B.

Tech First Year Course

Course Title- Chemistry-I (Concepts in Chemistry for Engineering)
Course Code- BTCH-101-18
Scheme& Credit – L-3, T-1, P-0, C-4

-Dr. Sanjeeb Sutradhar

1
 Distribution of Marks
Theory Practical
Subject Code- BTCH-101-18 Subject Code- BTCH-102-18
Total Marks- 100 Total Marks- 50
Internal – 40% ; Pass Marks=16% Internal – 30 ; Pass Marks=12
Attendance- 6% Attendance- 6
<75.0% - can’t appear final exam <75.0% - can’t appear final exam
75.0% =1 75.0% =1
75.1%-79.9% = 2 75.1%-79.9% = 2
80.0%-84.9% =3 80.0%-84.9% =3
85.0%-89.9% =4 85.0%-89.9% =4
90.0%-94.9% =5 90.0%-94.9% =5
95.0%-100.0%=6 95.0%-100.0%=6
Assignment or surprise quiz: 10% Internal Viva: 10
Middle Semester Term (MST) – 24% Practical Report – 20
External – 60% ; Pass Marks=24% External – 20 ; Pass Marks=8
End Semester Term: 60% End Semester Term: 20 2
 Atomic and Molecular Structure (L-12)
Schrödinger equation, Particle in a box solutions and their applications for conjugated
molecules and nanoparticles. Forms of the hydrogen atom wave functions and the plots of
these functions to explore their spatial variations. Molecular orbitals of diatomic
molecules and plots of the multicentre orbitals. Equations for atomic and molecular
orbitals. Energy level diagrams of diatomics. p-molecular orbitals of butadiene and
benzene and aromaticity. Crystal field theory and the energy level diagrams for transition
metal ions and their magnetic properties. Band structure of solids and the role of doping
on band structures.
References

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 Atomic Theory Timeline
~450 BC Democritus -Greek philosopher 1896 AD- J. J. Thomson– English Physicist
All matter around us is made of Discovered atoms have negative particles
indivisible tiny particles- “atomos” (electrons) using a cathode ray tube.

1909 AD- Robert Millikan– American

1803 AD- John Dalton – School teacher Physicist
Dalton’s Atomic Theory Measured the charge of an electron using oil
droplets.

1909 AD- Ernest Rutherford– New Zealand

Scientist
1839 AD- Michael Faraday– English chemist Positive charge is not like a pudding, but
structure of atoms is somehow related concentrated in the nucleus as shown in
to electricity the Gold Foil (alpha particle) experiment

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 Atomic Theory Timeline
1913 AD Henry Moseley –English Scientist 1924 AD Louis de Broglie –French Graduate
Each element contains a unique
number of protons. Student
*Electrons can act like
particles and waves (just
like light)
*Electrons occupy
orbitals. Orbitals are
nothing like orbits. They
are areas of probability
1911 AD- Niels Bohr – Danish physicist (90% of electron
probability)
Bohr’s atomic theory
*Electrons orbit the 1926 AD- Schrödinger- French Graduate
nucleus.
*Model based on the Student (Austrian)
hydrogen atom
*Energy of the
Wave Mechanical Model
electrons is quantized.

Classical Mechanics – Based on Newton's Laws of motion

Quantum Mechanics – Based on Schrödinger equation
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Schrödinger equation (Time Independent/Stationary State Wave
Functions)
Total energy of the electron using de-Broglie equation

Equation of wave motion

Double differentiation,

Comparing with wave motion equation, putting the 1/l2 and

rearranging

When electron moves in x, y, z (3-D co-ordinates), the equation becomes

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 Physical Significance of Y
Y = Mathematical significance
= No physical significance
Reason:
Sound wave- Amplitude increase or decrease of air pressure relative to static pressure
Electromagnetic wave- magnitude of electric or magnetic field associated with the wave
Electron wave- Not such property associate

But Y2= has physical significance

Sound wave/Electromagnetic wave- - Square of Amplitude gives intensity of light or sound
at that point
Electron wave- Intensity of electron wave i.e. Heisenberg Uncertainty Principle says that it
can interpreted as the probability of finding that electron at that point.

Y2 =0
Y2 = 90%
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 Characteristics of Y

1. Y (wave function) should be normalized

2. If there is more than one Y (wave function), the two must be orthogonal each other

or 1

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 Postulates of Quantum Mechanics (Time Independent)
Postulate 1: The state of a system is completely described by a wave function ψ (r,t)

Postulate 2: All measurable quantities (observables) are described by Hermitian linear

operators

Postulate 3: The only values that are obtained in a measurement of an observable “A”
are the eigenvalues “an” of the corresponding operator “”. The measurement changes
the state of the system to the eigen function of  with eigenvalue an

Postulate 4: If a system is described by a normalized wave function ψ , then the

average value of an observable corresponding to  is

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 Schrödinger equation (Time dependent)
Schrödinger’s time independent equation in 3-D is given by,

Equation of wave motion

Single differentiation,

Putting E=hn and rearranging

Substituting the EY in the Schrödinger’s time independent equation

Hamiltonian operator

These two equations are like statics and dynamics in classical mechanics 10
 Particle in a Box Solutions
Schrödinger’s time independent equation is given by,

Particle in box, V=0, Schrödinger’s equation becomes

For a given state of the system, energy is constant

General solution of this equation will be

Applying boundary condition Y=0, x=0 & Y=0, x=a

Eigen value of the energy

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12
 Application of the Particle in a Box for Conjugated Molecules
Eigen value of the energy n+1=LUMO
DE
n=HOMO

DE = (2n+1) h2/8ma2

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 Application of the Particle in a Box for Nanoparticles
Nanoparticles – At least one dimension in 1-100 nm

Reduction of size effect the chemical reactivity due to association of structure and
configuration of outermost electronic energy levels – Volume to surface area ratio

Quantum confinement effect: If the particle size is less than the wavelength of the
electron, the charge carriers 'may be treated as "particles in a box".

Since nanomaterials are closer in size to atoms or molecules, quantum mechanical laws
are used to describe their behavior.

In nanocrystals, the energy levels are well defined and the addition or subtraction of
one atom or electron to the nanocrystal measurably changes the electronic properties.

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 Forms of the H-Atom Wave Functions and the Plots of These
Functions to Explore Their Spatial Variations
For a central force law, the potential energy will depend only
on the distance from the force center. It is then convenient to
z
use spherical polar coordinates (r,q ,f )

In these coordinates, the Laplacian operator is

x

Time independent Schrödinger equation is

To separate variables,

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 Forms of the H-Atom Wave Functions and the Plots of These
Functions to Explore Their Spatial Variations
Now, differentiating the equation

Multiplied by , the equation becomes

r2 =0
R
Separate the radial and angular variables
r2
R

r2 = b
Radial equation, R
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 Forms of the H-Atom Wave Functions and the Plots of These
Functions to Explore Their Spatial Variations
Angular equation,

Further, separation of q and f, multiplied by sin2q

The above equation is valid only if they equal to common constant

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 Equations for Atomic and Molecular Orbitals

Atomic orbital – Wave function y for electrons in atoms

Case-I: Addition when two waves are in phase

Case-II: Subtraction when two waves are not in phase

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MOs of Diatomic Molecules and Plots of the Multicenter Orbitals
Different theories put forwarded from time to time
 Kössel-Lewis approach (1916): Based on Octet rule (Unable to explain the shape)

 Valence Shell Electron Pair Repulsion (VSEPR) Theory (1940) : Successful for
predicting shape p-block elements but subject of doubt on the effect of electron pair
repulsions

Quantum Mechanical Principles

 Valence Bond (VB) Theory (VBT) (1927): Hybridization concept introduced

 Molecular Orbital Theory (MOT) (1932): Explain magnetic properties for p-block
elements but not for TM

 Crystal Field Theory (CFT) (1930): Explain magnetic properties for d-block
elements and electrostatic approach
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 MOs of Diatomic Molecules and Plots of the Multicenter Orbitals
Order of increasing energy from Spectroscopic data for O2, F2

Order of increasing energy from Spectroscopic data for up-to N2

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Energy Level Diagrams of Diatomics

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Energy Level Diagrams of Polyatomic (CO)

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 p-Molecular Orbitals of Butadiene

s bond- sp2 hybrid orbitals

p bond- unhybridised p-orbitals (4 nos)
LCAO of these p-orbitals- y1, y2 (bonding)
and y3*, y4* (anti-bonding)
C2-C3 overlap < C1-C2 or C3-C4 overlap

 Partial overlap of C2-C3 gives partial

double bond character and allows the four
p electrons to be delocalized over all four
atoms (y1)
 4 p-orbitals overlap sideways on both side
(resonance/delocalization)
 Equally attracted in four C-atoms

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 p-Molecular Orbitals of Benzene

s bond- sp2 hybrid orbitals

p bond- unhybridised p-orbitals (6 nos)

Ring like cloud formation

Delocalization of p electrons makes more stable than normal p bond – Accounts
for extra stability to benzene

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 Aromaticity

Aromatic Compounds – Benzene and benzene like molecules in their chemical

behavior
Characteristics:
 They are usually cyclic compounds
 They are planar
 Despite unsaturation, these compounds undergo substitution reaction
 They are resonance stabilized
 Follow Huckel rule / (4n+2) rule where n = 0, 1, 2, 3, ……

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Classification of Aromatic, Antiaromatic, and Non-aromatic

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Aromaticity

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 Crystal Field Theory
 Bonding model explaining many important properties of transition-metal complexes

Central assumption of CFT:

 Metal-ligand connections are electrostatic interactions between a central metal ion and
a set of negatively charged ligands (or ligand dipoles) arranged around metal ion.

t2g

eg

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 Crystal Field Splitting-Octahedral

 eg (dx2-y2 and dz2) orbitals are repelled by an amount of 0.6 Δo

 t2g (dxy, dyz, dzx) orbitals to be stabilized to the extent of 0.4 Δo.
 Energy gap is referred to as D0 (10 Dq) , Crystal field splitting energy.

 CFSE = Stabilization energy+Repelled Energy = -n(t2g)x0.4 + m(eg)x0.6 29

 Crystal Field Splitting-Octahedral

 dz2 and dx2-y2 orbitals lie on the same axes as negative charges. There is a large,
unfavorable interaction between ligand (-) orbitals. These orbitals form the
degenerate high energy pair of energy levels.

 dxy , dyx and dxz orbitals bisect the negative charges. There is a smaller repulsion
between ligand & metal for these orbitals.

 Pairing energy Vs. D

Weak field D < PE = High Spin
Strong field D > PE = Low Spin

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 Crystal Field Splitting- Tetrahedral

 Td geometry doesn’t contain i (center of symmetry)

 Energy gap is referred to as Dt (10 Dq) , Crystal field splitting energy
Dt =4/9 Do

 Small D => High Spin

 CFSE=0.4 m(t2) - n(e)x0.6 31

Crystal Field Splitting Pattern Comparison (Oh & Td)

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Crystal Field Splitting- Square Planar

 Ligands along the Z axis are removed from

an octahedral complex to get a square planar
complex

 Mostly d8 (Majority Low spin) Strong field

ligands i.e., Pd2+, Pt2+, Ir+, Au3+

 Example: [Ni(CN)4]2- and [Pd(Cl)4]2-

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 Factors Affect the Magnitude of Do
 Magnitude of Do dictates increases with increasing oxidation state of the central
metal ion
Δ =10,200 cm-1 for [CoII(NH3)6]2+ and 22,870 cm-1 for [CoIII(NH3)6]3+
Δ =32,200 cm-1 for [FeII(CN)6]4- and 35,000 cm-1 for [FeIII(CN)6]3-

 In groups, heavier analogues have larger Δo. For hexaammine complexes

[MIII(NH3)6]3+: Δ = 22,870 cm-1 (Co); 34,100 cm-1 (Rh); 41,200 cm-1 (Ir)

 Nature of the ligand: Strong-field ligands interact strongly with d orbitals of metal
ions and give a large Do and Weak-field ligands interact more weakly and give a
smaller Do
For [CoIIIL6], Δ in cm-1: 13,100 (F-); 20,760 (H2O); 22,870 (NH3)
For [CrIIIL6], Δ in cm-1: 15,060 (F-); 17,400 (H2O); 26,600 (CN-)
 Geometry of the metal coordination unit affects Δ greatly. Td complexes ML4 have
smaller Δ than Oh complexes ML6: Δ = 10,200 cm-1 for [CoII(NH3)6]2+
= 5,900 cm-1 for [CoII(NH3)4]2+
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 Spectrochemical Series
Spectrochemical Series: An arrangement of ligands according to their ability to increase
Δ for a given metal center

Weak – I-, Br-, SCN-, Cl-, N3-, F-, H2NC(O)NH2, OH-, ox2-, O2-, H2O, NCS-, py, NH3, en,
bpy, phen, NO2-, CH3-, C6H5-, CN-, CO – Strong

High Spin Low Spin

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 High Spin and Low Spin Configuration (Oh)

d1,d2,d3 d4,d5,d6, d7 d8, d9

[Ti(H2O)6]3+ [Cr(H2O)6]2+ [Cr(CN)6]4-

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 John-Teller Distortion
Nonlinear complex is orbitally degenerate and asymmetrically filled, then the complex
distorts so as to remove the degeneracy and achieve a lower energy

d
d

[Cu(H2O)6]2+

d
d
Oh-complex = d1, d2,
LS and d4 d5,HS d6, and d7
Td-complex = d1, d3, d4, d6, d8, and d9
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 Energy Level Diagram for TM ions
Oh – Orbitals of the central metal atom divide by symmetry into four sets

Metal orbital Symmetry Label Degeneracy

s a1g 1
px, py, pz t1u 3
dx2-y2, dz2 eg 2
dxy, dyz, dxz t2g 3

Six symmetry-adapted linear combinations (SALC) of the six ligand orbitals can also
be formed

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General MO Energy Level Diagram for TM

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 Magnetic Moment of Coordination Compounds

Points to remember
 Coordination compounds must posses unpaired electron
 spin of a single electron is denoted by ms as +(1/2) or –(1/2)
 Formula for calculating magnetic moment

μeff = μs = 2√S(S+1) = √n(n+2) BM μeff= μS+L= √L(L+1) + 4S(S+1) BM

*T2g/T2 unsymmetrically filled

Non- spherical environment For a given value of the orbital quantum

may lead to quenching of the number, ml= –l to +l and L = Σ|ml|
contribution from orbital
angular momentum For d orbital electrons, ml = 2, 1, 0, -1, -2
If there is only 1-electron in the d
orbitals, L=2
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 Co(II) d7
K2CoCl4 [Co(H2O)6]Cl2

moisture
Blue Pink
heat

Dt
Do

Orbital contribution
No orbital contribution Magnetic
Magnetic moment µ = 5.20 BM
moment µ = 3.87 BM
higher than spin-only value 41
 Numerical Questions (H.W.)
The magnetic moment of a certain octahedral Co(II) complex is 4.0 mB. What is its d-
electron configuration?

The magnetic moment of the complex [Mn(NCS)6]4- is 6.06 mB. What is its electron
configuration?

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 Band Structure of Solids
 MOT extended to solids is known as Band Theory
 BT introduced in order to account for the
decreasing resistivity with increasing temperature
as well as other properties of semiconductor

Valence band: Energy band that consists of valence

electrons energy levels and the electrons of this band
are loosely bound to the nucleus of the atom.

Conduction band: Energy band that consists of free

electrons energy levels

Forbidden band/gap (band gap): Energy gap between

the valence band and the conduction band

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 Band Structure of Solids
 Based on conducting properties, the solids are classified as
Conductor, semiconductor, and Insulator

Conductor semiconductor (1eV) Insulator (6eV)

e.g. Cu, Pb e.g. Si, Ge e.g. Plastic, Paper

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 Temperature Effect on Solids
 Conductor is heated its resistance increases: Atoms vibrate more and the electrons find it
more difficult to move through the conductor

 Semiconductor is heated its resistance decreases: Electrons can be excited up to the

conduction band. Conductivity increases

 Semiconductor –
Intrinsic- Pure semiconductor
Extrinsic- Impurities added (doping) to make conductive
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 Role of Doping on Band Structures

 Role – Impurities or dopant to increase the number of electrons or holes in the

semiconductor (Fourth group in the periodic table and doesn’t alter the structure)

 Depending upon the type of dopant, extrinsic semiconductors are

classified as
n-type semiconductor (donor- free electron)
p-type semiconductor (acceptor-hole)
Acceptor Donor

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 n-type Semiconductor

 Inject Arsenic into the crystal with an implant step.

 Arsenic is Group-5 element with 5 electrons in its outer shell, (one more than silicon).
 This introduces extra electrons into the lattice which can be released through the
application of heat and so produces electron current
 Result here is an n-type semiconductor (n for negative current carrier) 47
 p-type Semiconductor

 Inject Boron into the crystal with an implant step

 Boron is Group-3 element with 3 electrons in its outer shell (one less than silicon)
 This introduces holes into the lattice which can be made mobile by applying heat. This
gives us a hole current
 Result is a P-type semiconductor (p for positive current carrier) 48
49