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A Review of General Chemistry
A Review of General 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:
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.
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.