Chapter 6 & 7

Atomic Structure and Periodicity

Amplitude

Speed of light = 3.0 x 108 m/s = c

Light is an electromagnetic wave.

l = c / n - This is the relationship between the wavelength and frequency

The distance between the peaks is called the wavelength (l) lambda. The amount of peaks per second is called the frequency (n) nu.

Higher Energy

Lower Energy

Wavelength of Visible Light in nanometers

The Rutherford-Bohr Atom

If the nucleus of the atom is positively charged, then why arent the electrons pulled into the nucleus of the atom?
Rutherford and Bohr came up with the idea that electrons orbit the nucleus similar to the way that the earth orbits the sun. The Rutherford-Bohr model of the atom is therefore called the planetary atomic model.

But the Orbits Are Quantized

Planck said that the orbitals were quantized

In order for an electron to move between quantized energy levels (ns), a quantized amount of energy must be added to an atom or given off. This quantized energy is equal to the difference between the energies of the final (nf) and initial levels (ni): DE = Ef - Ei

Quantized energy levels in hydrogen

Bohrs Model of the Hydrogen Atom

We know that in order for an electron to jump between each ring level atoms must be supplied the quantized amount of energy that is equal to the differences in the energy levels (DE= Efinal Einitial), but how do we calculate the amount of energy that each ring energy level (ns) is equal to in order to plug them into the above equation? Using Bohrs Equation below, we can calculate the energy values associated with each ring level (known as n) in a hydrogen atom:

En = (-RH) (1/n2)
Where RH = the Rydberg constant = 2.18 x 10-18J. n = the principle quantum # / energy shell level/ ring level
(This equation will be given to you on a test or on the AP exam) On the AP Exam they combine it together and the equation looks like:

En = -2.178 x 10-18 J / n2

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Einstein used the Photoelectric Effect to show us that the quantized amount of energy that is given off or absorbed by an atom (to move an electron between energy levels n or to completely eject an electron from an atom) is called a photon which are particles of light that move in wavelike functions. Einstein deduced that each photon possess a quantum of Energy, given by the equation:

Ephoton = hn
h= plancks constant=6.6251 x 10-34 J x sec
The energy of a photon of light is directly proportional to its frequency!

The Energy of a Photon of light emitted/absorbed as the electron undergoes a transition:

You can now plug Bohrs Equation En = (-RH) (1/n2) into DE= Efinal Einitial to get the quantized amount of energy necessary to move the electron between specific energy levels ns. You get the following equation:

DE = RH (1/ni2 - 1/nf2)
The change in the energy from different energy levels, ns, is equal to the energy of a specific photon of light!

DE = Ephoton = hv.
Therefore, to calculate the energy of a photon emitted/absorbed as the electron undergoes a transition from the ni level to the nf level we combine the above two equations to get:
DE = hv = RH (1/ni2 - 1/nf2)

Atomic Excitation and De-excitation

Excitation by absorption of light and de-excitation by emission of light

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de Broglies Wave-Particle Duality of Nature

de Broglie said that all waves act like particles and all particles act like waves. A specific example of this is light. Light acts like waves in that it is part of the electromagnetic energy spectrum and behaves like a wave. Light also acts like a particle in that it can be quantized. A specific amount of light is considered to be a photon, which will excite an electron inside of an atom into a higher state. This is all proved in the emission spectrum of atoms.

Electron Behavior
Electrons also follow de Broglies Wave-Particle Duality of Nature, just like light does. Electrons act like particles and they also act like waves. They act like particles because they are quantized and there is always a certain specific number of electrons that exist. You can not have half of an electron, therefore they are quantized and they act like particles. They also act like waves because they exist as wavelike patterns around the nucleus of an atom. There are specified areas that the wave of an electron can exist in, these areas are called orbitals.

The relationship between the circumference of an allowed orbital (2pr) and the wavelength of the electron is given by: 2pr = nl Where r = the radius of the orbit from the nucleus, l = the wavelength of the electron wave and n = 1, 2, 3integer number(s) of wavelengths.

Allowed Orbit

Therefore the size of the orbit, or r, must be quantized and only specific orbitals for electrons can exist.

Nonallowed Orbit

The Heisenberg Uncertainty Principle

Heisenberg stated that it is impossible to know the exact position and momentum of an object at the same time. This is because in order for us to locate the exact position of an electron, a photon of energy must hit the electron in order for us to visualize the light. This is an impossible thing to do with an electron because once an electron is hit with a photon of energy, then it will have a different amount of energy and its velocity and momentum will change. Instead, we simply say that there is a probability that the electron can be found in a certain region in space around the nucleus of an atom. (Calculated by the Schrodinger equation where the probability is proportional to the wave function squared y2 (psi) of the electron). This is known as Quantum Mechanics or wave mechanics.

Quantum Mechanics
In quantum mechanics, four quantum numbers are required to describe the distribution of electrons in the atom.
(1) The Principal Quantum Number (n) They are integral values: 1, 2, 3 that correspond to the energy of an orbital. It also relates to the distance of the electron from the nucleus. The larger n is, the greater the distance of the electron from the nucleus. Also, the greatest number of electrons possible in any one level of n is equal to 2n2. For example: if n=4 then 2(4)2 = 32 electrons can be in the 4 principal quantum number.

The Angular Momentum Quantum Number (l)

(2) The angular momentum quantum number (l)
Tells us the shape of the orbital. The values of (l) depend on the value of the principal quantum number, n. For a given value of n, l has possible integral values from 0 to (n-1). l = 0 to (n-1) Example: If n = 1, then l = 0 to (n-1) = 0 = l . If n = 2, then l = 0 to (n-1) = 0 to (2-1) = 0 and 1 = l The value of l is designated by the following letters:

Name of Orbital

Shells and Subshells

A collection of orbitals with the same value of n = the principal energy level is frequently called a shell. Subshells have different shapes and are referred to by the letters s, p, d, or f. The subshells of the 2 shell are therefore called the 2s and 2p subshells. The subscripts for subshells tell you where the orbitals lie on the x, y and z axis in 3D

The Magnetic Quantum Number (ml)

(3) The Magnetic Quantum Number (ml)
Describes the orientation of the orbital in space within a subshell. (This is the denotation of x, y and z in the subscript, such as: 2px, 2py, 2pz). The value of ml depends on the value of the l.

For every value of l, there are (2 l + 1) integral values of ml as follows (- l to + l ): - l, (- l + 1), 0, (+ l 1), + l Example: if l = 2 then ml = -2, -1, 0, 1, 2.

The Electron Spin Quantum Number (ms)

(4) The Electron Spin Quantum Number (ms) Describes the spin of the electron. The value of ms = either + ( ) or - ( ) Each orbital can hold two electrons in it of opposite spins. An example of this would be that the 1s orbital can hold a + and a electron for a total of 2 electrons in the 1s orbital. This also holds true for any other orbital such as the 3px orbital, which can hold a + and a electron, for a total of 2 electrons in the 3px orbital.

+ = Up =
Clockwise

- = Down =
Counterclockwise

Because of the spin of an electron, there are 2 electrons in every orbital with different spins on them

+ -= = Up Down

Electron Spin Quantum Number (ms) is the fourth quantum number and has a value of + or .

Relationships between Quantum Numbers and Atomic Orbitals

n = the principal quantum number l = 0 to (n-1) and s=0, p=1, d=2, f=3, g=4, h=5 (angular momentum) ml = -l, (- l + 1), 0, (+ l 1), + l (magnetic) ms = either + or - (electron spin)

n
1 2

l
0

ml
0

Number of Orbitals 1

Atomic Orbital Designations

1s

In a many-electron atom, each electron is simultaneously attracted to the nucleus and repelled by the other electrons. The electronelectron repulsion causes different subshells to be at different energies, as shown to the left.
We can estimate the energy of each electron by considering how it interacts with the average environment created by the nucleus and the other electrons in the atom. This allows us to treat each electron individually: The electron density between the nucleus and the electron of interest will reduce the nuclear charge acting on that electron. The net positive charge attracting the electron is called the Effective Nuclear Charge, Zeff. This is calculated with the following: Zeff = Z S (Where Z = # protons & S = the avg # electrons between nucleus and electron in ?).

Decreasing Zeff

Therefore, the positive charge experienced by outer-shell electrons is always less than the full nuclear charge because inner-shell electrons partly offset the positive charge of the nucleus. The inner electrons are said to shield the electrons from the full charge of the nucleus. This effect is called the shielding-effect. SUMMARY: In a many-electron atom, the energy of electrons increase as the Zeff decreases because the positive charge is not pulling the electrons close to the atom and therefore the further the electron is from the center of the atom, the more unstable and higher energy the electrons are.

Increasing

The Pauli Exclusion Principle

Remember how I said that there are 2 electrons in each orbital? And remember how each electron will have an opposite spin from one another (a + or - ), therefore they will have different ms values. The Pauli Exclusion Principle states that no two electrons in an atom can have the same four quantum numbers. If 2 electrons have the same n, l and ml values, (this means these two electrons are in the same atomic orbital), then they must have different ms values. Only two electrons may therefore occupy the same atomic orbital, and these two electrons have opposite spins. Therefore a filled Helium 1s orbital looks like: ____

Hunds Rule
Hunds Rule states that the most stable arrangement of electrons in subshells is the one with the greatest number of parallel spins. Example: Nitrogen has the atomic number 7, therefore it has 7 electrons. Lets fill the subshells. Nitrogen: ___ ___ ___ ___ ___ 1s 2s 2px 2py 2pz Now try Oxygen: ___ ___ ___ ___ ___ 1s 2s 2px 2py 2pz Writing the Electron Configuration for an atom is a way of condensing what we have just done.

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If an atom has unpaired electrons inside it, then it is attracted to a magnetic field and called Paramagnetic. Atoms with paired electrons are called Diamagnetic.

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The Noble Gases / The Octet Rule / Valence Electrons

The Octet Rule all atoms want to have their outermost orbital full. This generally means that they have 8 electrons in their outermost orbital.
Exceptions: 1) Hydrogen and Helium which only have a 1s orbital and can therefore only have 2 electrons in their outermost orbital. 2) Lithium and Beryllium which has only three electrons and it is therefore easier to get rid of one electron to have the full 1s orbital.

The Noble Gases the VIII column has their outermost orbital full and therefore they are happy atoms because they follow the octet rule. Valence Electrons the electrons that include all of the electrons in subshells which are past the last filled noble gas and have the same highest principle quantum #. Transition Metals have valence electrons inside the d orbitals as well.

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Noble Gases are happy atoms because their outermost orbital is full and they follow the octet rule.

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The Shorthand way to do electron configurations is to use the last noble gas filled in square brackets and then add on these configurations shown here

Exceptions to the electron configurations and orbital diagrams

Some atoms: Cr, Mo, Cu, Ag, Au are exceptions to the filling order rules. What would expect the electron configuration and orbital diagram for Cr and Cu to be?
Cr: Cu: But, actually They are: Cr: [Ar] 4s1 3d5 Cu: [Ar] 4s1 3d10

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This is an example of the scientist John Daltons chart of the elements in which he labeled the elements based on the atomic weight of the element. This was done in the early 1800s before the atomic number (or number of protons) was even understood.

The next logical step after atomic mass was to figure out a logical arrangement of the elements according to atomic mass. Around 1865, English Chemist John Newlands noticed that when the elements were arranged in order of atomic mass, every eighth element had similar properties. Newlands referred to this peculiar relationship as the law of octaves. But this law turned out stop working after Calcium. In 1864, the Russian chemist Dmitri Mendeleev created a much more extensive arrangement of the elements based upon the regular, periodic recurrence of properties.

Development of the Periodic Table

From 1834 1907 Dmitri Mendeleev copied down the 63 existing elements on individual cards and then arranged them in order of atomic mass. He played with these cards until he successfully came up with the first attempt at the periodic table of the elements. He made the first two periods shorter than the rest and realized from the properties of the elements, that some elements had not yet been discovered. For example: Mendeleev proposed the existence of an unknown element that he called eka-aluminum and predicted Ga its properties (shown on the left), before it was discovered, 69.9 u based solely on the trends of the rest of the periodic table he had created. Eka means first and symbolized the first element oC 30.15 under aluminum for the word eka-aluminum. Gallium was 5.94 g/ml later discovered after four years and proved his periodic arrangement of the elements to be a success!

Eka-Al
Mass M.P. 68 u Low

D 5.9 g/ml

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The Periodic Table of the Elements

A metal is a good conductor of heat and electricity. A nonmetal is usually a poor conductor of heat and electricity. A metalloid has properties that are intermediate between those of metals and nonmetals. In the table, the horizontal rows are called periods and the vertical columns are called groups or families. Group 1A elements are called Alkali Metals. Group 2A elements are called Alkaline Earth Metals. Group 7A elements are called Halogens. Group 8A elements are called Noble Gases.

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To find the radius of atoms, X-rays are passed through a crystal (made with the elemental atom) and a diffraction pattern that is unique to the element will emerge and can be measured for the radius of the atom.

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When comparing two different radii: Remember, going down the periodic table increases the radii dramatically, due to increasing the shell level of the atom. Transition metals have similar sizes of radii.

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Ionization Energy
Ionization energy is the amount of energy needed to pull off an electron from a gaseous monatomic atom. The factors that effect I.E. are: Nuclear Charge / Radius Shielding effect of the electrons Valence electrons Sublevels (1/2 and full filled sublevels)

Low Ionization Energy High Ionization Energy

Ionization Energy High

Ionization Energy

Ionization energy is the energy of losing an electron

From a gaseous atom

Low Ionization Energy

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Multiple Ionization Energies

Lets look at Aluminum, What is its electron configuration? [Ne]3s2 3p1 The First Ionization Energy: Al(g) Al+(g) + e- I1 = 580 kJ/mol The Second Ionization Energy: Al+(g) Al2+(g) + e- I2 = 1815 kJ/mol The Third Ionization Energy: Al2+(g) Al3+(g) + e- I3 = 2740 kJ/mol The Fourth Ionization Energy: Al3+(g) Al4+(g) + e- I4 = 11,600 kJ/mol

Electron Affinity
Electron Affinity is the amount of energy that is required to add an electron to an atom. Most atoms do not require energy in order to add an electron, instead they release energy because it usually makes the atom more stable. This is the reason why electron affinity energies have negative values associated with them. Remember exothermic reaction, energy leaves and the value is a negative number. You need to look at the atoms electron configuration in order to determine the electron affinity of the atom.

Electronegativity, EN
Low Electronegativity High Electronegativity High Electronegativity

Notice EN is a scale between 0 - 4 4 = high desire for negative charge 0 = low desire for negative charge

Low Electronegativity

Electronegativity is the ability of an atom, within a molecule, to attract shared electrons towards itself

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