Chapter 1 Electronic Configuration of Atoms 1.1 The Fundamental Particles 1. What are the fundamental particles in an atom?

Particle Proton Neutron Electron Relative Mass 1 a.m.u 1 a.m.u 1/1840 a.m.u Relative Charge +1 0/neutral -1

2. Proton number (atomic number) of an element is the number of proton in the nucleus of an atom 3. Nucleon number (mass number) of an element is the total number of proton and neutron in the nucleus of an atom 4. Isotopes refer to the atoms of the same element with the same proton number but different nucleon number. 5. Isotopy refers to the phenomenon of which atoms of same elements with same proton number but different nucleon number.

1.2

The Atomic Hydrogen Spectrum and Bohr’s Theory
1. Explain how hydrogen line spectrum is obtained? When an electrical discharge is passed through hydrogen gas at low pressure, a pink glow is observed. On examining with a spectroscope, a line spectrum is obtained. The spectrum consists of few series of DISCRETE LINES. Each line represents radiation of definite wavelength. According to Bohr, the electron in a hydrogen atom moves around the nucleus in a fixed energy level/shell. The energy of the electron in an atom must be quantized, given principal quantum numbers (n=1,2,3 or K,L,M) and starting from nucleus. Under normal conditions, the electron occupies the lowest energy level, the ground state(n=1) for the hydrogen atom. No energy is radiated by electrons at this state. When an atom is excited by absorbing energy (electric discharge/heat) the electron jumps to a higher energy level, the excited state. The excited state is, however, an unstable state and there is a strong tendency for the electron to get rid of its extra energy and returns to the ground state. This return may take place in one or more steps. When an electron undergoes a transition from a higher energy state to a lower energy state. A radiation is Planck’s Equation ∆E α f ∆E = hf emitted and the frequency of the radiation is given by Planck’s Equation. ∆E - energy difference between 2 shells h = Planck’s constant f = frequency of radiation (c/λ) In a discharge tube containing millions of hydrogen atoms, the individual atoms are excited to different extents and electronic transitions of many kinds are taking place giving rise to many lines in the spectrum. All transitions from higher energy levels to level n=1, emit radiation with frequency in ultraviolet (uv) region to form the Lyman Series whereas those to the level n=2 form Balmer series in visible light region The lines in the series becomes closer with increasing frequency and eventually form a continuous band of light known as the convergence limit. This shows that the difference in energy between successive energy levels becomes smaller with increasing distance from the nucleus

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2. Sketch an energy diagram to show electronic transitions which give rise to the first 5 lines in the Balmer Series of the hydrogen spectrum.

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Labeled energy axis and 7 energy levels. At least 7 energy levels which become closer with increasing distance from the nucleus. At least 5 electronic transitions to level n=2 with arrow Corresponding electronic transitions and line in the Balmer Series.

3.

3. Rydberg’s Equation

c=fλ….substitute to find frequency

4. The values of nf and ni for the different series of lines are shown :

Series Lyman Balmer Paschen Brackett Pfund

nf 1 2 3 4 5

ni 2,3,4…. 3,4,5…. 4,5,6…. 5,6,7… 6,7,8….

Region in EM spectrum Ultraviolet Visible Infrared Infrared Infrared

5. Given Hydrogen spectrum, Ionisation energy of hydrogen ∆E = hfNA 1000 **Frequency refers to the frequency of last line ** Unit in kJ/mol

The convergence limit corresponds to the point at which the energy of an electron within the electron within the atom is no longer quantized. At this point, the nucleus has lost influence over the electrons, the atom has become ionized. For the Lyman series, the convergence limit : H (g) → H+ (g) + ē 6. The convergence limit in the Lyman Series of the atomic hydrogen spectrum has a wavelength of 91.4 nm. Calculate the ionization energy of hydrogen.

7. The frequency for the first 6 lines in the Lyman Series of the hydrogen spectrum are 24.66, 29.23, 30.83, 31.57,32.21 (x 1014) The Rydberg Equation is

Based on the information given, plot a graph to determine the ionization energy of hydrogen.

F 24.66 29.23 30.83 31.57 31.97 32.21 From the graph, f0 is

n2 2 3 4 5 6 7

n22 4 9 16 25 36 49

1/ n22

Ionisation Energy =

1.3

Successive ionization energies and the electrons distribution When an atom with several electrons is provided with sufficient energy, the second, third, forth, electron can be released from the atom. The successive ionization energies provided information about the arrangement of electrons in the atom The graph shows the successive ionization energies of sodium.

What deductions could be made ? 1. 2. 3. 4. Sodium atom consists of 11 electrons The electrons are arranged in 3 shells The electronic configuration of sodium is 2.8.1 There is a large difference between the first and second (ninth and tenth) ionization energies because the second (tenth) electron comes from an inner shell which is nearer to the nucleus and thus is more strongly held by the nucleus. 5. The successive ionization energies increase because the net positive charge on the ion increases and thus the attractive force of the nucleus on the remaining electrons becomes stronger.

1.4

Sub-Levels In Higher Atoms And Atomic Orbitals 1. Further studies of emission spectra of atoms showed that many of the lines are not consist of single lines but two or more lines close together. This showed that within a given energy level there exist sub-levels. Theoretically, in a given quantum shell there are n possible sub-levels where n is the principal quantum number. Thus, in the first main energy level there is only one sub-level, the second two, the third three and the forth four. The various sub-level are indicated by the letters s,p,d and f. 2. The number of subshell in a given shell is as shown :

3. So, electron regarded not as traveling round the nucleus in a fixed path It occupies a region. What is orbital? Orbital is the region in space around the nucleus where there is high probability of finding an electron. 4. Orbitals are as shown.

*s-orbital *p-orbital

: spherical : dumb-bell

*x,y,z axes are perpendicular to each other. *The number of electrons in each shell is given as 2n2.

1.5

Electronic Configuration of Atoms

There are three rules that determine the way in which electrons in an atom may be distributed. a. Aufbau Principle Electrons fill the orbitals in the order of increasing energy, electrons accommodate orbitals of lowest energy first.
The order of occupancy of atomic orbitals :

b. Pauli Exclusion Rule Only two electrons can occupy the same atomic orbital and in order to do so, there must have opposite spin. (anti-parallel) c. Hund’s Rule When electrons are added successively to a set of orbitals of the same energy (p-orbitals or d-orbitals), the orbitals will first fill with one electron each with parallel spins before a second electron is added with opposite spin.

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