A Review of General Chemistry 1.

1 Introduction to Organic Chemistry

ELECTRONS, BONDS, AND MOLECULAR PROPERTIES In the early nineteenth century, scientists classified all
known compounds into two categories: Organic
Did you ever wonder . . . compounds were derived from living organisms (plants
what causes lightning? and animals), while inorganic compounds were derived
from nonliving sources (minerals and gases). This
Believe it or not, the answer to this question is distinction was fueled by the observation that organic
still the subject of debate (that’s right … scientists have compounds seemed to possess different properties
not yet figured out everything, contrary to popular than inorganic compounds. Organic compounds were
belief). There are various theories that attempt to often difficult to isolate and purify, and upon heating,
explain what causes the buildup of electric charge in they decomposed more readily than inorganic
clouds. One thing is clear, though—lightning involves a compounds. To explain these curious observations,
flow of electrons. By studying the nature of electrons many scientists subscribed to a belief that compounds
and how electrons flow, it is possible to control where obtained from living sources possessed a special “vital
lightning will strike. A tall building can be protected by force” that inorganic compounds lacked. This notion,
installing a lightning rod (a tall metal column at the top called vitalism, stipulated that it should be impossible to
of the building) that attracts any nearby lightning bolt, convert inorganic compounds into organic compounds
thereby preventing a direct strike on the building itself. without the introduction of an outside vital force.
The lightning rod on the top of the Empire State Vitalism was dealt a serious blow in 1828 when German
Building is struck over a hundred times each year. chemist Friedrich Wöhler demonstrated the conversion
of ammonium cyanate (a known inorganic salt) into
Just as scientists have discovered how to direct urea, a known organic compound found in urine:
electrons in a bolt of lightning, chemists have also
discovered how to direct electrons in chemical
reactions. We will soon see that although organic
chemistry is literally defined as the study of compounds
containing carbon atoms, its true essence is actually the
study of electrons, not atoms. Rather than thinking of
reactions in terms of the motion of atoms, we must
recognize that reactions occur as a result of the motion
of electrons. For example, in the following reaction the
curved arrows represent the motion, or flow, of Over the decades that followed, other examples
electrons. This flow of electrons causes the chemical were found, and the concept of vitalism was gradually
change shown: rejected. The downfall of vitalism shattered the original
distinction between organic and inorganic compounds,
and a new definition emerged. Specifically, organic
compounds became defined as those compounds
containing carbon atoms, while inorganic compounds
generally were defined as those compounds lacking
carbon atoms.
Throughout this course, we will learn how,
when, and why electrons flow during reactions. We will Organic chemistry occupies a central role in the
learn about the barriers that prevent electrons from world around us, as we are surrounded by organic
flowing, and we will learn how to overcome those compounds. The food that we eat and the clothes that
barriers. In short, we will study the behavioral patterns we wear are comprised of organic compounds. Our
of electrons, enabling us to predict, and even control, ability to smell odors or see colors results from the
the outcomes of chemical reactions. behavior of organic compounds. Pharmaceuticals,
pesticides, paints, adhesives, and plastics are all made
from organic compounds. In fact, our bodies are
This chapter reviews some relevant concepts
from your general chemistry course that should be constructed mostly from organic compounds (DNA,
familiar to you. Specifically, we will focus on the central RNA, proteins, etc.) whose behavior and function are
role of electrons in forming bonds and influencing determined by the guiding principles of organic
molecular properties. chemistry. The responses of our bodies to
pharmaceuticals are the results of reactions guided by
the principles of organic chemistry. A deep
understanding of those principles enables the design of SKILLBUILDER
new drugs that fight disease and improve the overall 1.1 Drawing constitutional isomers of small molecules
quality of life and longevity. Accordingly, it is not
surprising that organic chemistry is required knowledge LEARN the skill
for anyone entering the health professions. Draw all constitutional isomers that have the molecular
formula C3H8O.
1.2 The Structural Theory of Matter
Solution
In the mid-nineteenth century three individuals, Begin by determining the valency of each atom that
working independently, laid the conceptual foundations appears in the molecular formula. Carbon is tetravalent,
for the structural theory of matter. August Kekulé, hydrogen is monovalent, and oxygen is divalent. The
Archibald Scott Couper, and Alexander M. Butlerov each atoms with the highest valency are connected first. So,
suggested that substances are defined by a specific in this case, we draw our first isomer by connecting
arrangement of atoms. As an example, consider the the three carbon atoms, as well as the oxygen atom, as
following two compounds: shown below. The drawing is completed when the
monovalent atoms (H) are placed at the periphery:

This isomer (called 1-propanol) can be drawn in many

different ways, some of which are shown here:
These compounds have the same molecular
formula (C2H6O), yet they differ from each other in the
way the atoms are connected—that is, they differ in
their constitution. As a result, they are called
constitutional isomers. Constitutional isomers have
different physical properties and different names. The
first compound is a colorless gas used as an aerosol All of these drawings represent the same
spray propellant, while the second compound is a clear isomer. If we number the carbon atoms (C1, C2, and
liquid, commonly referred to as “alcohol,” found in C3), with C1 being the carbon atom connected to
alcoholic beverages. oxygen, then all of the drawings above show the same
connectivity: a three-carbon chain with an oxygen atom
According to the structural theory of matter, each attached at one end of the chain.
element will generally form a predictable number of
bonds. For example, carbon generally forms four bonds Thus far, we have drawn just one isomer that
and is therefore said to be tetravalent. Nitrogen has the molecular formula C3H8O. Other constitutional
generally forms three bonds and is therefore trivalent. isomers can be drawn if we consider other possible
Oxygen forms two bonds and is divalent, while ways of connecting the three carbon atoms and the
hydrogen and the halogens form one bond and are oxygen atom. For example, the oxygen atom can be
monovalent. connected to C2 (rather than C1), giving a compound
called 2-propanol (shown below). Alternatively, the
Figure 1.1 oxygen atom can be inserted between two carbon
atoms, giving a compound called ethyl methyl ether
(also shown below). For each isomer, two of the many
acceptable drawings are shown:
 Thomson (Cambridge University) demonstrated
evidence supporting the existence of Stoney’s
mysterious electron and is credited with discovering the
electron. In 1916, Gilbert Lewis (University of California,
Berkeley) defined a covalent bond as the result of two
atoms sharing a pair of electrons. As a simple example,
consider the formation of a bond between two
If we continue to search for alternate ways of hydrogen atoms:
connecting the three carbon atoms and the oxygen
atom, we will not find any other ways of connecting
them. So in summary, there are a total of three
constitutional isomers with the molecular formula Each hydrogen atom has one electron. When these
C3H8O, shown here: electrons are shared to form a bond, there is a decrease
in energy, indicated by the negative value of ΔH. The
energy diagram in Figure 1.2 plots the energy of the two
hydrogen atoms as a function of the distance between
them. Focus on the right side of the diagram, which
represents the hydrogen atoms separated by a large
distance. Moving toward the left on the diagram, the
Additional skills (not yet discussed) are required to draw hydrogen atoms approach each other, and there are
constitutional isomers of compounds containing a ring, several forces that must be taken into account: (1) the
a double bond, or a triple bond. Those skills will be force of repulsion between the two negatively charged
developed in Section 14.16. electrons, (2) the force of repulsion between the two
positively charged nuclei, and (3) the forces of
Practice the skill attraction between the positively charged nuclei and
1.1 Draw all constitutional isomers with the following the negatively charged electrons. As the hydrogen
molecular formula. atoms get closer to each other, all of these forces get
stronger. Under these circumstances, the electrons are
(a) C3H7Cl (b) C4H10 (c) C5H12 (d) C4H10O (e) C3H6Cl2 capable of moving in such a way so as to minimize the
repulsive forces between them while maximizing their
Apply the skill attractive forces with the nuclei. This provides for a net
1.2 Chlorofluorocarbons (CFCs) are gases that were force of attraction, which lowers the energy of the
once widely used as refrigerants and propellants. When system. As the hydrogen atoms move still closer
it was discovered that these molecules contributed to together, the energy continues to be lowered until the
the depletion of the ozone layer, their use was banned, nuclei achieve a separation (internuclear distance) of
but CFCs continue to be detected as contaminants in 0.74 angstroms (Å). At that point, the force of repulsion
the environment. Draw all of the constitutional isomers between the nuclei begins to overwhelm the forces of
of CFCs that have the molecular formula C2Cl3F3. attraction, causing the energy of the system to increase
if the atoms are brought any closer together. The lowest
1.3 Electrons, Bonds, and Lewis Structures point on the curve represents the lowest energy (most
What Are Bonds? stable) state. This state determines both the bond
As mentioned, atoms are connected to each length (0.74 Å) and the bond strength (436 kJ/mol).
other by bonds. That is, bonds are the “glue” that hold
atoms together. But what is this mysterious glue and
how does it work? In order to answer this question,
we must focus our attention on electrons.

The existence of the electron was first proposed

in 1874 by George Johnstone Stoney (National
University of Ireland), who attempted to explain
electrochemistry by suggesting the existence of a
particle bearing a unit of charge. Stoney coined the
term electron to describe this particle. In 1897, J. J.
Drawing the Lewis Structure of an Atom electron is placed by itself (unpaired) around
Armed with the idea that a bond represents a pair of the B, like this:
shared electrons, Lewis then devised a method for
drawing structures. In his drawings, called Lewis
structures, the electrons take center stage. We will
begin by drawing individual atoms, and then we will (b) Nitrogen belongs to group 5A on the periodic
draw Lewis structures for small molecules. First, we table, and it therefore has five valence
must review a few simple features of atomic structure: electrons. The periodic symbol for nitrogen (N)
is drawn, and each electron is placed by itself
• The nucleus of an atom is comprised of protons and (unpaired) on a side of the N until all four sides
neutrons. Each proton has a charge of +1, and each are occupied:
neutron is electrically neutral.
• For a neutral atom, the number of protons is balanced
by an equal number of electrons, which have a charge
of −1 and exist in shells. The first shell, which is closest
to the nucleus, can contain two electrons, and the Any remaining electrons must be paired up with
second shell can contain up to eight electrons. the electrons already drawn. In the case of
• The electrons in the outermost shell of an atom are nitrogen, there is only one more electron to
called the valence electrons. The number of valence place, so we pair it up with one of the four
electrons in an atom is identified by its group number in unpaired electrons (it doesn’t matter which one
the periodic table (Figure 1.3). we choose):

Practice the skill

1.3 Draw a Lewis dot structure for each of the following

atoms:

(a) Carbon (b) Oxygen (c) Fluorine (d) Hydrogen

The Lewis dot structure of an individual atom (e) Bromine (f ) Sulfur (g) Chlorine (h) Iodine
indicates the number of valence electrons, which are
placed as dots around the periodic symbol of the atom 1.4 Compare the Lewis dot structure of nitrogen and
(C for carbon, O for oxygen, etc.). The placement of phosphorus and explain why you might expect
these dots is illustrated in the following SkillBuilder. these two atoms to exhibit similar bonding
properties.

SKILLBUILDER 1.5 Name one element that you would expect to exhibit
1.2 drawing the lewis dot structure of an atom bonding properties similar to boron. Explain.

LEARN the skill 1.6 Draw a Lewis structure of a carbon atom that is
Draw the Lewis dot structure of missing one valence electron (and therefore bears a
(a) a boron atom and (b) a nitrogen atom. positive charge). Which second-row element does
Solution this carbon atom resemble in terms of the number
of valence electrons?
(a) In a Lewis dot structure, only valence electrons
are drawn, so we must first determine the
number of valence electrons. Boron belongs to
group 3A on the periodic table, and it therefore
has three valence electrons. The periodic
symbol for boron (B) is drawn, and each
Apply the skill
SKILLBUILDER
1.7 Lithium salts have been used for decades to treat 1.3 drawing the lewis structure of a small molecule
mental illnesses, including depression and bipolar
disorder. Although the treatment is effective, LEARN the skill
researchers are still trying to determine how lithium Draw the Lewis structure of CH2O.
salts behave as mood stabilizers. Solution
There are four discrete steps when drawing a Lewis
(a) Draw a Lewis structure of an uncharged lithium structure: First determine the number of valence
atom, Li. electrons for each atom.

(b) Lithium salts contain a lithium atom that is

missing one valence electron (and therefore bears a
positive charge). Draw a Lewis structure of the
lithium cation.
Then, connect any atoms that form more than one
Drawing the Lewis Structure of a Small Molecule bond. Hydrogen atoms only form one bond each, so we
The Lewis dot structures of individual atoms are will save those for last. In this case, we connect the C
combined to produce Lewis dot structures of small and the O.
molecules. These drawings are constructed based on
the observation that atoms tend to bond in such a way
so as to achieve the electron configuration of a noble
gas. For example, hydrogen will form one bond to Next, connect all hydrogen atoms. We place the
achieve the electron configuration of helium (two hydrogen atoms next to carbon, because carbon has
valence electrons), while second-row elements (C, N, O, more unpaired electrons than oxygen.
and F) will form the necessary number of bonds so as to
achieve the electron configuration of neon (eight
valence electrons).

Finally, check to see if each atom (except hydrogen) has

an octet. In fact, neither the carbon nor the oxygen has
an octet, so in a situation like this, the unpaired
electrons are shared as a double bond between carbon
and oxygen.

This observation, called the octet rule, explains why

carbon is tetravalent. As just shown, it can achieve an
octet of electrons by using each of its four valence
electrons to form a bond. The octet rule also explains Now all atoms have achieved an octet. When drawing
why nitrogen is trivalent. Specifically, it has five valence Lewis structures, remember that you cannot simply add
electrons and requires three bonds in order to achieve more electrons to the drawing. For each atom to
an octet of electrons. Notice that the nitrogen atom achieve an octet, the existing electrons must be shared.
contains one pair of unshared, or nonbonding, The total number of valence electrons should be correct
electrons, called a lone pair. In the next chapter, we will when you are finished. In this example, there was one
discuss the octet rule in more detail; in particular, we carbon atom, two hydrogen atoms, and one oxygen
will explore when it can be violated and when it cannot atom, giving a total of 12 valence electrons (4 + 2 + 6).
be violated. For now, let’s practice drawing Lewis The drawing above MUST have 12 valence electrons, no
structures. more and no less.
Practice the skill therefore has four valence electrons. Oxygen is in group
6A and has six valence electrons.
1.8 Draw a Lewis structure for each of the following
compounds: After identifying the appropriate number of electrons
(a) C2H6 for each atom in a Lewis structure, the next task is to
(b) C2H4 determine if any of the atoms exhibit an unexpected
(c) C2H2 number of electrons. For example, consider the
(d) C3H8 following structure.
(e) C3H6
(f) CH3OH

1.9 Borane (BH3) is very unstable and quite reactive.

Draw a Lewis structure of borane and explain the
source of the instability. Each line represents two shared electrons (a bond). For
our purposes, we must split each bond apart equally,
1.10 There are four constitutional isomers with the and then count the number of electrons on each atom.
molecular formula C3H9N. Draw a Lewis, structure
for each isomer and determine the number of lone
pairs on the nitrogen atom in each case.

Apply the skill

Each hydrogen atom has one valence electron, as
1.11 Smoking tobacco with a water pipe, or hookah, expected. The carbon atom also has the appropriate
is often perceived as being less dangerous than number of valence electrons (four), but the oxygen
smoking cigarettes, but hookah smoke has been atom does not. The oxygen atom in this structure
found to contain the same variety of toxins and exhibits seven valence electrons, but it should only have
carcinogens (cancer-causing compounds) as six. In this case, the oxygen atom has one extra
cigarette smoke. Draw a Lewis structure for each of electron, and it must therefore bear a negative formal
the following dangerous compounds found in charge, which is indicated like this.
tobacco smoke:

(a) HCN (hydrogen cyanide)

(b) CH2CHCHCH2 (1,3-butadiene)

1.4 Identifying Formal Charges

A formal charge is associated with any atom that does SKILLBUILDER

not exhibit the appropriate number of valence 1.4 calculating formal charge
electrons. When such an atom is present in a Lewis
structure, the formal charge must be drawn.
LEARN the skill
Identifying a formal charge requires two discrete tasks: Consider the nitrogen atom in the structure below and
1. Determine the appropriate number of valence determine if it has a formal charge:
electrons for an atom.
2. Determine whether the atom exhibits the
appropriate number of electrons.

The first task can be accomplished by inspecting the

periodic table. As mentioned earlier, the group number
indicates the appropriate number of valence electrons Solution
for each atom. For example, carbon is in group 4A and We begin by determining the appropriate number of
valence electrons for a nitrogen atom. Nitrogen is in
group 5A of the periodic table, and it should therefore
have five valence electrons. Next, we count how many Apply the skill
valence electrons are exhibited by the nitrogen atom in
this particular example. 1.14 If you are having trouble paying attention during a
long lecture, your levels of acetylcholine
(a neurotransmitter) may be to blame. Identify any
formal charges in acetylcholine.

In this case, the nitrogen atom exhibits only four

valence electrons. It is missing one electron, so it must
bear a positive charge, which is shown like this:

1.5 Induction and Polar Covalent Bonds

Chemists classify bonds into three categories:

(1) covalent, (2) polar covalent, and (3) ionic. These
categories emerge from the electronegativity values of
the atoms sharing a bond. Electronegativity is a
Practice the skill measure of the ability of an atom to attract electrons.
1.12 Identify any formal charges in the structures Table 1.1 gives the electronegativity values for elements
below: commonly encountered in organic chemistry.

When two atoms form a bond, one critical

consideration allows us to classify the bond: What is the
difference in the electronegativity values of the two
atoms? Below are some rough guidelines:
If the difference in electronegativity is less than 0.5,
1.13 Draw a structure for each of the following ions; the electrons are considered to be equally shared
in each case, indicate which atom possesses the between the two atoms, resulting in a covalent bond.
formal charge: Examples include C−C and C−H:
(a) BH4−
(b) NH2−
(c) C2H5+
The C−C bond is clearly covalent, because there is no This spectrum has two extremes: covalent bonds on the
difference in electronegativity between the two atoms left and ionic bonds on the right. Between these two
forming the bond. Even a C−H bond is considered to be extremes are the polar covalent bonds. Some bonds fit
covalent, because the difference in electronegativity clearly into one category, such as C−C bonds (covalent),
between C and H is less than 0.5. If the difference in C−O bonds (polar covalent), or NaCl bonds (ionic).
electronegativity is between 0.5 and 1.7, the electrons However, there are many cases that are not so clear-
are not shared equally between the atoms, resulting in cut. For example, a C−Li bond has a difference in
a polar covalent bond. For example, consider a bond electronegativity of 1.5, and this bond is often drawn
between carbon and oxygen (C−O). Oxygen is either as polar covalent or as ionic. Both drawings are
significantly more electronegative (3.5) than carbon acceptable:
(2.5), and therefore, oxygen will more strongly attract
the electrons of the bond. The withdrawal of electrons
toward oxygen is called induction, which is often
indicated with an arrow like this.

Another reason to avoid absolute cutoff numbers when

comparing electronegativity values is that the
electronegativity values shown above are obtained via
Induction causes the formation of partial positive and one particular method developed by Linus Pauling.
partial negative charges, symbolized by the Greek However, there are at least seven other methods for
symbol delta (δ). The partial charges that result from calculating electronegativity values, each of which
induction will be very important in upcoming chapters. provides slightly different values. Strict adherence to
the Pauling scale would suggest that C−Br and C−I bonds
are covalent, but these bonds will be treated as polar
covalent throughout this course.

If the difference in electronegativity is greater than

1.7, the electrons are not shared at all. For example, KILLBUILDER
consider the bond between sodium and oxygen in 1.5 locating partial charges resulting from induction
sodium hydroxide (NaOH).
LEARN the skill
Consider the structure of methanol. Identify all polar
covalent bonds and show any partial charges that result
from inductive effects:
The difference in electronegativity between O and Na is
so great that both electrons of the bond are possessed
solely by the oxygen atom, rendering the oxygen
negatively charged and the sodium positively charged.
The bond between oxygen and sodium, called an ionic
bond, is the result of the force of attraction between
the two oppositely charged ions. The cutoff numbers
(0.5 and 1.7) should be thought of as rough guidelines.
Rather than viewing them as absolute, we must view
the various types of bonds as belonging to a spectrum
without clear cutoffs (Figure 1.4).
Solution Apply the skill
First identify all polar covalent bonds. The C−H bonds
are considered to be covalent because the 1.16 The regions of δ+ in a compound are the regions
electronegativity values for C and H are fairly close. It is most likely to be attacked by an anion, such as
true that carbon is more electronegative than hydrogen, hydroxide (HO−). In the compound shown, identify the
and therefore, there is a small inductive effect for each two carbon atoms that are most likely to be attacked by
C−H bond. However, we will generally consider this a hydroxide ion.
effect to be negligible for C−H bonds. The C−O bond and
the O−H bond are both polar covalent bonds:

1.17 Plastics and synthetic fibers are examples of the

many materials made from repeating subunits of
carbon-containing molecules called polymers. Although
most synthetic polymers are prepared from fossil fuel
Now determine the direction of the inductive effects. sources, many researchers are exploring ways to make
Oxygen is more electronegative than C or H, so the polymers from renewable sources instead. One example
inductive effects are shown like this: is the synthesis of an epoxy resin polymer using a by-
product from cashew nut processing, another
compound isolated from corn cobs, and
epichlorohydrin, shown here. Identify any polar
covalent bonds in epichlorohydrin by drawing δ+ and δ−
symbols in the appropriate locations.

These inductive effects dictate the locations of the

partial charges:

Practice the skill

1.15 For each of the following compounds, identify any
polar covalent bonds by drawing δ+ and δ− symbols in
the appropriate locations:
Practically Speaking particles, also exhibited wavelike properties. Based on
Electrostatic Potential Maps this assertion, a new theory of matter was born.
In 1926, Erwin Schrödinger, Werner Heisenberg, and
Partial charges can be visualized with three Paul Dirac independently proposed a mathematical
dimensional, rainbow-like images called electrostatic description of the electron that incorporated its
potential maps. As an example, consider the following wavelike properties. This new theory, called wave
electrostatic potential map of chloromethane: mechanics, or quantum mechanics, radically changed
the way we viewed the nature of matter and laid the
foundation for our current understanding of electrons
and bonds. Quantum mechanics is deeply rooted in
mathematics and represents an entire subject by itself.
The mathematics involved is beyond the scope of our
course, and we will not discuss it here. However, in
order to understand the nature of electrons, it is critical
to understand a few simple highlights from quantum
mechanics:

In the image, a color scale is used to represent areas of • An equation is constructed to describe the total
δ− and δ+. As indicated, red represents a region that is energy of a hydrogen atom (i.e., one proton
δ−, while blue represents a region that is δ+. In reality, plus one electron). This equation, called the wave
electrostatic potential maps are rarely used by equation, takes into account the wavelike
practicing organic chemists when they communicate behavior of an electron that is in the electric field of a
with each other; however, these illustrations can proton.
often be helpful to students who are learning organic • The wave equation is then solved to give a series of
chemistry. Electrostatic potential maps are generated solutions called wavefunctions. The Greek
by performing a series of calculations. Specifically, an symbol psi (ψ) is used to denote each wavefunction
imaginary point positive charge is positioned at various (ψ1, ψ2, ψ3, etc.). Each of these wavefunctions
locations, and for each location, we calculate the corresponds to an allowed energy level for the electron.
potential energy associated with the attraction between This result is incredibly important
the point positive charge and the surrounding because it suggests that an electron, when contained in
electrons. A large attraction indicates a position of δ−, an atom, can only exist at discrete
while a small attraction indicates a position of δ+. The energy levels (ψ1, ψ2, ψ3, etc.). In other words, the
results are then illustrated using colors, as shown. A energy of the electron is quantized.
comparison of any two electrostatic potential maps is • Each wavefunction is a function of spatial location. It
only valid if both maps were prepared using the same provides information that allows us to
color scale. Throughout this book, care has been taken assign a numerical value for each location in three-
to use the same color scale whenever two maps are dimensional space relative to the nucleus.
directly compared to each other. However, it will not be The square of that value (ψ2 for any particular location)
useful to compare two maps from different pages of has a special meaning. It indicates the
this book (or any other book), as the exact color scales probability of finding the electron in that location.
are likely to be different. Therefore, a three-dimensional plot of ψ2
will generate an image of an atomic orbital (Figure 1.5).
1.6 Atomic Orbitals
Quantum Mechanics
By the 1920s, vitalism had been discarded. Chemists
were aware of constitutional isomerism and had
developed the structural theory of matter. The electron
had been discovered and identified as the source of
bonding, and Lewis structures were used to keep track
of shared and unshared electrons. But the Electron Density and Atomic Orbitals
understanding of electrons was about to change An orbital is a region of space that can be occupied by
dramatically. In 1924, French physicist Louis de Broglie an electron. But care must be taken when trying to
suggested that electrons, heretofore considered as visualize this. There is a statement from the previous
section that must be clarified because it is potentially order to understand some of the characteristics of
misleading: “ψ2 represents the probability of finding an orbitals. Consider a wave that moves across the surface
electron in a particular location.” This statement seems of a lake (Figure 1.6). The wave function (ψ)
to treat an electron as if it were a particle flying around mathematically describes the wave, and the value of
within a specific region of space. But remember that an the wave function is dependent on location. Locations
electron is not purely a particle—it has wavelike
properties as well. Therefore, we must construct a
mental image that captures both of these properties.
That is not easy to do, but the following analogy might
help. We will treat an occupied orbital as if it is a
cloud—similar to a cloud in the sky. No analogy is
perfect, and there are certainly features of clouds that
are very different from orbitals. However, focusing on
some of these differences between electron clouds
(occupied orbitals) and real clouds makes it possible to above the average level of the lake have a positive value
construct a better mental model of an electron in an for ψ (indicated in red), and locations below the
orbital: average level of the lake have a negative value for ψ
• Clouds in the sky can come in any shape or size. (indicated in blue). Locations where the value of ψ is
However, electron clouds have specific shapes and sizes zero are called nodes. Similarly, orbitals can have
(as defined by the orbitals). regions where the value of ψ is positive, negative, or
• A cloud in the sky is comprised of billions of individual zero. For example, consider a p orbital (Figure 1.7).
water molecules. An electron cloud is not comprised of Notice that the p orbital has two lobes: The top lobe is a
billions of particles. We must think of an electron cloud region of space where the values of ψ are positive,
as a single entity, even though it can be thicker in some while the bottom lobe is a region where the values of ψ
places and thinner in other places. This concept is are negative. Between the two lobes is a location where
critical and will be used extensively throughout the ψ = 0. This location represents a node. Be careful not to
course in explaining reactions. confuse the sign of ψ (+ or −) with electrical charge. A
• A cloud in the sky has edges, and it is possible to positive value for ψ does not imply a positive charge.
define a region of space that contains 100% The value of ψ (+ or −) is a mathematical convention
of the cloud. In contrast, an electron cloud does not that refers to the phase of the wave (just like in the
have defined edges. We frequently use lake). Although ψ can have positive or negative values,
the term electron density, which is associated with the nevertheless ψ2 (which describes the electron density
probability of finding an electron in a particular region as a function of location) will always be a positive
of space. The “shape” of an orbital refers to a region of number. At a node, where ψ = 0, the electron density
space that contains 90–95% of the electron density. (ψ2) will also be zero. This means that there is no
Beyond this region, the remaining 5–10% of the electron density located at a node. From this point
electron density tapers off but never ends. In fact, if we forward, we will draw the lobes of an orbital with colors
want to consider the region of space that contains 100% (red and blue) to indicate the phase of ψ for each region
of the electron density, we must consider the entire of space.
universe. In summary, we must think of an orbital as a
region of space that can be occupied by electron
density. An occupied orbital must be treated as a cloud
of electron density. This region of space is called an
atomic orbital (AO), because it is a region of space
defined with respect to the nucleus of a single atom.
Examples of atomic orbitals are the s, p, d, and f orbitals
that were discussed in your general chemistry textbook.
Phases of Atomic Orbitals
Our discussion of electrons and orbitals has been based
on the premise that electrons have wavelike
properties. As a result, it will be necessary to explore
some of the characteristics of simple waves in
Filling Atomic Orbitals with Electrons 3. Hund’s rule. When dealing with degenerate orbitals,
The energy of an electron depends on the type of such as p orbitals, one electron is placed in each
orbital that it occupies. Most of the organic compounds degenerate orbital first, before electrons are paired up.
that we will encounter will be composed of first- and The application of the first two principles can be seen in
second-row elements (H, C, N, and O). These elements the electron configurations shown in Figure 1.9 (H, He,
utilize the 1s orbital, the 2s orbital, and the three 2p Li, and Be). The application of the third principle can be
orbitals. Our discussions will therefore focus primarily seen in the electron configurations for the remaining
on these orbitals (Figure 1.8). Electrons are lowest in second-row elements (Figure 1.10).
energy when they occupy a 1s orbital, because the 1s
orbital is closest to the nucleus and it has no nodes (the
more nodes that an orbital has, the greater its energy).
The 2s orbital has one node and is farther away from
the nucleus; it is therefore higher in energy than the 1s
orbital. After the 2s orbital, there are three 2p orbitals
that are all equivalent in energy to one another. Orbitals
with the same energy level are called degenerate
orbitals.

As we move across the periodic table, starting with

hydrogen, each element has one more electron than
the element before it (Figure 1.9). The order in which
the orbitals are filled by electrons is determined by just
three simple principles:

1. The Aufbau principle. The lowest energy orbital is

filled first.
2. The Pauli exclusion principle. Each orbital can
accommodate a maximum of two electrons that have
opposite spin. To understand what “spin” means, we
can imagine an electron spinning in space (although this
is an oversimplified explanation of the term “spin”). For
reasons that are beyond the scope of this course,
electrons only have two possible spin states (designated
by ⇃ or ↾). In order for the orbital to accommodate two
electrons, the electrons must have opposite spin states.