T02/024 : ELECTROMAGNETIC RADIATION AND HYDROGEN LINE SPECTRUM Flashcards
What do quantum numbers describe?
- energy of e in an orbit
- position of e from nucleus
- shape and number of orbitals around its own axis
- orientation of the spinning of the electron round its own axis
MAPS
What are the four types of quantum number?
- principal quantum numer (n)
- azumuthal quantum number (l)
- magnetic quantum number(m)
- spin quantum number(s)
energy level, distance, energy,
What properties of an electron does the principal quantum number reveal?Explain using formulas.
- rep. main energy level i which the electron revolves round the nucleus e.g n=1,2,3,
- gives distance of e from nucleus(radius of the orbit) e.g
r = (E’oh^2n^2)/(πme^2 Z) - gives energy of an e in an orbit
E = -(me^4Z^2)/(8E’^2h^2n^2) - gives maximum number of e that can be accomodated in a given shell
= 2n^2
E’ is permittivity
sub-shell, max. e , angular
What properties of an electron does the azimuthal quantum number(l) reveal?
- rep a sub-shell within the principal sub-shell i.e
l=0 …………… s-sub-shell (s-orbital)
(s-sharp)
l=1…………… p-sub-shell (p-orbital)
(p-principal)
l=2 …………… d-sub-shell (d-orbital)
(d-diffused)
l=3 …………… f-sub-shell (f-orbital)
(f-fundamental) - determines the magnitude of orbital angular momentum
- explains the group of closely spaced lines in the hydrogen spectrum
- maximum number of e in a sub shell i.e
2(2l+1)
sharp, diffused, fundamental and principal
Describe the sub-shells defined by azimuthal quantum number.
The azimuthal quantum number (denoted as ℓ) defines the subshells or orbital angular momentum in an atom. It determines the shape of the electron’s orbital and its energy in a given shell (principal quantum number, n). For each value of n, the azimuthal quantum number ℓ can take integer values from 0 to n-1, and each value of ℓ corresponds to a specific type of subshell:
- ℓ = 0: This defines the s subshell (sharp). The orbital is spherical in shape. Each s subshell can hold a maximum of 2 electrons.
- ℓ = 1: This defines the p subshell (principal). The orbitals are dumbbell-shaped and oriented along the x, y, and z axes. A p subshell has three orbitals and can hold a maximum of 6 electrons.
- ℓ = 2: This defines the d subshell (diffuse). The orbitals have more complex shapes, often described as clover-shaped. A d subshell has five orbitals and can hold a maximum of 10 electrons.
- ℓ = 3: This defines the f subshell (fundamental). The orbitals are even more complex in shape. An f subshell has seven orbitals and can hold a maximum of 14 electrons.
- ℓ = 4 and higher: These correspond to g, h, i subshells, though they are not typically encountered in most ground-state atoms. Each follows the same rule, with increasing complexity in orbital shapes and a maximum number of electrons increasing by 4 per higher subshell (e.g., g can hold 18 electrons).
In summary, the azimuthal quantum number defines the number and type of subshells within a given shell, influencing the shape of the electron cloud and the total number of electrons that the subshell can accommodate.
(i)What is the number of sub-shells when the principal quantum number is n=5?
(ii)What are the type of sub-shells included?
(iii)What is the maximum number of e in each subshell?
(i) Number of sub-shells when n = 5:
The number of subshells is determined by the principal quantum number (n). For each value of n, the azimuthal quantum number ℓ can take integer values from 0 to n-1. So, when n = 5, the possible values of ℓ are:
- ℓ = 0 (s subshell)
- ℓ = 1 (p subshell)
- ℓ = 2 (d subshell)
- ℓ = 3 (f subshell)
- ℓ = 4 (g subshell)
Therefore, there are 5 subshells when n = 5.
(ii) Type of subshells included:
The types of subshells correspond to the values of ℓ:
- ℓ = 0 → 5s subshell
- ℓ = 1 → 5p subshell
- ℓ = 2 → 5d subshell
- ℓ = 3 → 5f subshell
- ℓ = 4 → 5g subshell
So, the subshells included are 5s, 5p, 5d, 5f, and 5g.
(iii) Maximum number of electrons in each subshell:
The maximum number of electrons in each subshell is given by the formula 2(2ℓ + 1), where ℓ is the azimuthal quantum number.
- 5s (ℓ = 0): Maximum electrons = 2(2(0) + 1) = 2 electrons
- 5p (ℓ = 1): Maximum electrons = 2(2(1) + 1) = 6 electrons
- 5d (ℓ = 2): Maximum electrons = 2(2(2) + 1) = 10 electrons
- 5f (ℓ = 3): Maximum electrons = 2(2(3) + 1) = 14 electrons
- 5g (ℓ = 4): Maximum electrons = 2(2(4) + 1) = 18 electrons
In summary:
- 5s can hold 2 electrons.
- 5p can hold 6 electrons.
- 5d can hold 10 electrons.
- 5f can hold 14 electrons.
- 5g can hold 18 electrons.
addition due to magnetic field, orbital orientations
What does the magnetic quantum number show?
- explains the additional number of spectral lines when the magnatic field is pplied.
- total number of orbital orientations in a given sub-shell
- takes values from -1, 0, +1
- l = 0; m = 0
l = 1; m = -1, 0, +1
l = 2; m = -2, -1, 0, +1, +2
l = 3; m = -3, -2, -1; 0; +1; +2; +3
up,down
Explain the spin quantum number and the different representations of an electron spin
The spin quantum number (denoted as ms) refers to the intrinsic angular momentum or spin of the electron.
Representation of electron spinning:
1)Clockwise (+ ½ ) or ( arrow pointing up) or (α spin)
2)Anticlockwise (- ½) or (arrow pointing down ) or (β spin)
Distinguish the type of atomic orbitals
Atomic orbitals are regions around the nucleus of an atom where there is a high probability of finding electrons. Each orbital is defined by a unique set of quantum numbers that describe its shape, size, and orientation. The four main types of atomic orbitals are s, p, d, and f, each having distinct shapes and capacities for holding electrons.
- s Orbitals:
Shape: Spherical.
Principal Quantum Number (n): Present in all energy levels (n = 1, 2, 3,…).
Azimuthal Quantum Number (ℓ): ℓ = 0.
Number of Orbitals: 1 s orbital per energy level.
Maximum Electrons: Can hold up to 2 electrons.
The size of the s orbital increases with increasing n, meaning that 1s is smaller than 2s, 2s is smaller than 3s, and so on.
- p Orbitals:
Shape: egg-shaped lobes
Principal Quantum Number (n): Present starting from the second energy level (n = 2, 3, 4,…).
Azimuthal Quantum Number (ℓ): ℓ = 1.
Number of Orbitals: 3 p orbitals (denoted as px, py, and pz) in each energy level starting from n = 2.
Maximum Electrons: Each p orbital can hold 2 electrons, so the total for all three p orbitals is 6 electrons.
The p orbitals are oriented along the three Cartesian axes (x, y, and z) and have a node at the nucleus.
- d Orbitals:
Shape: More complex; four of the five d orbitals have cloverleaf shapes, and one (dz²) is shaped like a doughnut with a ring around the center.
Principal Quantum Number (n): Present starting from the third energy level (n = 3, 4, 5,…).
Azimuthal Quantum Number (ℓ): ℓ = 2.
Number of Orbitals: 5 d orbitals (denoted as dxy, dyz, dxz, dx²-y², and dz²).
Maximum Electrons: Each d orbital can hold 2 electrons, so the total for all five d orbitals is 10 electrons.
d orbitals become important for transition metals, and they play a key role in bonding and magnetic properties.
- f Orbitals:
Shape: Even more complex than d orbitals, with intricate, multilobed shapes.
Principal Quantum Number (n): Present starting from the fourth energy level (n = 4, 5, 6,…).
Azimuthal Quantum Number (ℓ): ℓ = 3.
Number of Orbitals: 7 f orbitals.
Maximum Electrons: Each f orbital can hold 2 electrons, so the total for all seven f orbitals is 14 electrons.
f orbitals are significant for the chemistry of the lanthanides and actinides (rare earth elements).
Key Differences Between the Types of Orbitals:
Orbital Azimuthal Shape Number Maximum First Energy
Quantum of Electrons Level Number (ℓ) Orbitals Present
s 0 Spherical 1 2 n = 1
p 1 Dumbbell 3 6 n = 2
d 2 Cloverleaf 5 10 n = 3
f 3 Complex lobes 7 14 n = 4
Visual Representation:
s Orbital: Simple sphere around the nucleus.
p Orbital: Two lobes extending from either side of the nucleus (along the x, y, or z axis).
d Orbital: Four-lobed cloverleaf structures, except for the dz² orbital, which has a doughnut-like ring.
f Orbital: Complex multilobed shapes with no simple geometry.
Importance of Orbitals:
s Orbitals: Found in every atom and important for forming sigma bonds.
p Orbitals: Essential for forming pi bonds in molecules and contributing to molecular geometry.
d Orbitals: Critical in transition metal chemistry, complex ion formation, and magnetic properties.
f Orbitals: Important in lanthanides and actinides, affecting their unique properties and behavior in complex compounds.
Each type of orbital plays a significant role in the chemical bonding, structure, and properties of elements and compounds.
Describe the s-orbital
- accomodate max. of 2 e
- sypherically symmetrical in shape, non-directional and occur
What is a radial node?
a node is a region in space where the probability of finding an e is zero
3, egg
Describe p-orbitals
- occurs when l=1; m= -1, 0, +1; n>=2
- 3 p-orbitals
- each has 2 egg-shaped lobes on each side of the nucleus
- probability of finding e in each lobe is the same e.g degenrate orbitals (same energy level)
- Both lobes are separated by nodal plane which passes through the nucleus.
- The electron density on the plane and the nucleus is zero.
MUST DRAW!!
Draw/distinguish s and p orbitals
- draw lobes of p-orbitals and each corner of egg should be on -ve and +ve sides.
- each of the p-orbitals have 2 have 2 lobes ; eggs
- p-orbitals are on x,y,z axes.
- s orbitals look like circle on axis
Describe d-orbitals
- occurs when n>=3; l=2; m=-2,-1,0,1,2
- are dumbell shaped
- all 5 orbitals are degenerate
- Three of the d-orbitals lie in a plane bisecting the x-, y- and z-axes, the
remaining two lie in a plane aligned along the x-, y- and z-axes. - Four of the d-orbitals have four lobes each, but one has two lobes and a
collar.
lobes = eggs
Draw d-orbitals
- the orbitals :
- dxy, dxz, dyz - lobes(4) are not directly on axes but between axes mentioned i.e dxy, lobes are between x and y axes and one lobe in z axis.
- dx^2-dy^2 - 4 lobes are on x and y axes
- dz^2 - 2 lobes on z axis + a collar
Describe f-orbital shapes
- occur when n>= 4; l=3; m=-3,-2,-1,0,1,2,3
- 7 types of f-orbitals
- …
- ## take 14 e
State Pauli Exclusion Principle
no electrons in the same atom have the same 4 quantum nubers (n,l,m,ms).It follows that each orbital can occupy a maximum of 2 e with different ms values
Describe Aufbau Principle(building up principle)
each added e occupies a higher energy sub-shells only after the lower energy sub-shells are fully filled.
Describe Hund’s rule
single e with the same spin occupy an equal-energy orbital before additional electrons of opposite spins occupy the same orbital
eg if the electrons are 8 (4 go to s orbitals 2 pairs in different spins), the last 4 go to p-orbitals in one direction of spin
probability, wave function, forces,positions and velocities
Differentiate the definition of a sytem based on classical mechanics and quantum mechanics
- in classical mechanics, a system is defined by specifying all the forces acting on it, the positions and the velocities.
- quantum mechanics defines a system by the wave function.
- knowledge of q.m invloves probabilities rather than certainties.
Derive de Broglie’s wavelength equation
- De Broglie’s theory assumed that all small particles like e, protons, neutrons and atoms when in motion posses wave properties like wavelengh, amplitude and frequency.
wavelength = h/mc = h/mv
From Einstein’s equation, E = cp
From Planck’s constant, E = hv
… E = hc/wavelength
E/c= h/wavelength
p = h/wavelength
From Planck’s equation, E=hv
From Einstein’s equation, E=mc^2
mc^2 = hv = hc/wavelength
mc^2=hc/wavelength
mc=h/wavelength
wavelength = h/mc
wavelength = h/mc=h/mv
Describe Heisenberg uncertainity principle
- Heisenberg proposed that it is impossible to accurately determine the position and momentum of a very small particle simultaneously.If one was to observe a smnall particle like an electron, they’d have to irradiate it with light.The collision between the photon and the particle causes a change in the position and the momentum of the particle.
What is Heisenberg’s expression?
Δx * Δp >= h/4π
or
Δx * Δmv >= h/4π
Derive Schrodinger wave function
What are the conclusions/implications of De Broglie’s equation?
- everything in nature exhibits wave and particle properties.
- large objects mostly show particle-like behavior.
- small objects exhibit wave particles mostly.
Differentiate between a shell and sub-shell
A shell and a sub-shell are terms used in atomic structure to describe the arrangement of electrons around the nucleus of an atom. Here’s how they differ:
Shell:
- A shell refers to the main energy level of an atom and is denoted by the principal quantum number, ( n ) (e.g., ( n = 1, 2, 3, ) etc.).
- It represents the general region where electrons are likely to be found at a certain distance from the nucleus.
- Shells are labeled as ( K, L, M, N ), corresponding to ( n = 1, 2, 3, 4, ) respectively.
- Example: The first shell (( n = 1 )) is closest to the nucleus and has the lowest energy.
Sub-shell:
- A sub-shell refers to a subdivision of a shell and is defined by the azimuthal quantum number, ( l ), which determines the shape of the orbital within a shell.
- Sub-shells are labeled as ( s, p, d, f, ) corresponding to ( l = 0, 1, 2, 3 ), respectively.
- Each shell can contain one or more sub-shells depending on the value of ( n ).
- For example:
- ( n = 1 ) has one sub-shell: ( 1s ).
- ( n = 2 ) has two sub-shells: ( 2s ) and ( 2p ).
- ( n = 3 ) has three sub-shells: ( 3s, 3p, ) and ( 3d ).
Key Difference:
- Shell defines the energy level of an electron, while sub-shell specifies the type and shape of the orbital within that energy level.
Summary:
- Shell: Broad region defined by ( n ), e.g., ( n = 2 ) (L-shell).
- Sub-shell: Subdivision within a shell defined by ( l ), e.g., ( 2s, 2p ).
The energy of orbital is determined by the n+l rule.Define the rule?
1) Orbital having lower value of n+l will have lower energy e.g. 2s< 2p.
2) Orbitals having similar (n+l) values, the orbital with lower value of n
will have lower energy eg. 3p<4s.
List 2 methods of identifying elements
- flame test
- spectroscopy
emr,matter
Define :
1. Spectroscopy
2. Spectroscope
1.The study of interaction between emr and matter
2.A device used to study the group of wavelengths of light given off by an element
energy,electric and magnetic field?propagation?
what is electromagnetic radiation?
This is a stream of energy moving in the direction of propagation and perpendicular to electric and magnetic field.
What are the properties of electromagnetic radiation?
- do not require a medium to travel
- travel with the velocity of light, c
- have dual nature - exhibit particle and wave-like properties
- it has electric and magnetic components that travel perpendicular to each other and perpendicular to the direction of propagation.
Define(giving their SI units and symbols):
1.Wavelength
2.Frequency
3.Wave number
4.Velocity
- Wavelength (symbol = λ pronounced as “lambda”)(m)
- distance between two consecutive peaks in a wave.
2.Frequency(symbol = ν , pronounced as “nu”)(Hz =1/s)
- number of waves/cycles passing through a point on the x-axis per second.
- velocity (symbol = c)(m/s)
- velocity of light = 3 x 10^8 m/s
C = λ ν ……………………….Eq. 1
λ = c/ ν and ν = c/ λ …..Eq. 2
4.wave number(symbol ν , pronounced as nu bar)(m^-1)
- the reciproval of wavelength
ν = 1/ λ = ν/c ………………………..Eq. 3
What are the different types of emr?
1.Gamma rays
2.X-rays
3.UV Rays
4.Visible Light
5.Infrared rays
6.Microwaves
7.Radio waves
What are the different types of atomic and molecular transitions of emr?
1.Gamma rays - nuclear
2.X-rays - core-level electrons
3.UV Rays - valence electrons
4.Visible Light - valence electrons
5.Infrared rays - molecular vibrations
6.Microwaves - molecular rotations ; electron spin
7.Radio waves - nuclear spin
The interaction of electromagnetic radiation (EMR) with atoms and molecules causes transitions between different energy levels. These atomic and molecular transitions are classified based on the nature of the energy levels involved. Below are the main types of transitions:
1. Electronic Transitions
- What Happens: Electrons in an atom or molecule move between different electronic energy levels.
- Energy Requirement: High energy, typically in the UV or visible region.
- Examples:
- Absorption or emission of light in hydrogen atoms (Lyman, Balmer series).
- Excitation of electrons in pigments causing color.
2. Vibrational Transitions
- What Happens: Molecules change their vibrational energy state, often within the same electronic energy level.
- Energy Requirement: Moderate energy, typically in the infrared (IR) region.
- Examples:
- Infrared absorption spectroscopy (e.g., CO(_2) or H(_2)O detecting IR radiation).
- Molecules stretching and bending.
3. Rotational Transitions
- What Happens: Molecules transition between different rotational energy levels.
- Energy Requirement: Low energy, typically in the microwave region.
- Examples:
- Rotational spectroscopy in gases (e.g., water vapor, ammonia).
4. Spin Transitions
- What Happens: Changes in the orientation of particle spins (electrons, nuclei) relative to a magnetic field.
- Energy Requirement: Very low energy, typically in the radiofrequency region.
- Examples:
- Nuclear Magnetic Resonance (NMR) spectroscopy.
- Electron Spin Resonance (ESR) spectroscopy.
5. Ionization Transitions
- What Happens: An electron gains enough energy to escape the atom or molecule completely, leading to ionization.
- Energy Requirement: Very high energy, typically in the X-ray or UV region.
- Examples:
- Photoionization in X-ray absorption.
- Ionization of gases in electric discharges.
6. Molecular Orbital Transitions
- What Happens: Electrons transition between molecular orbitals, such as (\pi \rightarrow \pi^) or (n \rightarrow \pi^).
- Energy Requirement: Typically in the UV or visible region.
- Examples:
- UV-Visible spectroscopy used to analyze conjugated systems in organic molecules.
7. Inner-Shell Electronic Transitions
- What Happens: Electrons from inner shells (e.g., (K)-shell) are excited to higher energy levels.
- Energy Requirement: High energy, typically in the X-ray region.
- Examples:
- X-ray fluorescence (XRF) spectroscopy.
- Auger electron emission.
These transitions provide the basis for various spectroscopic techniques, each targeting specific energy levels to analyze the structure, composition, and dynamics of atoms and molecules.
What is an electromagnetic radiation spectrum?
- it is the entire range of electromagnetic radiations separated into different frequencies and wavelengths
briefly describe the properties of emr and their application
Properties of Electromagnetic Radiation and Applications
1. Rotational, Vibrational, and Electronic Spectroscopy
- Key Interaction:
- In these types of spectroscopy, the electric field component of electromagnetic radiation interacts with the molecular system.
- This interaction can induce changes in rotational, vibrational, or electronic energy levels of the molecule.
- Mechanism:
- The molecule absorbs radiation when the energy of the radiation matches the energy difference between two allowed energy levels.
- The absorption results in molecular transitions, such as:
- Rotational transitions in the microwave region.
- Vibrational transitions in the infrared (IR) region.
- Electronic transitions in the visible and ultraviolet (UV) regions.
- Applications:
- Rotational Spectroscopy: Identifies molecular structure and bond lengths.
- Vibrational Spectroscopy (e.g., IR spectroscopy): Determines functional groups in organic compounds.
- Electronic Spectroscopy (e.g., UV-Vis): Studies conjugated systems, molecular orbitals, and color in substances.
2. Electron Paramagnetic Resonance (EPR) and Nuclear Magnetic Resonance (NMR) Spectroscopy
- Key Interaction:
- In these techniques, the focus is on the magnetic field component of electromagnetic radiation interacting with magnetic properties of particles (electrons or nuclei).
- This is distinct from rotational, vibrational, and electronic spectroscopy, which rely on electric field interactions.
- Mechanism:
- EPR: Studies unpaired electron spins. A magnetic field aligns the electron spins, and microwave radiation causes transitions between spin states.
- NMR: Examines nuclei with a magnetic moment (like ( ^1H ) or ( ^13C )). A strong external magnetic field causes nuclei to align, and radiofrequency radiation induces transitions between nuclear spin states.
- Applications:
- EPR Spectroscopy:
- Analysis of free radicals and transition metal complexes.
- Studies of paramagnetic species in biological and chemical systems.
- NMR Spectroscopy:
- Structural determination of organic compounds and biomolecules.
- Quantitative analysis and studying molecular dynamics in chemistry and medicine (e.g., MRI imaging in clinical diagnostics).
Summary of Key Differences
- Electric Field Interaction: Used in rotational, vibrational, and electronic spectroscopy to induce transitions based on energy differences between molecular levels.
- Magnetic Field Interaction: Used in EPR and NMR spectroscopy to study spin dynamics and magnetic properties of particles.
Both approaches provide complementary insights into molecular and atomic systems.