General Chemistry 1

CHE1211

• Dr. Gigliotti
Exam 4 Material: Chapter 6 – Part 1
 Exam 4 Material: Chapter 6

The electromagnetic (EM) spectrum is the range of all types of electromagnetic radiation, a form of energy that has
oscillating electric and magnetic fields.

The EM spectrum is generally divided into seven regions based upon wavelength, frequency, and energy.

---gamma (δ) rays, X-rays, ultraviolet (UV) light, visible light, infrared (IR), microwaves, radio waves---

In the electromagnetic spectrum, there are many different types of waves with varying wavelengths. Our eyes are
sensitive to electromagnetic radiation which lies in a very small region of the electromagnetic spectrum labeled
"visible light".

Visible Light range of wavelengths  400 nm (violet) - 700 nm (red)

Recall: 1 nm = 1 x 10-9 m
All electromagnetic radiation travels at the same speed: the speed of light (c):

c = 2.9979 x 108 m/s
Forms of electromagnetic radiation like radio waves, light waves or infrared (heat) waves make
characteristic patterns as they travel through space. Each wave has a certain shape and length.

The distance between peaks (high points) is called wavelength. We denote wavelength by the Greek letter
lamda (λ) and measure it in metric units… usually m or nm.

There is an inversely proportional relationship between wavelength and the energy associated with
that form of radiation. (as λ↑, E↓, thus: λ↓, E↑)

The longer the wavelength, the less energy that form of radiation possesses
The shorter the wavelength, the more energy that form of radiation possesses.
Another way of comparing the type of electromagnetic radiation is to use frequency.
Frequency is how many complete wave cycles pass a specified point in a specific amount of time.

We denote frequency by the Greek letter, nu (ν). Frequency is measured in Hertz = Hz = wave cycles/second.

There is an proportional relationship between frequency and the energy associated with that
form of radiation. (as ν↑, E↑, thus: ν↓, E↓)

the lower the frequency, the less energy that form of radiation possesses
the higher the frequency, the more energy that form of radiation possesses
The speed at which radiation travels, the wavelength, and the frequency are
all related by one important equation:

Any electromagnetic wave's frequency (ν) multiplied by its wavelength (λ)

equals the speed of light (c).

c = λν

  radio station KUGN broadcasts at a frequency of 590 kHz. What is the

A
wavelength of the radio waves (in m)? Note: c = 2.9979 x 108 m/s

c = λν
rearranging the terms to solve for wavelength: λ = c/ν

Note: 1 Hz = 1 s-1
so…. 590 kHz = 5.9 x 105 Hz = 5.9 x 105 waves/s

λ = 
= 508.1355932 m
= 5.1 x 102 m
 Calculate the frequency of light with a wavelength of 126nm.
c = m/s
c = λν

 
Rearrange the terms of c = λν, to solve for ν :

ν = c/ λ

Note: the length unit in “c” is in meters, but the wavelength is in nanometers.

Recall that nano represents 10-9, so: 126 nm = 126 x 10-9 m

ν = Technically, this is incorrectly

written:

= 2.37142857 x 1015 /s To be properly written in

scientific notation, the
= 2.37 x 1015 /s coefficient should be a value
between 1-10.
So: 1.26 x 10-7
A Super Brief History of Quantum Theory:

Max Planck:

When solids are heated, they emit electromagnetic radiation over a wide range of wavelengths. (Think about the
red glow on the filament of a light bulb and the white light that is emitted from the bulb.) Physicists showed that
the amount of energy emitted by an object at a certain temperature depends on the wavelengths of light. But the
mathematics didn’t seem to work to prove it across all wavelengths of light.

Around 1900, physicist Max Planck realized that the math was unsupported, because it was based on an
assumption: that atoms and molecules could emit (or absorb) any amount of radiation.

Planck found experimental evidence to suggest that atoms and molecules could only emit (or absorb) energy in
discrete quantities, or individual units. This quantized energy is always emitted in whole number multiples of hν -
though he didn’t know why!

He derived the expression below:

The energy (E) of a single quantum of energy is given by:

E = hν
h = Planck’s constant: 6.626 x 10-34 J · s
ν = frequency of the radiation (s-1)

According to “Planck’s Quantum Theory of Radiation”, energy is always emitted as whole integral multiples of hν.
So: hν, 2 hν, 3 hν, etc. but not 1.52 hν, 3.54 hν, etc.
Albert Einstein:

In 1905, Albert Einstein used Planck’s theory to help explain another phenomenon in physics.
He theorized that not just the energy, but the light itself was quantized in the same manner.
Thus, instead of thinking about light as waves, he suggested thinking about light as a beam of
particles. We refer to these particles as photons.

Einstein said that the energy of 1 photon: Ephoton = hν

h = Planck’s constant: 6.626 x 10-34 J · s

ν = frequency of the light (s-1)

Einstein’s theory was troubling to many physicists. While the particle theory explained
some phenomena, it could not account for the known wave behavior of light.

Louis de Broglie:

In 1924, Louis de Broglie proposed that there is no fundamental difference in the makeup and
behavior of energy and matter; on the atomic and subatomic level, either may behave as if made
of either particles or waves. Thus, light is both “wave-like” and “particle-like”

This theory became known as the principle of wave-particle duality: elementary particles of both energy and
matter behave, depending on the experimental conditions, like either particles or waves.
 
How much more energy per photon is there in green light of wavelength of 532 nm
than in red light of wavelength of 635nm? c = x 108 m/s
E = hν and c = λν h = 6.626 x 10-34 J · s

We need to solve for energy (E): E = hν

however, frequency data was not given to us in the equation.

So: we need to calculate the frequency of both green and red light:
 
For green light (λ= 532nm): c = λν , rearrange the terms: ν=
νgreen = (2.9979 x 108 m/s) = 5.56 x 1014 /s
(539 x 10-9 m)
For red light (λ= 635nm): c = λν , rearrange the terms: ν=
νred = (2.9979 x 108 m/s) = 4.72 x 1014 /s
(635 x 10-9 m)

Now that we have the frequency data, we can calculate the energy (E) for each color of light:

Green: Ephoton = hν Egreen = (6.626 x 10-34 J · s)(5.56 x 1014 /s) = 3.68 x 10-19 J
Red: Ephoton = hν Ered= (6.626 x 10-34 J · s)(4.72 x 1014 /s) = 3.13 x 10-19 J

Egreen - Ered = 3.68 x 10-19 J - 3.13 x 10-19 J = 5.50 x 10-20 J more energy per photon in green
light than red!
Energy in Physical and Chemical Processes:
When a chemical reaction occurs, molecular bonds are broken and other bonds are
formed to make different molecules. 

Energy is always required to break a bond, which is known as bond energy. Thus,
bond-breaking is an endothermic process (requires energy to be absorbed).

H-H + energy  H + H DH-H = ΔHo = +436 kJ/mol

Although each molecule has its own characteristic bond energy, some generalizations
can be made:

For example: The exact bond energy of a C-H bond depends on the particular molecule
and what other bonds are present. However, all C–H bonds have a bond energy that is
nearly the same value, because they are all C–H bonds. It takes roughly 100 kcal of
energy to break 1 mol of C–H bonds.

So: the bond energy of a C–H bond is about 100 kcal/mol. 

 Some examples of where the energy to break chemical bonds comes from:
(1) from the kinetic energy associated with two particles colliding
(2) from an external agent:
ex) adding heat with a Bunsen burner
ex) exposing the reaction to electromagnetic radiation (photons of energy
from light)

It takes about 160 kJ of energy to break 1 mole of N-O bonds. (D N-O = 160 kJ/mol) Calculate the maximum
wavelength of light (in nm) for which one single N-O bond could be broken by a single photon.
Useful equations: E = hν c = λν
Recall
  that c and h are constants:
c = speed of light = 2.9979 x 108 m/s h = Planck’s constant = 6.626 x 10-34 J · s

In order to calculate the wavelength (λ), you need the know the frequency (ν). To get frequency you need
to use the equation: E= hν
However, you can’t just plug in E = 160 kJ/mol. That E is the energy to break 1 MOLE of N-O bonds, you
only need to break 1 bond! So: 160kJ/mol must be divided by Avogadro’s number of bonds /mole.

But also note that the units of h are J s , so the kJ must be converted to J before the math is done.

E = hν rearranging the terms: ν = = =

Once
  you know frequency (ν), you can solve for wavelength (λ).
c = λν rearranging the terms: λ = = = or 707 nm
Try another: It takes about 350 kJ of energy to break 1 mole of C-O bonds. (D C-O = 350 kJ/mol)
Calculate the maximum wavelength of light (in nm) for which one single C-O bond could be broken
by a single photon.
Useful equations: E = hν c = λν

Recall
  that c and h are constants:
c = speed of light = 2.9979 x 108 m/s h = Planck’s constant = 6.626 x 10-34 J · s

In order to calculate the wavelength (λ), you need the know the frequency (ν). To get frequency you need
to use the equation: E= hν
However, you can’t just plug in E = 350 kJ/mol. That E is the energy to break 1 MOLE of C-O bonds, you
only need to break 1 bond! So: 350 kJ/mol must be divided by Avogadro’s number of bonds /mole.

But also note that the units of h are J s , so the kJ must be converted to J before the math is done.

E = hν rearranging the terms: ν = = =

Once you know frequency (ν), you can solve for wavelength (λ).
c = λν rearranging the terms: λ = = = or 342 nm

Based upon the info provided in the last two questions: DN-O = 160 kJ/mol and DC-O = 350 kJ/mol

It is clear that the C-O bond must be a stronger bond than the N-O bond… because it takes more energy to break
a C-O bond apart! In order to better understand bonds, we must understand what causes them to form in the
first place. To do this, we must understand the electronic configuration of the atoms that make up the bonds.
In the 17th century, Sir Isaac Newton showed that sunlight is composed of
various color components that when combined produce a white light.

When you take white light and beam it

through a prism, it breaks up into the full
visible part of the EM spectrum- showing
all colors!

Interestingly, if you view the light emitted from “excited” individual atoms in the gas phase
(excited by adding energy- e.g. by burning or sending an electric current through ) and then
you beam that light through a prism, you WILL NOT see all colors of visible light. You will see
what looks like a “broken up” series of lines of varying colors.

Each element has its own distinct fingerprint of colors that it emits. We call this an element’s:
ATOMIC EMISSION SPECTRUM
 How can we see the individual line spectra for an atom?

www.flatworldknowlege.com

…using a spectroscope or a spectrophotometer!

Bohr’s Theory of the Hydrogen Atom

So why do line spectra occur? –> ask Physicist Niels Bohr

In 1913, physicists already knew that atoms contain protons and electrons. However, they thought
(incorrectly so) that the electrons whirled around the nucleus in circular orbits at high velocities.

However, according to the laws of classical physics, the negatively charged electrons should
eventually accelerate toward the positively charged nucleus and radiate away extra energy in the
form of electromagnetic radiation. Then the electrons would impact the protons in the nucleus and
annihilate themselves. THIS DOES NOT OCCUR!

To try to explain why this doesn’t occur, Niels Bohr theorized that the
electrons are only allowed to occupy certain orbits of specific energies.
Thus, he proposed that the orbits are “quantized”.

When atoms are energized (“excited”) ---by running an electrical

current through them or adding a heat source---, the electrons try to
“relax” back to their normal ground-state (lower energy state), by
radiating away the excess energy and dropping from the higher energy
orbit to a lower energy orbit.
Niels
  Bohr attributed the emission of radiation by an “excited” hydrogen atom to the electron dropping from a higher
energy orbital to a lower one, thus giving up a certain amount (or “quanta”) of energy in the form of light energy.

Building upon the work of Bohr, Johannes Rydberg mathematically showed that the energy that
an electron can occupy in a hydrogen atom can be explained by a single equation:

= -2
where: *n is the integer value (known as the Principle Quantum Number) that corresponds to the
energy shell where the electron resides
* the – sign signifies that the energy of the electron in the atom is lower than the energy of
a free electron which has no attraction for the + charged nucleus

So, as an electron moves closer to the nucleus, the value of n decreases which leads to a more negative value for E.
When n=1, which corresponds to the most stable energy state (the one with the least energy), we say the electron is in
its “ground state”.

Any n value > 1, is called an “excited state”, and the electron possesses more energy than in the ground state.

So… Radiant energy absorbed by an atom causes the electron to move from the ground state (n=1) to an
excited state (n>1).

Then… Radiant energy is emitted when the electron “relaxes” from a higher-energy state to a lower
energy state or even to the ground state.
***The quantity of energy involved in either type of change is determined by the difference in energy
levels between the initial and final states.
 Let’s try two problems: = -2

Calculate the energy of an electron in the n=3 state in a hydrogen atom.

  = -2

  = -2

  = -2

Calculate the energy of an electron in the n=5 state in a hydrogen atom.

  = -2

  = -2

  = -8
***The quantity of energy involved in either type of change is determined by the difference in energy
levels between the initial (ninitial) and final (nfinal)states.

  = -2   = -2

Combining the 2 equations to get ΔE:

  ΔE = -

  ΔE = 2
Simplifying gives us:

 ΔE = hν = 2
What can we determine from this Bohr/Rydberg equation?

We can calculate the energy emitted to move an electron between different energy orbits.
The transition results in the emission of a photon of frequency (ν) and energy (hν).
 ΔE = hν = 2

What is the wavelength of a photon (in nm) emitted during a transition from
the ni=5 state to the nf=2 state in the hydrogen atom?

  ΔE = 2.17987 x 10-18 J
ΔE = - 4.57773 x 10-19 J (*Note: the – sign just indicates that energy is emitted!)

Now that we know the amount of energy emitted, we can calculate the wavelength.
Recall: E = hν and c = λν,

So: λ = = or more simply: λ = = = 4.34 x 10-7 m

4.34 x 10-7 m x (1nm/ 10-9m) = 434nm

 In that last example when an electron “relaxes” from n=5 down to n=2, it emits
a photon of wavelength 434nm. Looking at the EM spectrum, we can see that
this corresponds to a wavelength in the visible portion of the spectrum.

434 nm corresponds to a violet color!

If you were the repeat the math in the previous slide for other the transitions, you would get
the exact line spectra you see for hydrogen.

n=6  n= 2 (wavelength of the photon emitted= 410 nm) – deep violet

n=5  n=2 (wavelength of the photon emitted= 434 nm) – violet
n=4  n=2 (wavelength of the photon emitted= 486 nm) – green-blue
n=3  n=2 (wavelength of the photon emitted= 656 nm) – red-orange
The wavelengths of the photons of energy that are emitted during transitions
are NOT exclusively in the visible portion of the EM spectrum.

Series nfinal ninitial Spectrum

Region
Lyman 1 2,3,4,… Ultraviolet
series
Balmer 2 3,4,5,… Visible &
series* Ultraviolet
Paschen 3 4,5,6,… Infrared
series
Brackett 4 5,6,7,… Infrared
series

It is only when the transition leads to an electron relaxing to n=2 (The Balmer
Series), will the wavelength of the photon emitted be in the visible portion of
the EM spectrum.
 Let’s try two problems: = -2
c = λν
c  = x 10 m/s h =
8  ΔE = hν = 2
6.626 x 10-34 J · s

Calculate the ΔE of an electron that is excited from n=1 to n=5.

 ΔE = 2

 ΔE = 2

 ΔE = 2
What is the wavelength of light (in nm) emitted when an electron in a hydrogen
atom relaxes from n=5 to n=3?
 ΔE = hν = 2
OK to remove the –
 ΔE = hν = -1 sign, because it
only tells that E was
 hν = = = 1 emitted

 = = 1.281 x 10-6 m

1.281 x 10-6 m x 1 nm/10-9m = 1281 nm infrared

 To be clear, this transitioning of electrons between energy levels is not a
phenomenon that is exclusive to hydrogen.

While the Bohr/Rydberg equation works very well for transitions between energy
levels of a hydrogen atom with only one electron, for atoms with multiple electrons,
this formula begins to break down and give incorrect results. The reason for the
inaccuracy is that the inner electrons can “shield” the outer electrons. The equation
is just too simplistic!