Atomic Theory and Structure 4

Quantum theory, which is a major part of how we now view the atom, can be said to have developed
between 1900 and 1930. What did people believe in 1900? For one thing, they thought of light as a wave.

1 Waves and Electromagnetic Radiation pages 208 – 210

All waves, whether waves in the ocean or waves in a string, share some characteristics.
{1} Draw a wave with the origin on this line:

At any time the string has many regions in which its vertical position is at a maximum, or wave crests,
and an equal number of regions where its vertical position is at a minimum, or wave troughs. The
transverse motion of the crests, or the troughs, is the velocity of the wave. There are two other features of
the wave you should know. Define the following, give the variable used for each and the units used for
each. For wavelength, label it on your wave above.

{2} wavelength (label on the wave above): distance between 2 consecutive peaks or troughs in a wave

variable: l units: m, nm, Å (angstrom = 1 x 10–10 m)

{3} frequency: number of waves or cycles per second passing a given point in space

variable: n units: cycles/s or 1/s or s–1 or Hertz (Hz)

{4} Now draw two waves, one with a larger wavelength and the other with a smaller wavelength. Label
the waves showing which has a larger/smaller wavelength, higher/lower frequency, and higher/lower
energy.

smaller wavelength larger wavelength

higher frequency, higher energy lower frequency, lower energy

{5} Describe in words the relationship between wavelength and frequency. Write the mathematical
expression showing how they are related to each other and to the speed of light.

wavelength and frequency are inversely proportional l ž n = c (speed of light)

High frequency photons are very penetrating and create a lot of ions and free radicals. This is why
exposure to very high frequency radiation is so damaging. Light is actually just one type of
electromagnetic radiation, with different colors as well as other types of electromagnetic radiation being
distinguished by their wavelengths. You should know the different types of electromagnetic radiation and
their wavelength order.
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{6} Draw a diagram showing each type of electromagnetic radiation, including the colors of
the visible spectrum. Label each end as to low/high energy, low/high frequency, and short/long
wavelength.
radio microwaves infrared visible ultraviolet x-rays gamma rays
waves
R O Y G B I V
low E, low n high E, high n
long l short l

You don’t need to memorize the specific values of wavelength and frequency for each type of
electromagnetic radiation, but you should know the range of wavelengths of the visible spectrum.

{7} In units of nanometers (nm), the visible light spectrum goes from ___400____ to __700____.

2 The Dual Nature of Light pages 210 – 212, 216 – 217

Isaac Newton
In the late 1600’s, Newton proposed that light was made of very small, very fast particles. The small size
of light particles allowed light beams to pass through each other without interference, while their high
speed let them go in straight lines. The particle nature of light also explained such things as reflection,
since bouncing particles were well known. Finally different colors of light were thought to be associated
with different sizes of light particles.

Yet even then some scientists thought that light consisted of waves, since they were also able to explain
the observed properties of light in terms of a wave model. However, light waves had a major problem.
What is the medium in which the waves propagate? This problem, combined with Newton’s enormous
prestige, caused the particle model of light to predominate for almost 200 years.

{8} Newton’s conclusion: light is a __particle__________.

Then in the early 1800’s a single experiment caused this sentiment to change. This experiment, which
Richard Feynman viewed as summing up all of quantum theory, is known as the double slit experiment.

Thomas Young, an English scientist, passed a light beam through a single slit to create a point, then he
passed it through two slits and finally projected the result. Go to the double slit experiment set up in the
lab to see his results.
{9} Draw the pattern of light that is projected by the double slit experiment.

The pattern that you see and that Young saw is called an interference pattern.
{10} What did this pattern mean about the nature of light? light is composed of waves adding/subtracting
to give the different amounts of light
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The interference pattern results from the interaction of waves as they leave the 2 slits in the experiment.
Draw the following:

{11} Draw two waves which are undergoing constructive interference. What amount of light is projected
in this case?

{12} Draw two waves which are undergoing destructive interference. What amount of light is projected in
this case?

{13} Young’s conclusion: light is a __wave______________.

Max Planck
The beginning of modern quantum theory is often given as 1900 and the event that signaled that
beginning was Max Planck’s explanation of blackbody radiation (a body which absorbs all wavelengths
of light). Planck developed a formula which explains that light is given off in packets.

{14} What do we now call these “packets” of energy?___quanta (singular is quantum)__

Planck also calculated that the energy of one of these packets is related to its frequency.
{15} Write Planck’s formula and define each of the variables.

E = hn E = energy of one quantum

h = Planck’s constant = 6.626 x 10–34 Jžs
n = frequency

{16} What is the energy of the lowest possible frequency of visible light? What is the energy of the
highest possible frequency of visible light?
400 nm: E = (6.626 x 10–34 Jžs) (2.998 x 108 m/s) = 4.97 x 10–19 J
4.00 x 10–7 m

700 nm: E = (6.626 x 10–34 Jžs) (2.998 x 108 m/s) = 2.84 x 10–19 J
7.00 x 10–7 m

{17} Planck’s conclusion: light (and energy) is a __particle__________.

3
Albert Einstein and the Photoelectric Effect
The photoelectric effect was first carried out in 1887 but not explained for almost 20 years.

In the photoelectric effect, a beam of light hits a metal surface and causes electrons to be emitted.
According to classical physics, the number and energy of the electrons emitted should depend on the
intensity of the light beam, which is the amount of light or the strength of the light from a particular light
source. So if a beam of light hits a metal surface and no electrons are emitted, you should just be able to
increase the intensity until electrons are able to leave the surface of the metal.

To explore the photoelectric effect, go to https://phet.colorado.edu/en/simulation/legacy/photoelectric

and download the photoelectric effect simulation.

At the top right, make sure the target metal says sodium. Slide the wavelength indicator to the red region
or about 700 nm. Then slide the intensity indicator to a higher percentage, watching to see if any electrons
are emitted or any current is recorded.

{18} Is red light capable of ejecting electrons from the surface of sodium metal? __no____

Set the intensity to about 50%, then slide the wavelength indicator to lower wavelengths until you see
electrons emitted.

{19} At what wavelength do electrons begin to leave the surface of sodium metal? What energy does this
wavelength correspond to?

539 nm = 5.39 x 10–7 m E = (6.626 x 10–34 Jžs) (2.998 x 108 m/s) = 3.69 x 10–19 J
5.39 x 10–7 m

{20} What happens when you slide the wavelength indicator to even lower wavelengths?

The electrons that are ejected move faster.

The photoelectric effect was not understood for years because of the assumption that light is a wave. If
light is a wave, then an electron on the surface of a metal should be able to absorb enough waves to
eventually leave the metal. But Einstein explained that because no electrons are emitted below a certain
minimum amount of energy, light must be considered a particle. Each particle of light hits an electron,
and if there is enough energy in that particle, the electron is emitted. If not, the electron drops back down
to ground state and we start over with a new particle of light.

{21} What did Einstein call these particles of light?__photons___________

So when light hits a piece of metal, each photon gives up all its energy to an electron. A low energy
photon will not give the electron enough energy to escape from the metal surface, while a high energy
photon will. The minimum energy needed for an electron to escape from a metal surface is called the
metal’s “work function.”

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{22} When a high energy photon hits an electron, what happens to the excess energy after the electron has
left the metal surface?

The excess energy is converted to kinetic energy so the electron moves faster.

Go back to the photoelectric effect simulation and find the maximum wavelength that will eject an
electron for zinc and for calcium.

{23} Calculate the minimum energy needed to eject an electron from zinc and from calcium. Then put the
metals in order of easiest to hardest to remove an electron.

Zn: 288 nm E = (6.626 x 10–34 Jžs)(2.998 x 108 m/s) / 2.88 x 10–7 m = 6.90 x 10–19 J

Ca: 427 nm E = (6.626 x 10–34 Jžs)(2.998 x 108 m/s) / 4.27 x 10–7 m = 4.65 x 10–19 J

easiest to remove e– __sodium____ < __calcium___ < ___zinc_____ hardest to remove e–

{24} Einstein’s conclusion: light is a __particle__________.

Louis de Broglie
In 1924 the French physicist Louis de Broglie proposed (in his doctoral thesis!) the startling idea that just
as light was both a particle and a wave, matter also had characteristics of both. He didn’t do any
experiments; he figured this out using data generated by other scientists. De Broglie’s equation says that
the wavelength of a particle is determined by its momentum (represented as “r” and equal to mass times
velocity). The equation is:
h h
λ = =
ρ mv

{25} Calculate the de Broglie wavelength of an electron with a velocity of 1.0 x 107 m/s. Pay special
attention to your units.

l= 6.626 x 10–34 Jžs = 7.3 x 10–11 m

–31 7
(9.11 x 10 kg)(1.0 x 10 m/s)

{26} Calculate the de Broglie wavelength of a 150. g baseball traveling at 90. miles per hour.

90. mi x 1 h x 1.609 km x 1000 m = 40. m/s

h 3600 s 1 mi 1 km

l= 6.626 x 10–34 Jžs = 1.1 x 10–34 m

(0.150 kg)(40. m/s)

5
It can be seen that large wavelengths, which are needed to make the effect observable, occur only in
particles with small masses. Thus it is not surprising that experiments in which particles are seen to have
wavelengths generally involve electrons. In fact the first experimental verification that particles have
waves, in 1927, involved electron diffraction. Similarly the consequence of particle waves with which you
are probably most familiar is the electron microscope. Since electrons are far more massive than photons,
de Broglie’s equation says they must have much smaller wavelengths. Thus electrons can detect much
smaller details than can photons.

{27} de Broglie’s conclusion: matter is a __wave______________.

So there is evidence that light is a wave and that light is a particle. Which is it? It turns out that in some
experiments light must be treated as a particle and in other experiments light must be treated as a wave.
The greater conclusion to be made is that energy is a form of matter, and that all matter exhibits both
wave and particle behavior. The smaller the matter is, the more likely you’ll treat is as a wave, and the
larger it is, the more likely you’ll treat is as a particle.

As the Double Slit Experiment and the Photoelectric Effect were investigated to determine the nature of
light, research was still underway as to the manner in which light interacts with atoms. In 1897, J.J.
Thomson realized that “cathode rays,” later called electrons, were fundamental particles and calculated
their charge/mass ratio. And in 1911, Ernest Rutherford that the atom contains most of its mass in a small,
dense nucleus. But the experiment that would lead to the Bohr model of the atom was the emission
spectrum of hydrogen.

3 Balmer and the Emission Spectrum of Hydrogen pages 213 – 214

It had been known since the early 1800’s that passing an electrical discharge through a sealed tube
containing a small amount of gas gave off light, as in a neon sign, but only at certain wavelengths.
{28} What is the name of a spectrum containing radiation only of specific wavelengths?
line spectrum

Of particular interest was the hydrogen spectrum, which was known to consist of four lines. Could a
formula be found which predicted or fit them?

Go to the lab station where the hydrogen bulb is set up with a spectroscope. Make sure the spectroscope is
lined up so that only light from the bulb is coming in and observe the spectrum.
{29} What is the wavelength of each of the four lines in the hydrogen spectrum? (You may only be able
to see three of the lines in our lab, so it would be preferable to look up these values.)
410 434 486 656

Dr. Johann Balmer, a Swiss school teacher, found a formula for the lines in the hydrogen spectrum.
Balmer took others’ data for the four hydrogen lines and found them to be consistent with the following
( ( (
formula: = R − . . The equation was later made more general and called the Rydberg equation,
) + -
which allows us to calculate all the spectral lines for hydrogen, not just the visible ones.
( ( (
Rydberg equation: = R . − .
) -/ -.

R is known as the Rydberg constant and has a value of 1.096776 x 107 m–1; n1 and n2 are positive integers
with n2 being a higher number than n1.

6
{30} Compare the Balmer and Rydberg equations. For the visible hydrogen spectrum lines, what is the
value of n1?__2__

{31} For the hydrogen spectrum line of highest wavelength, calculate n2.

( ( (
= (1.096776×10? m@( ) −
0.20 3 (456 7 B. C..

n2 = 3

4 The Bohr Model of the Atom pages 214 – 216

Bohr was struggling to explain the structure of the atom when, in 1913, he learned of Balmer’s results.
With these and with Planck’s ideas that energy is quantized, he was able to explain everything. His model
states:
1. Electrons can only exist in certain states or levels. Each is associated with a value of “n.”
2. The states with higher n are higher in energy.
3. An electron can be promoted to a higher state by absorbing a photon whose energy equals the
difference between the two states.
4. An electron dropping to a lower state emits a photon whose energy equals the difference between
the two states.

Taking Balmer’s formula, Bohr calculated the energy of an electron in a given energy level to be
E = –2.178 x 10–18 J (1/n2). What’s more useful is to calculate the difference between two energy levels,
or ΔE = Efinal – Einitial. Simplified, this equation becomes:
1 1
ΔE = hν = −2.178 x 10–(K J B − B
nN nO
{32} How many energy levels are there in an atom?
There are an infinite number of energy levels in an atom.

{33} When an electron is at the highest possible energy level, or the highest value of n, what is its
energy? What does this mean for that electron?

The energy of the electron is zero; this means it has been removed from the atom.

{34} Calculate the wavelength of the photon emitted when an electron drops from n = 2 to n = 1 in a
hydrogen atom. Is this photon visible in the hydrogen spectrum?

1 1
ΔE = −2.178 x 10–(K J B
− B
= −1.634×10@(K J
1 2

1.634 x 10–18 J = (6.626 x 10–34 Jžs)(2.998 x 108 m/s) / l

l = 121.6 nm not visible

Unfortunately in the 1920’s, additional experiments showed problems in the Bohr model. First, it did not
really address a problem known as the “death spiral” in which a circling electron is a charged particle
under constant acceleration and should therefore emit electromagnetic radiation and spiral into the

7
nucleus. Second, it did not work well for atoms heavier than hydrogen. Bohr modified his model to use
elliptical orbits, but even this hypothesis did not explain experimental observations. Although the
elliptical orbits are no longer accepted, they did lead to the l quantum number in modern atomic theory.

5 Heisenberg’s Uncertainty Principle pages 217 – 219

Of all the strange ideas which make up quantum theory, surely one of the strangest is the Uncertainty
Principle, proposed by Werner Heisenberg in 1927. The Uncertainty Principle can be stated in different
ways. In the most common form it says that no matter how carefully one measures them, the uncertainty
in the position of a particle times the uncertainty in its momentum must be greater than or equal to
Planck’s Constant divided by 2π (which is often referred to as ħ.) Thus, Heisenberg’s Uncertainty
Principle is stated as Δx ´ Δp ³ ħ.

This is usually explained by supposing that we want to make an extremely accurate measurement of the
position of a particle whose momentum we already know. To do this we would use a photon having a
very short wavelength. Since short wavelength photons have very high energy, the act of measuring the
position of the particle would move it and, thus, change its momentum. This explanation, although it was
originally put forward by Heisenberg, is somewhat misleading. It suggests that the uncertainty is some
sort of error in the measurement process. In fact, it is more fundamental than that.

6 Modern Theory of the Atom: the Quantum Mechanical Model pages 219 – 220
In 1926, building on the wave nature of particles, Erwin Schrödinger found that he could treat electrons as
waves and their motion as wave motion. Instead of trying to find an electron’s location, Schrödinger’s
equation is solved for something called the wave function and represented by the Greek letter psi (ψ). The
square of the wave function is proportional to the electron density. If we consider the electron to be a
cloud of negative charge, then ψ2 is proportional to the density of the electron cloud. If we consider the
electron to be a particle, then ψ2 is proportional to the probability of finding an electron at that spot.

Schrödinger’s equation gives us four quantum numbers: n, l, ml and ms. These quantum numbers allow us
to know the region of probability for an electron’s location.
{35} In what way are the Bohr model and the quantum mechanical model the same?

They both have electrons in energy levels designated by n.

{36} What do we call the regions with high probability of containing an electron? orbitals

7 Quantum Numbers pages 220 – 227

The first quantum number, n, is known as the principal quantum number.
{37} What are the possible values of n?

n = 1, 2, 3…

{38} What does the value of n tell you about the electrons it contains?

The value of n tells you the energy level of the electron, the relative size of the
orbital and the relative distance from the nucleus.
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The second quantum number, l, is called the angular momentum quantum number.
{39} What are the possible values of l?

l = 0, 1, 2 … n–1

{40} What does the value of l tell you about the orbital? The value of l tells you the shape of the orbital.

{41} Assign the proper letter designation to each value of l:

l = 0 1 2 3 4 …

letter: _s__ _p__ _d__ _f__ _g__ …

{42} Draw an s orbital, draw a p orbital, and draw two different types of d orbitals (though they are equal
in energy). Don’t draw an f orbital; you’ll never be asked to do that.

The third quantum number, ml, is referred to as the magnetic quantum number.
{43} What are the possible values of ml? ml = –l to +l

{44} What does the value of ml tell you about the orbital?

ml tells you the orientation of the orbital and the number of orbitals of that type.

The fourth quantum number, ms, is the spin quantum number.

{45} What are the possible values of ms?

ms = + ½ or – ½

{46} What does the value of ms tell you about the electron?

ms tells you the direction of the electron spin.

{47} Give the name of the principle which states that in an atom, no two electrons can have the same four
quantum numbers.
Pauli Exclusion Principle
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{48} Complete the table for the values n = 1 through n = 3.
value of n possible name of number of maximum number
value of l orbitals orbitals of electrons

1 0 1s 1 2

2 0 2s 1 2

2 1 2p 3 6

3 0 3s 1 2

3 1 3p 3 6

3 2 3d 5 10

8 Electron Configurations pages 229 – 238

Since the electron configuration, the arrangement of electrons in the levels and sublevels of an atom, is
what determines the chemical properties of an atom, using what we have learned to predict the electron
configuration of a given atom is of obvious interest. Before we start filling orbitals with electrons,
however, it is important to know that in one level, the s, p, d and f electrons do not have the same energy.

In a one-electron system, like hydrogen, different orbitals do have the same energy. But in a multi-
electron system, shielding becomes important. Electrons closest to the nucleus shield or block the other
electrons from the nucleus. Since they don’t feel the full force from the nucleus, they get further away.
Thus the general order of orbital energies is s < p < d < f. The effect is great enough that a 4s electron is
closer to the nucleus than a 3d electron.

{49} What principle states that electrons should be placed in orbitals from low to high energy?

Aufbau Principle

How do we know the proper order in which to fill orbitals for an electron configuration? We use the
periodic table.

{50} Who first organized the periodic table by periodic properties? He arranged the elements in
increasing order of what property?

Mendeleev first organized the table by periodic properties in order of increasing

atomic mass.

10
{51} On this periodic table, label the s, p, d, and f blocks. Label the energy level of each row in each
block.

1s 1s

2s 2p

3s 3p

4s 3d 4p

5s 4d 5p

6s 5d 6p

7s 6d 7p

4f

5f

Now the electron configuration can be written for any element.

{52} Write the expected electron configuration for each of the following elements:

H 1s1

Li 1s2 2s1

B 1s2 2s2 2p1

O 1s2 2s2 2p4

P 1s2 2s2 2p6 3s2 3p3

Mn 1s2 2s2 2p6 3s2 3p6 4s2 3d5

Zr 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d2

Ba 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2

Another point to remember is that these electron configurations are ground state configurations, meaning
all electrons are in the lowest possible energy levels. It is possible for an electron to be in an excited state,
which would result in a configuration with an electron in a higher energy orbital than it would usually be.

11
To get even more detail about the location of the electrons in their orbitals, an expanded electron
configuration can be written. This is also called an orbital diagram. Take oxygen, for example. How are
the four electrons in the 2p orbital arranged?
{53} Using the convention that each line below represents an orbital and the electrons are represented as
arrows, draw the 4 electrons in the 2p orbitals in their proper orientation.

2p h i h h

{54} Whose rule is this? What does this rule state? (Be careful that this rule does not state that electrons
don’t pair up. That is a consequence of the rule.)

Hund’s Rule: for the lowest energy configuration, the electron spins are aligned.

Electron configuration can be abbreviated by representing the core electrons with a noble gas in brackets.
For example, the abbreviated configuration of gallium would be [Ar] 4s2 3d10 4p1.
{55} Write the abbreviated electron configuration for each of the following elements:

Mn [Ar] 4s2 3d5

Sb [Kr] 5s2 4d10 5p3

Ba [Xe] 6s2

There are some elements which are exceptions, meaning they do not have the expected electron
configuration according to their position on the periodic table. For example, you would expect chromium
to have a configuration of [Ar] 4s2 3d4. Look at the orbitals involved:

{56} 4s h 3d h h h h h actual configuration: [Ar] 4s1 3d5

The 4s and the 3d orbitals are very close in energy. So rather than undergo the repulsion from being
paired in the 4s orbital, one of those electrons jumps to the empty 3d. Draw the electrons in their proper
orbitals above and fill in the superscripts for the actual configuration of chromium.

You don’t have to know which atoms have anomalous electron configurations, but you should be able to
provide possible reasons for the anomaly.

Finally, since most chemists study compounds rather than elements, it is important to predict the electron
configuration of ions. For the first 20 elements of the periodic table, the ion configuration is
straightforward. Take sodium, for example.
{57} Write the electron configuration for a sodium atom. 1s2 2s2 2p6 3s1

{58} When sodium becomes an ion, it loses _1__ electron(s) and has a charge of _+1_. Always remove
the valence electrons first, and write the electron configuration of a sodium ion:

Na+ 1s2 2s2 2p6

More surprising is what happens when electrons are removed from a transition metal atom.
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{59} Write the electron configuration for an iron atom.

Fe 1s2 2s2 2p6 3s2 3p6 4s2 3d6

Iron has two possible charges, Fe2+ and Fe3+. Though we write the 3d electrons last in the configuration,
iron loses its valence electrons first, meaning the 4s electrons. Remember, valence electrons are electrons
with the highest value of n.
{60} Write the configuration for Fe2+.

Fe2+ 1s2 2s2 2p6 3s2 3p6 3d6

This is typical for atoms with d electrons: the s electrons are removed before the d electrons to make an
ion.

After the two 4s electrons are lost, any additional electrons have to come from the 3d.
{61} Write the electron configuration for Fe3+.

Fe2+ 1s2 2s2 2p6 3s2 3p6 3d5

If an anion is being formed, electrons are added to the lowest possible unoccupied orbital.
{62} Write the electron configurations for N3– and S2–.

N3– 1s2 2s2 2p6 S2– 1s2 2s2 2p6 3s2 3p6

9 Colors of Transition Metal Compounds

Despite the way we draw them, the d orbitals in a sublevel are not quite at the same energy. Generally the
energy differences between d orbitals are similar to the energy of visible light. Therefore when visible
light strikes an ion with a partially filled d shell, it can be absorbed and used to promote a d electron to a
higher-energy orbital. Unfortunately you will not know what the energy is or what color results. For
example:
4s 3d
Na+ ___ ___ ___ ___ ___ ___ colorless

Ga3+ ___ E E E E E colorless

Ni2+ ___ E E E # # green

Cu2+ ___ E E E E # blue

A complex formed from an ion with color itself has color and a complex formed from a colorless ion is
colorless. However, the color of the ion and the color of the complex are usually different. The copper
ammonia complex, Cu(NH3)42+, is deep blue, and the iron thiocyanate complex, Fe(SCN)(H2O)52+, is dark
red.

Ions which contain highly-charged metal atoms usually have color, even if they have no d electrons. Two
examples of this are permanganate (MnO4–) which is purple and chromate (CrO42–) which is yellow.
You don’t have to memorize colors of compounds, but there may be information about the color of a
compound or ion given in an AP test question. Color questions sometimes show up on the chemistry SAT.
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10 The Shell Model of the Atom pages 274 – 275
The properties of an atom are related to how the outer electrons behave. A convenient way of explaining
the behavior of these electrons is by treating electrons as if they were arranged in a series of concentric
shells. (This is why the Bohr model is still widely used.) In this simplified model, the factors affecting the
outer electrons are their distance from the nucleus and something called the effective atomic number, Zeff.
Recall that the atomic number is always referred to as “Z.” This comes from the German word “zahlung”
meaning “number.”
The effective atomic number is the atomic charge which the outer electrons “see.” A small part of the
difference between Z and Zeff is due to the other valence electrons, which repel each other. However most
of the difference is due to the inner electrons. Since they lie between the valence electrons and the
nucleus, the inner electrons exert what is called a “shielding” effect on the valence electrons.

To investigate the shielding and effective nuclear charges of the first 18 elements, go to
http://www.oneonta.edu/faculty/viningwj/sims/effective_nuclear_charge_s.html.

11 Atomic Radius pages 289 – 291

Because electrons are on the outside of an atom, it is not straightforward to measure atomic size. Methods
to measure atomic radius include:
metallic radius: half the distance between adjacent nuclei in a metallic solid
covalent radius: half the distance between two identical atoms bonded together in a molecule
ionic radius: the distance between adjacent ions in an ionic crystal is the sum of their ionic radii
van der Waals radius: the minimum distance between two unbonded atoms is the sum of their
van der Waals radii

From top to bottom in a periodic table group, each atom has one additional energy level. Though there is
little difference in Zeff, the outer electrons have a higher value for n.

From left to right in a period, each atom has one additional electron and one additional proton. Since the
electrons are being added into the same energy level, they shield each other poorly and Zeff increases.

{63} Atomic Radius Trend:

As you go down in a group, atomic radius _____increases___________.

As you go from left to right in a period, atomic radius ___decreases________.

Remember that the differences as you go down in a group are larger than the differences as you go across
in a period. You should also remember that a cation is smaller than its corresponding neutral atom and an
anion is larger than its neutral atom. There are exceptions to all of the periodic trends but it is not
necessary to memorize them.

{64} Arrange the following in order of increasing atomic radius:

a. O, K, Ni, Ba b. Ru, Rh, Os c. N3–, O2–, F– d. S2–, Cl–, Al3+, Ca2+

O<Ni<K<Ba Rh<Ru<Os F-<O2-<N3- Al3+<Ca2+<Cl-<S2-

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12 Ionization Energy, Electron Affinity, and Electronegativity pages 284 – 289, 305 – 307
Other important trends have to do with how tightly the atom holds on to its outer electrons.

{65} Define the following:

a. ionization energy – Energy required to remove an electron from a gaseous atom or ion.

b. electron affinity – Energy change associated with the addition of an electron to a gaseous atom.

c. electronegativity – The ability of an atom in a molecule to attract shared electrons to itself.

Ionization energy (IE) can be understood by its relationship to the atomic radius and Zeff.

From top to bottom in a periodic table group, each atom has one additional energy level. Though there is
little difference in Zeff, the outermost electron has a higher value for n, is further from the nucleus and
therefore easier to remove.

From left to right in a period, each atom has one additional electron and one additional proton. Since the
electrons are being added into the same energy level, they shield each other poorly and Zeff increases.
With a higher Zeff it is harder to remove an electron.
{66} Ionization Energy Trend:
As you go down in a group, ionization energy ___decreases____________.

As you go from left to right in a period, ionization energy __increases__________.

When we discuss ionization energy, we normally mean the first ionization energy, the energy needed to
remove a single outermost electron. However atoms can lose more than one electron. So there is also a
second ionization energy – the energy needed to remove the second electron – and so on.

For questions involving second (or higher) ionization energies, you must consider the energy level from
which the electron is taken. Consider the following IE values:
first IE second IE
potassium 419 kJ/mol 3051 kJ/mol
calcium 590 kJ/mol 1145 kJ/mol

{67} To explain the much larger jump from first to second IE for potassium, write the electron
configurations for both potassium and calcium:

K [Ar]4s1 Ca [Ar]4s2

For both potassium and calcium the first electron is taken from the 4s sublevel. The second electron taken
from calcium is still a 4s, so the ionization energy increases only slightly. However, for potassium the
second electron is a 3p, which is lower in energy than a 4s and is much more difficult to remove.

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{68} Arrange the following in order of increasing first ionization energy:
a. O, K, Ni, Ba b. Ru, Rh, Os c. O, P, Rb, Hg, Po
Ba<K<Ni<O Os<Ru<Rh Rb<Hg<Po<P<O

Electron affinity (EA) is also related to atomic radius and Zeff, so if you know the atomic radius trend,
you can determine what happens to EA. Though some textbooks take the absolute value of the electron
affinity, we will consider it to be a negative number because energy is given off when an electron is added
to an atom. Some textbooks even go so far as to say that there are so many exceptions for EA that a trend
in each group is not significant, but let’s consider it anyway.

From top to bottom in a periodic table group, atomic radius increases. Though there are many exceptions,
when an electron is added, less energy is released due to the small Zeff experienced by that electron.

From left to right in a period, atomic radius decreases. An added electron would feel a greater Zeff, so
more energy is released. This agrees with the fact that metals (on the left side of the periodic table) don’t
gain electrons, but nonmetals (on the right side) do.

{69} Electron Affinity Trend:

As you go down in a group, the tendency to gain an electron ____decreases________.

As you go from left to right in a period, the tendency to gain an electron __increases________.

{70} Arrange the following in order of increasing tendency to gain an electron:

a. O, K, Ni, Sr b. Ru, Rh, Os c. O, P, Hg, Po

Sr<K<Ni<O Os<Ru<Rh Hg<Po<P<O

Electronegativity is different from the previous three trends in that it is not relevant for a single atom by
itself but for an atom in a covalently-bonded molecule. The value for electronegativity is also not
measured but calculated. Electronegativity is related to IE and EA. An atom that easily gains electrons
and is reluctant to lose electrons will have a high electronegativity.

{71} Electronegativity Trend:

As you go down in a group, electronegativity __decreases__________.

As you go from left to right in a period, electronegativity __increases__________.

{72} Arrange the following in order of increasing electronegativity:

a. Ga, Ge, As b. Ru, Rh, Os c. N, O, F, Cl

Ga<Ge<As Os<Ru<Rh N<Cl<O<F

N and Cl are very close. Most
calculated values of EN indicate
that N < Cl but the H-bonding ability
of N suggests the EN of N may be
larger than that of Cl.
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