0   9 
3
3p 3 1 1 1 2    − 6
    4 −  e  = 2r/a0
27 6  a0   3
16
 2s orbital
1s orbital
n=2, l=0,
n=1, l=0, No. of nodes =1
No. of nodes =n-l-1=0
3
1  1  2   − 4
3 R( n ,l ) (r ) =    2 − e
 1  2 − 2 2 2  a0   2
R( n ,l ) (r ) = 2  e
 a0 

17
 2p orbital
3s orbital
n=2, l=1,
n=3, l=0, No. of nodes =0
No. of nodes =2

3
1 1 2 −
3 R(r ) =    e 4
1 1 2
  2  − 6 4 6  a0 
R(r ) =    6 − 2  +  e
9 3  a0   9 

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 Radial part of wave function 

Radial Probability Function

4πr2R2 = The radial probability function (P). Pdr describes the probability of
finding the electron in a spherical shell of radius r and thick dr.

For any shape, P = r2R2

Maximum correspond to distance from nucleus at which

the electron has highest probability of being found.

19
 Radial part of wave function 

A radial distribution function for an orbital with QNs n and l has n-l
peaks, the outermost peak being highest.

20
 Angular part of wave function 

ψ(r,,) = R(r) ()() = Rn,l(r) Yl,ml(,)

Yl,m (θ,ϕ):

The angular function is determined by the quantum numbers

l and ml.

The angular function, Yl,m(θ,ϕ), describes shape of the

orbitals and their orientation in space.

21
 Angular part of wave function 

ψ(r,,) = R(r) ()() = Rn,l(r) Yl,ml(,)

Orbital l ml Y l, ml (,)

1
s 0 0  1  2
 
 4 
pz 1 0 1
 3  2
  cos
 4 
1
px 1 +1  3  2
  sin  cos 
 4 
1
py 1 -1  3  2
  sin  sin
 4  22
 Hydrogen atom

Hydrogen has special significance

•No approximation is required in solution of Schrödinger equation
•Can get expression for energy levels

For H atom the Schrödinger wave equation can be written as

Ĥψ=Eψ

−(ħ2/2m 2 +Ze2/r ) ψ = E ψ
23
 Solution of the Schrödinger wave equation
ψn,l,ml(r,,) = Rn,l(r)Yl,ml(,)
1s atomic orbital (n = 1, l = 0, ml = 0
3 1
 Z  2 − 2  1  2
 1s = 2  e   1
 a0   4   1  2
Y l, ml (,) =  
 4 
Radial part Angular part
3
 Z  2 − 2
R n, l = 2  e
 a0 

➢ It is a constant and does not depend on  and 

➢ S-orbitals are spherically symmetrical

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 2p atomic orbitals (n = 2, l = 1, ml = +1, 0, −1

3
1 Z 2
1
− / 2  3   z 
2
 2pz =    e    
2 6  a0   4   r 

Radial part (R n, l) Angular part (Y l, ml (,))

Note: Z is the atomic number and z is the z-direction/component

In polar coordinate the above equation becomes

3
1 Z 2
1
−  / 2 3 
2
 2pz =    e   cos (Since, z = r cosθ)
2 6  a0   4 
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 2p atomic orbitals (n = 2, l = 1, ml = +1, 0, −1

For H atom Z = 1, so
3
1 1 2 −  / 2 3  2
1

 2pz =    e   cos
2 6  a0   4 

➢ The angular variation of wave function depend

on cos .
➢ The probability density is proportional to cos2.
➢ The probability density has maximum value
along an arbitary axis (z-axis) on either side of the
nucleus ( at = 0 and 180o)

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2p atomic orbitals

ɵ cosɵ
0 1.0
15 0.96
30 0.86
45 0.70
60 0.50
75 0.26
90 0
105 -0.26
120 -0.50
135 -0.70
150 -0.86
165 -0.96
180 -1.0
27
2p atomic orbitals

ɵ cosɵ
0 1.0
15 0.96
30 0.86
45 0.70
60 0.50
75 0.26

90 0
105 -0.26
120 -0.50
135 -0.70
150 -0.86
165 -0.96
180 -1.0 28
 2p atomic orbitals
Similarly the wave functions (real part of wave functions) of
other two p-orbitals are given below:
3
1 1 2
1
− / 2  3 
2
 2px =    e   sin  cos (Since, x/r = sinθcos)
2 6  a0   4 
3
1 1 2
1
−  / 2 3 
2
 2py =    e   sin  sin  (Since, y/r = sinθsin)
2 6  a0   4 

29
3d atomic orbitals (n = 3, l = 2, ml = +2, +1, 0, −1, −2)
(dxy, dxz, dyz, dx²-y², dz²)

1
1  15  2
xy Similarly the dxz, dyz
 3dxy = R n, l  
4   r2
Y (θ, )
1
1  15  2
x2− y 2
 3dx²-y² = R n, l   Since the angular part contains
4   r2 two or more variables, so these
orbitals have shapes in two
1
axial directions or more.
1 5 2
2 z2− x 2− y 2
 3dz² = R n, l  
4  r2

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 Nodal surface(s) of atomic orbitals
node
Nodal surface is a surface with zero electron density.

Nodes appear naturally as a result of the wave nature of the electron

At the nodal surface the wave function changes its sign.

At nodal surface,  = 0
either R(r) = 0
or Y(,) = 0
Angular node
Radial node

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 Angular nodal surface

If Y(,) = 0, angular nodes result.

Angular node
Angular nodes are planar or conical.

Number of angular nodes = l

Orbital No. of angular nodes

s- orbital 0
p-orbital 1
d-orbital 2
f-orbital 3

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 Radial or Spherical nodal surface

If R(r) = 0, radial nodes or spherical nodes result.

Number of radial nodes = n−l −1

Orbital Radial Orbital Radial Orbital Radial

nodes nodes nodes
1s 0 2p 0 3d 0
2s 1 3p 1 4d 1
3s 2 4p 2 5d 2
Radial node

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Q. Describe the angular nodal surfaces for a 3dxy orbital, whose
angular wave function is
1
1  15  2
xy
Y = 4  
  r2

xz -plane
Ans. In nodal surfaces, Y = 0

Y = 0, when either x = 0 or y = 0
So the nodal surfaces are
x = 0 (yz plane)
and y = 0 (xz plane) yz -plane

34
Q. Why the lobes of dxy, dyz and dzx orbitals are in between
axes and the lobes of dx2−y2 is along the axes?

Ans: The nodal surfaces of dxy, dyz and dzx orbitals contains the
axes and hence their lobes lie in between axes. However, the
nodal surfaces of dx2−y2 orbital are x = y and x = −y. So the lobes
of dx2−y2 lie along the axial direction.

35
Q. Describe the spherical nodal surface of 2s orbital of hydrogen
atom. The radial component of 2s atomic orbital is:
3
1  1  2   − 4 (ρ = 2Zr/ao)
R( 2 s ) (r ) =    2 − e
2 2  a0   2

node

36
 Sign of atomic orbital
Sign of lobes does not mean electronic charge.
ɵ cosɵ
It represents the 0 1.0

phase/direction of wave + ve phase 15 0.96

function. 30 0.86
45 0.70
Atomic orbital along positive 60 0.50
axial direction has a positive 75 0.26
sign and negative axial 90 0
direction has a negative sign. 105 -0.26
120 -0.50
+ ve phase 135 -0.70
150 -0.86
165 -0.96
− ve phase
− ve phase 180 -1.0
37
 Sign of atomic orbital
The angular part of s-orbitals contain constant value, no variables. So there is no
change in sign.

The angular part of p-orbital contains either x or y or z. Since the x, y, or z direction

may be positive or negative, so the wave function along positive axis has a positive
sign and along negative axis has negative sign.

The angular part of dxy, dxz, dyz contain product of two component. So the product
of signs gives the sign of the lobe.
For dx²-y², the angular part contains x2−y2. so the wave function is positive along x-
direction (positive and negative) and negative along y direction.
For dz² , the angular function contains 2z2−x2−y2, so the wave function is positive
along z direction (both positive and negative) and negative in xy-plane.
38
 What we learn in atomic structure?

➢ Bohr’s model of atomic structure.

➢ de Broglie equation, Heisenberg’s uncertainty principle.

➢ Schrodinger atomic model or wave equation.

➢ Quantum numbers.

➢ Solutions (only wave function part) of Schrodinger equation.

➢ Nodal surfaces and sign of atomic orbitals.

39
Many-electron atoms
Hartree proposed that the wavefunction could be
expressed simply as a product of spin orbitals,
one for each electron: ψ(1,2,…) = ψ1(1)ψ2(2)…..

ψ(1,2,…) = ψ1(1)ψ2(2)…..
Each orbital may be thought of as being hydrogen-
like with an effective nuclear charge.

He
if one disregards the inter-electronic repulsion, the
ground state wavefunction of He may be written as
ψ(1,2) = (Z3/a03)1/2 e-Zr1/a0 (Z3/a03)1/2 e-Zr2/a0
The orbital approximation allows us to express the electronic
structure of an atom in terms of its:

configuration
the list of occupied orbitals

For example, corresponding to the configuration

1s2
with the 1s orbital being somewhat more compact
than in H (Nuclear charge being 2).
 Li
Three electrons
First two electrons occupy as: 1s2
with the 1s orbital being more compact than in He (Z=3)
Next electron? 1s3? NO!!!

Pauli exclusion principle

No more than two electrons may occupy a given orbital, and if two
electrons do occupy one orbital, then their spins must be paired
This principle forms the basis of the electronic structure of atoms,
chemical periodicity, and molecular structure.
A fundamental principle of Nature
•No two identical fermions (½ integer
spin) may occupy the same quantum
state simultaneously.
•Three types of particles from which
ordinary matter is made—electrons,
protons, and neutrons—are all subject
to it.
•Wolfgang Pauli: Pauli exclusion principle
•Impossibility to squeeze identical fermions into
each other - "rigidness" of ordinary matter
Pauli principle revisited
When the labels of any two identical fermions (½
integer spin) are exchanged, the total wavefunction
(including spin) changes sign. (ANTISYMMETRIC
under exchange)
Fermions ψ(2,1) = − ψ(1,2)
When the labels of any two identical bosons (integer
spin) are exchanged, the total wavefunction
(including spin) remains the same. (SYMMETRIC
under exchange).
Bosons ψ(2,1) = ψ(1,2)
Two electrons in same orbital (spatial wavefunction)
:
ψ(1,2) = (1)(2){spin part}
Pauli principle: ψ(1,2) = − ψ(2,1) (MUST FOLLOW!)
How spin part could be (for two electrons in an orbital)?
Either ()() or ()()? → opposite spin

A linear combination is appropriate:

()() + ()() and ()() - ()()
This allows one spin as  and one spin as  with
equal probability
 ψ(1,2) = (1)(2){spin part}
Spin part:
()()
()()
()() + ()() and ()() - ()()
Now, (1)(2) does not change sign when electrons
are changed (order or multiplying is immaterial and
(1)(2) is same as (2)(1). This is true for
()() and ()(). They are not allowed
How to obey Pauli principle then?
 ψ(1,2) = (1)(2){spin part}
How to obey Pauli principle then?

Consider electron exchange for

()() + ()()  (2)(1) + (2)(1)
Symmetric[SIGN UNCHANGED]
Violates Pauli principle
Consider electron exchange for
()() - ()()  (2)(1) - (2)(1)
 - [()() - ()()]
Antisymmetric [SIGN CHANGED]
One possibility is
ψ(1,2) = (1)(2) {()() − ()()}
Is acceptable
Here the spatial part is symmetric, and the spin part
antisymmetric.
The combination that survived Pauli principle has
paired spins (This is the content of Pauli principle) as
should be satisfied by the ψ
K SHELL COMPLETE! CLOSED SHELL;[He]
The third electron in Li must enter the n = 2 shell,
Three electrons occupy as: 1s2 2s? or 1s2 2p?
Equivalently written as: [He] 2s? or [He] 2p?
Last electron in 2s or 2p??
Are the s and p orbitals degenerate?
• Degenerate in H
• Not in many electron systems
• 2s and 2p orbitals are non-degenerate
• p electrons are lower in energy, d,….
• S electrons are lower in energy than p,…

WHY?
 Shielding and Penetration
The effective nuclear charge experienced by an electron will be
determined by its radial probability distribution function

In a many electron atom, each electron is shielded from the nucleus by

the others, and to a first approximation, each electron may be thought
of as experiencing an effective nuclear charge.
‘s’ electron penetrates more than a ‘p’ electron of the same shell
‘s’ electron experiences a greater effective nuclear charge than a ‘p’
electron of the same shell

In general therefore, in the same shell of a many-electron atom, the

order of energies of the orbitals is
s < p < d < f.

The ground electronic configuration of Li is therefore

1s22s1, or [He]2s1.
Building-up principle (Aufbau principle)
Order of occupation of atomic orbitals. Rules:
1. 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 5d 4f 6p…
2. Each orbital may accommodate up to two
electrons (Pauli exclusion principle)
 C
Six electrons
First four electrons
occupy as: 1s22s2
2p 2p 2p
Remaining two electrons
occupy as: 2p2
2s
On the basis of
electrostatic repulsion 1s
as: 2p1x 2p1y
1s22s2 2p1x 2p1y ; [He]2s2 2p1x 2p1y
Building-up (aufbau) principle
Rules:
3. Electrons occupy different orbitals of a given subshell before
doubly occupying any one of them.
4. In its ground state, atom adopts configuration with greatest
number of unpaired electrons (Hund’s rule of maximum
multiplicity).

Friedrich
Carbon
Hund

© Emilio segre visual archive

Eg., C 1s22s22px12py1 ; N 1s22s22px12py12pz1
Origin of Hund’s rule:
Spin Correlation – Electrons in different orbitals with parallel spins
have a quantum mechanical tendency to stay apart. This allows slight
shrinkage, leading to greater attraction to nucleus.

So using the Building-up principles the configuration of

multielectron system can be written and their periodic properties
can be explained
Tutorial
Atomic structure
 Q1. Identify the radial and angular part in the following wave functions:

ΨA = (1/πao3)1/2 exp-(r/ao)

ΨB = 1/8(2/πao3)1/2 (r/ao) exp-(r/2ao) Sinθ exp(-iΦ)

Ans 1. Radial part has been marked RED.

ΨA = (1/π) ½ (1/ao)3/2 exp-(r/ao)

ΨB = 1/8(2/ao3)1/2 (r/ao) exp-(r/2ao) (2/π)1/2Sinθ exp(-iΦ)

Q2. Find the total number of nodes (nodal surfaces) and the number of radial
(spherical) nodes in the following orbitals.

2p, 3s, 4d, 4f, 5p

Orbitals Radial
nodes
Ans 2. 1s 0
2s 1
The number of radial nodes = n – l - 1 3s 2
6s 5
The number of angular nodes = l (orbital quantum number) 2p 0
3p 1
For any atomic orbital, total number of nodes = n - 1 3d 0
4d 1
5d 2
4f 0
Q3. Calculate the magnitude of the orbital angular momentum of 3d orbital.

Orbital angular momentum:

Electrons orbiting around nucleus have quantized orbital angular momentum

Angular momentum = √[l(l+1)] ħ Where l = 0,1,2,3…. etc

For 3d orbital, l value is 2 : the magnitude is √6ħ

Note: that I is a vector quantity, its magnitude is given above but it has certain
orientations and that too are quantized.
Q4. What are the nodal surfaces of 3dx2−y2 orbital. Draw the atomic orbital and
explain the sign of each lobe.

Ans. The nodal surfaces are the surfaces where the wave
function becomes zero.
So,  3dx²-y² = 0, when x2−y2 = 0
x=y
or, x = −y
Hence the nodal surfaces are x = y and x = −y planes

Sign of lobes
For dx²-y², the angular part contains x2−y2, which is always
positive along x direction. Because x >> y in the lobe along
x direction. Similarly one explain that x2−y2 will be negative
in the lobes along y direction.
61
5. What are the significance of the two quantum numbers n and l ?

6. Can you illustrate the difference between electron density and radial
probability distribution for Ψ1S of hydrogen atom?
4.
Significance of quantum numbers
Q no. Allowed values Functions

n (principal) 1,2,3…………… energy & size of orbital

l (orbital/azimuthal) (n-1),(n-2)…. 0 shape & angular momentum

m (magnetic) ±l, ±(l-1),…….0 direction & behavior under magnetic field

s (spin) +1/2, -1/2
axial angular momentum due to spin of e-
 6.
Ψ1s = (1/πao3)1/2 exp-(r/ao)

By definition,
Probability density [P(r)] = |Ψ1s|2 = [exp (-2r/ao)]/πao3

Radial probability distribution = f(r) = P(r)× 4πr2 = [exp (-2r/ao)]/πao3 × 4πr2

Plot of Plot of
probability density vs r radial distribution vs r

|Ψ1s|2 4 πr2
|Ψ1s|2

r/a
r/ao r/ao
 Chemical Kinetics
Lecture 1

CY 1101

Books:
Physical Chemistry by Peter Atkins and Julio De Paula.
Chemical Kinetics by Kaith J. Laidler.
1
 Preliminaries
What?
Branch of physical chemistry that deals with study of the speed of a chemical
reaction (rate)

Why?
Helpful for understanding the mechanism of chemical reactions

Rate of a reaction?

Concentration
[B]
A B

Rate =

[A]

Time

2
 Generalized rate equation
A B

[Assuming C is the concentration A at any time t]

k is known as the rate constant

n is the order of the kinetics

Question:
A+B+C P

k depends on temperature, reactants and catalysts. For a particular reaction at const.

temp. k is constant
3
 Can we predict order from the net balanced equation of the
chemical reaction?

2HI → H2 + I2 (order = 2)

2N2O5 → 4NO2 + O2 (order = 1)

CH3CHO → CH4 + CO (order = 3/2)

So order cannot be theoretically predicted, it’s a purely experimentally determined

quantity.

Definition: Number of concentration terms on which the reaction rate depends.

Order is applied for overall reaction, no separate step is written to obtain it.

4
 Molecularity
According to the stoichiometry, 2 molecules are reacting in each of the examples

below,

(i) 2HI → H2 + I2

(ii) 2N2O5 → 4NO2 + O2

Mechanism of reaction (i)

H I H I H I This is a single step

reaction!
H I H I H I
hypothetical
structure

Definition: Number of molecules/atoms/ions actually colliding or reacting in

a single step.
Molecularity = order in the above example
5
 Molecularity

Mechanism of reaction (ii)

A) N2O5 → NO2 + NO3 (slowest) molecularity = 1

B) NO2 + NO3 → NO2 + O2 + NO molecularity = 2
C) NO + N2O5 → 3NO2 molecularity = 2

In a complex reaction like above, molecularity of the slowest step = order

Thus, in a single step reaction, molecularity = order

6
 Order vs molecularity

Molecularity

Always a whole number (non-zero), theoretically calculated and applies to a single step

Order
Can be whole number, zero or a fraction.
Experimentally calculated and applies to the overall reaction

Question:
CH3CHO → CH4 + CO (order = 3/2)

If molecularity cannot be a fraction, then how come the above reaction shows
fractional order in spite of being a multistep reaction?

(we will find the answer later while discussing free radical chain reactions)

7
 Rate expression in a stoichiometric equation

Example

8
 Integrated rate laws
To understand how much reaction will happen after a certain time

Zeroth order reaction

A B

Half life: The time it takes the initial concentration to be exactly half

Example: Reversed Haber’s process [2NH3 (g) → 3H2 (g) + N2 (g)]

Can you derive the unit of the rate constant for zeroth order?
9
 Integrated rate laws: First order reaction

In terms of disappearance of reactants

A→B

Questions:

A B

10
 Integrated rate laws: First order reaction

Examples:
i) 2N2O5 → 4NO2 + O2
ii) H2O2 → H2O + ½ O2

What is the alternate form of the integrated rate law of first order reaction?

…… to be continued in next lecture

11
 Chemical Kinetics
Lecture 2

CY 1101

1
 Integrated rate laws: First order reaction

Alternate form:
rate equation may also be conveniently expresses in terms of the product

A → B
initial concentration
concentration at t = t

Now, we can predict at any time

provided we know

2
 Integrated rate laws: First order reaction

Application of first order kinetics: Radioactive decay follows first order kinetics

Example:

3
 Integrated rate laws: First order reaction

Application of first order kinetics: certain Bacterial growth follows first order kinetics

Q: Can you draw N/No vs time plot?

4
 Integrated rate laws: Second order reaction

Case (i): where one type of reactant is being converted into product

A→P

Please note, the stoichiometry is not being considered

In terms of disappearance of the reactant:

← can you draw the graph plot?

Prove that the half life is dependent on the initial conc. in 2nd order kinetics
5
 Integrated rate laws: Second order reaction

Case (i): where one type of reactant is being converted into product

In terms of appearance of the product:

stoichiometry is not being considered

A → P
initial concentration
concentration at t = t

What’s the unit of

6
 Integrated rate laws: Second order reaction
Case (ii): where two types of reactants are being converted into product

A + B → P

Can you draw the plot of

vs time?
7
 Examples of second order reaction
i) H2 + I2 → 2HI
ii) CH3COOC2H5 + OH- → CH3COO- + C2H5OH (basic hydrolysis of ethyl acetate)

Third order reaction:

A + B +C → P (such examples are hardly known)

2A + B → P (few such examples are known!)

[considering stoichiometry]

We are not studying third order in details, as it is less common in chemistry.

Examples:
i) 2NO (g) + O2 (g) → 2NO2 (g)
ii) 2NO (g) + Cl2 (g) → 2NOCl (g)

8
 Pseudo first order reaction:
Hydrolysis of ester in water

CH3COOC2H5 + H2O → CH3COOH + C2H5OH

This is a truly second order reaction, but water is present at a large extent than ester!

For a second order reaction, we saw earlier that:

Please note, that water is there in such a large extent, its conc. remains unchanged
even after completion of the reaction

9
 Methods of determination of the order/rate law of a reaction

i) Method of integration (trial and error method/graphical method)

A→P

In terms of disappearance of products, we need to collect a series of

graph plot outcome order

linear zero
linear first
linear second

Disadvantage: Since best fit would give the order, accuracy is problem. For
fractional order or complex reaction, this method will fail.

10
 Methods of determination of the order/rate law of a reaction
ii) Differential method (van’t Hoff’s method)

For an unknown reaction: A→P

Now, we choose two different initial concentrations, i.e. c1 and c2

Thus, we can write:

11
 …….. continued

By taking logarithms of both the equation (1) & (2), we get:

By subtracting equation (4) from equation (3), we get:

& are the rates with initial concentration &

12
 Typical concentration versus time plot for a non-zero order
reaction:

= slope 1 at t → 0 (initial rate)

= slope 2 at t → 0 (initial rate)

Ideally, c vs. t plot is considered to be linear when t → 0. But for practical purpose
we apply an approximation that c vs. t plot behaves linearly within first 10%
of the reaction!

13
 Methods of determination of the order/rate law of a reaction
iii) Isolation method (Ostwald’s method)

…… to be continued in next lecture

14
 Chemical Kinetics
Lecture 3

CY 1101

1
Methods of determination of the order/rate law of a reaction
iii) Isolation method (Ostwald’s method)
This method works best for the following type of reaction:

A + B → P

Hereafter, we can use either method (i) or method (ii) to find α

Caution: Excess of one reactant should not cause any chemical change or affect
2
the mechanism.
Methods of determination of the order/rate law of a reaction
iv) Initial rate method
This method works best for the following type of reaction:

A + B → P

The same reaction is run twice by keeping [B] constant but doubling up [A]

The same strategy can be applied to obtain β also.

3
Simultaneous reactions (only first order cases)

4
Simultaneous reaction
i) Opposing reaction:
A B
Assumption:
1st order in both ways
and
achieves equilibrium

5
Simultaneous reaction
i) Opposing reaction:

Q: How to know ?

6
Simultaneous reaction
i) Opposing reaction: in terms of disappearance of reactant

A B

may be
zero, but we
don’t bother!

7
Simultaneous reaction
i) Opposing reaction: in terms of disappearance of reactant

(cont.)
……….

8
Simultaneous reaction
ii) Consecutive reaction:

A B C

Our ultimate goal

is to express c3
in terms of co ,
t and rate constants!

how to integrate?
9
 Simultaneous reaction
ii) Consecutive reaction:
………..(cont.)

10
 Simultaneous reaction
ii) Consecutive reaction:
………..(cont.)

So far, we have been able to express both c1 and c2 in Our ultimate goal
terms of co , t and rate constants! is to express c3
in terms of co ,
t and rate constants!

What are the implications of the above outcome?

11
 Simultaneous reaction
ii) Consecutive reaction: three extreme possibilities

k 1 ≈ k2

12 Source: https://employees.csbsju.edu/hjakubowski/classes/ch331/transkinetics/TK_6B2_Multi_Step_Rx.html
13
14
15
 Chemical Kinetics
Lecture 4

CY 1101

1
Simultaneous reaction
ii) Consecutive reaction: the salient features of case -iii)

slower decay

[C]
Conc.

[A]
[B] changes a little
over a major course
insignificant of the reaction! (STEADY STATE)
value of [B]

[B]

In the mechanism of many multi-step consecutive reactions, ‘steady state’

approximation is applied.

2
Simultaneous reaction
ii) Consecutive reaction: the condition of steady state
The approximation of steady state can be applied on the intermediates, where the
build-up of intermediate is at a low concentration and must be removed following
a fast reaction.

Now we revisit the same problem under steady state approximation

A B C
intermediate

we get back
case-iii) !

3
Simultaneous reaction
Application of the steady state approximation:

Free radical chain reaction

A group of consecutive reactions that proceeds through free radical intermediates

generated in a series of self-repeating sequence

Example: The Bodenstein mechanism (1906) of the formation of HBr (g)

Over all reaction: H2 (g) + Br2 (g) hν 2HBr (g)

(1) Br2 2Br chain initiation

hν
(2) Br + H2 HBr + H chain initiation
(3) H + Br2 HBr + Br chain initiation
(4) HBr + H H2 + Br chain initiation
(5) Br + Br Br2 chain initiation

4
Simultaneous reaction
Free radical chain reaction

……cont.

try it yourself!

5
Simultaneous reaction
Free radical chain reaction

i) Identify the following steps: chain initiation, chain propagation & chain termination

ii) Prove that the following reaction follows a order kinetics.

i) Cl2 2Cl

ii) Cl + CO COCl

iii) COCl + Cl2 COCl2 + Cl

iv) 2Cl Cl2

try it yourself!

6
Simultaneous reaction
ii) Parallel reaction:

7
Simultaneous reaction
ii) Parallel reaction:
……cont.

example

From the above two equations, we can find both the rate constants by appropriate
experiments!

8
Simultaneous reaction
Concept of pre-equilibrium
A more complicated mechanism where the intermediate is in equilibrium
with the reactants:

pre-equilibrium A+B I P

9
 Simultaneous reaction
pre-equilibrium under steady state

A+B I P

In earlier case we assumed is negligibly small. Now we assume, with formation

of I, it slowly gets decayed into P as well in a non-negligible extent.

10
 Chemical Kinetics
Lecture 5

CY 1101

1
Theoretical insight of rate constant: The Arrhenius equation

Fact: Rate of a reaction increases with T, gets 2 to 3 times with every 10K rise.
Arrhenius proposed an empirical equation to account for it.

Arrhenius equation (1889):

A: Pre-exponential factor or frequency factor

Eact: Energy of activation

Can we measure energy of activation?

2
 ….. continued
If we measure the rate constant at two different temperature, then we can write….

Note, A is hypothesized
to be independent of T,
depends on the nature of
the reaction

Subtracting equation (2) from (1), we get:

Q: Can you measure the value of A from the above plot?

3
 What’s the relationship between energies of activation and equilibrium constant?

A B (assuming T is constant)

From, the above 2 equations we get,

4
 The significance of activation energy
According to Arrhenius, the molecules must acquire a certain energy, before
they would undergo chemical transformation.

In other words, molecules must be in the activated state before the reaction
Can proceed.
Energy profile diagram

exothermic
reaction

5 Source: chemguide.co.uk
 Transition state

Cl Cl Transition state
H
H

energy

H Reaction coordinate H

Cl Cl - Cl- Cl
H H

H H
Transition state
 Transition state

Keto–enol tautomerism
 Transition state
Keto–enol tautomerism
 Catalysis:
A catalyst offers an alternate pathway for the reaction, usually involving a lower
energy of activation

endothermic
reaction

Source: socratic.org
10
 Classification of Catalysis:

catalysis

homogeneous heterogeneous

both the catalyst and the phases of the catalyst

the reactants and the reactants are
are within the same phase different

example: enzyme-catalysis example: hydrogenation of ethylene

on Ni surface (solid-gas reaction)

11
 Enzyme catalysis: homogeneous aqueous phase reaction

enzymes are biomolecules: proteins

they have a particular region/groove

where it binds with reactants (substrate)
and called as active site

Source: cen.acs.org Some important digestive enzymes

12
Mechanism: Lock & key
Binding (first) step is proposed to be reversible, while the next step is irreversible

Each active site of an enzyme is specific to a particular substrate!

v
Substrate (S)
(P)

Substrate
(E)
(ES)
Source: scienceabc.com
13
Proposed mechanistic pathway:

E + S ES P+E

Goes on cyclically!

The above situation is identical with the case discussed in slide 09 of Lecture 04!

Question is which approach should we adopt?

Option A: Pre-equilibrium?

Option B: Steady-state?

14
Proposed mechanistic pathway: Under pre-equilibrium condition

E + S ES P+E

Q: Is there any problem, if above condition is applied?

A: Yes, there is a big problem…..

According to the above condition, ES will be more interested to form

E and S rather than E and P!

That means, there won’t be any effective catalysis!

15
Proposed mechanistic pathway: Steady-state approximation

E + S ES P+E

But here is one problem, we cannot measure [E]!

We can only measure [E]o (initial enzyme conc.) and [S]

Therefore, we need to express [E] in terms of [E]o and [ES]

How to do it?

Lets approach the same problem from the beginning with application of
steady-state approximation!
16
Proposed mechanistic pathway: Steady-state approximation

E + S ES P+E

17
=

Michaelis-Menten equation for enzyme kinetics:

….. continued

This is called Michaelis-Menten equation for enzyme kinetics

In enzyme kinetics, rate = speed = velocity (denoted by )

18
Michaelis-Menten equation for enzyme kinetics:
….. continued
final working form
of the Michealis-Menten
equation

How to graphically represent the above equation (velocity vs. [S] plot)?

at lower [S], y = mx , at high [S], y = const.

19
Michaelis-Menten equation for enzyme kinetics:
….. continued

Therefore, the Michaelis-Menten equation can be re-written as

……. equation (4)

Physical significance of Michaelis constant:

20
Physical significance of Michaelis constant:

Can you tell which enzyme performs better catalysis, the one with a
Lower KM or higher KM value?

…… to be addressed in the next lecture

21
 Chemical Kinetics
Lecture 6

CY 1101

1
Michaelis-Menten mechanism for enzyme kinetics:
Michaelis-Menten equation can be re-written as

……. equation (4)

Enzyme with a lower KM value will require less [S] to reach saturation speed.

So an enzyme with lower KM value will have higher affinity with the substrate.

2
Michaelis-Menten mechanism for enzyme kinetics:

Caution: KM is the measure of enzyme’s affinity to the substrate but it is

not the measure of enzyme’s efficiency!

Also, KM and Vmax are independent with each other!

Alternatively, k3 is also called as kcat

So, higher the turn over number, better is the enzyme.

The measure of enzyme’s efficiency is the ratio

The enzyme carbonic anhydrase has turn over number ~ 105

Q: How to calculate turn over number?

A:

3
Michaelis-Menten mechanism for enzyme kinetics:
How to determine maximum velocity for an enzyme?

Definitely from rate (velocity) versus [S] data!

However, before the era of non-linear curve fitting by softwares; people used to
face problems regarding the best fit of velocity versus [S] plot.

Two scientists named Lineweaver and Burk invented a more accurate way
to determine Vmax from the data of velocity and [S].

4
 The Lineweaver-Burk plot:

slope =

Also known
as the
actual data points double-reciprocal
plot

?
5 Find the value of the intercept on the independent axis
 The kinetics of enzyme inhibition:
There are situations when the action of enzyme gets inhibited! That means
action of enzyme is either slowed down or halted. Usually inhibitors are
pharmaceutical agents.

Aspirin (drug) inhibits and enzyme that catalyzes the 1st step of forming
prostaglandin cause of pain in some cases

Q: What’s the importance kinetics of enzyme inhibition?

A: It helps us to understand various metabolic pathways in organisms

We will learn about few important types of enzyme inhibition.

6
 Types of enzyme inhibition

reversible irreversible

enzyme not destroyed technically destroys

product is formed the enzyme

competitive

uncompetitive

mixed

7
 Competitive inhibition:

The inhibitor (I) competes with the substrate (S) to bind at the active site.
Here I and S are geometrically similar.

Scheme: E P+E

E NO product!
Kinetics:

8
 Kinetics of competitive inhibition:

……continued

9
 Kinetics of competitive inhibition:

……continued

Can you express the kinetics of competitive inhibition in Lineweaver-Burk form?

10
 Kinetics of competitive inhibition:
……continued
slight rearrangement of equation (1) gives us….

intercept slope

11
 The Lineweaver-Burk plot of competitive inhibition:
……continued
Also, the equation (2) can be written as

Note that the slope of competitively inhibited reaction contains a variable [I]

12
 The salient features of competitive inhibition:
uninhibited:

inhibited:

In this type of inhibition with increasing [I]:

So, in competitive inhibition, the enzyme takes more substrate to reach the same
maximum velocity!
or, with a fixed value of [S], the enzyme shows slower rate!

13
 Clinical example of competitive inhibition:

14
 Chemical Kinetics
Lecture 7

CY 1101

1
Uncompetitive inhibition:

E + S ES E+P
+
I

Inhibitor binds to the ES complex!

ESI NO product!

Scheme:

NO product!

2
Uncompetitive inhibition (kinetics):
Uncompetitive inhibition (kinetics):
Uncompetitive inhibition (kinetics):
Uncompetitive inhibition (kinetics):
Uncompetitive inhibition (kinetics):

Slope is unchanged
with increasing intercepts
on vertical axis.

7
Uncompetitive inhibition (graphical presentation):

apparent Lineweaver-Burk plot

KM changes!
8
competitive inhibition uncompetitive inhibition
 Mixed inhibition:

E + S ES E+P
+ +
I I

NO product! EI + S ESI NO product!

Scheme:

10
Mixed inhibition:
Mixed inhibition:
Mixed inhibition:
 Mixed inhibition (kinetics):

both slopes & intercepts

on vertical axis changes!

14
 Mixed inhibition (graphical presentation):

Lineweaver-Burk plot

15
 Tutorial problems
Q 1. Draw the velocity vs. [S] plot for competitive inhibitor with increasing [I].

Q 2. Draw the velocity vs. [S] plot for uncompetitive inhibitor with increasing [I].

Q 3. In uncompetitive inhibitor what happens to the apparent Michaelis constant,

and apparent maximum velocity and velocity?

Q 4. Using the approximation of steady-state, derive the following equation for

uncompetitive inhibitor.

(symbols have their usual meaning)

16
 Tutorial problems
Q 5. Using the approximation of steady-state, derive the following equation for
mixed inhibitor.

(symbols have their usual meaning)

Q 6. When α = α’ in the above equation, it gives rise to a very rare and special
inhibition, called non-competitive inhibition! Draw both the velocity vs. [S] plot
and Lineweaver-Burk plot for the above inhibition with increasing [I].

Q 7. In non-competitive inhibitor what happens to the apparent Michaelis constant,

and apparent maximum velocity and velocity?
Answer the same for the case of mixed inhibition.

17
 Simultaneous reaction
Free radical chain reaction

i) Identify the following steps: chain initiation, chain propagation & chain termination

ii) Prove that the following reaction follows a order kinetics.

i) Cl2 2Cl

ii) Cl + CO COCl
iii) COCl + Cl2 COCl2 + Cl

iv) 2Cl Cl2

try it yourself!

18
 Chemical Kinetics
Lecture 8

CY 1101

1
Heterogeneous Catalysis:
In general:

solid phase serves as the catalyst, gas/liquid phase is the substrate.

In this course, we would study heterogeneous catalysis between solid phase (catalyst)
and gas (substrate).

Such heterogeneous catalysis goes through Solid-Gas intermediate, which is roughly

equivalent to the ES complex of enzyme catalysis.

Solid-Gas intermediate gas molecules adsorbed

on solid surface

Next, we discuss the mechanistic steps of solid-gas heterogeneous catalysis.

2
Heterogeneous Catalysis (solid-gas): Mechanistic steps
g p
c c
g v v
a a p

solid surface

Steps: i) diffusion ii) adsorption iii) reaction iv) desorption

Real life example: hydrogenation of ethylene on Ni surface

H H
C2H2 H H
H2
C C C C H
H
H2 H H
H2 H H

Ni

diffusion adsorption reaction

3
Role of surface in heterogeneous catalysis:

To offer an alternate pathway, which involves lower activation energy barrier!

Which is the slowest step among these four?

i) diffusion ii) adsorption iii) reaction iv) desorption

Ans: ii) adsorption The rate determining step!

Thus, the rate of a heterogeneous reaction = rate of adsorption

How does rate of adsorption depend on the concentrations of molecules?

- We have to learn a basic equation for adsorption of gas on solid surface

4
Theory of adsorption of gas on solids by Irving Langmuir (1932)

Schematics of Langmuir’s model:

Thermodynamic consideration:
i) Process goes through multiple slow & reversible steps
ii) Instantaneous equilibrium is achieved in each step

Langmuir’s major assumptions:

i) Surface contains a fixed number of equivalent adsorption sites
ii) One molecule sits on one adsorption site (monolayer)
iii) After adsorption, molecules don't move or interact with each other

5
Mathematical derivation of Langmuir’s adsorption theory

adsorption

desorption

Since any step of adsorption process is under equilibrium as shown above,

6
 ……………..continued

adsorption

desorption

Mathematical form of
Langmuir’s adsorption
theory

7
 Graphical representation of Langmuir’s adsorption equation

pre
p
Such 𝞱 vs p plot is analyzed under constant temperature. Such plot is known as
adsorption isotherm.

……… also known as Langmuir’s adsorption isotherm equation

8 https://www2.stetson.edu/~wgrubbs/datadriven/langmuir/langmuirwtg.html
 Kinetics of gas-solid reaction:

Since, adsorption is the rate determining step,

rate of heterogeneous reaction fraction gas molecules adsorped 𝞠

Where, Z is the rate constant

Since the reaction is measured in terms of the pressure of the gaseous reactants,

= (rate of decrease of pressure)

Now, there are three different situations possible under solid-gas reaction

9
 Situation (I): A single gas gets absorbed to form product
g p
c c
g v v
a a p

solid surface

Case (i) : When p is very small or ‘ap’ is negligible compared to unity

First order kinetics Example: decomposition of PH3 on W

Case (ii) : When p is very high or unity is negligible compared to ‘ap’

Zero order kinetics Example: decomposition of PH3 on W

Case (iii) : When p is neither very small or too high

Order is more than zero but less than 1 (fractional order)

10
 Situation (II): simultaneous adsorption of two different gas
molecules at adjacent sites
A p
c c
B v v
A B p

solid surface

11
 Solutions of 𝞱A and 𝞱B

The Langmuir-Hinshelwood mechanism

12
 The Langmuir-Hinshelwood mechanism:

General Example: Catalytic conversion reaction in automobiles

Catalyst (s)
CO (g) + O2 (g) CO2 (g)

A special case:

Second order kinetics

Example: Hydrogenation of ethylene on Cu surface

13
 Situation (III): A gas-phase molecule collides with another
molecule already adsorbed on the surface

A c c
B B v v

solid surface

The Eley-Rideal mechanism

Example: Hydrogenation of ethylene on Ni surface (shown in slide 3)

14
 Industrial application of heterogeneous catalysis

Solid catalysts Function Examples

Metals Hydrogenation, Fe, Ni, Pt, Ag
Dehydrogenation

Semiconducting Oxidation NiO, ZnO, MgO,

oxides & sulfides Desulfurization MoS2

Insulating oxides Dehydration Al2O3, SiO2, MgO

Acids Polymerization H3PO4, H2SO4,

Isomerization Alumino silicates,
Cracking zeolites
Alkylation

15
 Tutorial problems:
1. In the Eley-Rideal mechanism, prove that (i) the rate determining step is the collision
of gas molecule A with the adsorbed molecule when the partial pressure of B is too high
(ii) the kinetics is of second order, when the partial pressure of B is too low.

A c c
B B v v

solid surface

2. Suggest the form of the rate law for the deuteration of NH3 in which D2 adsorbs
Dissociatively but not extensively (that is Kp ≪ 1, with p the partial pressure of D2),
and NH3 (with partial pressure p’) adsorbs at different sites.

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3. Calculate the surface area (m2) of the solid surface from the adsorption isotherm plot
given below. Here, the adsorbed gas has the surface area 0.43 nm2

0.0083
1/v (cm-3) at STP

0.0077

0.0071

0.0065

0 25 50 75
1/p
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 Simultaneous reaction from Lecture 4
Application of the steady state approximation:

Free radical chain reaction

A group of consecutive reactions that proceeds through free radical intermediates

generated in a series of self-repeating sequence

Example: The Bodenstein mechanism (1906) of the formation of HBr (g)

Over all reaction: H2 (g) + Br2 (g) hν 2HBr (g)

(1) Br2 2Br chain initiation

hν
(2) Br + H2 HBr + H chain initiation
(3) H + Br2 HBr + Br chain initiation
(4) HBr + H H2 + Br chain initiation
(5) Br + Br Br2 chain initiation

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 Simultaneous reaction
Free radical chain reaction

……cont.

try it yourself!

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