GENERAL CHEMISTRY 1 LECTURE UNIT No.

3
(ELECTRONIC STRUCTURE OF ATOM)

Engr. Edgie L. Estopace School of Chemical Engineering and Chemistry Mapua Institute of Technology
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CONTENT
1. 2. 3. 4. 5. 6. 7. Quantum Theory Photoelectric effect Bohrs Theory Dual Nature of the Electrons Quantum Mechanics Quantum Numbers Electronic Configuration

The Electromagnetic Spectrum

Visible light is a small portion of the electromagnetic radiation spectrum detected by our eyes. Electromagnetic radiation includes radio waves, microwaves and X-rays. Described as a wave traveling through space. There are two components to electromagnetic radiation, an electric field and magnetic field.

The Wave Nature of Light

Wavelength, , is the distance between two corresponding points on a wave. Amplitude is the size or height of a wave. Frequency, , is the number of cycles of the wave passing a given point per second, usually expressed in Hz.

Plancks Quantum Theory

Higher T = shorter (higher E) maximum.
Couldnt explain with classical physics. As T , the wavelength of maximum intensity shifts toward the blue

Plancks Quantum Theory

Classical theory:

no restriction on the E emitted by hot atoms. didnt fit experimental data. Planck: atoms emit E in packets (E is quantized) each packet has a minimum energy a quantum of energy Equantum = h radiation = hc/radiation (h = Plancks constant = 6.626x10-34 J s)

The Wave Nature of Light

The fourth variable of light is velocity.

All light has the same speed in a vacuum.

c = 2.99792458 x 108 m/s The product of the frequency and wavelength is the speed of light.

c
Frequency is inversely proportional to wavelength.

The Wave Nature of Light

Refraction is the bending of light when it passes from one medium to another of different density. Speed of light changes. Light bends at an angle depending on its wavelength. Light separates into its component colors.

The Wave Nature of Light

Electromagnetic radiation can be categorized in terms of wavelength or frequency. Visible light is a small portion of the entire electromagnetic spectrum.

Example Problem 6.1

Neon lights emit an orange-red colored glow. This light has a wavelength of 670 nm. What is the frequency of this light?

The Particulate Nature of Light

Photoelectric effect: light striking a metal surface generates photoelectrons. The lights energy is transferred to electrons in metal. With sufficient energy, electrons break free of the metal.

Electrons given more energy move faster (have higher kinetic energy) when they leave the metal.

The Particulate Nature of Light

Photoelectric effect is used in photocathodes. Light strikes the cathode at frequency . Electrons are ejected if exceeds the threshold value 0. Electrons are collected at the anode. Current flow is used

Photoelectric Experiments
a) For > 0, the number of electrons emitted is independent of frequency. Value of 0 depends on metal used. b) As light intensity increases, the number of photoelectrons increases. c) As frequency increases, kinetic energy of emitted electrons increases linearly. d) The kinetic energy of emitted electrons is independent of light

The Particulate Nature of Light

The photoelectric effect is not explained using a wave description but is explained by modeling light as a particle. Wave-particle duality - depending on the situation, light is best described as a wave or a particle. Light is best described as a particle when light is imparting energy to another object. Particles of light are called photons. Neither waves nor particles provide an accurate description of all the properties of light. Use the model that best describes the properties being examined.

The Particulate Nature of Light

The energy of a photon (E) is proportional to the frequency ( ). and is inversely proportional to the wavelength ( ). h = Plancks constant = 6.626 x 10-34 J s

hc

Example Problem 6.2

The laser in a standard laser printer emits light with a wavelength of 780.0 nm. What is the energy of a photon of this light?

The Particulate Nature of Light

Binding Energy - energy holding an electron to a metal. Threshold frequency, o - minimum frequency of light needed to emit an electron. For frequencies below the threshold frequency, no electrons are emitted.

For frequencies above the threshold frequency, extra energy is imparted to the electrons as kinetic energy.
Ephoton = Binding E + Kinetic E

This explains the photoelectric effect.

Example Problem 6.3

In a photoelectric experiment, ultraviolet light with a wavelength of 337 nm was directed at the surface of a piece of potassium metal. The kinetic energy of the ejected electrons was measured as 2.30 x 10-19 J. What is the electron binding energy for potassium?

Atomic Spectra
Atomic Spectra: the particular pattern of wavelengths absorbed and emitted by an element. Wavelengths are well separated or discrete.

Wavelengths vary from one element to the next.

Atoms can only exist in a few states with very specific energies. When light is emitted, the atom goes from a higher energy state to a lower energy state.

Atomic Spectra

Electrical current dissociates molecular H2 into excited atoms which emit light with 4 wavelengths.

Atomic Spectra and the Bohr Atom

Every element has a unique spectrum. Thus we can use spectra to identify elements. This can be done in the lab, stars, fireworks, etc.

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The Bohr Atom

Bohr model - electrons orbit the nucleus in stable orbits. Although not a completely accurate model, it can be used to explain absorption and emission. Electrons move from low energy to higher energy orbits by absorbing energy. Electrons move from high energy to lower energy orbits by emitting energy. Lower energy orbits are closer to the nucleus due to electrostatics.

The Bohr Atom

Excited state: grouping of electrons that is not at the lowest possible energy state. Ground state: grouping of electrons that is at the lowest possible energy state. Atoms return to the ground state by emitting energy as light.

Atomic Spectra and the Bohr Atom

The Rydberg equation is an empirical equation that relates the wavelengths of the lines in the hydrogen spectrum.

1 R 2 n1

1 n2 2

R is the Rydbergconstant R 1.097 107 m -1 n1 n 2 ns refer to the numbers of the energylevelsin the

emissionspectrum hydrogen of
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Atomic Spectra and the Bohr Atom

SP3. What is the wavelength of light emitted when the hydrogen atoms energy changes from n = 4 to n = 2?

n 4 and n1 2 n 22 4 and n1n 2 2 4 and n1 2 1 1 1

1 1 11 1 R 12 R n 2 n22 R n 2 1 n1 n 2
1 2

1 2 n2 1 2 4

1 7 -1 1 71 -1 1 1.097 10 m 1.097 2 10 2m 2 2 4 2 1 1.097 10 m

7 -1

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1 1 4 16

Atomic Spectra and the Bohr Atom

In 1913 Neils Bohr incorporated Plancks quantum theory into the hydrogen spectrum explanation. Here are the postulates of Bohrs theory.
1.

Atom has a number of definite and discrete energy levels (orbits) in which an electron may exist without emitting or absorbing electromagnetic radiation.
As the orbital radius increases so does the energy 1<2<3<4<5......

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Atomic Spectra and the Bohr Atom

2. An electron may move from one discrete energy level (orbit) to another, but, in so doing, monochromatic radiation is emitted or absorbed in accordance with the following equation.
hc

E 2 - E1 E2

E E1

Energy is absorbed when electrons jump to higher orbits. n = 2 to n = 4 for example Energy is emitted when electrons fall to lower orbits. n = 4 to n = 1 for example 27

Atomic Spectra and the Bohr Atom

3. An electron moves in a circular orbit about the nucleus and it motion is governed by the ordinary laws of mechanics and electrostatics, with the restriction that the angular momentum of the electron is quantized (can only have certain discrete values).
angular momentum = mvr = nh/2 h = Plancks constant n = 1,2,3,4,...(energy levels) v = velocity of electron m = mass of electron r = radius of orbit

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Atomic Spectra and the Bohr Atom

Light of a characteristic wavelength (and frequency) is emitted when electrons move from higher E (orbit, n = 4) to lower E (orbit, n = 1). This is the origin of emission spectra.

Light of a characteristic wavelength (and frequency) is absorbed when electron jumps from lower E (orbit, n = 2) to higher E (orbit, n= 4) This is the origin of absorption spectra.

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Atomic Spectra and the Bohr Atom

Bohrs theory correctly explains the H emission spectrum. The theory fails for all other elements because it is not an adequate theory.

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The Wave Nature of the Electron

In 1925 Louis de Broglie published his Ph.D. dissertation. h A crucial element of his dissertation is that electrons have wave-like properties. mv The electron wavelengths are described by the h de Broglie relationship. Planck s constant

m mass of particle v
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velocity of particle

The Wave Nature of the Electron

De Broglies assertion was verified by Davisson & Germer within two years. Consequently, we now know that electrons (in fact all particles) have both a particle and a wave like character. This wave-particle duality is a fundamental property of submicroscopic particles.

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The Wave Nature of the Electron

Example 5-9. Determine the wavelength, in m, of an electron, with mass 9.11 x 10-31 kg, having a velocity of 5.65 x 107 m/s.
Remember Plancks constant is 6.626 x 10-34 Js which is also equal to 6.626 x 10-34 kg m2/s2.

h mv 34 2 2 6.626 10 kg m s -3 1 7 9.11 10 kg 5.65 10 m/s 1.29 10

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The Wave Nature of the Electron

SP4. Determine the wavelength, in m, of a 0.22 caliber bullet, with mass 3.89 x 10-3 kg, having a velocity of 395 m/s, ~ 1300 ft/s. You do it! Why is the bullets wavelength so small compared to the electrons wavelength?

h mv 34 2 2 6.626 10 kg m s -3 3.89 10 kg 395 m/s 3.89

34

4.31 10

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The Quantum Mechanical Picture of the Atom

Werner Heisenberg in 1927 developed the concept of the Uncertainty Principle. It is impossible to determine simultaneously both the position and momentum of an electron (or any other small particle). Detecting an electron requires the use of electromagnetic radiation which displaces the electron!
Electron microscopes use this phenomenon

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The Quantum Mechanical Model of the Atom

Quantum mechanical model replaced the Bohr model of the atom. Bohr model depicted electrons as particles in circular orbits of fixed radius. Quantum mechanical model depicts electrons as waves spread through a region of space (delocalized) called an orbital. The energy of the orbitals is quantized like the Bohr model.

The Quantum Mechanical Model of the Atom

Diffraction of electrons shown in 1927.

Electrons exhibit wave-like behavior.

Wave behavior described using a wave function, the Schrdinger equation. H is an operator, E is energy and function. is the wave

Potential Energy and Orbitals

Total energy for electrons includes potential and kinetic energies. Potential energy more important in describing atomic structure; associated with coulombic attraction between positive nucleus and negative electrons. Multiple solutions exist for the wave function for any given potential interaction. n is the index that labels the different solutions.

Potential Energy and Orbitals

can be written in terms of two components.

Radial component, depends on the distance from the nucleus. Angular component, depends on the direction or orientation of electron with respect to the nucleus.

Potential Energy and Orbitals

The wave function may have positive and negative signs in different regions. Square of the wave function, 2, is always positive and gives probability of finding an electron at any particular point. Each solution of the wave function defines an orbital. Each solution labeled by a letter and number combination: 1s, 2s, 2p, 3s, 3p, 3d, etc. An orbital in quantum mechanical terms is actually a region of space rather than a particular point.

Quantum Numbers
Quantum numbers - solutions to the functions used to solve the wave equation. Quantum numbers used to name atomic orbitals.

Vibrating string fixed at both ends can be used to illustrate a function of the wave equation.

Quantum Numbers
When solving the Schrdinger equation, three quantum numbers are used. Principal quantum number, n (n = 1, 2, 3, 4, 5, )

Secondary quantum number, l

Magnetic quantum number, ml

Quantum Numbers
The principal quantum number, n, defines the shell in which a particular orbital is found. n must be a positive integer

n = 1 is the first shell, n = 2 is the second shell, etc. Each shell has different energies.

Quantum Numbers
The secondary quantum number, l, indexes energy differences between orbitals in the same shell in an atom. l has integral values from 0 to n-1. l specifies subshell Each shell contains as many l values as its value of n.

Quantum Numbers
The energies of orbitals are specified completely using only the n and l quantum numbers. In magnetic fields, some emission lines split into three, five, or seven components. A third quantum number describes splitting.

Quantum Numbers
The third quantum number is the magnetic quantum number, ml. ml has integer values.

ml may be either positive or negative.

mls absolute value must be less than or equal to l. For l = 1, ml = -1, 0, +1

Quantum Numbers

Note the relationship between number of orbitals within s, p, d, and f and ml.

Example Problem 6.5

Write all of the allowed sets of quantum numbers (n, l, and ml) for a 3p orbital.

Visualizing Orbitals

s orbitals are spherical p orbitals have two lobes separated by a nodal plane. A nodal plane is a plane where the probability of finding an electron is zero (here the yz plane). d orbitals have more complicated shapes due to the presence of two nodal planes.

Visualizing Orbitals
Nodes are explained using the Uncertainty Principle.

It is impossible to determine both the position and momentum of an electron simultaneously and with complete accuracy.
An orbital depicts the probability of finding an electron.

The radial part of the wave function describes how the probability of finding an electron varies with distance from the nucleus. Spherical nodes are generated by the radial portion of the wave function.

Visualizing Orbitals

Cross sectional views of the 1s, 2s, and 3s orbitals.

The Pauli Exclusion Principle and Electron Configurations

The spin quantum number, ms, determines the number of electrons that can occupy an orbital. ms = 1/2

Electrons described as spin up or spin down.

An electron is specified by a set of four quantum numbers.

The Pauli Exclusion Principle and Electron Configurations

Pauli Exclusion Principle - no two electrons in an atom may have the same set of four quantum numbers. Two electrons can have the same values of n, l, and ml, but different values of ms. Two electrons maximum per orbital.

Two electrons occupying the same orbital are spin paired.

Orbital Energies and Electron Configurations

Electrons in smaller orbitals are held more tightly and have lower energies. Orbital size increases as the value of n increases.

True for hydrogen atoms, but not entirely true for multielectron atoms.
As nuclear charge increases, orbital size decreases. Electrons interact with other electrons as well as the positively charged nucleus.

Orbital Energies and Electron Configurations

For electrons in larger orbitals, the charge felt is a combination of the actual nuclear charge and the offsetting charge of electrons in lower orbitals. The masking of the nuclear charge is called shielding. Shielding results in a reduced, effective nuclear charge.

Orbital Energies and Electron Configurations

The energy ordering for atomic orbitals is 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, and 7p. An orbitals size and penetration when treated quantitatively produces the order of filling represented. Electronic configurations are written in order of energy for atomic orbitals.

Hunds Rule and the Aufbau Principle

Aufbau principle - when filling orbitals, start with the lowest energy and proceed to the next highest energy level. Hunds rule - within a subshell, electrons occupy the maximum number of orbitals possible. Electron configurations are sometimes depicted using boxes to represent orbitals. This depiction shows paired and unpaired electrons explicitly.

Example Problem 6.6

What is the electron configuration for the sulfur atom?

Hunds Rule and the Aufbau Principle

A simplified depiction uses superscripts to indicate the number of electrons in an orbital set. 1s2 2s2 2p2 is the electronic configuration for carbon. Noble gas electronic configurations are used as a shorthand for writing electronic configurations.

Relates electronic structure to chemical bonding. Electrons in outermost occupied orbitals give rise to chemical reactivity of an element. [He] 2s2 2p2 is the shorthand for carbon

Hunds Rule and the Aufbau Principle

The inner electrons, which lie closer to the nucleus, are referred to as core electrons. Core electrons can be represented by the noble gas with the same electronic configuration. The outer electrons are usually referred to as valence electrons. Valence electrons are shown explicitly when a noble gas shorthand is used to write electronic configurations. Valence electrons determine reactivity.

Example Problem 6.7

Rewrite the electron configuration for sulfur using the shorthand notation.

The Periodic Table and Electron Configurations

The periodic table and the electronic configurations predicted by quantum mechanics are related. The periodic table is broken into s, p, d, and f blocks. Elements in each block have the same subshell for the highest electron. Structure of periodic table can be used to predict electronic configurations.

The Periodic Table and Electron Configurations

The shape of the periodic table can be broken down into blocks according to the type of orbital occupied by the highest energy electron in the ground state. We find the element of interest in the periodic table and write its core electrons using the shorthand notation with the previous rare gas element. Then we determine the valence electrons by noting where the element sits within its own period in the table.

Electron Configurations of Transition Metals

4th period and heavier elements
Pick the noble-gas core. Add ns Add (n 1)d (d steps down) Add np

Sn (5th period, group 4A). Noble-gas core: [Kr]

Complete 5s and 4d. 2 e- into 5p: [Kr] 4d10 5s2 5p2

Electron Configurations of Transition Metals

Tc (5th; 7B; 5 einto 4d) [Kr] 4d5 5s2

Ni (4th; 8B; 8 e- into 3d)

[Ar] 3d8 4s2

Cu (4th; 1B; 9 e- into 3d)

Cu has lower E with filled dblock and half-filled s-block

[Ar] 3d9 4s2

[Ar] 3d10 4s1

Electron Configurations of Transition Metals

Cr Mn Cu Zn Sc Ti V Fe Co Ni 2 2 2 3d 3d 3d 3d1 4s3d2 4s3d3 4s2 5 4s13d5 4s3d6 4s2 7 4s2 8 4s2 10 4s1 10 4s2 3d 3d
Mo Tc Pd Ag Cd Nb Ru Rh Y Zr 2 2 2 4d 4d 4d 4d1 5s4d2 5s4d4 5s1 5 5s14d5 5s4d7 5s1 8 5s1 4d10 4d10 5s1 10 5s2 Re Au Hg La Hf Ta W Os Ir Pt 2 2 2 2 5d 5d 5d 5d1 6s5d2 6s5d3 6s5d4 6s2 5 6s5d6 6s2 7 6s2 9 6s1 10 4s1 10 6s2 5d 5d

Note: filled and filled shells have extra stability

Ion Electron Configurations

Same approach. Positive ion: remove one e- for each + Negative ion: add one e- for each -

S2- (16 + 2) = 18 eS [Ne] 3s2 3p4 S2- [Ne] 3s2 3p6

Rb+ (37 - 1) = 36 eRb [Kr] 5s1 Rb+ [Kr] or

or

[Ar]

[Ar] 3d10 4s2 4p6

Ion Electron Configurations

Isoelectronic = equal number of e-.

A-group ions usually adopt the nearest noble-gas configuration many ions are isoelectronic.

[He] 2s2 2p6 [Ne] 3s2 3p6

O2S2-

FCl-

Ne Ar

Na+ Mg2+ Al3+ K+ Ca2+

Transition Metal Ions

When filled, Ens > E(n -1)d . ns e- are lost first.

Fe

[Ar] 3d6 4s2

Fe2+
Fe3+

[Ar] 3d6
[Ar] 3d5 [Ar] 3d5 [Ar] 3d3 [Ar]

Mn

[Ar] 3d5 4s2 Mn2+ Mn4+ Mn7+

Example Problem 6.8

Use the periodic table to determine the electron configuration of tungsten (W), which is used in the filaments of most incandescent lights.

End of Lecture Unit No. 3

The study of various spectra is one of the fundamental tools that chemists apply to numerous areas of their work.

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CONTENT
1. 2. 3. 4. 5. 6. 7. Quantum Theory Photoelectric effect Bohrs Theory Dual Nature of the Electrons Quantum Mechanics Quantum Numbers Electronic Configuration

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GENERAL CHEMISTRY 1 LECTURE UNIT No. 3

(ELECTRONIC STRUCTURE OF ATOM)

Engr. Edgie L. Estopace School of Chemical Engineering and Chemistry Mapua Institute of Technology
73