Chemical Thinking I

Chemical
Thinking
Volume I
University of Arizona
Chemical Thinking
Preface
The chemical thinking curriculum introduces an alternative way of conceptualizing the introduc-
tory chemistry curriculum for science and engineering majors. The curriculum has been designed
with the following goals in mind:
• Present chemistry as a powerful way of thinking rather than as a static body of knowledge
• Use essential questions in the discipline to guide the presentation and discussion of relevant
content
• Emphasize conceptual understanding of core concepts and ideas in chemistry
• Build student understanding through carefully designed learning progressions based on exist-
ing research in chemistry education
• Offer many opportunities for students to engage with core concepts and ideas through activi-
ties that ask them to analyze data, model chemical systems, and generate evidence-based
explanations
• Create opportunities for students to demonstrate and self-assess their understanding via the
application of their knowledge and skills in solving relevant integrated problems
• Engage students in thinking about important issues in four critical areas of interest for the
science and technology of the 21st century: energy sources, environmental issues, life and
medicine, and materials by design
• Take advantage of diverse educational tools that allow students to explore chemical ideas and
phenomena in interactive ways
The chemical thinking curriculum has been developed, tested, and implemented at the University
of Arizona. We thank all the students, instructors, and educational staff that had made it possible.
The project was initially funded by the National Science Foundation (DUE-0736844).
Vicente Talanquer
John Pollard
Chemical Thinking I
Contents
U1. How do we distinguish substances? 2
M1. Searching for differences................................................................4
M2. Modeling matter...........................................................................18
M3. Analyzing particles........................................................................36
M4. Determining composition.............................................................58
U2. How do we determine structure? 82

M1. Analyzing light-matter interactions..............................................84
M2. Looking for patterns....................................................................100
M3. Predicting geometry...................................................................124
M4. Inferring charge distribution......................................................144
U3. How do we predict properties? 166

M1. Analyzing molecular structure...................................................168
M2. Considering different scales.......................................................190
M3. Characterizing ionic networks....................................................202
U4. How do we characterize chemical processes? 228

M1. Modeling chemical reactions.....................................................230
M2. Understanding proportions........................................................246
M3. Tracking energy...........................................................................260

1
UNIT 1
How do we
distinguish
substances?
Our world is characterized by its diversity at all levels,
from the wide variety of living organisms to the multi-
tude of materials present in everything that surrounds
us. Understanding the diversity of the material world
has been particularly important for the survival of hu-
mans on Earth. The ability to detect, identify, separate,
and quantify different types of substances has allowed
us to take advantage of the many natural resources that
our planet has to offer. These same abilities are also
likely to help us save Earth from the environmental
consequences of our decisions and actions.
The central goal of this Unit is to help you under-

stand and apply basic ideas and ways of thinking
to distinguish the different substances present in a
variety of systems of interest. Although the ideas and
models that we will discuss are useful in many relevant
contexts, to illustrate their power we will analyze many
examples related to our Earth’s atmosphere, trying to
answer questions such as:
What is it made of?

How do we separate its components?
How do we identify them?
How do we explain their properties? Blue Marble
How do we model their behavior? NASA
2
Chemical Thinking
UNIT 1 MODULES
M1. Searching for Differences

Identifying differences that allow us to
separate components.
M2. Modeling Matter
Using the particulate model of matter to
explain differences.
M3. Analyzing Particles
Analyzing differences in particle compo-
sition and mass.
M4. Determining Composition
Characterizing differences in particle
composition.
3
4
Searching for
Differences
Most things in our surroundings are complex systems composed of many sub-
U1: MODULE 1
stances in different states of matter. For example, the air we breathe contains at
least a dozen different substances, from oxygen gas to microscopic water droplets
to solid sodium chloride particles. This chemical complexity may be a blessing or
a curse. On the one hand, this diversity of substances and phases has allowed the
emergence of life on Earth and the development of the rich
natural resources that sustain it. On the other hand, the
large number of substances found in a single breath
makes it difficult to detect, identify, and isolate the
things that can threaten that same life.
The large number of substances present in our
own bodies, and in most of the systems with which
we interact on a daily basis, poses a constant chal-
lenge to many professionals. How do we detect the
presence of cholesterol in a complex mixture, such as
Earth’s
blood? How do we identify the pollutants that may be Atmosphere
present in drinking water? How do we know what substances are NASA
in the soil or in the minerals that are extracted from the ground? The answers to
these questions require some “chemical thinking,” as illustrated in the following
challenge.
THE CHALLENGE Extracting Oxygen

Imagine that you were interested in separating pure oxygen from the atmo-
sphere for commercial purposes. You may want to sell it to hospitals for using
in the treatment of pneumonia, emphysema, and other respiratory diseases.
• How would you separate oxygen from other air components?

• What properties of this substance would help you separate it?
Make a list of potential strategies that you would follow to solve this problem.
Then, share and discuss your ideas with one of your classmates.
Module 1 will help you develop the type of chemical reasoning that is used to
answer questions similar to those posed in the challenge. In particular, the central
goal of Module 1 is to help you recognize distinctive properties of chemical sub-
stances that can be used to identify and separate them.
Chemical Thinking U1 How do we distinguish substances? 5
Differentiating Characteristics
In modern times, many people are interested in finding out the chemical composi-
tion of a variety of things in their surroundings. Everybody now expects food labels
http://www.chem.arizona.edu/tpp/chemthink/resources/U1_M1/Ozone.html
Total Ozone
to list the contents of what they eat. Many cities around the world monitor the
presence of well known atmospheric pollutants on a regular basis. Artificial satel- Low High
lites detect and quantify the amounts of important
substances in our atmosphere, such as ozone (see
Figure 1.1) and carbon dioxide, every day. The abil-
ity to detect or identify all the substances present
in a given system is an extraordinary achievement
CLICK TO PLAY
of human kind. Most of the systems we encounter,
natural or artificial, are mixtures of many different
substances. Many of these mixtures are homoge-
neous: combinations of substances that have uni-
form composition and properties and may look like
single substances, such as clean air and drinking wa-
ter. Other mixtures are heterogeneous and they are
composed of visibly different substances that can be
in the same or in different phases (e.g., solid, liquid, or gas), as is the case of many Figure 1.1 NASA has developed
and launched in space instruments
minerals on Earth and our own body. The composition and properties of some sys- that allow constant monitoring of
the amount of ozone in the strato-
tems remain constant for long periods of time, but in other situations they change sphere. Click on the image to see
how ozone amounts vary during
on a regular basis. Given the diversity of the materials in our world, how can we the year over Antarctica.
determine their chemical composition?
The chemical analysis of the substances present in any given system is
based on a simple assumption made by chemists about the nature of the world:
Each substance, no matter how simple or complex, has at least one differentiating
characteristic that makes it unique. If we find this differentiating property and are
able to measure it, we will be in a good position to detect, identify, separate, and
quantify the amount of that substance in a variety of places and circumstances.
Choosing Properties LET’S THINK
Air is a mixture of many substances, including nitrogen, oxygen, carbon diox-

ide, argon, and water. Which of the following properties of substances would
be good “differentiating characteristics” to separate each component?
Temperature Mass Viscosity

Boiling Point Density Volume
Pressure Solubility Concentration
Share your ideas with one or more classmates. Make sure to:
• Identify the basic features that you think a good differentiating charac-
teristic should have.
• Discuss why some properties in this list are not good differentiating
characteristics.
6 MODULE 1 Searching for Differences
Good differentiating characteristics are properties that do not depend on the

amount of substance that we have (intensive properties). These are properties
such as melting point, density, and conductivity. Properties that depend on the
amount of substance (extensive properties), such as mass and volume, are not
differentiating characteristics because they can take many values for the same sub-
stance or similar values for different ones. Being an intensive property, however,
is not good enough for purposes of identification. Temperature and pressure are
intensive properties of a system, but they cannot be used as differentiating charac-
teristics for any substance because they are properties of the entire system, and not
of its individual components. Good differentiating characteristics are properties
with unique values for each substance, that do not vary with the size of the sample,
and that can be selectively measured.
For example, the boiling points of the different components
of the air in the atmosphere are very useful differentiating char-
Table 1.1 Air Main Components
acteristics to separate them. The boiling point is the temperature
Boiling Temperatures ( 1 atm) at which a substance transforms from liquid to gas at a given
Substance pressure and, in general, takes values that vary from substance
o
C K
to substance. The boiling temperature also corresponds to the
Water 100 373.15
temperature at which the gas turns into a liquid. As a result, if
Oxygen -182.9 90.20 we were to cool down an air sample at sea level, we would see
Argon -189.3 87.36 the different air components condensing at the temperatures
Nitrogen -195.8 77.36 shown in Table 1.1, which are the boiling temperatures at at-
mospheric pressure at sea level (normal boiling points). This
information can be used to identify the substance that is condensing and separate
it from the mixture.
USEFUL TOOLS transformed into degrees Kelvin using the

following relationship:
The differentiating characteristics of chemi-
cal substances are conventionally mea- [K] = [oC] + 273.15
sured at constant atmospheric tempera-
ture and pressure. These quantities can Thus, for example, the boiling point of wa-
be expressed in a variety of units that you ter (= 100 oC) corresponds to
must recognize and be able to manipulate.
[K] = 100 oC + 273.15 = 373.15 K
Units of Temperature. In the International
System of Units (SI), temperature is mea- Units of Pressure. In the SI, pressure is mea-
sured using the Kelvin scale. This is an ab- sured using units called Pascals (Pa). One
solute temperature scale in which the zero pascal is equivalent to a pressure of one
of the scale (0 K) corresponds to the low- newton per square meter (1 N/m2). In sci-
est temperature that can be theoretically ence and engineering it is also common to
achieved. Increments in temperature are use the standard atmosphere (atm) as unit
measured in Kelvins (K). of pressure, where 1 atm is approximately
Another temperature scale used in sci- equal to the average atmospheric pressure
ence and engineering is the Celsius scale. In at sea level in our planet. Another common
this system, the zero of the scale is defined unit is “millimeters of mercury” (mm Hg or
as the freezing point of water (0 oC) and Torr). Conversions between these different
100 oC corresponds to the boiling tempera- units can be performed using the following
ture of the same substance. A temperature conversion factors:
measurement in degrees Celsius can be
1 atm = 101, 325 Pa = 760 mm Hg
Phase Transitions
The transformation of a pure substance from one phase to another at constant

pressure occurs at a well defined temperature that can be used as differentiating
characteristic. During this phase transition, or phase change, the chemical nature
of the substance is preserved and the transition temperature can be measured with
great accuracy and precision using digital devices. Understanding phase behavior
is crucial for designing successful strategies to identify and separate many sub-
stances of interest. For example, extracting oxygen from air, caffeine from coffee
beans, and medicines from plants.
Changing Phases LET’S THINK
It is almost certain that you have seen ice melting and liquid water boiling. Imag-
ine that you had a sample of solid water at -20 oC at atmospheric pressure and
you heated it up supplying energy at a constant rate until the temperature reached
120 oC. If during the experiment you were to measure the temperature (T) of the
sample as a function of time (t), as well as the amount of energy absorbed by the
system during the heating process (DE), what would you expect to see if you were
to plot the data using the following types of graphs?
T(oC) DE
100
By Mysid (Own work) [CCA: Public domain] via Wikimedia Commons

0
t 0 100 T(oC)
Based on your prior knowledge and experience:
• Predict how temperature will change as a function of time. Keep in mind

that solid water turns into a liquid at 0 oC and that the liquid becomes a gas
at 100 oC.
• Predict how the total amount of energy absorbed by the system (DE) will
change as the temperature (T) of the system increases. Consider whether How does the temperature of
the system change as
more, or less, energy will be required to change the sample from solid to water ice melts?
liquid than from liquid to gas (HINT: DE = 0 at the t = 0; DE > 0 when the
system absorbs energy; DE < 0 when the system releases energy).
• Compare your predictions with those of another classmate. Discuss how
your predictions would change if you were cooling down a gas sample or
you were working with a different substance.
Share your ideas with a classmate and clearly justify your reasoning.
Phase transitions between two different states of matter share many similari-
T(oC)
ties independently of the chemical nature of the system of interest. For example,
Vapor cools
during a change of state at constant pressure the temperature of the system re-
mains constant until one of the phases has been fully transformed into the other.
and condenses
Tb The transition points define the range of temperatures within which each phase is
Liquid cools
stable at any given pressure. In the case of water, the liquid phase is stable between
0 oC (solid-liquid) and 100 oC (liquid-gas) at 1 atm of pressure. Within these two
and solidifies points, adding energy to the system will result in increasing temperature; remov-
Tm
Solid cools
ing energy from the system will cause the temperature to decrease. However, at the
phase transition, the energy added or removed induces a change of state without
t altering the actual temperature of the system as shown in Figure 1.2.
Some changes of state require the addi-
Figure 1.2 Cooling curve for a Common
generic substance that under- tion of energy, as is the case of the transitions Phase
By Flanker, penubag (Own work) [CCA: Public domain]

goes two phase transitions, from from solid to liquid (melting), liquid to gas Changes
gas to liquid at Tb and from liquid
to solid at Tm. (boiling), and from solid to gas (sublima-
via Wikimedia Commons

tion). The reverse processes (solidification,
condensation, and deposition, respectively)
release energy that needs to be removed
from the system if we want the phase transi-
tion to occur. As shown in Figure 1.3, these
Tm Tb T(oC) energy changes occur at constant tempera-
G ture and the amount of energy absorbed or
released varies from substance to substance.
In fact, the energy per unit of mass exchanged during a phase transition is also a
L differentiating characteristic of the material. In general, the larger the change in
density induced by the phase transition, the larger the energy transfer.
During a phase transition many of the physical properties of the substance
S
DE change. Some of these changes can be quite large, as illustrated by the drastic
decrease in density in the transition from liquid to gas. A phase transition is a pro-
Figure 1.3 Amount of energy totypical example of a physical change in which the transformation does not alter
released (DE) as a function of the chemical nature of the substance involved. In some cases, adding or removing
temperature (T) during cooling of
a generic substance that under- energy from the system could cause the substance to chemically decompose or to
goes two phase transitions, from
gas to liquid at Tb and from liquid react with other substances before the phase change occurs. In these cases, it is not
to solid at Tm. possible to use phase behavior as a differentiating characteristic for the substance
of interest.
USEFUL TOOLS gy invested in applying a force of one new-

ton (1 N) through a distance of one meter
Adding energy to a system or removing (1 m).
energy from it are common strategies to
change its properties. Being able to mea- Another commonly used unit of energy is
sure or indirectly determine the amount of the calorie (cal). One calorie (1 cal) is ap-
energy that is exchanged is critical to con- proximately equal to the amount of energy
trol the change. In science and engineering, needed to increase the temperature of one
energy is commonly measured using the gram (1 g) of water by 1 oC. Energy mea-
following units: sured in calories can be transformed into
joules using the following conversion factor:
Units of Energy. In the International System
of Units (SI), energy is measured in joules 1 cal = 4.184 J
(J). One joule (1 J) is equivalent to the ener-
Phase Diagrams
The temperatures at which a substance undergoes a phase transition depend on the

value of the external pressure. This means that the range
of temperatures in which each phase is stable changes
with pressure. For example, liquid water is stable between
0 oC and 100 oC at 1 atm of pressure but if the pressure is
increased to 50 atm, melting will now occur at -0.37 oC
while boiling will take place at 262.5 oC. In this case, in-
creasing the pressure widens the range of temperatures in
which liquid water is stable. By carefully measuring the
temperatures at which a phase transition occurs at dif-
ferent pressures one can build a graphical representation
that depicts the zones of stability for each phase and their
Figure 1.4 Phase diagram for
corresponding boundaries (the temperatures and pressures at which a transition a generic substance. The letters
to another phase will occur). These graphical representations of phase change and show the phase that is stable at
that particular temperature (T)
stability are called phase diagrams (see Figure 1.4) and each substance will have a and pressure (P): Gas (G), liquid
(L), or solid(L). The solid lines
characteristic phase diagram. show the T and P values at which
a phase transition will occur.
The Case of Water LET’S THINK
The following tables include experimental information about the tempera-

tures at which water undergoes a phase transition at different pressures.
Liquid-Gas Liquid-Solid Solid-Gas

T P T P T P
(K) (mm Hg) (K) (mm Hg) (K) (mm Hg)
273.16 4.58 273.16 4.58 248.15 0.475
324.77 100 273.16 100 253.15 0.774
339.65 200 273.15 200 258.15 1.24
http://www.chem.arizona.edu/tpp/chemthink/resources/U1_M1/graph.html
356.15 400 273.15 400 263.15 1.95
366.68 600 273.15 600 268.15 3.01
374.58 800 273.15 800 273.16 4.58
• Each of these tables includes data that can be used to build the three
main boundaries in the phase diagram for water. Click
CLICK TO PLAY
on the image to launch a graphing tool and use it to

build the phase diagram in the range from 240 K to
380 K and from 0 to 800 mm Hg.
• Show on the diagram the areas in which the solid, liq-
uid, and gas phases are stable.
• Estimate the boiling point of water in Tucson, Arizona where the atmo-
spheric pressure is close to 700 mm Hg.
• Discuss with one of your classmates whether any of the phase transi-
tions in the diagram may be induced by changing the pressure at con-
stant temperature.
In a pressure-temperature phase diagram like that shown in Figure 1.5, the

transition lines do not only define the specific temperature (T) and pressure (P) at
which a phase change occurs but they also specify the conditions under which the
two phases can simultaneously exist as stable phases.
Supercritical
Fluid
It is common to say that the two phases coexist or are
Liquid in equilibrium with each other under such conditions.
Solid Consequently, three different phases can coexist with
PRESSURE
Critical
Point each other at the temperature and pressure that cor-
responds to the point in which two phase transition
lines intersect. This particular state is called a triple
Gas
point. For water, for example, the solid-liquid-gas
Triple triple point occurs at 0.01 oC and 4.58 mm Hg. The
Point temperature and pressure at the triple point have spe-
cific values for every substance and thus they can be
used as differentiating characteristics.
TEMPERATURE
The phase transition between the solid and the liq-
uid phase, or between the solid and the gas phase of a pure substance always leads
Figure 1.5 Pressure-tempera-
ture phase diagram for a generic to an abrupt density change as the phase change occurs. However, the transition
substance showing the location between the liquid and gas phases exhibits a different behavior. The liquid and the
of the different phase transi-
tions, the triple point, and the gas have sharply different densities at low temperatures and pressures but the two
critical point.
phases become more alike as temperature and pressure increase. At certain values
of T and P, characteristic for every substance, both phases become identical and
the possibility of observing an actual phase change disappears beyond this critical
point (see Fig. 1.5). At temperatures and pressures higher than the critical point,
the gas and liquid phases are indistinguishable from each other and the substance
is said to exist as a supercritical fluid.
LET’S THINK Comparing Phase Behavior

Consider the pressure-temperature phase diagrams for water and carbon dioxide:
218
73
Water
Liquid Liquid
P (atm)
P (atm)
10 Solid
Solid Gas
1.0 5.2
0.00603 Gas 5
1.0
Carbon
Dioxide
0.01 100 374 -78 -57 0 31

T (oC) T (oC)
• Identify the stable phase of each substance at 1 atm and 40 oC.

• List the phase changes that this stable phase may undergo by increasing or decreasing
a) the temperature and b) the pressure. Estimate the temperatures and pressures at which
these phase changes will take place.
• Analyze what particular features of each of the phase diagram are responsible for such differ-
ent phase behaviors.
The liquid-gas transition line in a pressure-temperature phase diagram is also

called the vapor pressure curve. At any given temperature, a liquid enclosed in a
sealed container evaporates to a certain extent producing vapor that 1000
exerts pressure on its surroundings. The higher the temperature, the
higher the rate of evaporation and the larger the pressure exerted by A B C
800
the vapor (or vapor pressure). Boiling occurs when the vapor pres-
sure of a liquid becomes equal to the external pressure acting on the
P (mm Hg)
fluid as the gas can then freely escape. The liquid-gas transition line 600
thus traces the value of the vapor pressure of the liquid at different
temperatures. Liquids that are more volatile (evaporate more eas-
400
ily) have higher vapor pressures than less volatile fluids at any given
temperature (see Figure 1.6). Consequently, volatile liquids have
lower boiling points as their vapor pressures become equal to the 200
external pressure at lower temperatures. The comparison of vapor
pressure curves for different substances is very useful in the process 280 300 320 340 360 380
of separating mixtures in gaseous or liquid states as it helps predict T (K)
the order in which different substances will separate.
Figure 1.6 Vapor pressure
curves for A) Methanol B) Etha-
Separations nol, and C) Water. A is more
volatile than B; B is more volatile
than C.
Now that we have a better understanding of the general phase behavior of pure
substances, we can use our knowledge to analyze and discuss how important sepa-
ration techniques are used in chemical analysis. Not all separation techniques rely
on phase properties or phase behavior to separate substances, but some of the most
commonly used strategies do. Among them we find: Filtration, crystallization,
and distillation.
Filtration: This technique is based on the mechanical separa-

tion of substances in the solid state from substances in a fluid
By Ahanix1989 (Own work) [CCA: Public

phase (liquid or gas) by using a physical barrier which only the
domain] via Wikimedia Commons

fluid can pass. The separation of the two types of phases is never
complete as some solid will pass through the filter and some
fluid will be attached to the solid material. The efficiency of the
separation will largely depend on the filter’s thickness and pore
size. Air filters are commonly used to improve air quality in
house, building, and car engine and ventilation systems.
Car Air Filter
Crystallization: In this strategy, the formation of a solid phase is induced

by changing the temperature or the concentration of the com-
ponents in a fluid (liquid or gas) mixture, or by adding other
substances. In a mixture of substances, these changes affect the
solubility of one substance in the other and the components are
likely to separate. The solid phase that is formed tends to be a
pure crystalline material. Crystallization is commonly used in
processes such as the extraction of common salt from sea wa-
ter and the production of pure silicon for computer chips and
Insulin Crystals, by NASA/Marshall other electronic devices.
Distillation: This technique is used to separate substances in a liquid mixture tak-

ing advantage of differences in the boiling points of the various components. The
method involves a phase change from liquid to gas and subsequent reconversion
of the separated substances to the liquid phase. In a simple distillation,
By John Kershaw (Derivative: Thresa Knott) [CCA: Share Alike 3.0] via Wikimedia Commons
the liquid mixture is heated up in a flask. When the boiling point of

the most volatile component is approached, the mixture boils and
the temperature remains relatively constant until most of the volatile
substance becomes a vapor. The vapor produced can be directed to
a condenser where it cools down and transforms back into a liquid
that can be collected. By continuously heating the liquid mixture, the
same process can be repeated until all components are separated.
Separation by distillation is never perfect and it is common to
redistill the different portions or fractions of liquid that are collected.
To improve the separation, particularly for substances with similar
boiling points, one may use fractional distillation (see Figure 1.7). In
this case, the evaporating fluid passes through a vertical column with
trays or plates placed at different heights. The temperature decreases
gradually from the bottom to the top of the column and substances
condense on different plates depending on their boiling points: the
Figure 1.7 Main components of most volatile substances will condense at lower temperatures and will
a fractional distillation apparatus. be found towards the top of the column; the least volatile substances will condense
on the bottom plates.
LET’S THINK Distilled Spirits
Hard liquors or spirits, such as brandy, whisky, and tequila, are commonly
produced by fermentation of carbohydrate-rich natural products. In the pro-
cess, a mixture containing water (C), ethanol (B), methanol (A), and many
other components is generated. Methanol needs to be removed because of its
toxic properties; water is extracted to produce beverages with various concen-
trations of ethanol.
• What would you expect

1000
to happen as you heat up
the alcoholic mixture?
In which order will the A B C
800
three main substances
separate? At which
P (mm Hg)
600
temperatures will each
fraction distill?
400
• Based on the vapor
pressure curves, would
you see any advantage in 200
changing the pressure at
which the distillation is 280 300 320 340 360 380
T (K)
performed? Why?
FACING THE CHALLENGE condense. The liquefied air is then heated up and
distilled in one or two different distillation col-
umns, depending on the desired products.
Separating Air More than half of the oxygen extracted from
air by cryogenic distillation is used to produce steel.
The concepts, ideas, and ways of thinking intro- The rest is consumed for
duced in this module can be applied to the chemi-
By Deglr6328 (Own Work) [CCA: Share Alike 3.0]

medical applications,
cal analysis of a variety of systems, from the atmo- water treatment, and to
sphere in our planet to the oil spilled in the Gulf

power rocket fuels. On
of Mexico in 2010. For example, let us go back to the other hand, the ar-
our original challenge: the separation of substances gon that is produced in
present in the air we breathe. the process is used to fill
The separation of air components can be use- incandescent lights, cre-
ful for a variety of reasons. We may want, for ex- ate inert atmospheres
ample, to know the proportion in which different to avoid undesirable
substances are present in the air. Or we may be in- chemical reactions, and Solid Argon Melting
terested in eliminating atmospheric pollutants. We in cryosurgery (application of extreme cold to
could also be interested in “mining” air; this means eliminate diseased tissue) to destroy cancer cells.
to extract from air substances that have commer- Nitrogen also has important industrial appli-
cial value. In fact, air is the main source of nitro- cations, such as in the creation of safe atmospheres
gen, oxygen, and inert gases such as argon used in fuel systems in military aircraft or on top of liq-
for industrial or medical purposes. These three uid explosives. The gas is also used to create modi-
substances are the main components of Earth’s at- fied atmospheres to preserve packaged food. One
mosphere: of the main uses of the nitrogen extracted from air
is in the synthesis of ammonia, one of the most
Air Components highly-produced substances in the world because
Substance % Volume Tb (oC) of its central role in the production of fertilizers
and explosives.
Nitrogen 78.084 -195.79
Liquid nitrogen is also widely used in cryogen-
Oxygen 20.957 -182.95 ics, the study and production of very low tempera-
Argon 0.934 -185.85 tures (lower than -150 oC) and the investigation of
the properties of materials under such conditions.
These air components are actually separated Some substances acquire surprising properties at
using a technique called cryogenic air distillation. very low temperatures, such as losing all electrical
How does this work? Well, the first step is to fil- resistivity and becoming superconducting materi-
ter the air to eliminate solid als. Superconductors are
particles and then compress used to produce magnets
it to pressures between 5 to that generate strong mag-
10 atm. The mixture is then netic fields, such as those
passed through another fil- required for Magnetic Res-
tering system that allows the onance Imaging (MRI).
removal of water and car- This noninvasive medical
bon dioxide. The processed imaging technique allows
air is then cooled down to doctors to visualize inter-
temperatures as low as -200 nal structures and func-
o
C (73 K), conditions under tions in our bodies.
which all main components Air Distillation Column
By photographer- Company (Own Work) [CCA: Share Alike 3.0] via Wikimedia Commons
Let’s Apply
Investigating Other Planets
The analysis of the atmosphere of other planets in our Solar System is of central importance for
understanding not only how our planet originated but for exploring the possibility of life beyond
Earth. The table below summarizes relevant information for the atmospheres of Venus, Earth, and
Mars:
ASSESS WHAT YOU KNOW
Venus Earth Mars

Distance from Sun in
0.723 1.00 1.50
Astronomical Units (AU)
Average Surface 460 oC (day) 20 oC (day) -5 oC (day)
Temperature 460 oC (night) 10 oC(night) -85 oC(night)
500 oC (highest ) 58 oC (highest) 27 oC (highest)
Extreme Temperatures
400 oC (lowest) -88 oC (lowest) -143 oC (lowest)
Air Density at
65 kg/m3 1.2 kg/m3 ~0.020 kg/m3
ground level
Atmospheric pressure
92 atm 1.0 atm 0.0059 atm
at ground level
78% Nitrogen 95.3% Carbon Dioxide
Atmosphere 96.5% Carbon Dioxide
21% Oxygen 2.7% Nitrogen
composition 3.5% Nitrogen
~1% Water 0.13% Oxygen
(Main components) 0.002% Water
0.035% Carbon Dioxide 0.03% Water
As you can see, the at-

mospheric conditions in
104
these three planets are very
different. Consequently, 103
the same substances may
exist in different states of 102
Pressure (atm)
matter from one planet to

another. The phase behav- 101
ior of every substance in a
given planet can be pre- 1.0
dicted using the respective CARBON
10-1
phase diagrams. In partic- DIOXIDE
ular, we include the phase 10-2
diagrams of water and car-
bon dioxide. Notice, that 10-3
-120 -80 -40 0 40 80
pressure in these diagrams
is represented using a loga- Temperature (oC)
rithmic scale.
1 MPa
WATER
Pressure 1 KPa
1 Pa
0 100 200 300 400 500 600 700 800 900 1000

Temperature (K)
Your Predictions
Answer the following questions based

on the information provided and
your own knowledge of the phase
behavior of chemical substances.
Earth You may also need to do some ba-
NASA
sic research to find relevant phase
behavior data for other substances present Venus
in these planets. NASA
• What is the state of matter of water and carbon dioxide at day

and night in each of these three planets? Justify your answer by
showing on the phase diagrams the states of matter of the differ-
ent substances in each of the planets.
• Would it be possible to find solid carbon dioxide (dry ice) in
any of these three planets? Justify your answer.
• Would it be possible to find liquid nitrogen in any of these
planets? Justify your answer.
• The United States and Soviet Union have sent many spacecraft
to Venus. Some flew by the planet, some orbited around it, and
some descended through the atmosphere. Imagine that you
were able to get a sample of Venus’ atmosphere, how would you
propose to separate its main components? In which order would
Mars you be able to separate them? Write a detailed description of
NASA what you propose to do and what you would expect to happen
at each step of the separation process.
• Would it be possible to find a planet in which both water and
carbon dioxide exist in liquid form? If yes, what average tem-
perature and pressure would this planet have?
Let’s Apply
Refining Petroleum
Crude oil or petroleum is a mixture of hundreds of substances, most of them made of hydrogen
and carbon (hydrocarbons). The mixture is a thick black liquid in
which different substances that are solid, liquid, and gases at room
By Luigi Chiesa (Own work) [CCA: 3.0 Generic] via Wikimedia Commons
temperature are present. In an oil refinery, crude oil is separated into
“fractions” (mixtures that consist of compounds with similar boiling

points) by fractional distillation.
During the distillation process, crude oil is injected into a boiler
and heated. The vapor passes into a distillation column with a tem-
perature gradient, coolest at the top, hottest at the bottom. There are
plates or trays across the column with holes through which the rising
vapor passes through. Different substances condense in trays at differ-
ent temperatures according to their boiling points.
Imagine that you have to separate the components of different
samples of crude oil extracted from the ground. What strategies
would you follow? Let’s explore how well you can apply the concepts,
ideas, and ways of thinking introduced in this module.
Problem Mixture 1
A rich fuel mixture containing the 10.0

following hydrocarbons has been ex-
tracted from underground:
A B
Vapor Pressure (atm) [Log Scale]
A. Propane
B. Butane
C. Neo-Pentane C
D. 2-Heptene 1.0
The mixture is at an initial tempera-

ture of 5 oC. Based on the data pro- D
vided:
• Identify a differentiating char-

acteristic that you could use to 0.1
-30 -10 10 30 50 70
separate each of the components. Temperature (oC)
• Design a procedure to separate
each component. Describe the steps that you would follow and
the outcome of each step in the separation process.
Problem Mixture 2
The second mixture you have to separate contains the following components listed in order of
increasing melting (Tm) and boiling temperatures (Tb) at atmospheric pressure:
Substance Tm(oC) Tb (oC) Substance Tm(oC) Tb (oC)

Methane -182 -164 Pentadecane 10 271
Propane -188 -42 Hexadecane 18 287
Butane -138 -0.5 Heptadecane 21 302
Hexane -95 69 Nonadecane 33 330

Heptane -91 98 Tricosane 49 380
Octane -57 126 Tetracosane 52 391
Nonane -53 151 Pentacosane 54 402
Dodecane -10 216 Tetracontane 81 524
Your task is to design a fractional distillation column to separate the following five fractions:
1. Liquid fuels less volatile than water that can be used to power vehicles at all temperatures
between the lowest (5 oC) and the highest (38 oC) By Tysto (Own work) [CCA: Public domain] via Wikimedia Commons
average temperatures in Tucson, Arizona (the fuel
should remain liquid in that range of tempera-
tures).
2. Gaseous fuels that can be used for cooking and
heating houses in Tucson.
3. Liquids with a higher volatility than water that
can be used as solvents in industries and labs.
4. Dense oils that can be used as lubricants in cars
and machinery (these substances may be solid or
liquid depending on the temperature in Tucson). Gasoline and diesel are most often produced by
fractional distillation
5. Solid paraffin waxes that can be used to make
candles in Tucson.
15 oC
Assume that the temperatures at the top and bottom of your column
are 15 oC and 360 oC, respectively.
• What is the minimum number of distillation plates or trays,

beyond the top and bottom exhausts, that are needed to complete
the separation?
• At what temperatures should each of these trays be placed to
ensure that the desired fractions separate?
• What substances will be mixed in each of the fractions extracted
from the column?
360 oC
18
Modeling
Matter
The assumption that every single substance in our surroundings has at least one
U1: MODULE 2
differentiating characteristic that makes it unique is at the base of chemical analy-
sis. What causes these differences? Why does water boil at 100 oC while oxygen
boils at -183 oC? Why is carbon dioxide a gas at room tem- Why are
Materialscientist(talk)) [CCA: Share Alike 3.0]

diamond and
perature while pure carbon is a solid under the same condi- graphite so
tions? To explain these differences, humans through history different if
By UIser:Itub (Derivative:
both are made
have developed “models” of matter. In general, models are of carbon?
simplified representations of objects or processes built to
better describe, explain, predict, and even control their
properties and behavior. Some of these models may be
concrete, as the model of a bridge used by an engineer
to understand how the system responds to stress. Some models are
abstract, including entities that may be treated as tangible objects (e.g.,
force, energy) but actually represent abstract concepts or ideas that help us make
sense of properties and events.
Modeling substances and processes is at the core of chemical thinking. It is
through modeling that chemists have been able not only to analyze and explain
the diversity of the material word, but to design strategies to create new materials.
Many of the models used in chemistry are abstract and refer to entities that cannot
be seen by the naked eye. That sometimes makes chemical thinking challenging.
However, the explanatory and predictive power of those models is extraordinary.
THE CHALLENGE Clouds

The formation of clouds in the atmosphere is of critical importance to sustain
life on Earth. Clouds are necessary for precipitation to occur and help regulate
the energy absorbed and reflected by the planet. By Axel Rouvin (Own work)
• How do you think clouds form?

[CCA: Public domain]
• Based on what you know, how would you “model”

the process of cloud formation in the atmosphere?
Share and discuss your ideas with one of your classmates.
Module 2 will help you develop the type of chemical reasoning that is used to
answer questions similar to those posed in the challenge. In particular, the central
goal of Module 2 is to help you understand and apply the particulate model of
matter to explain differences in the phase behavior and related physical prop-
erties of diverse substances in our world.
Particulate Model of Matter

The tasks of analyzing and synthesizing substances has been greatly simplified by
the development of models of their internal composition and structure. Since
By Heron (Own work) [CCA: Public domain]

ancient times, humans have proposed different models to explain and predict
the properties of matter. Aristotelians, for example, thought of all substances

as composed of four elementary principles: water, fire, air, and earth
(Figure 1.8). It was thought that these “elements” gave a substance its
characteristic properties depending on the proportion in which they
were present. Other greek philosophers, like Leucippus and Democritus
thought of matter as made up of small indivisible particles called “atoms” mov-
ing around in empty space. In this model, differences in substance properties were
attributed to the existence of atoms with an infinite number of different shapes
and sizes that could move and arrange in diverse ways. Although our theories and
Figure 1.8 The four Aristotelian
models of matter have evolved considerably over the years, some core assumptions elements and their associated es-
sential properties.
about the composition and structure of the substances in our world are similar to
those of the ancient Greeks. For example, we still consider the existence of atoms
as essential components of matter although we model them in different ways.
During the 18h and 19th centuries, chemists and physicists accumulated
enough experimental evidence to support a model of matter that proposes that
all substances are composed of small particles in constant movement. This par-
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M2/powersoften.html
ticulate model of matter has become one of the most powerful ideas of modern
science as it can be used to explain and predict the physical properties of many
materials. This model is based on the following fundamental assumptions:
Assumption 1. Any macroscopic sample of a substance is composed of an ex-

tremely large number of very small identical particles.
CLICK TO PLAY
In a first approximation, these “particles” may be thought of as very small
rigid objects. However, as discussed in the second part of this module, we
will need to assume that these particles have internal structure if we want
to better explain the physical and chemical properties of matter. The size of
the particles is assumed to be pretty small, of the order of one billionth of a
meter, or one nanometer (1 nm = 1 x 10-9 m), although the actual value will
vary from substance to substance. Thus, a macroscopic sample of any sub-
stance will be composed of trillions of billions of the same type of particles.
For example, one milliliter (1 mL) of liquid water contains approximately
3.35 x 1022 water particles. This number is similar to the estimated number
of stars in the entire Universe! Imagining the world at this small scale can be
difficult, but chemists have devised ways to simplify the challenge.
Relative Size LET’S THINK

Click on the image on this page to open an interactive image that illustrates the relative sizes of
different components of the human body, from a hand to a cell to a DNA molecule.
• Estimate how many times smaller is an atom in a DNA molecule than a human cell.
20 MODULE 2 Modeling Matter
The particles of matter are expected to be so small that they cannot be seen
by the naked eye or even using an optical microscope. That is why it is common
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M2/partmodel1.html
CLICK TO PLAY to make references to the “submicroscopic world” when describing matter at the
particulate level or scale. Experimental results suggest that these particles also have
very small masses. For example, a single particle of the oxygen we breathe has a
mass close to 5.3 x 10-23 g. This is a billion billion times less massive than a tiny
speck of dust!
Assumption 2. Particles of matter are constantly moving in random directions

through empty space.
The particulate model of matter is also based on the ideas that the particles
that make up a substance are in constant random motion through void space (see
Figure 1.9 Representation of a Figure 1.9). It is this motion which allows us to explain, for example, why gases
gas using the particulate model
of matter. The sides of this square and liquids exert pressure on the walls of their containers. This pressure can be
should be assumed to be only a
few nanometers long. Click on seen as the result of the force per unit area exerted by particles of the fluid that
the image to open an animated
simulation collide with the particles of the container. The pressure depends on the number of
particles contained in a given volume; the larger the number of particles and the
smaller the volume, the grater the pressure. The pressure also depends on how fast
the particles are moving; the faster the particles move, the larger the pressure they
create. However, what determines the speed at which the particles are moving? In
the next activity you will explore the answer to this question.
USEFUL TOOLS Numbers larger than one can be written in sci-

The study of the properties of chemical sub- entific notation by increasing the exponent by
stances often requires the measurement of one for each place the decimal point is moved
quantities that can be very large or very small. to the left. For numbers smaller than one, the
To simplify the representation and manipula- exponent is decreased by one for each place
tion of these amounts it is common to use sci- the decimal point is moved to the right.
entific notation and multiple or submultiples of
standard measurement units. Multiples/Submultiples: In the International
System of Units (SI) prefixes are added to pro-
Scientific Notation: In this notation, numbers duce a multiple or a submultiple of the original
are represented as the product of a real num-
unit. All multiples and submultiples represent a
ber A and a power of ten:
power of ten. The following table summarizes
some of the most common prefixes used to ex-
A x 10n
press units in chemistry:
where the coefficient A is a number greater
than or equal to 1 and less than 10, and the Name hecto- kilo- mega- giga-
exponent n is an integer. Numbers greater than Larger Symbol h K M G
one have positive exponents; numbers smaller
than one have negative exponents. For exam- Factor 10 2
10 3
10 6
109
ple, the number 54000 is expressed in the fol-
lowing way: Name centi- milli- micro- nano-
Smaller Symbol c m m n
54000 = 5.4 x 10000 = 5.4 x 104
Factor 10 -2
10 -3
10 -6
10-9
The number 0.00054 is written as:
For example, the size of a water particle,
0.00054 = 5.4 x 0.0001 = 5.4 x 10 -4 0.00000000028 m, can be expressed as
0.28 nm (nanometer) using the nano prefix.
Particle’s speed LET’S THINK

Imagine that you had a sample of pure liquid water, water vapor, and water ice at this substance’s
triple point (273.16 K, 4.58 mm Hg). If you could measure the speed of the water particles at the
submicroscopic level:
• In which state of matter would you expect particles to have the lowest average speed? In
which phase would the average speed be greatest?
• Would you expect all of the particles in a given phase to be moving at the same speed?
• How would you expect the average speed of particles in the different phases to change when
the temperature is increased or decreased?
Share and discuss your ideas with one of your classmates, and clearly justify your predictions.
One of the most common difficulties in applying the particulate model of

matter to describe, explain, or predict the properties and behavior of a substance is
that we often project the macroscopic properties that we observe or measure to the
submicroscopic level. Thus, for example, people may think that particles in a solid
are moving at lower speeds than particles in a fluid because solids seem more static; T1
others may consider that particles in a solid only move when the actual object is T2
Fraction of Particles
T3
moving. We need to be careful with this type of thinking because the properties
that we measure in a macroscopic sample are often quite different from the proper-
ties of the individual particles that make up the system. T1< T2< T3
In the particulate model of matter, the average speed of particles depends on
two main variables: the temperature of the system (T) and the mass of the indi-
vidual particles (m). In particular, temperature is seen as a measure of the average
kinetic energy per particle (< Ek >) given by 0 250 500 1000 1250
v (m/s)
(1.1) < Ek > = 1/2 m < v >2 Figure 1.10 Distribution of par-
ticle speeds for the same sub-
stance at different temperatures.
where < v > represents the average particle speed. The higher the temperature,
the greater the average kinetic energy per particle in the system and the faster the
particles will move. Consequently, particles of the same substance in two different
coexisting phases at a certain temperature will have the same average kinetic en-
0.4
m1
ergy, and thus the same average particle speed independently of the state of matter
of the material.
Fraction of Particles
0.3
At any given temperature, individual particles that make up a substance move m1> m2> m3> m4
m2
at different speeds. Some particles move faster than others; many of them move at
0.2
speeds close to the average value. This is illustrated in Figure 1.10 where we show m3
the typical shape of the distribution of speeds for a generic gaseous substance at
0.1
m4
three different temperatures. As shown in this figure, as the temperature increases
the fraction of particles with low speeds decreases while the fraction of those with
high speeds increases. Substances made up of particles of different masses will v (m/s)
have different speed distributions at any given temperature (see Figure 1.11), but Figure 1.11 Distribution of parti-
their average kinetic energy will be the same. According to equation (1.1), lighter cle speeds for different substanc-
es at the same temperature.
particles should then have higher average speeds than heavier particles at any given
temperature.
Assumption 3. Particles interact with each other and the strength of these
interactions depends on distance.
The existence of phase transitions between different states of matter can be ex-
plained if we assume that particles attract each other at relative long distances but
repel each other when they come into close proximity (Figure 1.12). Without
these interactions all substances would always exist in a single phase.
LET’S THINK Phase Changes
The core assumptions of the particulate model of matter, together

with basic physics principles to predict the dynamic effects of
the interaction between particles, can be used to build computer
simulations to analyze the predictions of the model under differ-
CLICK TO PLAY
ent conditions:
• Use this simulation to analyze the effect of changing tem-

perature on the speed and spatial distribution of particles in
a simple substance. Study the behavior of the system in the
presence and in the absence of interactions between particles.
Share and discuss your findings with one of your classmates.
Note: Repulsion between particles at short distances is modeled by assuming that particles behave
like hard billiard balls (they strongly repel each other at distances smaller than their own diameter).
According to the particulate model of matter, a solid phase forms as a result

of the attractive interactions between particles. These interactions keep particles
together at low temperatures when their average kinetic energy is relatively low.
Attractive and repulsive interactions constrain the movement of
Distance particles that cannot freely move from one place to another. As
the temperature increases, the average speed of the particles in-
creases and they gain some freedom to move around each other,
Interaction Force (N)
which explains the fluidity of the liquid phase. At higher tem-

peratures, when the liquid transforms into a gas, most particles
acquire enough kinetic energy to move across the entire system
barely influenced by their interactions. The stronger the attractive
interactions between particles, the more energy will be needed to
separate them and induce a phase transition from solid to liquid
Repulsion Attraction or from liquid to gas. Within this model, differences in melting
and boiling points are attributed to differences in the strength of
the interactions between particles at the submicroscopic level. As
Distance (m)
we will discuss in more detail in Unit 3, making sense of these
Figure 1.12 Representa- differences in terms of the specific composition and structure of the particles of
tion of the interaction force
between two particles of ar- matter is critical to explain the diverse properties of the substances in our world.
gon as a function of distance
between any two particles. The particulate model of matter can be used to explain and predict the proper-
By convention, repulsive
forces are assigned positive ties and behavior of a variety of systems and phenomena. To illustrate it, in follow-
values and attractive forces ing sections we will apply the model to the analysis and understanding of a) the
negative values.
properties of gases and b) the nature of phase transitions.
Modeling Gases
Substances that exist in the gas phase at room temperature play a central role in
our lives. We breathe in air containing gaseous substances such as oxyge, and we
breathe out air richer in other gases such as carbon dioxide. This gas is also one
of the main products of the combustion of the fossil fuels that we use to generate
electricity and power our cars. The rapid increase of the concentration of carbon
dioxide in the atmosphere in the last two hundred years is thought to be the main
cause of global warming. Understanding gas properties and behavior is thus of
central relevance in modern times.
The study of the properties of gases was of central importance in the develop-
ment of modern chemistry. Through the study of the properties of the different
gaseous substances chemists were able to build many of the models and theories
that guide chemical thinking nowadays. Although the gas phase is perhaps the
simplest in structure at the particulate level, many people struggle to understand
its properties because most gases cannot be seen or felt. So, it is not uncommon to
think that gases have no weight or that the particles of matter become smaller or
lose mass when a substance turns into a gas. Modeling and analyzing the gas phase
at the submicroscopic scale may help us dispel some of these misconceptions.
Most substances become gases at high temperatures and low pressures. Under
those conditions, we can imagine the particles that make up the system to be far
apart from each other and rarely crossing paths. So, in a first approximation, the In which ways
particulate model of a gas could be simplified by assuming that particles do not are these types
of particulate
interact with each other at all; the only interactions that they experience are with representations of
solids, liquids, and
the walls of their container. This is a reasonable hypothesis if the average distance gases limited or
between particles is much larger than their own size. What can this simple model inaccurate?
predict about the properties and behavior of gases? Let’s explore it.
Ideal Gases LET’S THINK
The simulation included in this activity is based on a model that neglects all interactions between
particles and treats their interactions with the walls of the container as perfectly elastic collisions
(no kinetic energy is lost during the collision). Use this simulation to analyze the effect on the
pressure (P) exerted by the particles on the walls of the container by:
a) Changing the temperature (T) at constant volume (V) and number of particles (N);
b) Changing V at constant T and N;
CLICK TO PLAY
c) Changing N at constant T and V.
The simulation will allow you to collect the value of the average pressure in
the system as a function of different variables. Use the load button to collect
data making sure that the pressure is stabilized before registering its value.
• Use your data to sketch three graphs that show how P changes with increasing T, V, or N
when the other variables are held constant.
• Share your results and ideas with one of your classmates. Discuss what types of mathemati-
cal equations could best describe the relationships between P and T, P and V, and P and N
predicted by this model of gases.
Our simplified particulate model of gaseous substances predicts that the pres-
sure (P) of a gas is directly proportional to both the absolute temperature (T,
measured in kelvin) and the number of particles (N) in the system, and inversely
proportional to the volume (V). This behavior is actually observed in many gases
at high temperatures and low pressures; when this happens it is said that the sub-
stance behaves as an “ideal gas.” The quantitative relationship between pressure,
temperature, volume, and number of particles in the ideal gas model can be ex-
pressed in mathematical terms as:
(1.2) P = kB ( N T / V )
where the proportionality constant kB = 1.380 x 10-23 J/K is known as Boltzmann

constant. One of the most interesting features of this relationship, also called the
ideal gas law or ideal gas equation of state, is that none of the quantities in equa-
tion (1.2) depends on the chemical composition of the actual system. The ideal gas
model predicts that all substances, independently of their chemical structure and
composition, will behave identically under conditions of temperature and pressure
where the interactions between their particles can be neglected. This prediction of
universal behavior has been confirmed experimentally and it is one of the greatest
accomplishments of the model.
The ideal gas model works well when describing and predicting the behavior
of gases at high temperatures and low pressures. However, problems arise when
the effects of interactions between particles cannot be neglected. In the absence of
particle interactions a gas would never turn into a liquid or a solid. Consequently,
the closer we get to the conditions under which a gaseous substance will undergo
a phase change, the worse the predictions of the ideal gas model will be. To predict
the behavior of “real” gases we need to understand how particle interactions affect
the behavior of these systems.
LET’S THINK Real Gases
The simulation in this activity allows you to turn on or off particle interactions in the particulate
model of a simple substance, as well as to change the strength of the attractive forces. Use the
simulation to investigate the effect of particle interactions on the pressure of a gas.
• Analyze how the average pressure changes as you turn on

the repulsive interactions but not the attractive interactions.
CLICK TO PLAY
Repulsions between particles are modeled by assuming that

the particles behave like hard billiard balls. Investigate how
the magnitude of the effect of the repulsive interactions de-
pends on the temperature, volume, and number of particles
in the system.
• Analyze how the average pressure changes as you increase the strength of the attractive
interactions keeping repulsive interactions on. Investigate how the magnitude of this effect
depends on the temperature, volume, and number of particles in the system.
Discuss your results with one of your classmates and suggest possible explanations for what you
observe in each case.
Particle interactions affect gas properties because they alter particle movement.
For example, given that particles repel each other at close distances, there is less
effective space for particles to move. Their movements are more constrained; it is
as if the particles were in a container with a smaller effective volume. The larger
the particles, the smaller the free available space and the more frequently these
particles will collide with the walls of the container. This in turn should result in
higher pressures than those predicted by the ideal gas model.
Attractive interactions will also constrain particle movement as forces will
change particles’ velocity, both speed and direction. On average one can expect
particles that are attracted to each other to spend more time close together and
to interact less frequently with the walls of the container; this will result in lower
pressures than those associated with ideal gas behavior.
The net outcome of these competing effects on gas properties will depend on
factors such as the size of the container, the external temperature, the number and
size of the particles present in the system, as well as on the strength of the attrac-
tive interactions between them.
Modeling Phase Transitions

We have seen how the particulate model of matter can be used to describe, explain,
and predict the properties of substances in the gas phase. As we will discuss in the
following paragraphs, the same model can be applied to analyze the properties
and behavior of materials in the liquid and the solid phases, as well as to study the
transition between different states of matter.
A phase change is a very interesting event given that two or more phases with
rather different properties can coexist during the transition. Understanding this
By Markus Schweiss (Own Work) [CCA: Share Alike 3.0]

phenomenon has not been easy. For many years natural philosophers and scientists
thought that the chemical nature of substances actually changed during a change

of state. The observable properties of, for example, liquid water and water vapor
are so different that is not surprising that people had problems thinking of them
as the same substance (Figure 1.13). However, chemical analysis revealed that no
chemical change occurred during a phase change and the particulate model of
matter helped make sense of the results.
One of the most fundamental ideas to understand when using the particulate
model of matter is the concept of emergence. The particulate model relies on
the assumption that many macroscopic properties of a substance that are observ- Figure 1.13 It is common
to think that the bubbles in
able or measurable in our laboratories may not be the same as the properties of boiling water are made of
the individual particles that compose the system. Many macroscopic properties oxygen and hydrogen par-
ticles, instead of water par-
“emerge” from the spatial distribution, movement, and interactions between the ticles. What do you think?
many of particles present in a macroscopic sample of the material. So, for example,
a solid is more rigid than a fluid because the strong interactions between particles
in close proximity in the solid phase make it difficult for them to move around
and separate. An alternative explanation would be to think that particles in the
solid state are hard and become softer as we increase the temperature. However,
experiments suggest that hardness is not a property of each individual particle but
rather a property that emerges from the interactions between the many particles in
a system. Emergent properties and behaviors are common in our surroundings. A
traffic jam, an ant colony, and even the movement of people in a busy intersection
emerge from the interaction between multiple components.
LET’S THINK Emergent Properties
Consider the following intensive properties of a substance:
Density Viscosity Color Boiling Temperature Malleability

• Which of these properties are emergent properties of the substance and which of them are
properties of the individual particles that compose the system?
• How would you expect the value of each of these properties to differ for samples of the sub-
stance that have 10, 102, 1012, and 1023 particles?
• Which other emergent properties of a substance can you identify?
Share and discuss your ideas with a classmate, and clearly justify your reasoning.
The temperatures at which phase transitions occur are in fact emergent proper-
ties of substances. According to the particulate model of matter, individual particles
do not melt or boil with changing temperature or pressure; they do not become
smaller or larger, or softer or harder, during a phase change. The overall strength of
the interaction forces between particles does not change with tem-
perature and pressure either. The only thing that changes during
By Nandiyanto (Own work) [CCA: Public domain]
the phase transition is how particles are distributed in space and

the amount of energy that they have. Because the temperature at
which a substance boils is an emergent property of a system with

many particles, we cannot expect a nanoscopic droplet of water
comprised of 20 particles to boil at the same temperature as a mac-
roscopic droplet of the same substance with 1022 particles (Figure
1.14). In fact, it is likely that the nanoscopic droplet would gradu-
ally evaporate and never actually boil because each of its particles is
not subject to the attractive force of many others. The particulate
model of matter can still be applied to explain and predict the be-
havior of systems made up of a few particles, but predicted proper-
ties will be different from those of macroscopic samples.
Figure 1.14 Electron micros- We have seen that to induce a phase transition in a macroscopic sample of a
copy images of silica nanoclu-
sters of different sizes. The material we need to provide or extract energy from the system. However, once the
properties of nanoaggregates transition point is reached, the temperature remains constant until the transforma-
tend to vary dramatically with
their size and shape. tion is complete. Why does this happen? How can the temperature stay constant
when energy is being added to or removed from the system? Let us analyze this
phenomenon using the particulate model of matter.
In a dynamic system of interacting particles, energy can be present in two main
forms, kinetic energy (Ek) due to particle motion (Equation (1.1)) and potential
energy (Ep) due to particle interactions. The potential energy can be conceived as
energy stored in the system of interacting particles and its value changes as particles
approach or move way from each other. The potential energy always decreases as
particles move in the same direction as the forces between them. If the particles at-
tract each other, Ep decreases as the particles get closer together; if the particles repel
each other, Ep decreases as the particles move away from each other. The reduction
in potential energy due to the action of internal forces results in a gain in kinetic
energy. In general, the change in the value of the potential energy, DEp, is a measure
Figure 1.15 The potential
of the energy that needs to be invested (DEp > 0) or removed (DEp < 0) from a sys- energy (Ep) of a pair of par-
ticles that attract each other
tem of particles to change their relative positions. decreases as the distance (r)
By convention, the value of potential energy is set to zero when the interacting between them decreases. By
convention, the maximum
particles are at an infinite distance from each other (i.e., when the interaction force potential energy is set to be
zero when the distance (r) be-
between them is zero). As a result, the potential energy of particles that attract tween the particles is infinite.
each other always has a negative value (Ep decreases as the particles move towards
each other), and this value
becomes more negative as
the particles get closer to-
gether (Figure 1.15). A pair
of particles that move under
the influence of their attrac- Attractive Force
tive force will gain kinetic
energy as particles approach
each other and will lose po- Potential
tential energy in the process. Energy
The stronger the attractive Decreases
force between the particles,
the greater the decrease in
the potential energy of the system when the particles get closer together (and the
greater the increase in their kinetic energy).
In situations when particles repel each other, their potential energy increases
(becomes more positive) as the particles get closer together. This increase in po-
tential energy is accompanied by a decrease in the kinetic energy of the particles
(particles slow down as they get closer due to the repulsive forces between them).
Particles that move away from each other under the action of their repulsive force,
lose potential energy but gain kinetic energy as they separate.
Potential Energy Plot LET’S THINK

The following graph shows the calculated potential energy for the interaction of two argon par-
ticles as a function of distance.
• Identify on the graph the range of distances

where the particles attract each other and
the range of distances where they repel each
other (Hint: Analyze how Ep is changing
Potential Energy (J)
with increasing distance). Is there a distance

where the force between them is zero?
• Describe what would happen to the poten- Distance
tial energy and to the kinetic energy of two
argon particles initially separated by a large
distance if they were to move freely under
the influence of their interaction force. Distance (m)
For substances in the solid or liquid phase, attractive and repulsive

interactions between particles tend to keep them at distances where the
E Liquid Gas average force is close to zero and the potential energy is at a minimum.
Particles of substances in these states of matter have much lower potential
energy (more negative) than the same particles in the gas phase, where
the potential energy due to particle interaction is almost zero. To induce a
phase transition from liquid to gas energy needs to be provided to separate
the particles and increase their potential energy (Figure 1.16). During a
Kinetic Energy liquid to gas phase transition the temperature remains constant because
Potential Energy the energy provided through heating is transformed into potential energy
and not into kinetic energy of the particles (remember that temperature
is a measure of the average kinetic energy per particle). In the reverse process, the
Figure 1.16 During the phase tran- change from gas to liquid, particles lose potential energy and gain kinetic energy as
sition from liquid to gas, the total
kinetic energy of the particles in the they get closer together. As particles in the system collide with the container they
system remains constant while the
total potential energy increases, go- transfer their excess kinetic energy to the surroundings. We then say that energy is
ing from a negative value to almost
zero for particles in the gas phase. released in the form of heat. In a similar fashion, energy will be needed to separate
particles in the melting of a solid and energy will be released in the solidification of
a liquid. The energy released or absorbed during a phase transition due to changes
in the potential energy of the system is often called latent heat.
A Central Idea
One central idea in chemical thinking is that many of the changes that we ob-
serve in our surroundings, from phase transitions, to the mixing of substances, to
chemical reactions, can be seen as the result of two competing phenomena. On
the one hand, the particles that make up a system are constantly moving in ran-
dom directions and with random speeds. Random movement and collisions tend
to lead to states in which particles are homogeneously distributed in the available
space. On the other hand, attractive interactions between particles may lead to the
formation of small clusters or large conglomerates of particles. The outcome of the
competition between random motion and attractive interactions will depend on
the strength of such interactions and on factors such as temperature and pressure.
Predicting the changes that a system may undergo can be simplified by analyz-
Liquid-Like Configurations
ing two critical elements:
a. The potential energy of the different states available to the system;
b. The number of configurations that particles can take in each of those states.
Derivative from image by Mark Bishop
Comparing the potential energy of two different states allows us to evaluate the
energy cost associated with a change. If changing from one state to another re-
quires a high energy input, the change will be less likely to occur, particularly at
low temperatures. On the other hand, comparing the number of configurations
that the particles can take in each state allows us to assess how easily they may
rearrange. If particles can be in many different configurations in a given state, the
probability for them to move away from that state will be low.
Gas-Like Configurations Consider, for example, the liquid and gas states. Particles are closer and attract
each other more strongly in the liquid phase than in the gas phase. Thus, the po-
Figure 1.17 Particles can
tential energy of the liquid is lower than that of the gas. From this perspective, the
adopt many more configura- liquid phase is more “energetically” favored than the gas phase (as it takes energy
tions in the gas phase than in
the liquid or solid phases. to change from liquid to gas). However, there are many more configurations that
particles can take in the gas phase than in the liquid phase (Figure 1.17) because
gaseous particles may occupy the entire volume of the container. Consequently, Figure 1.18 Placing the different
states of a system in a Potential Ener-
random motion is more likely to induce a change to the gas phase. Which of these gy-Configuration diagram can be use-
effects is dominant depends on factors such as temperature. At low temperatures, ful to predict which state is more like-
ly to exist under different conditions.
where little energy is available, escaping the lower energy state is more difficult and The likelihood of different states may
be influenced by changing tempera-
the liquid state is more likely to form. At high temperatures, random motions will ture (T) and pressure (P).
likely take the system to the gas phase.
The construction of potential energy-configuration (PEC) Favored at Low P
diagrams like the one shown in Figure 1.18 can help us analyze
and predict the likely changes that a system may undergo given Favored at High P
some basic knowledge about the properties of available states. In
Ep Gas
general, a system is likely to evolve to those states that have the
larger number of configurations and the lower potential energy.
This happens because once particles randomly adopt those types
Favored at Low T
Favored at High T
of states, the probability of them changing to other states will be
pretty low. States that have low potential energy and a low num- Liquid
ber of configurations are likely to be adopted only at low temper-
atures, when the energy available is not enough to overcome at-
tractive interactions between particles in the system. States with
high potential energies and a large number of configurations will
become more favored at high temperatures, while those states
with high potential energy and a low number of configurations
will be the least favored under most normal conditions.
# Configurations
PEC Diagrams LET’S THINK

The potential energy-configuration (PEC) diagram to the
Ep
right shows the liquid and gas states for nitrogen (represent-
ed as blue circles) and oxygen (represented as red circles).
The gaseous states for both substances are represented as
overlapping because they have similar potential energies and
number of possible configurations.
• Use the PEC diagram to predict which substance, nitro-

gen or oxygen, is likely to have a higher boiling point?
Clearly justify your reasoning. # Configurations
Liquid crystals are substances that can exist in states

of matter with properties intermediate between
those of liquids and crystalline solids.
• Build a PEC diagram to represent these three SMECTIC

phases of a liquid crystal and discuss the phase
changes that will take place when changing ISOTROPIC NEMATIC
temperature.
Share and discuss your ideas with a classmate, and

clearly justify your reasoning.
Analyzing Changes LET’S THINK

A critical skill in chemical thinking is to be able to describe, explain, and predict the changes in diverse
types of systems based on the analysis of the properties of available states under particular conditions. Let us
explore how well you can do it.
Evaporation
By Jarombouts (Own Work)

[CCA: Share Alike 3.0]
Even when the temperature of a small pond of water never reaches
100 oC, the water evaporates and the pond disappears.
• How could you explain this phenomenon based on the ideas

discussed in this module?
Sweating
By Kullez (Own Work)
via Flickr Commons
Our body uses “sweating” as a cooling mechanism.

[Generic 2.0]
• How does this work?

• How would you explain it based on the particulate model of matter?
Solid Transformations Ep Diamond

Analyze the potential energy-configuration diagram for diamond
Materialscientist(talk)) [CCA: Share

Alike 3.0] via Wikimedia Commons
By UIser:Itub (Derivative:
and graphite, two different forms of carbon.
• Which of these phases of carbon is the most favored based on

potential energy and number of configurations?
• What changes would you expect to see when the temperature
is increased? Graphite
• What would you expect to see when the pressure increases?
# Configurations
Degassing
By en:User:Spiff (Own Work)

Oxygen dissolved in water escapes when water is heated up.
• Build a potential energy-configuration diagram to explain this phe-

nomenon.
FACING THE CHALLENGE water crystals. Solid carbon dioxide (dry ice), can
also be used as this material reduces the tempera-
ture to such low values that ice crystals form spon-
From Clouds to Proteins taneously from the vapor phase.
How can everything that we have discussed in this Most clouds in our planet form in the lowest
module be used to understand the formation of region of the atmosphere, called the troposphere.
clouds in our planet? Clouds are large atmospheric Higher layers of the atmosphere tend to be too dry
objects made up of small liquid droplets or tiny for the nucleation process to occur. However, some
crystals of water and other minor components. clouds that form in the winter polar stratosphere,
Clouds form as hot air raises in between 15,000 to 25,000 m
the atmosphere and rapidly ex- above sea level, play a crucial
pands due to reduced atmospheric role in our planet. Nucleation in
By Axel Rouvin (Own work) [CCA: Public domain]

pressures at higher altitudes. In or- these clouds occurs at tempera-
der for the gas to expand, particles tures close to -80 oC. The clusters

in the ascending air need to push that form at these temperatures
particles in their surroundings and are mixtures of water with other
transfer part of their kinetic ener- substances such as nitric acid and
gy. The average kinetic energy of sulfuric acid. These droplets and
the particles in the raising air de- crystals trap pollutants and ac-
creases, and thus the system cools celerate chemical processes that
down. At this lower temperatures, consume ozone particles in the
the attractive forces between water stratosphere. The phenomenon
particles cause them to aggregate of ozone depletion in our plan-
into clusters or nuclei that may grow into larger et is thus strongly associated to the formation of
droplets by the addition of more water particles. these types of clouds.
In order for nuclei to grow, the rate at which Nucleation is not only important in the for-
water particles escape from the cluster should be mation of clouds. Most phase transitions in our
smaller than the rate at which other water particles surroundings are initiated via the nucleation of na-
deposit onto it. For this to happen, clusters have noscopic droplets, bubbles, or crystals. Inducing
to reach a critical size in which there are enough and controlling the formation of these nuclei are
particles in the system to hold it together through ways we have to influence the properties of the new
attractive interactions. The formation of nuclei, or phase that emerges from the process. The develop-
the nucleation process, is facilitated by the pres- ment of new materials via nanotechnology relies to
ence of other substances that attract water particles a great extent on the ability to stop the nucleation
and act like centers on which the water nuclei can process when clusters of particles reach the proper
form. Typical nucleation centers include dust and size. In biochemistry, the nucleation of protein
sodium chloride crystals. Liquid droplets tend to crystals is a necessary step to determine the struc-
form at low altitudes, but ice crystals are prevalent ture of enzymes and other important components By Mathias Klode (Own Work) [CCA: Share Alike 3.0]
at higher elevations. of our cells. However,

Humans have developed strategies to “seed producing good crys-
clouds,” this is to artificially induce the formation tals for analysis can
of nuclei in regions where the concentration of wa- be extremely challeng-
ter particles is not enough for them to aggregate ing. In all these cases,
spontaneously. Cloud seeding often requires the understanding phase
dispersion in the atmosphere of solid substances transitions at the par-
with a crystalline structure similar to ice, such as ticulate level is an in-
silver chloride, which induces the nucleation of valuable asset. Protein Crystal
Let’s Apply
Up and Down our Planet
The properties of gases change when you move up and down in Earth’s atmosphere or underwa-
ter. This table lists temperature and pressure data gathered at various altitudes in the atmosphere
and various depths in the ocean:
Atmosphere Hydrosphere (middle latitudes)

Altitude Temperature Pressure Depth Temperature Pressure
(km) (K) (atm) (km) (K) (atm)
0 293 1.0 0 293 1.0
1 287 0.883 0.1 290 11
2 280 0.779 0.2 279 21
3 273 0.687 0.3 278 31
4 267 0.607 0.4 277.4 41
LET’S THINK Your Lungs
Imagine that you model your lungs as a 5 L sealed balloon filled with an ideal
gas at sea level:
• How will the volume of your lungs change as you climb up to the top of a
mountain at 5 km above the sea level? Estimate the volume of your lungs at
the top of the mountain.
• How will the volume of your lungs change as you dive down into the ocean
to 100 m below sea level? Estimate the volume of your lungs at the bottom
of your dive.
• Why would you need pressurized tanks for scuba diving? Why
By Soljaguar (Own Work)

would it be necessary to exhale and rise slowly when ascending
from the ocean depths?
• How do the problems that you might have in scuba diving com-
pare with those of a pilot climbing to a higher altitude in a pres-
surized plane?
• Build a particulate representation of the air inside your lungs (the balloon)
as you move from 5 km above sea level to 100 m below the ocean surface.
How would the following properties change as you descend a) Average
speed of the particles; b) Mass of a single particle; b) Volume of a single
particle; d) Distribution of the particles inside the balloon.
Cooking
By US Department of Agriculture
Recipes for cooking with boiling water need to be modified based on the altitude

of the place where you cook.
• Why is that? How would you explain it?

• How does a change in pressure affect the potential energy and the number
of configurations available to a system in liquid or gas state?

In the Beach
Sodas contain pressurized carbon dioxide at a pressure close to 2 atm.

Imagine that you were to take a soda can out of a cooler and open it
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M2/submicro.html
on the beach in a warm day at 300 K.
• How would the average kinetic energy of the carbon dioxide

particles in the system change when the can is opened?
CLICK TO PLAY
• How would the average potential energy of the carbon dioxide
particles in the system change?
• Use the interactive tool to build a particulate representation of
a nanoscopic portion of the can at the moment it is opened.
• Build a potential energy-configuration (PEC) diagram showing
the state of the can before and after it is opened.
Share and discuss your ideas with one of your classmates, and clearly
justify your reasoning.
Forming Clouds
When cold pressurized beverages such as this are opened, it

is common to observe the formation of small “cloud” around
the opening (see image). A similar phenomenon is respon-
sible for the formation of clouds when air ascends in the at-
mosphere and quickly expands.
• How would you explain this phenomenon using the

particulate model of matter?
Share and discuss your ideas and justify your reasoning.

Let’s Apply
Fighting Intuition
The properties and behavior of matter at the submicroscopic level sometimes defies our intuition.
We are not used to building explanations about the things that we observe in our daily lives based
on the movement and interactions of myriads of submicroscopic particles that we cannot see with
our eyes. Testing and recognizing the limits of our intuitive ways of describing and explaining the
world is crucial in the process of becoming a better chemical thinker. Thus, in these pages we pose
a few challenges to test your reasoning.
• Evaluate the answer given by some students to the following questions. Share and discuss
your ideas with a classmate. Discuss what misunderstandings or intuitive ideas may lead
students to make mistakes and select incorrect answers.
Cooling
A cook takes a hot iron frying pan off the stove to cool. What happens as the iron pan cools?
a. The mass of the iron particles increases, so the pan gets a tiny bit heavier.
b. The mass of the iron particles does not change, so the pan remains the same.
c. The distance between the iron particles decreases, so the pan gets a tiny bit smaller.
d. The distance between the iron particles does not change, so the pan remains the same.
Several students selected answer A as correct. What do you think?
The following diagram represents a magnified view of a small portion

of a steel tank filled with helium gas at 20 °C and 3 atm pressure. The
dots represent the distribution of helium atoms. Which of the follow-
ing diagrams best illustrates the distribution of helium atoms in the
steel tank if the temperature is lowered to –100 °C (helium is still a
gas at this temperature)?
a. b. c. d.
A chemistry student chose representation a. What do you think?

Substance Properties
Why does solid water (ice) float in liquid water?
a. The particles of liquid water are heavier than the particles of ice.
b. The particles of ice have a smaller volume than the particles of liquid water.
c. The particles of ice are farther apart than the particles of liquid water.
d. The particles of liquid water are more rigid than the particles of ice.
A chemistry student thinks that options a and c are correct. What do you think?

Why does liquid candle wax flow but solid candle wax does not?
a. Because the particles of liquid candle wax are softer than the particles of solid candle wax
b. Because the particles of liquid candle wax weigh less than the particles of solid candle wax
c. Because the particles of liquid candle wax are moving but the particles of solid candle wax
are not
d. Because the particles of liquid candle wax can easily move past one another but the particles
of solid candle wax cannot
A chemistry student thinks that options d in the only one correct. What do you think?
Particle Properties
Following is a list of properties of a sample of solid sulfur:

i. Brittle, crystalline solid. ii. Melting point of 113 oC.
iii. Density of 2.1 g/cm .
3
iv. Reacts with oxygen to form sulfur dioxide.
Which, if any, of these properties would be the same for one single particle of sulfur obtained
from the sample?
A chemistry student thinks that all these properties of solid sulfur would be the same for
one single particle of sulfur. What do you think?
Which of the following processes will make the particles that make up a substance larger?
a. Freezing b. Boiling c. Condensing d. None of them
A chemistry student selected a (freezing). What do you think?
Solid, liquid, and gaseous water coexist at the triple point (0.01 oC and 0.006 atm). In which of
these phases do water particles have the lowest average speed at 0.01 oC and 0.006 atm?
a. Gas b. Liquid
c. Solid d. The average speed is the same in the three phases
A chemistry student selected d (the average speed is the same in the three phases). What
do you think?
36
Analyzing
Particles
The particulate model of matter can be used to explain why different substances
U1: MODULE 3
have different properties. These differences are due to the presence of interaction
forces between particles that vary in type and strength. Why are the interaction
forces different? To answer this question, we need to zoom into the submicrosco-
pic world to better understand the structure of matter. Chemists have shown that
if we know the specific nature of the particles that compose a substance,
we can predict its properties. How can we determine the
specific characteristics of nanoscopic particles that we
cannot see or isolate in a conventional chemistry lab?
The characterization of the particles that make up a
chemical substance is one of the major goals and chal-
lenges in chemistry. The task is accomplished in a vari- What is the mass of
ety of clever and creative ways that generate information a single molecule of
butane?
about the mass, chemical composition, and structure of these
particles. In this module, we will introduce the models used to describe the differ-
ent composition and structure of the particles that make up the diverse substances
in our world. Then, we will analyze the type of thinking that is used to determine
the mass of these particles and the number of particles present in a given amount
of substance. This information is critical for many important tasks, from deter-
mining the concentration of pollutants in the air we breathe to measuring the
concentration of diverse metabolites in our blood.
THE CHALLENGE Air Pollution

Modern technology allows us to quantify the concentration of different types
of pollutants in the atmosphere.
• If someone told you that the concentration of ozone in the place you
live is 2 x 10-4 mg/L, what would you need to know to determine how
many particles of ozone you breathe per liter of air that you take in?
• Why would these numbers be important to know?
Module 3 will help you develop the type of chemical thinking that is needed
to solve problems similar to the one presented in this challenge. In particular, the
central goal of Module 3 is to introduce the atomic model of substances and
discuss how to use information about atomic and molecular masses to calculate
the number of particles of different types present in a system of interest.
Atomic Model of Substances

Helium Atom
It is a fundamental assumption in modern chemical thinking that substances in
our world have different properties because they are made of particles with different Hydrogen
compositions and structures. In particular, in the atomic model of substances it is Molecule
proposed that the particles that compose the substances in our surroundings have
internal structure. They are made up of smaller units called atoms which are held
together by strong attractive forces called chemical bonds. These internal forces
are much stronger than the forces acting between different particles in the system.
There are only a few substances composed of particles that are single atoms; argon
Water
and helium are two examples. Most substances have a more complex submicrosco-
Molecule
pic structure. For example, many of them are made up of particles where two or
more atoms of the same or different types are bonded together. These composite Figure 1.19 Particles of he-
particles are called molecules (Figure 1.19). All of the molecules of a given sub- lium are made of single at-
oms; particles of hydrogen
stance are assumed to be identical to each other but different from the molecules are made up of molecules
with two identical atoms;
of a different substance. Differences between molecules result from differences in particles of water are made
the types of atoms present in them, differences in the way these atoms are arranged up of molecules with three
atoms, two hydrogen atoms
in space, or both. A molecule’s composition and structure determines how the and one oxygen atom.
molecule will interact with other particles of similar or different type.
Particles in the Atmosphere LET’S THINK

The image in this activity shows a particulate representation of a nanoscopic section of the air in
our atmosphere.
• How many different substances are present in this

system?
• Which substances in air are made up of particles that
are single atoms and which are made up of molecules?
• Air is a mixture of substances. How is a mixture dif-
ferent from a single substance at the particulate level?
Share and discuss your ideas with a classmate, and clearly

Note: The following color code is commonly used to represent atoms of different types:
Argon Hydrogen
Oxygen
Carbon Nitrogen
The atomic model of substances allows us to make sense of many observations

and experimental results about the properties of substances and their mixtures.
For example, if we assume that air is a gaseous mixture of several substances each
of them characterized by a particular type of particle, then that explains why the
different components can be separated by simply cooling down the mixture. The
strength of the interaction between different types of particles can be expected to
be different and substances will condense at different temperatures. But how do
we know how particles differ from each other? How do we know that molecules
38 MODULE 3 Analyzing Particles
By Dnn87 (Own Work)

of carbon dioxide are made up of two oxygen atoms and one carbon atom, or that
nitrogen molecules have two atoms of the same type? Although we will take some
Sodium time to build the answers to these questions through the following units, we can
present some experimental evidence that supports this model.
Through experimentation, chemists have identified two major types of sub-
stances. There are some substances that cannot be decomposed into simpler stable
substances by any physical or chemical procedures. There is no known experimen-
tal technique that allows us to take a sample of these substances and split it into two
or more different stable substances. We call these types of substances elementary
substances (Figure 1.20). They include, for example, the oxygen, nitrogen, and
argon that we separate from air in the atmosphere. There are, however, substances
By Enricoros (Own Work)
that we can split into two or more simpler stable substances by inducing a
via Wikimedia Commons chemical reaction. We call these types of substances chemical compounds;
water and carbon dioxide are two typical substances in this group. Water
can be separated into the elementary substances hydrogen and oxy-
gen, while carbon dioxide can be decomposed into carbon, another
Silicon elementary substance, and oxygen. Whenever a chemical compound
undergoes this decomposition, the proportion of elementary substances
that are recovered is always the same. For example, during the decomposition of
water we always produce twice the volume of hydrogen gas than oxygen gas.
The atomic model of substances allows us to explain the above macro-
scopic differences in the behavior of elementary substances and chemi-
Sulfur cal compounds in the following way. Elementary substances cannot be
decomposed into two or more stable substances because they are made
up of particles, atoms or molecules, that contain one single type of atom.
Chemical compounds can be decomposed into other substances because
their particles contain two or more different types of atoms that can rear-
Figure 1.20 Samples of dif- range to produce elementary substances. When this happens, the relative
ferent elementary substances,
together with a particulate rep- amount of the elementary substances that are produced is determined by the
resentation at the nanoscale. ratio of the different types of atoms that make up the particles of the compound.
LET’S THINK What are they?

Analyze the following particulate representation of nanoscopic samples of elementary substances,
chemical compounds, and mixtures
• Classify each of the images as a repre-

sentation of an elementary substance, a
compound, or a mixture of substances.
• In the case of mixtures, identify what
types of substances, elementary or
compound, are present in them.
• Identify the state of matter in which
each of the substances or mixtures is
represented to be.
From the perspective of the atomic model of matter, elementary substances

are the most simple stable substances that we know. They are composed of identi-
cal particles made up of free or bonded atoms of the same type. The isolation and
identification of the various elementary substances in Nature has allowed chem-
ists to identify all of the different types of atoms that make up the particles of all
substances, natural and synthetic, in our world. Up to this day, over a hundred
different types of atoms have been identified. Each of these species of atoms is
recognized as a different chemical element. The list of these elements is presented
in the following “Periodic Table of the Chemical Elements” (Figure 1.21). Each
type of atom or element in this table is assigned a symbol that, as we will see later,
greatly simplifies its representation. Atoms or elements in a given column in the
Periodic Table are said to be in the same “group,” while those in the same row be-
long to the same “period.” The location of an element in the Periodic Table is not
arbitrary and provides information about its chemical reactivity.
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M2/pt.html
Figure 1.21 Periodic Table
CLICK TO PLAY
of the Chemical Elements
displaying the symbols com-
monly used to represent
each type of atom. Click on
the image to display an inter-
active Periodic Table.
Each of the atoms or elements listed in this table has the same name as the
elementary substance whose particles are made up by that type of atom. However,
it is important to recognize that the properties of the atoms included in the Peri-
odic Table are not necessarily the same as the properties of the particles that make
up the elementary substance nor the properties of the actual chemical substance.
For example, the oxygen that we found in the atmosphere is made up of molecules
composed of two atoms of oxygen each. The structure and properties of these
molecules are different from those of a single oxygen atom. Similarly, a sample of
copper is made up of many copper atoms bonded together in a metallic network; By de:user:Tomihahndorf (Own Work)
this sample conducts electricity. Electrical conductivity is a property of a large col-

lection of atoms and cannot be defined for a single atom.

Elementary substances are traditionally subdivided into three main groups:
Metals, metalloids or semimetals, and nonmetals, based on similarities in physical
and chemical properties. Metals are usually solids at room temperature and con-
duct heat and electricity remarkably well; most nonmetals, in the other hand, are
gases under the same conditions and are poor conductors of heat and electricity.
Metalloids share some properties of metals and nonmetals. The symbols of the Iodine
Nonmetallic
atoms that make up the particles of these different types of substances are com- Elementary Substance
monly displayed with different colors on the Periodic Table (Figure 1.21). It is
also common to refer to the types of atoms that make up these different groups of
substances as metallic, metalloid (or semimetal), and nonmetallic elements.
Chemists have developed a variety of ways to represent the composition, struc-

ture, and properties of the actual chemical substances in our surroundings and of
the models used to describe, explain and predict their behavior (see Figure 1.22).
At the macroscopic level we can use actual images of the substances or descriptions
of their measured properties. At the submicroscopic level, we can create drawings or
create dynamic animations and simulations to try to represent different types of
particles. Additionally, chemists have developed a sophisticated symbolic language
to represent the composition and structure of chemical substances. A chemical
formula, for example, is a symbol that conveys information about the atomic
Figure 1.22 Different ways composition of a given substance. Thus, the chemical formula for oxygen gas is
of representing elementary
substances. The labels (g), O2(g), where the subindex is used to show that every single molecule of this sub-
(l), (s), indicate the state of
matter of the substance.
stance is made of two oxygen (O) atoms and the label within parenthesis indicates
the state of matter (g, gas; l, liquid; s, solid) of a macroscopic sample.
Macroscopic Submicroscopic Symbolic
Ar
Atomic
Elementary
Substance
Argon
Gas Ar(g)
N2
By Cory Doctorow
(Own Work) [CCA:
Share Alike 2.0], via
Wikimedia Commons
Molecular
Liquid
Nitrogen N2(l)
Elementary
Substance P4
By Tomihahndorf Solid
(Own Work) [CCA:
Public domain], via
Wikimedia Commons
Red
Phosphorus
P4(s)
Most substances in Nature are not elementary substances but chemical com-
pounds. As mentioned before, chemical compounds are substances whose parti-
cles are made up of bonded atoms of two or more different types. Chemists classify
chemical compounds into two major groups: Ionic and molecular (or covalent)
compounds, based on their physical and chemical properties. Ionic compounds
tend to be solids with high meting points that conduct electricity when dissolved
Caffeine in water or in the liquid state (molten). Molecular compounds exist in different
Molecule states of matter and, in general, are not good electrical conductors in any phase.
C8H10N4O2 Differences in properties can also be explained based on the composition and
structure of these substances at the submicroscopic level.
Molecular compounds often result from the chemical combination of nonme-
Cholesterol tallic elements (see Figure 1.21). When these types of atoms combine they tend to
Molecule form molecules, this is, independent particles composed of two or more bonded
C27H46O atoms of different types. For example, water is a molecular compound in
which each of its molecules contains two hydrogen atoms and one oxygen
atom. The chemical formula of liquid water is thus H2O(l). Numerical sub-
indexes after an atomic symbol are used in chemical formulas to show the
number of atoms of a given type in the particles of the compound (see Figure
1.23). From the perspective of the atomic model, the wide number and diver-
sity of molecular compounds in our world is due to the possibility of having many
different types of molecules that differ in composition, size, and structure.
Color Code Macroscopic Submicroscopic Symbolic
CO2
Solid
C
Carbon
Dioxide
CO2(s)
H
N NH3
O
Ammonia
Gas NH3(g)
Ionic compounds result from the combination of metallic and nonmetallic Figure 1.23 Different
ways of representing
elements. Their particular properties can be explained by assuming that their sub- molecular compounds.
microscopic structure is different from that of molecular compounds. In particu-
lar, ionic compounds are not seen as composed of individual molecules but of
electrically charged particles arranged in crystalline networks (Figure 1.24). These
charged particles are called ions and they can be atoms or molecules with a net
electrical charge. An ionic network is made up of positively charged ions (cations)
and negatively charged ions (anions) attracted to each other by electrostatic forces.
The ratio of anions to cations in any sample of this type of substances is such that
the material has no net electrical charge. These different ions gain mobility when
the solid compound is molten or dissolved in water and that explains why ionic
compounds conduct electricity under such conditions. Typical examples of ionic
compounds include sodium chloride, the major component in common salt, and
calcium carbonate, the main component in limestone.
Color Code Macroscopic Submicroscopic Symbolic
Na+
By Choba Poncho Solid
Cl
NaCl(s)
(Own Work) [CCA:
Public domain], via
Wikimedia Commons
Sodium
Chloride
H
Cl–
N NH4+
By Walkerma (Own Solid
Work) [CCA: Public
domain], via Wikime-
dia Commons
Na Ammonium
Chloride
NH4Cl(s)
Given that ionic compounds are not made up of molecules, their chemical Figure 1.24 Different
ways of representing
formula conveys different information than that of a molecular compound. The ionic compounds.
chemical formula of an ionic compound, or its formula unit, simply establishes
the lowest ratio of cations to anions in the system. For example, the formula unit
of sodium chloride is NaCl, which indicates that the ionic network of this chemi-
cal compound is composed of sodium cations (Na+) and chloride anions (Cl–) in a
ratio of one to one (1:1). The formula unit of calcium fluoride is CaF2, which tells
us that calcium cations (Ca2+) and fluoride anions (F–) are present in a 1:2 ratio.
LET’S THINK Submicro and Symbolic
The ability to translate from submicroscopic (particulate) representations

of matter to symbolic language and vice versa is a critical skill in chemical
thinking. The following images show submicroscopic representations of sev-
eral pollutants in our atmosphere in different states of matter.
• Write the chemical formulas of each of theses substances.
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M2/submicro.html
Cl
O
• Create submicroscopic representations of the
following substances. Use the interactive tool
on this page to make your drawings.
CH4(g) KCl(s)
NO(g) Cl2(l)
Share and discuss your ideas with one of your classmates. CLICK TO PLAY
Throughout this book we will use a variety of visual representations of chemi-

cal compounds at the submicroscopic level using drawings and symbols of differ-
Methane ent types. These diverse representations are intended to emphasize different char-
acteristics or properties of the represented atoms, molecules, or ionic networks.
CH4
For example, the so-called space-filling representations are typically used to em-
phasize the relative size of the atoms that compose a system. On the other hand,
ball-and-stick representations highlight the connectivity between different atoms
in a molecule or ionic network. In both cases, the representations allows us to de-
Molecule velop a better sense of the three dimensional geometry of the objects of interest.
In general, modern computational technology has helped us generate many types
of static and dynamic images to better visual-
ize the modeled submicroscopic world. All these
representations have limitations that may create
misconceptions. For example, chemical bonds
in ball-and-stick representations are depicted
as solid rods connecting two atoms. However,
these bonds are not physical objects but only
Space-Filling strong interaction forces between atoms.
Representation Ball-and-Stick Representation
CLICK TO PLAY
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M2/ch4.html
Phases and Components LET’S THINK

The image below is a representation of a nanoscopic portion of the surface of a soft drink can:
• How many different phase are present in this system? Which phases
are these? How many substances are present in each phase?
• How many of the substances in this system are a) elementary sub-
stances; b) chemical compounds? Write their chemical formulas.
• In which of the different phases present in the system: a) Are the
attractive forces between particles the strongest? b) Is the average
potential energy per particle the lowest (most negative)? c) Is the
average particle speed the highest? d) Is the average kinetic energy
per particle the lowest? Justify your answers.
• Which of the components seems to have the lowest vapor pressure?
USEFUL TOOLS The name of a binary ionic compound includes

Chemists have not only created useful ways of the name of the cation followed by the name of
representing chemical substances at the macro- the anion. For example, NaCl is named sodium
scopic, submicroscopic, and symbolic levels, but chloride while Al2O3 is called aluminum oxide.
they have also developed a systematic language Notice that the number of each type of ion
to name each chemical element and compound present in the formula unit is not included in the
in our world. Understanding this “chemical no- name of the compound.
menclature” greatly simplifies chemical thinking
and communication. Let us explore how to name Molecular Compounds: The name of a binary
molecular and ionic compounds made up of two molecular compound is also derived from the
different types of atoms, or binary compounds:
atoms that made up their molecules. In this
case, the name of the atom farthest to the left in
Ionic Compounds: The name of binary ionic
the Periodic Table (Figure 1.21) goes first. If both
compounds results from the combination of the
types of atoms are in the same group, the atom
names of the positive ions (cations) and negative
farthest down in the table is named first. So, for
ions (anions) present in the system.
example the name of the compound CO2 begins
with “carbon”, and that of SO2 with “sulfur.”
The cations have the same name as the atom
from which they derive. These are atoms of
The name of the second component of the
metallic elements that acquired a positive
molecular compound is built by adding the suffix
charge. For example, Na+ is the sodium ion while
-ide to the root the atom’s name. Greek numeral
Al3+ is the aluminum ion. Some atoms can form
prefixes are used to indicate the number of at-
more than one type of positive ion and a Roman
oms of each type (mono- for one; di- for two; tri-
numeral in parenthesis is used to distinguish one
three). However, this numeral is not added if the
cation from another. For example, Cu+ is named
molecule only has one atom of the element that
the copper(I) ion, while Cu2+ is the copper(II) ion.
is named first. The following examples illustrate
the application of these rules:
The name of the anions is built by adding the
suffix -ide to the root of the name of the atom
CO Carbon monoxide
from which the ion is derived. These are atoms
CS2 Carbon disulfide
of nonmetallic elements. Thus, Cl– is the chloride
N2O Dinitrogen monoxide
ion while O2– is the oxide ion.
PCl3 Phosphorus trichloride
Relative Masses
Atoms, molecules, and ions have masses and sizes so small that they cannot be
measured directly with a balance or similar instruments. It is thus necessary to
rely on indirect measurement techniques to accomplish the task. In particular, the
problem has been solved by comparing the masses of macroscopic samples of dif-
ferent substances containing the same number of particles. For example, imagine
that you had two tanks of gas containing the same number of particles but two dif-
ferent substances such as helium and argon. If you measured the mass of the gas in
each tank you would find out that the argon gas sample is ten times heavier than
the helium gas sample with the same number of particles. What does this mean
from the perspective of the atomic model of substances? Given that argon and he-
lium are elementary substances made up of single atoms, it implies that each atom
of argon (Ar) should be ten times more massive than each atom of helium (He). If
we knew the mass of a helium atom, we could calculate the mass of an argon atom
Figure 1.25 If these gas tanks or vice versa. If we could measure or calculate the number of atoms in any of the
contain the same number of
particles of each substance, how samples, we could also calculate the mass of the individual atoms.
many times heavier is an oxygen
atom than a hydrogen atom? The problem of determining atomic or molecular masses is intimately con-
nected to the challenge of figuring out how to collect samples of different sub-
stances with the same number of particles, and how to determine the actual num-
ber of particles in these samples. The application of the particulate model of matter
provides a nice solution to these challenges. Let’s investigate how.
LET’S THINK Mass Effect?
We can use a simulation of an ideal gas to explore the effect of changing the mass of the particles
on the pressure of the system at any given temperature and volume. In this computer simulation,
particles with different masses can be used to model different chemical substances. Click on the im-
age to launch the simulation of an ideal gas and begin your analysis.
CLICK TO PLAY
• Explore the effect of the mass of the particles on the average pressure of
an ideal gas at constant temperature, volume, and number of particles.
Remember to wait until fluctuations in the value of the average pres-
sure are minimal before collecting any data.
• Use the results of your investigation to propose a strategy to experi-
mentally prepare two samples of different gases with the same number of particles.
The results of our exploration suggest that under the conditions in which
the ideal gas model provides a good description of the behavior of gaseous sub-
stances, equal volumes of two different gases at the same temperature and pressure
will contain the same number of particles. In fact, we could have predicted this
outcome by simply analyzing equation (1.2) for the ideal gas law, which can be
re-expressed as:
(1.3) N = P V / ( kB T ).
This model predicts that the number of particles for an ideal gas is solely deter-
mined by the values of P, V, and T independently of the mass of the particles;
equal volumes of two different gases at the same T and P should then have the
same number of particles. By simply comparing the masses of equal volumes of
gas at the same temperature and pressure, we can determine the relative masses of
the particles that make up each gas; this should work as long as the gases behave
ideally. This approach to determining the relative masses of particles was first pro-
posed by Amadeo Avogadro in 1811, who was also the first to suggest based on
experimental data that equal volumes of different gases at the same temperature
and pressure would have the same number of particles (Avogadro’s Hypothesis).
Unknown Masses LET’S THINK

Imagine that the mass of three identical tanks separately containing hydrogen gas [H2(g)] and
two unknown elementary substances were measured at the same temperature and pressure:
• How many times more massive is an A atom than a H atom?

• How many times more massive is a B atom than a H atom?
• If you were to assign a mass of “1.0” to a hydrogen atom in an
arbitrary unit, what would the relative masses of the A and B
atoms be when expressed in that unit?
• How would the relative masses change if you decided to arbi-
trarily assign a relative mass of “2.0” to an A atom?
• Is one of the scales of relative masses that you generated better than the other? If yes, how?
Share and discuss your ideas and results with one of your classmates.
Using methods similar to the ones you applied in the last activity, together
with careful measurements of the proportions in which different types of atoms
chemically react with each other, chemists have been able to determine the “aver- Figure 1.26 Click on the image
to display a Periodic Table of the
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M3/ptm.html
age relative atomic mass” of all the known atoms. These values are expressed in Chemical Elements listing the aver-
age relative mass of each atom.
so-called “atomic mass units” (amu) and are listed in the Periodic Table of the
Chemical Elements displayed by clicking on Figure 1.26. These numbers are de- CLICK TO PLAY
termined by choosing one type of atom as a reference (as you did it in the last ac-
tivity) and they allow us to calculate
how many times more massive one
atom is with respect to another. For
example, given that the relative mass
of one atom of sulfur (S) is close to
32 amu and that of an oxygen atoms
(O) is 16 amu, we can infer that a
sulfur atom is, on average, twice as
massive as an oxygen atom. In Mod-
ule 4 of Unit 1 we will analyze in
more detail how the relative atomic
masses have been determined using
modern analytical techniques.
LET’S THINK Number of Atoms
The list of average relative atomic masses is very useful in chemistry and many other disciplines in
which it is important to figure out the relative number of particles of different species in a system.
To understand it, imagine that you were in the business of buying and selling precious metals and
had the following samples: 107.9 g of Ag(s), 197.0 g of Au(s), and 195.1 g of Pt(s).
• Which of the three samples has more atoms? Why?

• How many grams of palladium metal, Pd(s), would you need to weigh to have as many atoms
as in 107.9 g of Ag(s)?
• How many grams of copper metal, Cu(s), would you have to weigh to have half the number of
atoms that you have in 197.0 g of Au(s)?
• Based on these results, why do you think it is useful to know the relative masses of the differ-
ent atoms in the periodic table?
Share and discuss your ideas with one of your classmates., and clearly justify your answers.
Number of Particles
One can think of the relative masses of the different atoms in the Periodic Table
Figure 1.27 Click on the image in Figure 1.26 as indicative of how much more massive each type of atom is than
to display a sequence of repre-
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M3/avogadro.html
sentations based on number of a reference atom with an assigned mass of 1 amu (one atomic mass unit). For
pennies that may help you grasp
how large Avogadro’s Number is. example, helium atoms (He), with a relative mass of 4.003 amu are, on average,
four times more massive than the reference atoms while argon atoms (Ar), with
a relative mass of 39.95 amu, are close to forty times heavier than the
reference particles. This implies that if we were to weigh 1.000 g of the
reference atoms and 4.003 g of He atoms, both samples should have
the same number of atoms. In fact, a sample of 39.95 g of Ar atoms
should also be composed of the same number of atoms. So, whenever
we weigh masses of different types of atoms and these masses are equal
in magnitude to each atom’s average relative atomic mass, we should
have samples with the same number of atoms. This fact is very useful
as it allows us to use the mass of our samples, a quantity that we can
measure, to compare number of particles without having to know how
many of them are present in each system. In this way, based on the data
listed in the Periodic Table we can predict that 20.0 mg of calcium, with
a relative atomic mass of 40.08 amu, will have approximately half the number of
CLICK TO PLAY
atoms present in 9.0 mg of beryllium, with a relative atomic mass of 9.012 amu.
Although comparing number of particles using relative masses is useful,
it would be easier if we could just measure or calculate the actual number of
particles in any given sample. Fortunately, chemists have devised approaches to
do so. In particular, they have experimentally determined the number of atoms
in samples of substances with a mass equal in magnitude to their average rel-
ative mass expressed in grams. For example, the number of particles in 4.003
g of helium, 9.012 g of beryllium, or 40.08 g of calcium. This number, called
Avogadro’s Number NA, is very large (see Figure 1.27) and has a constant value
equal to 6.022 x 1023 particles.
Molecular Species LET’S THINK
Some elementary substances are made up of molecules rather than single at-
oms. That is the case for hydrogen, H2, nitrogen, N2, oxygen, O2, fluorine, F2,
phosphorus, P4, sulfur, S8, chlorine, Cl2, bromine, Br2, and iodine, I2. We need
consider this fact when trying to figure out the relative mass of their particles
or the number of molecules in a given sample.
• If the average relative atomic mass of oxygen atoms is 16.00, what is the
average relative mass of oxygen molecules O2?
• How many grams of phosphorus should you weigh to have 6.022 x 1023
molecules of this substance?
• How many molecules should we expect to have in 35.45 g of chlorine
gas?
Share and discuss your ideas and results with one of your classmates.
From the chemical point of view, having information about the number of
particles in a sample of a given substance is frequently more relevant than knowing
its mass. Thus, it is convenient to define a unit of measurement that can be used
to simplify the quantification of the number of particles in a system of interest.
Avogadro’s Number, NA = 6.022 x 1023, has been chosen as the base to build such
unit of measurement. In particular, the new unit measurement, called a mole
(1 mol), is defined as the amount of substance that contains one Avogadro’s Num-
ber of particles of such substance. Based on our previous discussion, together with
the information provided in the Periodic Table in Figure 1.26, we can say that
4.003 g of helium is 1 mol of helium atoms, 39.95 g of argon is 1 mol of argon
atoms, and 38.00 g of fluorine, made up of F2 molecules, is 1 mol of these mol-
ecules. One mole of any substance always contains 6.022 x 1023 particles.
Measuring the amount of substance using the mole as a unit is a way of ex-
pressing how many times, or what fraction of, an Avogadro’s Number of particles
of a given substance we have in our hands. For example, if someone says that they
have 3.0 mol of copper (Cu) atoms in a bag, we know the bag contains Figure 1.28 The dozen,
just as the mole, is a unit
of amount of substance.
It allows us to simplify the
3.0 x (6.022 x 1023) = 1.8 x 1024 Cu atoms. counting in systems com-
posed of discrete things.
On the other hand, if they have 0.10 mol of silver (Ag) atoms in the same bag,
there will be
0.10 x (6.022 x 1023) = 6.0 x 1022 Ag atoms
in the system. In general, if n is the amount of substance expressed in moles, the

number of atoms in the sample N can be calculated using the following relation-
ship:
(1.4) N = n x NA
LET’S THINK The Mole
To assess your understanding of the “mole”, evaluate the veracity of the following statements: a) The
mass of one mole of neon (Ne) atoms is 20.18 amu; b) The mass of one potassium atom is 39.10
g; c) The mass of 1.2 x 1023 aluminum (Al) atoms is 53.96 g; d) One mole of O2 molecules weighs
16.00 g; e) Three moles of palladium are made up of three atoms; f ) 106.4 g of Pd(s) have the same
number of atoms as one mole of He atoms.
If you judge that a statement is incorrect, rewrite it to make it true.
The mass of one mole of particles of any substance is called its molar mass M and
is equal to the mass of 6.022 x 1023 particles of the substance. M is traditionally
ONE MOLE
expressed using the units g/mol. The molar mass of elementary substances made
32.07 g S up of atoms has the same magnitude as their average relative atomic mass. Thus,
253.8 g I2
the molar mass of helium is 4.003 g/mol and that of calcium is 40.08 g/mol. These
are the masses of 6.022 x 1023 atoms of each of these substances. For molecular
elementary substances, such as hydrogen and oxygen, the molar mass is equal to
24.31 g Mg the mass of one mole of molecules and has to be calculated taking into account
63.55 g Cu the number of atoms present in each molecule:
MOLAR MASS M(H2) = 2 x M(H) = 2 x 1.008 = 2.016 g/mol
The same procedure can be applied to calculate the molar mass of any molecular
compound, using the chemical formula to determine the number of atoms of each
type in its molecules. For example, the molar mass of carbon dioxide is:
M(CO2) = M(C) + 2 x M(O) = 12.01 + 2 x 16.00 = 44.01 g/mol
The molar mass of an ionic compound, such as aluminum chloride AlCl3(s), rep-
resents the mass of 6.022 x 1023 formula units of this substance:
M(AlCl3) = M(Al) + 3 x M(Cl) = 26.98 + 3 x 35.45 = 133.33 g/mol

By Andrew Magill (Derivative from Original)
[CCA: 2.0 Generic] via Flickr Commons
The molar mass of a substance is a useful quantity as it can be used to calculate

the amount of substance n present in any sample; once n is calculated we can use
equation (1.4) to determine the number of particles in the system. The amount of
substance (in moles) n is a measure of how many times larger, or smaller, the mass
M(H2O) = of the sample m is compared to the molar mass of the substance M:
18.02 g/mol
(1.5) n=m/M
For example, if we know that a medium-size car releases around 400. g of CO2(g)
into the atmosphere per mile that it moves, we can calculate the amount of sub-
stance n and the number of particles N that it emits along that distance:
n = m / M = 400. / 44.01 = 9.08 moles of CO2(g)

N = n x NA = 9.08 x 6.022 x 1023 = 5.47 x 1024 CO2 molecules.
LET’S THINK Breathing AIr
As we move to higher altitudes, the concentration of oxygen gas in the atmosphere decreas-
es as shown in the following table. This reduces the likelihood of oxygen molecules, O2,
dissolving in our blood. As a result, we may suffer hypoxia (oxygen deprivation).
h (km) C (g/L) n (mol/L) N (molecules/L)

0 (Sea level) 0.283
0.7 (City of Tucson) 0.260
8.8 (Top of Mount Everest) 0.111
12 (Airplane cruising altitude) 0.065
• Use the information in the table to calculate the amount of substance n and the num-
ber of molecules N per liter of air at different altitudes. Analyze how many times fewer
molecules there are at the different altitudes compared with the number at sea level.
Share and discuss your ideas with a classmate.
USEFUL TOOLS tity is expressed. To do the conversion one

needs to:
One critical chemical thinking skill is the abili-
a) Identify the original and the new units of
ty to use experimental results for the mass or
the quantity to transform. For example, if we
volume of different substances and calculate
want to know how many atoms of carbon are
the number of particles in the system. One
present in 0.030 moles of this chemical ele-
can use equations (1.4) and (1.5) to accom-
ment, we can set the problem as:
plish the task, but sometimes it is easier to
rely on appropriate conversion factors. Let’s
0.030 mol (old unit) = ? atoms (new unit)
analyze how to do it.
b) Multiply the original quantity by the proper
Factor-Label Method. This problem-solving unit conversion factor that will replace the old
strategy is based on the fact that any number units by the new ones by cancellation:
can be multiplied by one without changing its
value. The challenge is to express the multi- 6.022 x 1023 C atoms
plicative “one” as a proper unit conversion 0.030 mol C(s) x
factor. 1 mol C(s)
Unit conversion factors can be built
from any two terms that describe equivalent c) Perform the mathematical operations indi-
amounts of a physical or chemical quantity. cated by the resulting expression:
For example, we can use the identity
0.030 x 6.022 x 1023 = 1.8 x 1022 C atoms
1 mol of atoms = 6.022 x 10 atoms
23
Using this approach we can directly transform

to build these two unit conversion factors: from mass to number of atoms, or vice versa,
using a single unit conversion factor:
1 mol of atoms 6.022 x 1023 atoms
or 12.01 g of C(s)
6.022 x 1023 atoms 1 mol of atoms 1.8 x 1022 C atoms x
6.022 x 1023 C atoms
These types of unit conversion factors can be
used to transform the units in which a quan- = 0.36 g of C(s).
Quantification
The ideas presented in the previous sections are useful for quantifying the number
of moles or particles of substances present in different states in diverse environ-
Figure 1.29 The transforma- ments. If the substance is in the solid state, for example, we can measure the mass
tion from mass (m) to number (m) of the sample using a balance and use the molar mass (M) of the substance to
of particles (N), or vice versa,
is facilitated by calculating the calculate the number of moles (n). These number of moles can then be converted
moles of substance using the
molar mass (M) and Avoga- into number of particles (N) using Avogadro’s Number (NA). Figure 1.29 sum-
dro’s Number (NA). marizes the relationships that can be used to accomplish these transformations:
AMOUNT
n=m/M OF N = n x NA
SUBSTANCE
m=nxM n n = N / NA
NUMBER OF
MASS PARTICLES
m NA = 6.022 x 1023 N
If the substance of interest is a liquid, we need information about the density
(d) of the fluid to calculate the number of particles present in the system. The mass
of a volume V of the sample will be given by: m = V x d. Once the mass is known,
the number of moles (n) and the number of particles (N) can be determined using
the relationships summarized in Figure 1.29.
In many situations, the substances of interest are dissolved in a liquid solvent
such as water. When working with an aqueous solution of a given substance A
(the solute), it is common to express the concentration of A in the mixture as the
ratio of the number of moles solute A, n(A), to the volume, V, of the solution:
[A] = n(A)/V. The quantity [A] is known as the “molar concentration” or the “mo-
larity” of solute A. Common units for the molar concentration are mol/L, also
expressed as “M” (molar).
LET’S THINK Molar Concentration

Many substances that we use or interact with in our daily lives are dissolved in water forming aqueous
solutions. In these cases, it is important to know how to quantify their amounts or concentrations.
• Commercial vinegar contains close to 5 g of acetic acid (CH3COOH) per 100 mL of solution.
What is the molarity of acetic acid in vinegar?
• Household bleach is approximately a 0.85 M solution of sodium hypochlorite (NaOCl). How
many grams of NaOCl are present in a cup (~250 mL) of bleach?
• The average molarity of citric acid (C6H8O7) in orange juice is close to 0.01 M. Imagine you
wanted to prepare a solid tablet containing as much citric acid as that present in 500 mL of
orange juice. What mass of citric acid would you need to measure?
• Aqueous solutions of sodium chloride (common salt) used for brining foods have concentra-
tions close to 3.5% in mass. What is the molarity of these solutions?
Share and discuss your ideas with a classmate, and clearly justify your ideas.
Many substances of interest in our surroundings are in the gas state. In these
cases, we can apply our knowledge about the macroscopic and submicroscopic
properties of gases to develop a strategy to estimate the number of moles or the
number of particles in a given sample. For example, if we assume that the gases
behave ideally, we can use equation (1.3) to determine the number of particles
N given information about the temperature T, pressure P, and volume V of the
system. Using the relationship between amount of substance n and number of par-
ticles as expressed by equation (1.4), we could also calculate the value of number
of moles (n) given by:
(1.6) n = N / NA = P V / ( NA kB T ) = P V / ( R T )
where the constant R = NA x kB is known as the universal gas constant (see Figure R values Units
1.30). This expression can also be used to make quick estimations about the vol- 8.314 J K–1 mol–1
ume or the pressure of certain mass m of a gaseous substance with a molar mass M
0.08206 L atm K–1 mol–1
at any temperature. For this purpose we can combine equations (1.5) and (1.6) to
generate the following expression for the equation of state of an ideal gas: 1.986 cal K–1 mol–1
Figure 1.30 The universal

(1.7) P V = n R T = m R T / M. gas constant R can be ex-
pressed in different units.
Using this relationship, we can estimate the volume in liters (L) occupied
by 1 mol of gas at certain pressure and temperature. In particular, let’s take T =
273.15 K (0 oC) and P = 1 atm (760 mmHg), which are traditionally identified
as standard conditions for temperature and pressure (STP) in experimental mea-
surements. Using equation (1.7), together with the value of R in proper units (see
Figure 1.30), we get:
nRT 1 x 0.08206 x 273.15

V= = = 22.41 L
P 1
If we assume that gases behave ideally, this volume will be the same independently
of the type of substance that we have. When T and P change, the volume of a gas
changes and so does the density or concentration of the gaseous substance.
Identification LET’S THINK

The equation of state of the ideal gas as expressed in equation (1.7) can also be used to find the iden-
tity of unknown gases by using their molar mass M as differentiating characteristic. Imagine that you
measured the volume occupied by 2.8 x 10-3 g of an unknown pollutant at standard temperature and
pressure. Your results show that the gas sample occupies a volume of 2.24 mL.
• What is the molar mass of the pollutant?

• If you knew that the pollutant is a chemical compound made of carbon and oxygen, could
you infer what its chemical formula is?
Gaseous substances in our environment are normally mixed with other com-
ponents forming homogeneous solutions, as is the case of the air that surrounds
us. Thus, it is common to use concentrations rather than total amounts when
quantifying their presence in any given system. The concentration give us infor-
mation about how much of a substance we have per unit volume of the mixture.
For example, we could indicate how many micrograms per cubic meter (mg/m3),
how many moles per liter (mol/L), or how many molecules per cubic centimeter
(molecules/cm3) of a certain substance we have. No matter what units we use, the
ideas discussed in this module can be applied to convert from one unit to another.
LET’S THINK Clean Air
The Environmental Protection Agency (EPA) has set National Ambient Air Quality Standards for
various pollutants. These standards set the maximum concentrations not to be exceeded in certain
average time (as measured at 25 oC and 1 atm):
Pollutant Max (mg/m3) Average Time mol/L # molecules/mL

CO(g) 1.03 x 101 8-hour
NO2(g) 9.97 x 10–2
Annual
SO2(g) 7.85 x 10–2
Annual
• Express the maximum concentrations for these different substances in moles/L and number
of molecules/mL? (1 m3 =1000 L; 1 L =1000 mL; 1 g = 1000 mg).
• How much would the concentration limits change if the temperature was 0 oC?
Share and discuss your ideas and calculations with a classmate.
LET’S THINK Harvesting Air
Most of the nitrogen and oxygen that we use for practical purposes are extracted from air. But
exactly how much of each of these chemical elements can we get from every liter of air?
• Based on what you have learned in this module, design and implement a strategy to calcu-
late the mass in grams of oxygen and nitrogen that can be extracted per liter of air at stan-
dard temperature and pressure.
• Analyze how your results would change at higher altitudes, where the pressure may decrease
to half its value at sea level and the absolute temperature may be lower by 10%.
The following information may be useful in completing this task:
a. The %volume of N2(g) and O2(g) in the atmosphere are

78.08% and 20.95%, respectively.
b. The volume of one mole of ideal gas at STP is 22.41 L.
c. For an ideal gas, V = nRT/P.
Discuss and share your ideas with one of your classmates.

FACING THE CHALLENGE [O3(g)], and sulfur dioxide [SO2(g)].

Carbon monoxide is a toxic substances that we
cannot detect with our senses. Once it enters into
Clean Air? the bloodstream, it disrupts the delivery of oxy-
Our ability to monitor the quality of the air we gen throughout the body. CO(g) is often produced
breathe strongly depends on the clever applica- when carbon-containing compounds are burned
tion of many of the ideas discussed in this module. in closed spaces with limited oxygen supply, such
Ambient monitoring, this is the determination of as in stoves or inside the combustion engines of
pollutant concentration in ambient air, can now our cars. Carbon monoxide poisoning is respon-
By Wurstsalat (Own work) [CCA: Sahre Alike 3.0], via Wikimedia Commons
be done in real-time us- sible for the death of millions
ing instruments that can of people every year in devel-
measure very small con- oping countries. Thus, moni-
centrations with very fast toring its concentration in
response times (seconds to local environments is of cen-
minutes). Many of these tral importance. In the US,
measurements are based emissions of CO(g) by cars
on the determination of dropped 60% from 1990 to
the amount of light ab- 2005 thanks to technological
sorbed by individual pol- advances in car manufactur-
lutants, absorption that is ing.
frequently proportional to the concentration of Ozone is a gas with a sharp odor, one that can
molecules of that substance in an air sample. In- be smelled around photocopier and electric mo-
formation about amount of substance (in moles) tors. It is a toxic substance that harms lung func-
or number of molecules can then be expressed in tion and irritates the respiratory system. O3(g) is
terms of mass per unit volume if we know the mo- produced through the interaction of other pollut-
lar mass of the pollutant and the temperature and ants with high-energy radiation from the Sun. This
pressure at which the measurements were taken. substance is one of the most closely monitored in
Most major cities and towns in the world are urban areas, and one of the main causes of envi-
equipped with air-quality monitoring stations that ronmental alerts in large cities.
track the concentration of pollutants, sometimes Nitrogen dioxide and sulfur dioxide are also
on an hourly basis. These concentrations are then toxic substances that cause irritation of the respira-
compared to the air-quality standards in force and tory system. One of the main sources of NO2(g) is
alerts, warnings or emergencies may be declared the burning of gasoline in car engines. The burning
if the air quality is not satisfactory. In the United of coal for the production of electric power is the
States, the Clean Air Act passed in major source of SO2(g) emissions.
1970 requires the Environmen- Regulations enacted through the
tal Protection Agency (EPA) to Clean Air Act have helped re-
set National Ambient Air Quality duce local average concentrations
Standards for pollutants consid- of NO2(g) by 46% and those of
ered harmful to public health and SO2(g) by 71% in the last thirty
the environment. These standards years in the US.
define maximum expected con- The concentrations of these
centrations of six major pollutants major pollutants in metropolitan
in clean outdoor air. These pol- areas are used to calculate the so-
lutants include four atmospheric called Air Quality Index (AQI)
gases: carbon monoxide [CO(g)], traditionally listed in the daily
nitrogen dioxide [NO2(g)], ozone forecast section of newspapers.
By EPA
Let’s Apply
Ozone Matters
Some chemical elements can exist in different forms, or allotropes. That is the case of oxygen,
which in its most stable form is made up of O2 molecules, but can also exist as ozone, a substance
composed of molecules with three oxygen atoms, O3. Ozone gas affects the respiratory system even
at very low concentrations and damages the leaves and needles of trees.
O3(g) is called a secondary pollutant because it is not directly emitted into the atmosphere, but
produced from chemical reactions between O2(g) and other pollutants such as NO2(g), stimulated
by the presence of sunlight. Ozone concentrations are monitored regularly in major cities across
the world. In the US, the EPA has set the clean air quality standard for this substance at an average
of 0.16 mg/m3 at 25 oC and 1 atm over an 8-hour period.
Concentrations
The following map shows the evolution of O3(g) concentrations in Tucson, Arizona on No-
vember 6, 2013.
• Analyze the variations CLICK TO PLAY

in the concentrations mg/m3
of O3(g) along the +0.736
day. How would you 0.228 - 0.735
http://www.airinfonow.com/html/ozone.html
explain these changes? 0.208 - 0.227
• Estimate the lowest
0.188 - 0.207
and highest concen-
trations of ozone in 0.169 - 0.187
moles/L. 0.149 - 0.167
• Concentration of O3 0.133 - 0.148

above 0.17 mg/m3 are 0.116 - 0.132
considered harmful.
What is this limit in 0.0087 - 0.115
molecules/L? 0.0060 -0.0086
• What is this limit in 0.0030 - 0.0059

moles of O3 per mole 0 - 0.0029
of air at 25 oC? (Hint:
Calculate the volume in liters of 1 mole air at 25 oC?
• How would the lowest and the highest concentrations of O3(g) change if the temperature
decreased from 25 oC to 5 oC?
Share and discuss you ideas with a classmate, and clearly justify your reasoning.
Breathing
On average, people take 24,000 breaths each day. One single breath has a volume
close to 0.5 L.
• Estimate the total number of particles in one single breath of air at STP condi-
tions.
• Estimate the total number of O3 molecules breathed by one person living in
Tucson on August 18, 2010 assuming an average concentration of 0.1 mg/m3
of O3 across the day.

• Estimate the total number of O2 molecules breathed by the same person
during the day. What percentage of all the oxygen particles breathed by this
person were O3 molecules?
Share and discuss your ideas with one of your classmates, and clearly justify your
reasoning and procedures.
Good Ozone
The graph on this page (NASA source) shows the concentration of ozone as a
function of altitude in the atmosphere. The region with high ozone concen-
trations defines the so-called “ozone layer.” The concentration in this graph is
expressed in parts per million in volume (ppmv). One ppmv of O3 is equiva-
lent to 1 mole of O3 in one
100
million moles of air.
Thermosphere
80
• Estimate the volume
of one mole of air at
T = -40 oC
P = 2 x 10–3 atm
Altitude (km)
60
the temperature and Mesosphere
pressure where ozone
40
concentrations reach
their maximum.
20
• Use your result and the Stratosphere
data from the graph 0

Troposphere
to estimate the num- 0 3 6 9
Ozone (ppmv)
ber of moles, the mass
in grams, and the number of particles of O3 in one liter of air in the
ozone layer.
Discuss your ideas with a classmate, and clearly justify your reasoning and
procedures.
Let’s Apply
Greenhouse Gases
Some atmospheric gases, such as CO2(g) and CH4(g), absorb infrared radiation emitted by both the
Sun and our own planet, trapping thermal energy in the atmosphere. They are called greenhouse
gases and help sustain average global temperatures favorable to life on Earth. They are also thought
to be responsible for the current increase in average temperatures across the world (global warm-
ing) due to their much higher concentration in the atmosphere compared to pre-industrial times.
The following table includes important information for the analysis of the properties and effects of
major greenhouse gases in our planet:
Substance Concentration* Concentration* Lifetime GWP

(Pre-1750) (Recent Times) (Years) (over 100 years)
CO2(g) 504 mg/m3 695 mg/m3 variable 1
CH4(g) 459 mg/m3 1224 mg/m3 12 25
N2O(g) 486 mg/m 3
581 mg/m 3
114 298
CCl2F2(g) 0 2.61 mg/m3 100 10,900
*At 25 C and 1 atm
o
The lifetime in this table is a measure of the average time it takes for the concentrations of
a given substance to return to its natural value following an increase in its concentration in the
atmosphere. The global warming potential (GWP) is a measure of the thermal energy trapped per
unit mass of the greenhouse gas relative to that of a reference gas (CO2(g)). The GWP is calculated
over a specific time interval as its value depends on the lifetime of each species.
Concentrations
Using the concentrations provided in the table for the different green-
house gases:
• Calculate the percent increase in the concentration of each gas in

the atmosphere from pre-industrial to present time. Investigate
what are the main sources of these four substances in modern so-
cieties, and propose an explanation for why some concentrations
have increased more than others.
• Express all the concentrations in the table in moles/L and in
number of molecules/mL.
Share and discuss you ideas and calculations with a classmate, and
clearly justify your reasoning and procedures.
GWP
The scale for the global warming potential (GWP) of a substance is set using CO2(g)
as a reference; in particular, the GWP for this gas is taken to be equal to one. Thus, if
the GWP for CH4(g) is 25, this implies that 1.0 g of methane traps the same amount
of thermal energy in the atmosphere as 25.0 g of CO2(g) do. Based on this informa-
tion:
• Estimate the number of molecules of CO2 needed to trap as much thermal

energy as:
a) 1 molecule of CH4;

b) 1 molecule of N2O;
c) 1 molecule of CCl2F2;
• Which would be the advantages and disadvantages of expressing GWP as ther-
mal energy trapped per molecule rather than per gram of substance?
reasoning and procedures.
CFC’s
Chlorofluorocarbons (CFC’s), such as CCl2F2, are synthetic substances that were

used as refrigerants in cars and air conditioning systems but have been banned
due to their ability to react with ozone in the stratosphere and thus destroy the
ozone layer. Although present in very small concentration in the atmosphere,
CFC’s tend to have a very high GWP and are responsible for close to 10% of
atmospheric warming. CClF3
Although chlorofluorocarbons (CFC’s) were banned in 1996, there are still ap-
proximately 100 million functioning air conditioning units that use CCl2F2. If
each of these air conditioning units contains 1.1 kg of this compound and leaks CCl3F
25% a year:
• How many moles of CCl2F2 molecules are added to the atmosphere yearly?
• How many moles of CO2 molecules would have a warming effect equiva-
lent to that of the amount of CFC released every year?
• Americans produce close to 1.97 x 103 kg of CO2(g) per capita every year.
How many people would be needed to produce CO2(g) in amounts that
could have the same warming effect as the CFC released?
CHClF2
reasoning.
58
Determining
Composition
Most of our discussions about the properties of different substances have been
U1: MODULE 4
based on the assumption that we somehow know, or can know, the chemical
composition of the particles of matter. We say, for example, that
water molecules, H2O, are made of two hydrogen atoms and
one oxygen atom and can use this information to calculate
water’s molar mass. Even in dealing with more complex sub-
stances such as the most common form of hemoglobin in
human blood, we dare to claim that its chemical formula
is C2952H4664N812O832S8Fe4. How do we know? Our ability
to generate reliable information about the chemical com-
position of substances is based on the clever combination
of experimental evidence gathered using a variety of analytical Hemoglobin
techniques, together with theoretical principles and models of matter Molecule
at the submicroscopic level that guide the collection and interpretation of data.
The development of experimental strategies that can be used to derive the
chemical composition of substances relies to a great extent in models of the struc-
ture of matter at the “subatomic” level. This is, models devised to describe, explain,
and predict the internal structure of the atoms that make up molecules or ionic
networks. Thus, we need to zoom into an even smaller length scale to better un-
derstand what atoms are made of and what distinguishes one atom from another.
THE CHALLENGE Volatile Compounds
Many household products such as paints, varnishes, cosmetics, and adhesives

contain volatile substances that easily evaporate and pollute indoor air.
• How could you determine the chemical composition of these volatile

compounds?
• What would you measure to establish, for example, what percentage of
their mass is made of carbon or oxygen atoms?
Module 4 is designed to help you develop the type of chemical thinking that is
needed to characterize the chemical composition of a substance of interest. In par-
ticular, the central goal of Module 4 is to discuss how to use experimental data
to determine the atomic composition of the particles that make up a chemical
compound.
Subatomic Model of Matter

According to the atomic model of matter, differences in properties between sub-
stances are the result of differences in the atomic composition of their particles.
But what makes an atom different from each other? For example, why do oxygen
atoms have a relative mass of 16.00 amu while the mass of argon atoms is close
By Zátonyi Sándora, (ifj.) (Own work)

to 40.00 amu? The answers to these types of questions are important if we want

to devise strategies to identify the different types of atoms present in the particles
that make up a substance.
Experimental clues about the internal structure of atoms have been gathered
by many natural philosophers and scientists across centuries. Of particular rel-
evance were those experiments that revealed that matter had electrical properties.
For example, experiments showed that solid materials rubbed against each other Figure 1.31 The trajectory
could acquire electrical charge of opposite signs; that metallic substances allowed of electron beams (cathode
rays) is affected by the pres-
the movement of electric charge from one region to another; that metals could ence of a magnet. This indi-
cates that electrons have an
emit charged particles when heated up or when illuminated with certain types of electric charge.
light; and that some chemical elements, called radioactive elements, would trans-
form into other elements by emitting charged particles. All this evidence suggested
that atoms were made up of subatomic particles with electrical charge. The chal-
lenge was then to model how these particles were arranged inside an atom to best
explain the known properties of matter.
Comparing Models LET’S THINK

Positive
In 1904, Joseph J. Thomson proposed that atoms may be modeled as com- Charge
posed of tiny “corpuscles” with negative charge enclosed in a sphere of positive
charge that made the whole atom electrically neutral (plum pudding model of
the atom). In fact, Thomson discovered the existence of the negatively charged
particles, later called electrons, in an experiment in which electrons were
forced out of materials by applying a strong electric field (see Figure 1.31). Negative
Charge
Positive
Charge
In 1911, Ernest Rutherford proposed a different atomic model. In this case,
electrons were assumed to move through empty space, circling around a
nucleus composed of an equivalent number of positive charges due to the
attractive interactions between opposite charges. Positive particles in the
Negative
Charge nucleus were assumed to be much more massive than the electrons.
Imagine that you designed an experiment to test these two models in which a beam of positively
charged particles (similar in size and mass to an atomic nucleus in Rutherford’s model) were di-
rected at high speed at a thin piece of metal made of atoms arranged as shown in these images:
• What would each of the models predict will happen to the beam
of positively charged particles as it interacts with the atoms in the
system? Would the models predict particles to go through the thin
metal foil, bounce back, or at least deviate from their trajectory?
60 MODULE 4 Determining Composition
Experiments such as the one described in the previous activity were conducted
by Hans Geiger and Ernest Marsden, under the direction of Ernest Rutherford,
CLICK TO PLAY in 1909. They observed that most positively charged particles in the beam passed
through the thin metal foil without much change, but a small fraction
of them suffered major deviations from their original trajectory. These
experimental results can be better explained by Rutherford’s planetary
model of the atom (see Figure 1.32) which proposes that most of the
mass of an atom is concentrated in a positively charged tiny nucle-
us while most of the atom’s volume, where electrons are in constant
movement, is empty space.
Many aspects of Rutherford’s model of the atom at the subatomic
level have been experimentally confirmed in the past hundred years.
So, the modern atomic model also conceives atoms as particles com-
posed of tiny nuclei but made up of two types of subatomic particles:
positively charged particles, called protons, together with particles
Figure 1.32 Rutherford’s with no net electrical charge, called neutrons. A single proton (p+) has a mass of
atomic model best explains
the results from Geiger-Mars- 1.673 x 10–27 kg and an electric charge of +1.602 x 10–19 Coulombs (C); a single
den’s experiment. Click the neutron (n0) is slightly more massive than a proton, with a mass of 1.675 x 10–27
image to play the animation.
kg. On the other hand, a single electron (e-) has a negative electric charge equal in
magnitude to that of a proton, –1.602 x 10–19 C, but its mass (me = 9.109 x 10–31
kg) is over 1800 times smaller than that of the nuclear particles. The radius of a
typical atomic nucleus is over ten thousand times smaller than the radius of the
actual atom. So, if the radius of an atom is a fraction of a nanometer, the radius of
the atomic nucleus is only a few femtometers (1 fm = 1 x 10–15 m; see Figure 1.33).
This is analogous to a pinhead in the middle of a football stadium.
~10–10 m ~10–14 m
neutron
Nucleus NUCLEUS
Figure 1.33 Representation electrons proton
of the subatomic model of the
atom. The yellowish volume
represents the space where
ATOM
electrons move.
By convention, it is common to express atomic charges using the charge of

a proton as the unit of measurement. Thus, in these elementary charge units the
charge of a proton is equal to +1 and that of an electron is equal to –1. Atoms are
neutral entities with no net electric charge. This implies that a neutral atom has the
same number of protons and electrons. To explain the existence of ions, the model
assumes that atoms can lose or gain electrons. For example, if a particle loses one
electron its net charge will be +1, given that there will be one more proton than
electrons. If the particle gains one electron, its net charge will be –1 as now there
will be more electrons than protons. Given that the mass of an electron is very
small compared to that of other subatomic particles, losing or gaining a few elec-
trons does not significantly change the atomic mass.
One of the most fundamental assumptions of the subatomic model of matter

is that the identity of an atom is determined by the number of protons in its nucleus,
also called its atomic number Z. Thus, while all hydrogen atoms have only one
proton in their nuclei (Z = 1), the nuclei of all carbon atoms have six protons
(Z = 6) and those of uranium atoms have ninety two of these subatomic particles
(Z = 92). The atomic number is in fact the property that is used to sequentially
arrange the different types of chemical elements in the Periodic Table. Thus, when
an atom loses or gains electrons and becomes an ion, its chemical identity is pre-
served because its atomic number has not changed. This does not imply, however,
that the physical and chemical properties of the ions will be the same as that of
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M4/ms.html
their parent atoms; in fact, they usually are quite different. Figure 1.34 Click on the im-
age to open an animation of
The subatomic model of matter has guided the development of experimental the internal processes in a
techniques that are very useful in the task of determining the composition and mass spectrometer.
structure of the particles that make up a substance. Such is the case of

a powerful analytical technique known as Mass Spectrometry (MS). In
this technique, a sample of the substance to be analyzed is ionized by pro-
viding enough energy to free some electrons from nuclear attraction and
to break molecules apart (see Figure 1.34). The fragments that are formed
tend to be cations with a +1 electric charge and they can thus be acceler-
ated and separated using a combination of electric and magnetic fields.
Ions with different mass-to-charge ratios (called m/q or m/z ratios) follow
different trajectories in a magnetic field and thus reach different areas in
a detector. A mass spectrometer provides information about the relative
mass of each of the different types of ions that are generated and about the relative CLICK TO PLAY
proportion in which the ions are produced. As we will see later in this module, this
information is very valuable in the process of characterizing chemical substances.
Neon’s Case LET’S THINK

Imagine that you take a sample of natural neon gas, Ne(g), and run it through a mass spectrom-
eter. The image in this activity sketches the mass spectrum that you would get. The horizontal axis
establishes the value of the m/q ratio for the ions that
will be generated; this quantity can be seen as a direct
measure of the relative mass of the different ions. The 90.48%
vertical axis provides information about the percent
abundance of the ions produced during the analysis.
% Abundance
• Given that neon is an atomic elementary sub-

stance, how do you explain that the experiment 0.27%
produced three peaks with distinctive relative
masses instead of one?
9.25%
• What do these results tell you about the atomic
composition of natural Ne(g)?
18 19 20 21 22 23
m/q
Share and discuss your ideas with a classmate. Build a
model about the atomic composition of Ne(g) that may explain these experimental results.
Atomic Diversity
If all the atoms in a pure sample of an atomic elementary substance were identi-
cal, the mass spectrum of the substance should produce a single peak given that
all the atoms should have the same relative mass. The fact that this is not the case
for many of them, as we saw for the case of Ne(g) in the past activity, suggests that
there are different types of atoms in a natural sample of these elementary substanc-
es. But how is this possible if we already established that elementary substances are
made up of atoms of the same type? Given that the mass of an atom is essentially
determined by the sum of the masses of protons and neutrons in their nuclei, this
experimental puzzle has been solved by proposing that atoms of the same chemi-
cal element have the same number of protons (same atomic number Z), but may
differ in the number of neutrons that they have. If we define the mass number
A of an atom as the sum of the number of protons and neutrons in its nucleus,
Figure 1.35 Mass spectrum for (1.8) A = # p+ + # n0,

boron (B). For purposes of repre-
sentation, it is common to scale
all results so that the maximum we can say that there are atoms of a given chemical element that have the same
relative abundance is at 100. The
actual %Abundance of each iso- atomic number Z but different mass number A. These atoms are said to be iso-
tope is shown.
topes.
Stable isotopes of a chemical element exist with different percent abun-
Relative Abundance
80.1%
dance (%Abundance) in Nature. This information can be derived from the
mass spectrum of the chemical substance. For example, boron (Z = 5) has
two stable isotopes that can be represented using the following symbolism:
19.9% A 10 11
Z 5B 5 B
m/q As indicated by the mass spectrum in Figure 1.35, the percent abundance
of the isotope with 5 neutrons in the nucleus (boron-10, A = 10) is 19.9%, while
that for the isotope with 6 neutrons per atom (boron-11, A = 11) is 80.1%. This
information can be used to calculate the average relative atomic mass (r.a.m.) of
this chemical element, defined as the weighted mean mass of all of the isotopes
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M4/ptis.html
in a natural sample of the substance. To do this calculation we need to know the

relative atomic mass of each of the isotopes as well as their percent abundance,
information that can be derived from the mass spectrum:
(1.9) r.a.m. =
S(Relative mass isotope x %Abundance)
Figure 1.36 Click on the im- 100
age to display a Periodic Table
of the chemical atoms that in-
cludes information about most 10.01 amu x 19.9 + 11.01 amu x 80.1
abundant isotopes. r.a.m = = 10.8 amu
100
This is actually the procedure used to calculate the average atomic mass of the
elemental atoms listed in the periodic table in Figure 1.36, where we also include
information about the three most abundant isotopes for each of the different types
of atoms. As shown in this table, there are elements, such as fluorine (F) and phos-
phorus (P), that only have one stable isotope, while most heavy atoms do not have
CLICK TO PLAY any stable isotopes as they tend to be radioactive.
By convention, the scale of relative atomic masses for different isotopes in Na-
ture has been set by assigning a value of exactly 12.00 amu to the relative atomic
mass of the isotope of carbon with a mass number A =12 (carbon-12). This is the
standard used to define the scale for the m/q-axis of mass spectrometers and to
precisely define the mole and Avogadro’s number. Based on this standard, a mole
of a substance is defined as the amount of substance that contains as many par-
ticles as there are atoms in 12.00 g of the isotope carbon-12; this is one Avogadro’s
Number (6.022 x 1023) of particles.
MS Identification LET’S THINK

Mass spectrometry is commonly used to identify chemical substances. Imagine, for example, that
you were assigned to find the identity of a toxic gas emanating from local sewage. You suspect the
substance is a molecular elementary substance with the generic chemical formula X2. The mass
spectrum of this substance is shown on this page.
• How many stable isotopes should atom X have to explain the observed number of peaks in
this mass spectrum?
100
• Use the spectrum to estimate the
relative atomic mass of each of 75.76% 57.40%
80
Relative Abundance
the stable isotopes;

36.73%
• What is the composition of the 60
particles responsible for each of
the peaks in this spectrum? 40
24.24%
• What is the average relative
atomic mass of atom X? The 20
5.87%
%Abundance of each species is
shown on the spectrum. 0
30 40 50 60 70 80
• Which chemical element is this? m/q
Share and discuss your ideas with a classmate, and clearly justify your reasoning and procedures.
Mass spectrometry is particularly useful in the determination of the relative

mass and molecular structure of chemical compounds. Take for example, the case Figure 1.37 Mass spectrum of
of water that produces a mass spectrum like that shown in Figure 1.37. The rela- water, H2O.
tive mass of the water molecule, 18 amu, can be inferred from 100
the location on the m/q-axis of the peak for the heaviest ion,
which corresponds to the molecular ion H2O+. The other ma- 80
H2O+
Relative Abundance
jor peak, with a relative mass of 17 amu, reveals the formation

of a molecular fragment in which one hydrogen atom has been 60
lost, the ion OH+. Additionally, there is a very small peak at 16
40
amu, corresponding to the ion O+, which does not form in great OH+
quantities during the experiment. The analysis of the potential O+
20
composition of the different fragments generated by MS is a use-
ful aid in the process of establishing the molecular structure of 0
15 16 17 18 19 20 21
chemical compounds. m/q
Often, but not always, the peak with the highest m/q value in the mass spec-
Figure 1.38 Mass spectrum of trum results from the detection of the molecular ion M+ (the ion of the intact
methane CH4. molecule), while peaks at lower m/q correspond to molecular fragments. How-
100 ever, the determination of the relative mass of the molecular
compound from its mass spectrum should be done taking into
CH4+
Relative Abundance
80 account that a fraction of the molecules in the sample will be

60
CH3+ made up of different isotopes. Thus, we may see small second-
ary peaks corresponding to molecular ions composed of the less
40 abundant isotopes. For example, the mass spectrum for meth-
CH2+ ? ane (CH4) in Figure 1.38 has a large peak corresponding to
20 CH+
C+ molecular ions CH4+ with a relative mass of 16 amu. These
0 ions are made up of the most stable isotopes of carbon and
11 12 13 14 15 16 17 18 hydrogen, carbon-12 and hydrogen-1. However, the spectrum
m/q
reveals the existence of a small fraction of CH4+ ions composed
of carbon-13 atoms with a relative mass of 17 amu. The actual average molecular
mass of this compound should thus be calculated taking into account the relative
mass and abundance of the different isotopic species. Although the mass spectrum
of large molecules can be quite complex, the determination of the molecular mass
of the substance and the analysis of the fragmentation pattern provide invaluable
clues about the composition and molecular structure of the chemical compound.
LET’S THINK MS Analysis

Methanol (CH4O) is a volatile chemical compound used extensively in the synthesis
of important products, such as plastics and gasoline additives. This substance is ranked
among the top five chemicals released into the atmosphere in the US. It is considered
a toxic substance that causes eye and respiratory track irritation. Consider the mass
spectrum for this substance:
• Identify the peak that

100
likely corresponds
to the molecular ion
80
Relative Abundance
CH4O+ and estimate its

relative molecular mass; 60
• Based on the chemical
formula of methanol 40
and data from the spec-
20
trum, infer the chemi-
cal composition of the
0
different ions that led 0 10 20 30 40
to all the visible peaks m/q
in this spectrum.
• Try to identify those peaks in the mass spectrum that may correspond to ions
made up of less abundant isotopes of carbon, hydrogen, or oxygen.
Share and discuss your ideas with a classmate, and clearly justify your reasoning and
procedures.
Combustion Analysis
In general, mass spectrometry provides qualitative information about the types
of atoms that are present in a chemical compound; in particular, we can use their
relative masses to identify them. However, MS does not necessarily tell us the
number of atoms of each type that make up a molecule, or the percentage of the
mass of a compound that corresponds to atoms of a given element. To generate
this information we need to use other methods, such as combustion analysis.
As its names indicates, combustion analysis is based on burning a known
amount of the substance of interest in the presence of oxygen gas O2(g). During
this process, chemical compounds of well known composition, such as H2O(g)
Figure 1.39 Typical experi-
and CO2(g), are formed and collected, weighing their masses with precision (see mental setup for combustion
Figure 1.39). This information is then used to determine the mass percentages of analysis. Modern instruments
perform this analysis in an au-
the different chemical elements present in the sample. tomated manner.
Combustion analysis generates elemental composition in mass percentage that

can be used to determine the chemical formula of the compound. To better un-
derstand how the method works, let us discuss a specific example step by step.
Recently, the analysis of some cosmetics has revealed the presence of a potentially
toxic substance. Combustion analysis of this molecular compound indicates the
following chemical composition in percent mass: 54.53% carbon (C), 9.152%
hydrogen (H), and 36.32% oxygen (O). To determine the chemical formula of
this compound we can follow a systematic procedure:
1. Assume that you have a 100.0 g of the substance and calculate the total mass of
each type of atom or element present in the system. In this case we get:
m(C) = 100.0 x 0.5453 = 54.53 g m(H) = 100.0 x 0.09152 = 9.152 g
m(O) = 100.0 x 0.3632 = 36.32 g
2. Calculate the number of moles (n = m/M) of each type of atom present in the
sample. The molar masses of the elemental atoms are needed to complete this
calculation:
1.000 mol C
n(C) = 54.53 g C x = 4.540 mol C
12.01 g C
1.000 mol H
n(H) = 9.152 g H x = 9.079 mol H
1.008 g H
1.000 mol O
n(O) = 36.32 g O x = 2.270 mol O
16.00 g O
3. Compare the amounts of the different atoms that make up the substance by
taking mole ratios with respect to the type of atom present in the lowest amount:
ratio(C/O) = 4.540 mol C / 2.270 mol O = 2.000 C to 1.000 O
ratio(H/O) = 9.079 mol H / 2.270 mol O = 4.000 H to 1.000 O
These mole ratios state the proportion in which different types of atoms are pres-
ent in the system. In our specific example, these ratios indicate that we have twice
the number of carbon atoms and four times the number of hydrogen atoms per
atom of oxygen in each of the molecules that make up the substance. We can
use this information to establish the so-called empirical formula of the chemical
compound. The empirical formula states the simplest whole number ratio of the
atoms or ions present in a molecule or formula unit of a chemical compound. In
Figure 1.40 Mass spectrum of our example, the empirical formula is C2H4O.
the potentially toxic substance
found in cosmetics.
4. Calculate the relative mass (or the molar mass) of an
100
empirical formula of the compound and compare it to the
relative mass (or the molar mass) of the actual compound as
Relative Abundance
80
determined by, for example, mass spectrometry. In our case
60 M+ we have:

40 M(C2H4O) = 2 x 12.01 + 4 x 1.008 + 16.00 = 44.05 g/mol
20
The molar mass of the unknown compound X, as de-
0 termined from the mass spectrum in Figure 1.40, is
0 20 40 60 80 100 88.10 g/mol. Taking the ratio of these two values we get
m/q
M(X) / M(C2H4O) = 88.10 / 44.05 = 2.000. The ratio of
masses suggests that the molecules of the compound contain two times the number
of each type of atom as present in the empirical formula. Thus, we can conclude
that the actual chemical formula of the unknown substance should be C4H8O2.
This is, in fact, the chemical formula of dioxane, a probable human carcinogen.
The determination of the chemical formula of a chemical compound using this

procedure is usually straightforward. However, complications may arise in estab-
lishing the empirical formula, particularly in those cases where the mole ratios as
calculated in step 3 are not whole numbers. In these situations, all the mole ratios
need to be multiplied by a common factor that transforms them into the lowest
whole numbers that maintain the same proportions. For example, imagine that
Dioxane you obtain the following mole ratios in the analysis of a molecular compound
Molecule made up of carbon, hydrogen, and oxygen atoms:
ratio(C/O) = 2.000 C to 1.000 O ratio(H/O) = 3.333 H to 1.000 O
To transform these mole ratios into the smallest whole numbers without changing
the actual proportions, we should multiply both of them by 3. This leads to a 6 to
3 proportion for C to O atoms, and a 10 to 3 proportion for H to O atoms. The
empirical formula of this compound results then to be C6H10O3.
Chemical Formulas LET’S THINK

Consider these two problems related to the analysis of pollutants in the air we breathe:
The analysis of the exhaust gases from

motor traffic reveals the presence of a 100
carcinogenic substance. Combustion
analysis reveals that the substance 80 M+
Relative Abundance
contains 92.26% C and 7.74% H.
The mass spectrum of the substance 60
is shown.
40
• Estimate the molar mass of this
molecular compound; 20
• What is the empirical formula of
this compound? 0
0 15 30 45 60 75 90
• What is the molecular formula m/q
of this compound?
The analysis of indoor air in some Tuc-

100
son homes treated for termites reveals
the presence of a harmful substance
80 that affects the nervous system. Com-
Relative Abundance
bustion analysis provides the follow-

60 ing percent composition: 29.31% C,
1.476% H, and 69.22% Cl.
40
• Estimate the molar mass of this
M+ molecular compound;
20
• What is the empirical formula of
0 this compound?
0 100 200 300 400 500
m/q • What is the molecular formula
of this compound?
Share and discuss your ideas with a classmate, and clearly justify your procedures.
Combine and Conquer

We started Unit 1 by discussing the importance of separation techniques based
on specific differentiating characteristics in the process of analyzing chemical sub-
stances. Our work in this module has shown us how we can use methods of ele-
mental analysis, such as mass spectrometry and combustion analysis, to determine
the chemical composition of the particles that make up elements and compounds.
To finish Unit 1 it seems appropriate to describe how these different analytical
techniques can be combined to answer the central question of the Unit: How do
we distinguish substances? In particular, we will focus on the combination of two
powerful strategies, chromatography and mass spectrometry.
One of the most powerful set of separations techniques currently used in in-
dustrial, medical, and scientific research labs around the world receives the name
of chromatography. These separations strategies are based on the recognition that
the strength of the interaction forces between different substances will depend
on the chemical composition and structure of their atoms, ions, or molecules.
In general, chromatographic techniques involve the passing of a mix-
Standard B ture in liquid or gas phase (mobile phase) through a stationary phase,
A
typically a liquid or a solid deposited on a plate or enclosed in a chro-
matographic column. Components of the mixture in the mobile phase
that are strongly attracted to the stationary phase will take more time
to pass through the system and will exit at later times than those that
Unknown A B exhibit weaker interactions. Modern chromatographs include detectors
that register the time at which each substance exits the plate or column
(retention time), and the amount of substance that passes through it.
Thus, chromatography can be used to separate the components of the
mixture and to quantify the relative amounts in which they are present
in a sample (see Figure 1.41).
Figure 1.41 Typical chromatograph The combination of gas chromatography (GC) with mass spectrometry (MS)
showing the separation of chemical
compounds with retention times tR. in a combined technique known as GC/MS is perhaps one of the most powerful
The area under each peak is propor-
tional to the amount of substance. identification methods used nowadays in diverse fields, from forensic investiga-
Retention times can be used to iden-
tify substances in a mixture by com-
tions to environmental analysis. A GC/MS system is composed of a gas chromato-
parison to standards graph in which the evaporated mixture is carried by an inert gas through a capil-
lary column covered with a microscopic layer of liquid that serves as a stationary
phase. At the end of the chromatograph, a mass spectrometer takes the place of the
detector, analyzing each substance as it exits from the chromatographic column.
The combination of information about retention times and fragmentation pat-
terns provides solid evidence about the identity of each substance in the mixture.
LET’S THINK Modeling Separations
http://www.cbc.arizona.edu/tpp/chemthink/resources/U1_M4/chroma.html
Modeling the separation of substances in a chromatographic column can help us not only
better understand how the process occurs, but also identify the best conditions for separat-
ing a mixture if we have information about the properties of its components.
The simulation included in this activity allows you to investigate the effect of changing the
relative strength of the interactions between two substance and the stationary phase in a gas
chromatograph, as well as the flow rate at which the mixture is passed through the column.
• Use the simulation to determine the minimum

ratio of interaction strengths for substances B
CLICK TO PLAY
and R that allows you to fully separate the two

components at a given flow rate.
• Investigate how the flow rate affects substance
separation at constant interaction strength.

FACING THE CHALLENGE in less than five

minutes and detect
Portable GC/MS
VOCs in concentra-
Indoor Air tions of a few ppbv.
Have you ever wondered about the quality of the A sample of in-
By Inficon
air you breathe inside your home or at your dorm? door air may have
Indoor air quality may be affected by the presence from 50 to hundreds
of a wide variety of gaseous substances released by, of different VOCs.
among other sources, household products, build- Among the most
ing materials, furnishings, and heating systems. common substances in this group we found form-
In particular, many household products are made aldehyde (CH2O), dichloromethane (CH2Cl2),
with volatile substances that although not highly and benzene (C6H6), a well known human carcin-
toxic may have chronic effects. Paints, varnishes, ogen. At home, the most common source of form-
and waxes, as well as cleaning, disinfecting, and aldehyde are pressed wood products made of wood
cosmetic products typically contain solvents that particles and wood fibers mixed with adhesives
readily evaporate at room temperature. The mol- that contain urea-formaldehyde resins. CH2Cl2
ecules of these solvents tend to have a backbone of is a chemical compound found in products such
carbon and hydrogen atoms, and thus are gener- as paint strippers, adhesive removers, and aerosol
ally classified as organic compounds. spray paints. Among the main indoor sources of
Volatile organic compounds, or VOCs, can benzene we have stored fuels and paint supplies,
potentially induce a variety of health problems together with car engine emissions in garages.
such as eye and respiratory track irritation, head- However, about 50% of the human exposure to
aches, and nausea. Some of them are known to benzene in the US results from smoking tobacco
cause cancer in animals and, probably, in humans. or from inhaling tobacco smoke.
The extent and nature of the health effects depends VOCs such as benzene and toluene (C7H8)
on factors such as level of exposure and length of are also important pollutants in outdoor air. These
By Tom Murphy VII (Own work) [CCA: Public domain] via Wikimedia Commons
time exposed. However, little is known about the chemical compounds are common constituents of
health effects from expo- lead-free gasoline and
sure to VOCs at the con- evaporate directly to the
centrations usually found atmosphere. Once in
in homes, which have the air, they react with
been shown to be 2 to 5 oxygen and nitrogen
times higher than those compounds to produce
detected in outdoor air. other pollutants that we
As you can imagine, identify as smog.
fast and easily portable Volatile organic
instruments to detect and compounds are not only
identify VOCs in differ- generated by human
ent indoor environments are highly valued. GC/ products and activities. In fact, over 80% of all
MS is the most common analytical technique used VOCs released into the atmosphere have a natural
for this purpose. In many cases, the indoor air source. The aroma of pine or sandalwood is caused
samples are collected in canisters or sorbent tubes by the evaporation of a group of VOCs called ter-
(containers filled with a solid adsorbent material) penes from their leaves. Our own body produces
and subsequently analyzed in an environmental hundreds of VOCs that can be detected in our
lab. This procedure may take from a few hours to breath. Abnormal concentrations of these sub-
several days. However, portable GC/MS systems stances in our blood have been used as evidence in
have been developed that can analyze air samples the diagnosis of lung disease.
Let’s Apply
Organobromines
Organobromines are organic compounds made up of molecules in which carbon atoms are bonded
to bromine (Br) atoms. For many years, these substances were used for a variety of purposes,
from gasoline additives, to fire extinguishers, to pesticides. However, their use has been banned
or discouraged because of the damage that gaseous bromine compounds can cause to the ozone
layer. Volatile organobromine compounds can survive in the atmosphere long enough to reach the
stratosphere where Br atoms are 50 times more damaging to ozone than Cl atoms from CFCs.
Some of these bromine compounds may also affect human health. Thus, monitoring their presence
in the environment has become increasingly important.
Natural Compounds
Some organobromines are produced naturally by marine organisms in large amounts. Com-
bustion analysis of the most common natural organobromine, which is also widely used as a
pesticide, reveals the following chemical composition: 12.65% C, 3.18% H, and 84.17% Br.
• What is the empirical formula of this chemical compound?
MS analysis of this compound produced the mass spectrum shown on this page. Given that
bromine is known to have two
stable isotopes with the follow- 100
ing %Abundance: Bromine-79,
50.69%; Bromine-81, 49.31%: 80
Relative Abundance
• Would you expect the chemi- 60

cal formula to be different
from the empirical formula? 40
• Which peaks in this spec-
trum are associated with the 20
main two molecular ions M+
for the compound? What iso- 0
0 20 40 60 80 100
topes of each element should
m/q
be present in these ions?
• Estimate the relative mass of the main two molecular species and their %Abundance.
Use this information to calculate the average relative mass of the compound.
• Infer the chemical composition of the ions associated with the three most abundant
peaks in the spectrum.

Gasoline Additive
One of the most toxic organobromines, once an important constituent of antiknock

mixtures for leaded gasoline, has the following elemental composition: 12.79% C,
2.14% H, and 85.07% Br. The mass spectrum for this substance is shown below.
• What is the empirical formu- 100

la of this compound?
• What is its molecular for- 80
Relative Abundance
mula?
60

Share and discuss your ideas with
40
a classmate, and clearly justify
your ideas and procedures. M+
20
0
0 40 80 120 160 200
m/q
Atmospheric Species
Once in the stratosphere, high energy radiation from the Sun can brake the bonds
between bromine atoms and carbon atoms in organobromines compounds. Free
bromine atoms then react with themselves or other species, generating things such
as HBr, BrO, HOBr, and Br2. The detection of these types of species has been used
to follow the temporal evolution of ozone depletion in the stratosphere.
Imagine that you wanted to use some form of mass spectrometry to detect these
four species in the atmosphere. To do so, it would be useful to predict how their
mass spectra would look like.
• Using information about

100
the atomic structure, relative
mass, and percent abundance
of the main isotopes of the 80
Relative Abundance
atoms present in these spe-

cies (see Figure 1.36), sketch 60
the mass spectrum that each
of them could be expected to
40
generate.
Compare your sketches with those 20

of another classmate. Explain your
ideas and resolve any differences in 0
your predictions. m/q
Let’s Apply
VOCs in Ground Water VOC Pollution in US Aquifers
In 2006, the US Geological Survey (USGS)

published the results of a major research study
on the presence of VOCs in ground water in
the United States. As part of the National Wa-
ter Quality Assessment Program, the occur-

rence of 55 well known VOCs was analyzed in
about 2,400 domestic wells and about 1,100
public wells across the country. The project re- Total concentration, mg/L
No detection or less than 0.02
0.02 to less than 0.2
lied on the application of analytical techniques 0.2 to less than 1
1 to less than 10
10 or greater
similar to those described in this module.
The results of this study indicated that many of the Nation’s aquifers are vulnerable to low-level
(< 1 mg/L) VOC contamination, showing the need to more closely monitor the presence of these
compounds in the environment.
100 Major Pollutants

80
A
The USGS ground water study
Relative Abundance
10.06% C
revealed that 15 different VOCs
60 0.85% H
account for most of the pollu-
89.09% Cl
tion in domestic and public
40
wells. Relevant information to
20 derive the chemical formulas of
two of the most common pol-
0 lutants found in ground wa-
0 40 80 120 160 ter is shown on this page. The
m/q source of pollutant A, the most
frequently detected compound,
100 is attributed, in part, to the re-
cycling of chlorinated waters to
80 B aquifers. Pollutant B is a solvent
Relative Abundance
14.49% C used in dry cleaning.

60 85.51% Cl
• Identify the molecular ion
40 peak on each mass spec-
trum.
20
• What are the chemical
0 formulas of these two com-
0 40 80 120 160 200 pounds?
m/q
Where From?
Where To? By Martina Rathgens
(Own Work)
[CCA: 2.0 Generic],
via Flickr Commons
The central goal of this Unit was to help you

understand and apply basic ideas and ways of ZOOMING IN
thinking that can be used to distinguish the dif-
ferent substances present in
a variety of systems of
interest, such as the
atmosphere in our
planet. In this pro-
cess, we have dis-
cussed how mod-
els of matter at the The determination of the mass and chemical
particulate, atomic, composition of the particles of matter is certainly
Earth and subatomic scale very useful in the characterization of chemical
NASA
are useful intellectual tools substances. However, the experimental evidence
in the design of experimental strategies that al- gathered by chemists over the past two hundred
lows us to separate, detect, identify, and quantify years suggests that the true identity of a chemical
the wide variety of chemical elements and com- substance relies on its molecular or ionic struc-
pounds in our world. These models also guide us ture. This is, the specific way in which atoms or
in the interpretation of experimental results and ions are bonded to each other and arranged in
in the generation of explanations and predictions space. Thus, our goal in the next Unit is to help
about the properties and behavior of matter. you develop ways of thinking that can be used
Our analysis started at the macroscopic level, to predict the atomic and molecular structure of
recognizing the types of properties that can serve substances. To do so, we will have to discuss how
as differentiating characteristics in the separa- the analysis of the interaction of light with mat-
tion and identification of chemical substances. ter has been crucial in the development of the
Then, we recognized the need to zoom into the experimental techniques
particulate scale to understand how phase behav- and theoretical models
ior, and many other physical properties of matter, that are currently used to
seem to emerge from the dynamic interactions of determine the geometry
From Microsoft Office
myriads of tiny particles. But to truly understand of molecules in molecular

the diversity of the material world, we needed to compounds and the ar-
explore the composition of matter at the single rangement of ions in three
particle level, analyzing the particle’s mass and dimensional networks
atomic composition. This task demanded that in ionic compounds.
we zoomed even deeper into the atoms, trying But before we move
to uncover their inner structure. In this journey on, let us explore if
from the macroscopic to the subatomic scales, we “YOU ARE READY” by assessing your ability to
gathered powerful tools for exploring and think- apply what you have learned in this Unit to the
ing about the world that surrounds us. analysis of some interesting problems.
74 Are You Ready?
Are You Ready? Titan

NASA
Titan is the largest moon of Saturn. It has a dense atmosphere and there is data that suggests that stable
bodies of liquid are present on its surface. The Cassini-Huygens robotic spacecraft mission arrived in Sat-
urn in 2004 and is currently studying the chemical composition of the planet and its moons, including
Titan. The following table and graphs summarize important information about Titan:
TITAN Additional Information
This temperature does not vary much during the

Average surface tempera-
93.7 K day or the seasons
ture
(min ~90 K; max 94 K)
The atmospheric pressure on Earth

Average surface pressure 1.47 atm
is close to 1 atm.
Air density at ground level 5 kg/m3 The air density on Earth is 1.2 kg/m3
Atmosphere composition 80-85% N2; Compared to 78% N2; 21% O2

(% in Volume) 5-25% Ar; 3-6% CH4 in our planet
Hydrosphere composition 72% C2H6; Compared to ~100% H2O

(% in Mass) 22.4% CH4; 5.6% N2 in our planet
The central goal of this activity is that you demonstrate that you can apply
chemical thinking to explain and predict the properties and behavior of the
substances present in a real system, such as Titan.
Exploring Titan
Methane
The figure depicts the phase diagram of methane

(CH4), one of the main components of the atmo-
sphere and hydrosphere in Titan.
• Label on the diagram the stable phase in

each of the three major regions.
• What is the stable phase of CH4 on the
surface of Titan? Justify your answer using
the diagram.
• Can we expect to see CH4 in gaseous form
anywhere in this moon? If yes, at what alti-
tudes? Justify your answer in one sentence.
CH4 C2H6 The Liposphere
The graph depicts the vapor pressure graphs

for methane (CH4) and ethane (C2H6), the
major components in Titan’s hydrosphere
(also called the liposphere).
• Estimate the temperatures at which each

of these substances boils on the surface
of Titan.
• Propose a strategy to separate these two
components from a sample of Titan’s
liposphere.
Relative Numbers
If you separated 10.0 g of a hydrosphere sample,
• How many times more molecules of ethane (C2H6) than of methane (CH4) would you find in that
sample? (Check the available data for information about the % of mass of each of these compo-
nents in Titan’s hydrosphere).
76 Are You Ready?
Exploring Titan Huygens on Titan

NASA
Lakes in Titan
A scientist has proposed that if the lakes of Titan were
made of pure methane (CH4) they would freeze when
the wind blows and the lakes evaporate, even if the
temperature of the atmosphere is slightly above the
freezing point for CH4.
• Use the particulate model of matter to explain

why this is a reasonable hypothesis.
Ocean’s Bottom
A sample of the bottom of Titan’s ocean (bottom of the liposphere) shows that one of
the main components is a solid hydrocarbon. The analysis of this substance by mass
spectrometry leads to the spectrum that is shown. Elemental analysis reveals the follow-
ing compositions: 92.26% C and 7.74% H.
• What is the empirical formula of 100

this substance?
80
Relative Abundance
Based on the mass spectrum for this sub-

stance, shown on this page: 60
• What is the molecular formula of 40

this substance? Justify your answer.
20
0
8 12 16 20 24 28 32
m/q
Probing
Imagine that an elastic balloon carrying analytical equipment is used as a probe to explore Titan’s
atmosphere.
• Would the volume of the balloon increase or decrease as it descends through the atmosphere?
Justify your reasoning using the particulate model of matter.
Are You Ready?

Titan’s Haze
Titan’s atmosphere has a characteristic haze that seems to absorb
high energy radiation from the Sun, in a similar way as the ozone
layer in our planet. The space filling representations of the mol-
ecules that seem to be present in this haze are shown on this page.
• What is the chemical formula of each of these substances?
The concentration of one of the most abundant species in this

haze, HCN, is estimated to be close to 0.1 ppmv (part per million
in volume).
• What is the %mol of this substance in Titan’s haze?
Representations
Based on your work on this activity, togeth-
er with the information provided, build a
particulate representation of a cross sec-
tion of Titan. Provide the information that
is requested for each region of the planet:
Atmosphere
Number of elements
Number of compounds
Number of pure substances
Liposphere
Number of elements
Number of compounds
Bottom of Liposphere
Number of elements
Number of compounds
CLICK TO PLAY
78 Are You Ready?
Are You Ready?

Bombardier beetles have an amazing defense mechanism. They produce a mixture of chemical compounds
that can undergo a violent chemical reaction. When they are threatened, they squirt the mixture into a
reaction chamber where proteins accelerate the chemical process. The reaction releases oxygen gas, O2(g),
and generates enough heat to bring the mixture to the boiling point and vaporize a fraction of it.
Two Phases
The mixture produced by the beetle is a heterogeneous system composed of two liquid
phases. One of the phases is rich in water, H2O(l), hydrogen peroxide, H2O2(l), and
several other chemical compounds. The other phase is mostly a mixture of hydrocar-
bons (water and hydrocarbons do not dissolve much into each other). To analyze the
hydrocarbon-rich phase, we need to separate it from the water-rich phase.
• Design an experimental strategy to achieve this separation.
Separation and Elemental Analysis
Analysis of the hydrocarbon-rich mixture using gras

chromatography (GC) reveals the pres-
ence of more than 25 different com-
pounds. The most important component
in this mixture is the substance that reacts
with H2O2(l) to produce O2(g) and large Chromatograph
amounts of energy. Information about
By Patrick Coin (Own work) [CCA: Share Alike 2.5] via Wikimedia Commons
the elemental composition of this chemi-
cal compound X are shown on this page.
• What is the molar mass of 100

this chemical compound?
80 X
Relative Abundance
• What is the empirical for- 65.45% C

mula of the compound? 60 5.49% H
• What is the molecular for- 29.06% O
mula of the compound? 40
Share and discuss your ideas 20

with a classmate.
0
0 20 40 60 80 100 120
m/q
Bombardier Beetle
Other Components
GC analysis of the hydrocarbon-rich phase reveals that the major com-

ponent in this mixture has the molecular structure shown to the side.
• What is the chemical formula of this compound?

PENTADECANE
• What is its molar mass?
Phase Behavior
The analysis of the phase behavior of compound X

produces the phase diagram shown to the side:
• What is the stable phase of this substance at

room temperature (20 oC)?
• What are the normal melting and boiling
points of this substance?
Relative Amounts
Quantitative measurements indicate that the concentration of H2O2(l) in the water-rich phase is close to
0.25 g/mL, while that of compound X is about 0.1 g/mL. If the density of liquid water, H2O(l), is close
to 1.0 g/mL:
• How many molecules of H2O are there per molecule of compound X?

• How many molecules of H2O2 are there per molecule of compound X?
• If the density of pentadecane is close to 0.77 g/mL, compare the number of molecules in 1 mL of
the hydrocarbon compared to the number of molecules in 1 mL of H2O.
Share and discuss your ideas with a classmate, and clearly justify your ideas and procedures.
80 Are You Ready?
Bombardier Beetle
Submicroscopic Representation
CLICK TO PLAY
• Use all of the information that you
have gathered to create a sub-
microscopic representation of a
nanoscopic sample of the mixture
produced by the beetle. Your repre-
sentation should include molecules
of the four major components in
the proportion in which they are
actually present in the mixture. The
interactive tool included in this
page may facilitate your work.
By Thomas Eisner et al.(2000) The Journal of Experimental Biology, 203, 1265-1275
Modeling the Process
The chemical reaction inside the beetle produces O2(g) and enough energy to
increase the temperature of the mixture to values as high as 100 oC. Under
those conditions, close to one fifth of the liquid mixture is vaporized. We
could try to model the system by imagining a closed container with two main
components, one in gas phase and the other in liquid phase.
• Use the simulation that you CLICK TO PLAY

can access in this page to
identify the right balance
of attractive interactions
between different particles
in the system to generate a
mixture in which one com-
ponent is a liquid and the
other is a gas at a particular
temperature.
• Use this particulate model
of the system to predict what would happen if you were to open a small
hole in the container.
Share your ideas with a classmate. Discuss how this simple particulate model
of the reaction chamber inside a bombardier beetle can be used to explain
how its defense mechanism works.
Unit 1: Image Attributions

Module 1
P2 & P3: Background “Blue Marble” by NASA; P4: “Earth’s Atmosphere” by NASA; P5: Fig. 1.1 Derivative from video by NASA; P7: “Melting
icecubes” by Mysid (Own work) [Public domain] http://commons.wikimedia.org/wiki/File:Melting_icecubes.gif; P8: Center right derived from
“Phase change - en” by Flanker, penubag (Own work) [Public domain] http://commons.wikimedia.org/wikiFile:Phase_change_-_en.svg; P11:
Center right «Dirty-air-filter» by Ahanix1989 (Own work) [Public domain] http://commons.wikimedia.org/wiki/File:Dirty-air-filter.jpg, bottom
left “Insulin Crystals” by NASA/Marshall; P12: Fig. 1.7 “Fractional distillation lab apparatus” by John Kershaw (Derivative: Theresa knott) [Share
Alike 3.0] http://commons.wikimedia.org/wiki/File:Fractional_distillation_lab_apparatus.svg, bottom right Own work; P13: Top right “Argon
ice 1” by Deglr6328 (Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/File:Argon_ice_1.jpg, bottom center “Coldbox” by pho-
tographer - Company.(Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/File:Coldbox.JPG; P15: Center left “Blue Marble” by
NASA, center right “Venus” by NASA, bottom left “Mars” by NASA; P16: top right “Colonne distillazione” by User:Luigi Chiesa (Own work)
[3.0 Generic] http://commons.wikimedia.org/wiki/File:Colonne_distillazione.jpg, bottom right Own work; P17: Center right “Gas-pump-Indi-
ana-USA”by Tysto (Own work) [Public domain] http://commons.wikimedia.org/wiki/File:Gas-pump-Indiana-USA.jpg.
Module 2
P18: Top right Derivative of “Diamond and graphite2” by User:Itub (Derivative: Materialscientist (talk)) [Alike 3.0] http://commons.wikimedia.
org/wiki/File:Diamond_and_graphite2.jpg, Bottom right “Clouds” by Axel Rouvin (Own Work) [Public domain] http://commons.wikimedia.
org/wiki/File:Clouds.JPG; P19: Fig. 1.8 “Four elements representation” by en:User:Heron (Own Work) [Public domain] http://commons.wiki-
media.org/wiki/File:Four_elements_representation.svg; P19: Bottom right Derivative from the video “Powers of ten” by Charle & Ray Eames -
http://www.powersof10.com/film; P26: Center right Own work; P25: Fig. 1.13 “Kochendes wasser02” by Markus Schweiss (Own work) [Share
Alike 3.0] http://commons.wikimedia.org/wiki/File:Kochendes_wasser02.jpg; P26: Fig. 1.14: “Mesoporous Silica Nanoparticle” by Nandiyanto
(Own work) [Public domain] http://commons.wikimedia.org/wiki/File:Mesoporous_Silica_Nanoparticle.jpg, P28: Bottom right derivative from
image by Mark Bishop; P30: Top right “Watervapor cup”by Jarombout (Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/
File:Watervapor_cup.jpg, Center left “Sweat or rain” by Kullez (Own work) [Generic 2.0] https://www.flickr.com/photos/kullez/5598159209/,
Center right Derivative of “Diamond and graphite2” by User:Itub (Derivative: Materialscientist (talk)) [Alike 3.0] http://commons.wikimedia.
org/wiki/File:Diamond_and_graphite2.jpg, Bottom left “Soda bubbles macro” by en:User:Spiff (Own work) [Public domain] http://commons.
wikimedia.org/wiki/File:Soda_bubbles_macro.jpg; P31: Center “Clouds” by Axel Rouvin (Own Work) [Public domain] http://commons.wiki-
media.org/wiki/File:Clouds.JPGBottom right “Lysozyme crystal1” by Mathias Klode (Own work) [Share Alike 3.0] http://commons.wikime-
dia.org/wiki/File:Lysozyme_crystal1.JPG; P32: Bottom left “Buzo” by Soljaguar (Own work) [Share Alike 3.0] http://commons.wikimedia.org/
wiki/File:Buzo.jpg; P33: Upper left “Starchy-foods.” by US Department of Agriculture [Public domain] http://commons.wikimedia.org/wiki/
File:Starchy-foods..jpg
Module 3
P38: Fig. 1.20 Top left “Na (Sodium)” by Dnn87 (Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/File:Na_(Sodium).jpg,
Center left “SiliconCroda” by Enricoros (Own work) [Public domain] http://commons.wikimedia.org/wiki/File:SiliconCroda.jpg; P34: Top right
Own work, Fig. 1.20 Own work; P39: Bottom right “Iod kristall” by de:user:Tomihahndorf (Own work) [Public domain] http://commons.wi-
kimedia.org/wiki/File:Iod_kristall.jpg: P40: Fig. 1.22 Center left “Liquidnitrogen” by Cory Doctorow (Own work) [Share Alike 2.0] http://com-
mons.wikimedia.org/wiki/File:Liquidnitrogen.jpg., Bottom left “Phosphor rot” by Tomihahndorf -(Own work) [Public domain] http://commons.
wikimedia.org/wiki/File:Phosphor_rot.jpg; P41: Fig. 1.24 Center left “Sodiumchloride crystal 01” by Choba Poncho (Own work) http://com-
mons.wikimedia.org/wiki/File:Sodiumchloride_crystal_01.jpg, Bottom left “Ammonium chloride” by Walkerma (Own work) [Public domain] via
Wikimedia Commons - http://commons.wikimedia.org/wiki/File:Ammonium_chloride.jpg; P53: Center “Santiago30std” by Wurstsalat (Own
work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/Fitxer:Santiago30std.jpg, Bottom center by EPA; P54: Own work derived from
information at http://www.airinfonow.com/html/ozone.html; P55: Bottom right by NASA.
Module 4
P59: Fig. 1.31 “Katódsugarak mágneses mezőben(3)” by Zátonyi Sándor, (ifj.) (Own work.) [Share Alike 3.0] http://commons.wikimedia.org/
wiki/File:Kat%C3%B3dsugarak_m%C3%A1gneses_mez%C5%91ben(3).jpg; P69: Top right “Hapsite” by Inficon, Bottom center “EWM paint
2007” by Tom Murphy VII (Own work) [Public domain] http://commons.wikimedia.org/wiki/File:EWM_paint_2007.jpg; P72: Top right by
US Geological Survey, Center & Bottom left Own work; P73: Top right “Blue drop” by Martina Rathgens (Own work) [2.0 Generic] https://
www.flickr.com/photos/riviera2008/2970609301/, Own Work, Center left “Blue Marble” by NASA, Bottom right Derivative from Microsoft
Office Image; P74 & P75: Background “Titan” by NASA, Own Work; P76 & P77: Background “Huygens on Titan” by NASA; P78 &
P79: Background “Brachinus spPCCA20060328-2821B” by Patrick Coin (Own work) [Share Alike 2.5] http://commons.wikimedia.org/wiki/
File:Brachinus_spPCCA20060328-2821B.jpg, Own work; P80: Left Source: Thomas Eisner et al.(2000) The Journal of Experimental Biology,
203, 1265-1275.
General
Activity icons: Clip art from Microsoft Office; Molecular structures: Derived from online public software (Chemical Education Digital Library,
Jmol) and via Wikimedia Commons (Public domain images).
UNIT 2
How do we
determine
structure?
The identity of a chemical substance is determined by its structure at
the submicroscopic level. The way in which electrons are arranged in
atoms or molecules, the manner in which atoms or ions are bonded to
each other in molecules or ionic networks, the specific distribution of
these particles in three dimensional space - all of these factors make a
given substance unique and determine its physical and chemical prop-
erties. The quest for uncovering identities in chemistry is thus tightly
linked to the search for models and experimental methodologies that
allow us to gather evidence about structure at the nano scale.
The central goal of Unit 2 is to help you develop ways of thinking

that can be used to uncover and predict the atomic and molecular
structure of substances. Although the ideas, models and experimental
techniques that we will discuss can be applied in a wide variety of con-
texts, to illustrate their power we will pay particular attention to the
analysis of molecular substances that sustain, support or threaten life in
our planet. In particular, we will try to address questions such as:
How do we explore their electronic structure?

How do we investigate their molecular structure?
How can we predict their molecular structure?
How can we predict electron distribution in these molecules?
82
Chemical Thinking
UNIT 2 MODULES
M1. Analyzing Light-Matter Interactions

Using spectroscopy to obtain information about the
structure of matter.
M2. Looking for Patterns
Using experiments and models to infer and predict
atom connectivity in molecules.
M3. Predicting Geometry
Predicting the three dimensional geometry of mol-
ecules.
M4. Inferring Charge Distribution
Analyzing the distribution of electrons in molecules.
83
84
Analyzing
Light-Matter
Interactions
One of the most important applications of chemical thinking in various fields,
U2: MODULE 1
from forensic analysis to drug design, involves the determination of the structure
of the particles that make up a substance. We may want to determine the geom-
etry of the molecules of cocaine to better understand how this drug interferes with
brain activity. We may be interested in characterizing the three dimensional struc-
ture of a protein to design a chemical substance that can inhibit its action inside
the cells of a pathogen we want to eliminate. For this purpose, chemical scientists
have developed a set of powerful intellectual and practical tools that help them
explore or predict how atoms or ions are bonded to each other in
[NoDerivs 2.0 Generic] via Flickr Commons

the particles of a given substance (connectivity) and how they
By William Chien (Own work)

are arranged in space (geometry). Many of these tools rely on
experimental information derived from the analysis of the
interaction of the substance of interest with some form of
electromagnetic radiation. It is through the analysis of the
electromagnetic radiation absorbed or emitted by a substance
that we can reveal its internal structure. This information has
also been used by chemical and physical scientists to build theoreti- Different atoms
emit light of char-
cal models to explain and predict the properties of matter. acteristic colors.
THE CHALLENGE In our Blood

The presence of some metals, such as lead, arsenic, and mercury in human
blood can lead to serious diseases. However, some other metals such as iron
and copper are essential to health in very small amounts. Metal compounds
are known to emit light of different colors when heated.
• How would you detect the presence of these metals in blood?
Design a potential strategy that could help solve this problem.
This module will help you develop the type of chemical thinking that is used
to answer questions similar to those posed in the challenge. In particular, the cen-
tral goal of Module 1 is to help you understand how to use experimental data
on the light emitted or absorbed by chemical substances to derive information
and build models about atomic and molecular structure.
Chemical Thinking U2 How do we determine structure? 85
Spectroscopy
One of the central questions that we want to investigate in this unit is how we can
use visible light, or any other form of electromagnetic (EM) radiation, to derive
information about the structural properties of chemical substances. In particular,
we would like to use results from the analysis of light-matter interactions to de-
termine atom connectivity and geometry in molecules and ionic networks, as well
as to detect, identify, and quantify the amount of different substances present in a
system. We would also be interested in using such experimental evidence to gener-
ate models about atomic and molecular structure that could help us explain and
predict the properties of materials. We will be able to face this challenge through
information derived using a set of experimental techniques generically known as
spectroscopy. These analytical methods are based on the analysis of different types
of EM radiation absorbed or emitted by chemical substances. However, to better
understand how this works, we need to discuss some basic properties of EM radia-
tion.
EM radiation is a form of energy that can be generated by accelerating par- Figure 2.1 Representation of
an EM wave showing its basic
ticles that have an electric charge. This radiation takes the form of self-propagating components: Electric field (E);
waves that travel through matter or through vacuum at a characteristic speed (v) magnetic field (B), propagation
direction (k). This wave is charac-
that depends on the nature of the medium. EM waves are comprised of electric terized by its wavelength l.

By SuperManu (Own work) [Share
and magnetic fields that oscillate in phase per-
pendicular to each other and perpendicular to E
the direction in which the wave propagates (see
Figure 2.1). Different types of EM radiation can k
be characterized by either wavelength (l) or fre- B
quency (n). The wavelength l is a measure of the
distance over which the shape of the wave is repeated; the frequency n indicates
the number of repeating waves that cross a certain point of space per unit time.
These two quantities are not independent from each other and their relationship
depends on the speed at which the waves travel through a certain medium.
LET’S THINK
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/Wave.html
Wave Properties
You can use the simulation included on this page to determine the relationship between wave-
length (l), frequency (n), and speed of propagation (v) for EM waves
traveling through water. You can change the value of l (measured in
meters, m) and observe the corresponding changes in n (measured in
s-1, also called Hertz, Hz).
CLICK TO PLAY
• How does n change with increasing l? Build graphs of a) n

as a function of l and b) n as a function of 1/l (you may use the
graphing tool also included on this page). Use this information to
derive a mathematical relationship between these two variables.
• Based on your data, what is the actual average speed (v) of EM
waves in water.
Share and discuss your results and ideas with a classmate.

86 MODULE 1 Analyzing Light-Matter Interactions
The wavelength l, frequency n, and speed of propagation v of a wave are re-

lated to each other through the following mathematical relationship:
(2.1) l x n = v.
In the particular case of EM waves traveling through vacuum the speed of propa-
gation has the constant value v = c = 3.00 x 108 m/s. This value is the same no
matter what the wavelength or frequency of the radiation is. This is not necessarily
the case for EM radiation traveling through a material medium, such as glass or
water, where wave speed depends somewhat on wavelength.
Depending on its wavelength or frequency, EM radiation is classified as be-
longing to different types as illustrated in Figure 2.2. The different EM radiation
types span the so-called electromagnetic spectrum and they include X-rays, ul-
Figure 2.2 Electromagnetic traviolet (UV) radiation, infrared (IR) radiation, and radio waves, as well as EM
spectrum. The visible region radiation that is visible to the human eye (visible light). The visible part of the
of the spectrum has been
re-scaled to show the range spectrum includes radiation with l values that range from approximately 400 nm
of wavelengths characteris-
tic of different light colors. (violet region of the spectrum) to 700 nm (red region of the spectrum).
Increasing Frequency (n)
By Philip Ronan, Gringer (Own work) [Share Alike 3.0] via Wikimedia Commons
Increasing Wavelength (l)
Visible Spectrum
Increasing Wavelength (l) in nm
Detector
The distinction between different types of EM radiation is relevant in chem-
istry because chemical substances interact in distinctive manners with different
types of radiation. The type of EM radiation absorbed or emitted by a chemical
l
By ADInstruments (Derivative)
Sample
Spectrum
substance is, in fact, a differentiating characteristic of the material. Additionally,
we can obtain different types of structural information by analyzing the EM ra-
diation emitted or absorbed by a substance in the IR region of the EM spectrum
or, for example, the UV region. That is why there are a variety of spectroscopic
EM Radiation techniques, such as IR spectroscopy, UV-visible spectroscopy, and microwave
Source
spectroscopy. In all of these different techniques, the actual instruments include
Prism
detectors that measure the intensity of the EM radiation that passes through a
sample or that is emitted by a substance when heated or stimulated in some other
Figure 2.3 A typical absorp-
tion spectrometer includes a way (such as using other types of EM radiation). The detection is done at different
EM radiation source, a device wavelengths which allows us to build a spectrum that shows the intensity of the
to split the radiation into specif-
ic wavelengths, and a detector. radiation absorbed or transmitted as a function of l or n (see Figure 2.3).
Absorption Spectra LET’S THINK

When a chemical substance is analyzed using absorption 1.0
spectroscopy, the spectrometer generates a spectrum that
provides information about either the fraction of EM 0.9
radiation of a specific wavelength that was absorbed by the
Transmittance
substance (Absorbance) or the fraction of that EM radia- 0.8 CO2(g)
tion that went through the sample without being absorbed
0.7
(Transmittance). Consider, for example, the following
spectra for O2(g) and CO2(g), two vital substances in our
0.6
planet: 4.20 4.30 4.40
Wavelength (mm)
• What types of EM radiation were used to generate
each of these spectra? 1.5
• How would you interpret the information provided O2(g)

by each of these spectra? What information do the 1.0
peaks at different wavelengths or frequencies convey?
Absorbance
• What do you think these spectra tell us about how
0.5
chemical substances interact with EM radiation?
Share and discuss your results and ideas with a classmate, 0

50 55 60 65 70
and clearly justify your reasoning. Frequency (GHz)
Quantization
Based on the subatomic model of matter discussed in Unit 1, one could expect
atoms and molecules to interact with EM radiation because they are made up of
charged particles (electrons and protons) that are constantly moving. Electrons
and protons could either be affected by the oscillating electric and magnetic fields
of an EM wave, or they could generate EM radiation as they accelerate. In either
case, these phenomena lead to a transfer of energy between the charged particles
and their surroundings. The charged particles either absorb energy when interact-
ing with incoming EM radiation or release energy when generating EM radiation.
But, how much energy is actually transferred?
An answer to this question was proposed by Max Planck in 1900 while trying
to generate a model to describe, explain, and predict how the intensity of the EM
radiation generated by an object depends on the frequency of the radiation and the
temperature of the object. In order to explain existing experimental results Planck
had to assume two basic things:
a. The energy transferred (E) through light-matter interactions is proportional

to the frequency (n) of the EM radiation according to this expression:
(2.2) E=hxn
where h = 6.626 x 10–34 J s is a constant known a Planck’s constant.

b. Energy transfer during light-matter interactions only occurs in integer mul-

tiples of the elementary unit of energy E = h n.
This last assumption implies that whenever matter interacts with EM radiation of
certain frequency n, the total energy transferred is always an integer multiple of
hn; this is, there is no way to transfer energy in amounts such as 1/2 hn or 3/4 hn,
or 200.5 hn using radiation with frequency n. The second of Planck’s postulates
indicates that energy transfer in light-matter interactions is quantized: it can only
take a set of discrete values instead of any possible value. This idea was unexpected at
Figure 2.4 In a photoelectric de-
vice, light with a frequency higher Planck’s time, to the point that even he doubted its validity. However, the concept
than a threshold value ejects elec-
trons from a solid surface. Elec- of “energy quantization” became one of the most powerful and revolutionary
tron emission is detected by the ideas of modern science.
presence of an electric current.
The suggestion that energy was quantized in light-matter interactions opened
the door to new ways of thinking about both the actual nature of EM ra-
diation and the internal structure of atoms and molecules. Albert Einstein,
for example, relied on this idea to propose a new model to conceptualize
light. At the beginning of the twentieth century scientists were puzzled
By PhET (Screenshot)
by the fact that when the surface of a solid is exposed to EM radiation

e-
with a frequency above certain threshold value, radiation is absorbed and
electrons are emitted with a kinetic energy proportional to the frequency
of the incident radiation (photoelectric effect; see Figure 2.4). Classical
views of this phenomenon suggested that the kinetic energy should be pro-
portional to the intensity of the EM radiation instead. Based on Planck’s
ideas, in 1905 Einstein solved the puzzle by proposing that EM radiation was
composed of discrete “quanta” of energy, called photons, rather than as continu-
ous waves. The energy of each of these photons depends on the frequency of the
radiation as stated in Planck’s relation in Equation (2.2). According to this mod-
el, electrons are ejected by direct interaction with those photons with an energy
E = hn above the threshold value, and the larger the frequency of the photon, the
larger the amount of energy transmitted to the charged particles. This new way of
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/spectraline.html
conceptualizing EM radiation implies that not only are light-matter interactions
quantized, but that quantization is an intrinsic property of light.
LET’S THINK Emission Spectra
The idea of energy quantization also allowed scientists to make sense of the nature of the absorp-
tion and emission spectra of different chemical substances. In particular, the analysis of the EM
radiation emitted by elemental atoms when heated, or absorbed when
they were exposed to a light source, led to the proposal of new sub-
atomic models of the atom. Consider the emission spectra of different
types of atoms included in the interactive tool in this activity:
CLICK TO PLAY
• In which ways are the spectra of different atoms similar or different?
• How would you use the idea of quantization of energy to explain the nature of these spectra?
• What do these experimental results suggests about the internal structure of atoms?
Share and discuss your results and ideas with a classmate, and clearly justify your reasoning.
The discrete line structure of the emission spectra of the atoms of different
elements, as seen in the previous activity, indicates that these particles
emit EM radiation with specific frequencies. These frequencies hap- Emission
pen to correspond to those of the light absorbed by these same atoms Hydrogen Line Spectrum
when exposed to a source of EM radiation (see Figure 2.5). This phe- Absorption
nomenon has been explained by assuming that electrons in atoms can (visible light background)
only exist in certain energy levels; this is, their energy is also quantized. 400 nm 500 nm 600 nm 700 nm
In order for an electron to change its energy level, it needs to absorb or release Figure 2.5 Emission and absorp-
a photon with an energy equal to the difference between two existing energy lev- tion spectra for hydrogen in the
visible range. Emission and ab-
els (see Figure 2.6). Thus, the location of the absorption or emission lines of the sorption lines have the same l.
spectra in the wavelength or frequency scales give use direct information about the
allowed energy levels for electrons in atoms.
Absorption Emission
Energy Ground State Excited State

n=4
n=3
n=2
DE
n=1
Figure 2.6 Different lines in the
If we assign a different label n = 1, 2,... to each allowed energy level for elec- absorption or emission spectra
trons in an atom as shown in Figure 2.6, the energy of each level can be represent- of atoms correspond to electron
transitions between different en-
ed as Ei. According to the model just described, the absolute value of the energy ergy levels.
difference between any two levels DE = Ej - Ei should then satisfy the relationship
(2.3) |DE| = h x n
where n is the frequency of a single photon absorbed or emitted by an electron

moving between those two energy levels; DE is thus energy per photon absorbed
or emitted (J/photon). Given that a macroscopic sample of any substance contains
myriads of atoms, the actual energy absorbed or emitted by all the atoms in the
sample that undergo this transition will be an integer multiple of this number. For
example, if one mole of atoms absorb or emit a photon with energy hn, the total
energy absorbed or released ET will be ET = NAhn, where NA is Avogadro’s number.
The electrons in most atoms or molecules of a given substance at standard
conditions of temperature and pressure tend to occupy the lowest energy levels
that are available in the system. We say that they tend to exist in their ground state.
When the substance is heated or exposed to EM radiation of the proper frequen-
cies, electrons may absorb energy and move to higher energy levels. We say then
that they are in an excited state. Changes in the energy level of an electron should
be associated with changes in both its speed and its average position with respect
to the nucleus of the atom. A variety of atomic models have been developed to
describe and predict these changes. Let us explore some of them.
LET’S THINK Atomic Models
The results from emission and absorption spectroscopy experiments were of central importance in
the process of testing and developing subatomic models of
the atom at the beginning of the twentieth century. The in-
CLICK TO PLAY
teractive simulation that you can access in this activity shows
the typical results of an experiment designed to generate the
absorption spectrum for hydrogen atoms (Experiment sec-
tion). Open the simulation, click to show the spectrometer,
and turn on the light source (gun) to generate white light
(stream of photons with multiple frequencies):
http://www.cbc.arizona.edu/tpp/chemthink/sim/atom.jnlp
• Carefully analyze what happens in the system as the white light interacts with the hydrogen
gas in the box. Make sure that you understand the relationship between what you observe and
the data registered by the spectrometer.
• Turn on the source of monochromatic light (EM radiation of a specific wavelength or fre-
quency). Reset the experiment and change the wavelength of the incident light to identify the
specific values for different absorption lines in the spectrum. You can control light intensity
(number of photons per second) by changing the speed of the simulation.
The simulation also allows you to explore the predictions of different atomic models about the results
of the interaction between light and the hydrogen atoms (Prediction section):
• The Billiard Ball Model (by Dalton), the Plum Pudding Model (by Thomson), and the Clas-
sical Solar System Model (by Rutherford), failed to explain the results of light absorption
experiments. Analyze why these models were unable to reproduce the experimental data.
Bohr’s Atomic Model was the first to qualitatively explain the quantized nature of light absorption
by matter and to quantitatively predict the actual wavelength of the absorption lines. Bohr proposed
that the energy of electrons in atoms was quantized: it could only take certain specific values deter-
mined by the number of protons in the atomic nucleus.
• Analyze the predictions of Bohr’s atomic model. Show the electron energy level diagram and
analyze the relationship between an electron’s energy level and its location in space. Also ana-
lyze the relationship between energy level and kinetic energy (as determined by the electron’s
speed) and potential energy (as determined by its distance from the nucleus).
• Determine the wavelength needed to induce an electron transition from n=1 to n=3 and calcu-
late the energy difference DE between these two energy levels.
de Broglie’s and Schrödinger Atomic Models are based on the assumption that electrons in atoms
are better conceptualized as waves rather than as discrete particles. This behavior limits our ability
to predict the actual position of electrons at any given time. In particular Schrödinger’s model, the
current scientific view of an atom, establishes that we can only predict the probability of finding
electrons in certain regions of space.
• Use the simulation to analyze how these two models conceptualize the relationship between
energy transitions and changes in an electron’s distribution in space.
According to the current model of the atom, also known as the quantum me-
chanical model, atoms can exist in different electronic energy states depending on
how their electrons are distributed among various energy levels. The absorption or
emission of energy by an atom is associated with electron transitions between dif-
ferent energy levels. The energy difference between these energy levels can be de-
duced from spectroscopic data. For example, based on the simulation used in the
last activity the absorption of light with l = 122 nm induces an electron transition
from the ground state with n =1 to the excited state with n = 2 in the hydrogen
atom. Thus, using equations (2.1) and (2.3), we have:
hc 6.626 x 10–34 x 3.00 x 108

DE = h n = = = 1.63 x 10-18 J
l 122 x 10–9
This is the energy needed to promote a single electron from n = 1 to n = 2 in a
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/vibmodes.html
hydrogen atom. The total energy ET required to induce this change in a mole of
hydrogen atoms is then given by: CLICK TO PLAY
ET = NADE = 6.022 x 1023 x 1.63 x 10-18 = 9.82 x 105 J/mol = 982 kJ/mol
Electron transitions in atoms typically involve absorption or emission of en-

ergy from a few hundred to a few thousand kJ/mol. The type of EM radiation that
provides this amount of energy is typically in the visible and the ultraviolet regions
of the EM spectrum. The energy absorbed by electrons can be large enough to pro-
mote them to states in which they actually detach from the atom. Thus absorption
of high energy EM radiation, particularly in the ultraviolet, X-ray, and gamma ray
regions of the EM spectrum can result in the formation of ions.
Spectroscopic data strongly suggests that electron energy levels in atoms are
quantized. How do we explain it? In the quantum mechanical model of the atom,
energy quantization is seen as a direct result of the intrinsic properties of sub-
atomic particles. Based on ideas originally proposed by Louis de Broglie in 1924, Figure 2.7 A two-dimensional
the modern model of the atom assumes that electrons in confined systems, such surface, like that of a drum, can
only vibrate in certain modes.
as atoms or molecules, behave like standing or stationary waves. Such waves, like
the ones that can be established on a guitar string or a drum’s surface, occur only
in a discrete set of wavelengths or frequencies (see Figure 2.7). In musical instru-
ments this results in discrete sets of possible harmonics or overtones. In atoms, the
consequence is the existence of discrete electronic states.
If energy is associated with the frequency of each allowed standing wave, as is
the case for photons (E = hn), then quantization of energy is a natural consequence 10 nm By Stroscio et al. (Own work) [Public
domain] via Wikimedia Commons
of the wave-like behavior of electrons. While the allowed frequencies in musical

instruments such as pianos and guitars depend on the mass, length, and tension
of their strings, the quantized states in an atom are determined by the mass and
number of electrons in the system, together with the strength of the interactions
between electrons and protons in the atom. The wave-like behavior of electrons
has been experimentally confirmed in a variety of ways. For example, in 1993 a
group of scientists were able to confine electrons on the surface of metals inside Figure 2.8 Quantum corral:
Scanning Tunneling Microscope
nanoscopic rings made with other types of atoms. The electrons trapped in these image of individual cobalt at-
oms arranged in a circular ring
“quantum corrals” generate a wave pattern similar to that created by standing on a copper surface exposing
quantum electron waves.
waves on the surface of a drum (compare Figure 2.7 and Figure 2.8).
The wave-like properties of matter at the submicroscopic level impose im-

portant limitations on what we can know about the behavior of particles at this
r scale. For example, it is impossible to simultaneously measure both the position
and momentum (i.e., mass times velocity) of a particle with unlimited precision;
x this restriction is known as Heisenberg’s Uncertainty Principle. Thus, we cannot
y determine the trajectories followed by electrons in atoms because that would re-
quire precise knowledge about their position and velocity as a function of time.
CLICK TO PLAY The most that we can predict or determine experimentally is the probability of
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/deloc.html
finding electrons in certain region of the space at a given time. For that reason,
modern descriptions of the internal structure of atoms refer to electron densities
rather than to electron trajectories. These electron densities are a measure of the
probability of electrons being present in specific locations.
In the quantum model of the atom, different electron states are character-
ized by different mathematical functions that describe the corresponding electron
waves. These wave functions are mathematical tools that can be used to calculate
the electron probability densities. Electrons with different energies are described
by different wave functions. In particular, their kinetic energy is directly related to
the wavelength of their associated wave function. As is the case for photons, the
shorter the associated wavelength the higher the kinetic energy of the electrons.
This relationship has important consequences in chemistry because an electron’s
wavelength is determined by the size of the space in which it can move around.
The smaller the volume, the shorter the electron’s wavelength and the higher its
kinetic energy. Thus, for example, electrons forced to move close to the nucleus in
an atom will have higher kinetic energies than those electrons that are farther away
Figure 2.9 Probability densi-
ties r of an electron confined and can move through a larger volume. The kinetic energy of some of these elec-
inside a flat surface . The more
“localized” an electron is, the trons can further decrease when atoms bond to other atoms and form molecules;
larger its kinetic energy. Thus
delocalization, or redistribution
bonding increases the space in which electrons can “delocalize” (Figure 2.9). But
of electrons in a larger space, before we talk more about chemical bonding, let us analyze what spectroscopic
reduces their kinetic energy.
measurements can tell us about molecular properties.
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/molspec.html
LET’S THINK Molecular Spectroscopy
Molecules absorb and emit EM radiation of different types. The changes induced by these pro-
cesses depend on the wavelength of the radiation. Consider the interactive tool included on this
page that simulates the interaction of a water molecule with EM radiation of different types:
• What types of changes are induced by the different types of EM radiation that interact with
the molecule?
• Which of these changes requires more or less energy to
occur? Roughly estimate the amount of energy, in kJ/
mol, that is necessary to induce each type of transition.
• Would you expect all types of molecules to absorb the
same types of radiation? What factors may influence
how different molecules interact with EM radiation?
Share and discuss your results and ideas with a classmate. CLICK TO PLAY
Molecular Transitions
Just like atoms, molecules also exist in quantized energy states. However, they not
only exhibit quantized electronic states, but also vibrational and rotational energy
states. By using different types of EM radiation, one can explore transitions be-
tween these different types of energy states and derive valuable information about
electronic and molecular structure. For example, radiation in the UV and visible
regions of the EM spectrum tends to induce electron excitations. Given that elec-
trons play a central role in keeping atoms together in a molecule, these changes
may result in bond breaking and atom separation. The energy required for these
Figure 2.10 Energy scale for
changes to occur ranges from a few hundreds to over a thousand kilojoules per different types of molecular
transitions.
mole. This suggests that energy differences between electronic levels in molecules
are of the order of 102 to 103 kJ/mol.
EM radiation of lower frequency, and thus lower energy, E (kJ/mol)
in the IR range stimulates transitions between different vibra-
tional states. Quantization of molecular vibrations implies that
Electron Excitation
103
molecules can only exist in a discrete set of vibrational levels. Bond Breaking
DE UV-visible
Energy differences between these different levels is of the order 102
of 10-1 to 102 kJ/mol. On the other hand, microwave radia-
tion induces molecular transitions between different rotational
states. The energy needed for these changes to happen is of the 101
Change in
order of thousandths to tenths of kilojoules per mole (10-3 to Vibrational State DE Infrared
10-1 kJ/mol). Common sources of energy, such a gas flame, an 1
incandescent bulb, or our own body emit most of their energy
in the form of IR radiation. Thus, they tend to stimulate vi- 10–1
brational transitions in the molecules that surround them. In
Change in
general, knowing how much energy is needed to induce differ- Rotational State 10–2 DE Microwave
ent molecular transitions is useful in predicting the changes that
substances may undergo when exposed to different energy sources.
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/infspec.html
CO2 vibrations LET’S THINK
The spectra of chemical substances in different regions of the EM spectrum are like fingerprints
that can be used as differentiating characteristics to detect or identify them. Consider the IR ab-
sorption spectrum of CO2(g) as represented in the interactive tool on this page. In this spectrum,
radiation transmittance is shown as a function of “wavenumber,” a quantity commonly used to
represent data in IR spectroscopy and defined as the inverse of the wavelength 1/l.
• What types of vibrational states are accessible to the

CLICK TO PLAY
CO2 molecule according with this simulation?

• Estimate the amount of energy, in kJ/mol, that is nec-
essary to induce each type of vibrational transition.
• What does the simulation tell you about how excited
molecules relax back to their ground state?
Share and discuss your results and ideas with a classmate, and justify your reasoning and numerical
procedures.
As you may have noticed in the last activity, IR spectra are characterized by the
presence of absorption bands of different widths. This may seem surprising given
that we stated that vibrational energy states are quantized. If that is the case, why
do we observe absorption over a range of frequencies rather than at very
0 well defined values (single peaks or lines)? The existence of broad absorption
bands in molecular compounds is due to the multiple interactions between
0.1
atoms in the same molecule and between different molecules in the system.
Transmittance
Molecules are dynamic entities that are constantly undergoing small rear-
0.2 CO2(g)
rangements. The mere presence of other particles in their vicinity may alter
0.3 the distribution of electric charge in the molecule, introducing tiny changes
in the vibrational and rotational energy levels that are allowed. From this
0.4 perspective not allthe molecules of the same substance are identical to each
1.600 1.610 1.620
Wavelength (mm) other and thus absorb EM radiation of slightly different frequencies. Given
that common spectrometers cannot detect these small variations in absorp-
Figure 2.11 High Resolution tion frequencies, these instruments register absorption over a continuous frequen-
IR spectrum of CO2(g).
cy range. However, there are high resolution spectrometers that clearly reveal the
quantized nature of the transitions (see Figure 2.11).
Molecular spectroscopy is a powerful analytical tool that has greatly simpli-
fied the detection and identification of chemical substances in complex chemical
environments, some of which may not be directly accessible. For example, in 2004
NASA launched the Aura spacecraft designed to study Earth’s air quality
and climate. Aura is equipped with four main analytical instruments that
use UV, visible, IR, and microwave radiation to scan the atmosphere and
study its chemistry and dynamics. The spacecraft repeats its journey around
the globe every 16 days to provide atmospheric measurement over virtually
every point on Earth in a repeatable pattern (see Figure 2.12 and Figure
2.13). This permits us to follow the evolution of over 20 different chemical
substances over time across the planet. The detection and quantification of
these substances are based on available information about their emission
and absorption spectra over a wide range of frequencies. The Aura mission
Figure 2.12 Aura Mission is just one of many examples in which molecular spectroscopy is the tool of choice
(NASA): NO2 concentration
over the US from September for chemical analysis.
to November 2004.
Emission UV IR MW
h (km)
50
18
Troposhere
0
Figure 2.13 Aura Mission: Different types
of spectroscopic measurements permit
detection of several chemical species at
different altitudes (h) in the atmosphere.
O3 H2O CO HNO3 NO2 HCl ClO
FACING THE CHALLENGE vided is enough to break chemical bonds within

the sample and produce free ground-state atoms
or ions. The instrument also has a radiation source
Detecting Metals containing the same metal we are looking to de-
Chemical compounds of metallic elements are tect. The metal is excited to generate EM radiation
pretty common in our planet. These substances characteristic of its emission spectrum, which is
tend to be ionic compounds made up of ions ar- passed through the vaporized sample. If the metal
ranged in crystalline networks. Most minerals be- of interest is present in the mixture it will absorb
long to this group of substances and erosive pro- the incoming EM radiation. The amount of radia-
cesses dissolve them in water. Thus, both seawater tion absorbed will be proportional to the metal’s
and freshwater contain relatively high concentra- concentration. Comparative measurements of
tions of metal ions such as Na+, K+, Mg2+, and light intensity with and without the sample can
Ca2+, together with traces of many other heavier then be used to quantify the metal’s concentration.
ions such as Ba2+, Sr2+, Cu2+, and Fe3+. Consider- AAS can be used to determine the concen-
ing that water is the major component of most life tration of close to 70 different metals in solution
forms, metal ions are also present in living organ- down to parts per billion (mg/L). In environmental
isms. In humans, Na+ and K+ play a central role and food analysis, AAS is the preferred method for
in cell transport; Ca2+ facilitate cell communica- monitoring the concentration of toxic metals in
tion processes while Mg2+ helps maintain normal air, drinking water, and drinks such as wine, beer
muscle and nerve function. Other metals found in and fruit juices. During the production of pharma-
trace amounts in our bodies are also vital, such as ceutical products it is common to use metal com-
iron for oxygen transport in blood and copper for pounds to facilitate the synthesis of drugs; AAS is
the activation of important cellular processes. used to monitor the concentration of metals in the
Given the importance of metal ions in the final products. At the industrial level many raw
anatomy and physiology of life, their detection materials are examined using AAS to ensure that
and quantification in our surroundings or inside the concentration of toxic impurities, such as lead,
our bodies are frequent practices in environmental meet official standards. The technique is also em-
or clinical analysis. In either case, atomic absorp- ployed by the mining industry to determine the
tion spectroscopy (AAS) is one of the most com- concentration of metals in ores and decide wheth-
mon analytical methods used to accomplish the er it is worth investing in their extraction.
task, particularly in those situations in which met- Many pathological conditions in humans re-
al ions are expected to be present in trace amounts. sults in changes in the concentration of metal ions
The technique developed in the extracellular fluid.
by A. Walsh in 1955 is Total lead in gasoline
Changes in these compo-
based on the fundamen- 100 (thousand of tons) 160 nents are often lethal and
tal principles of energy Lead concentration
in blood (ppm)
thus rapid procedures are
quantization discussed in 140 required for the analy-
this module. 80 sis of body fluids (e.g.,
An atomic absorp- blood, saliva, sweating).
120
tion spectrometer in- 60 Instrumental techniques
cludes a device to va- such as AAS, or emission
porize and atomize the 100 spectroscopy, are thus
sample. This can be done 40 used routinely in clinical
using a flame or a graph- laboratories for the rapid
1976 1977 1978 1979 1980
ite furnace that can reach diagnostic and manage-
YEAR
temperatures as high as ment of diseases.
The detection of lead in human blood using AAS
3000 oC. The energy pro- has led to the banning of lead from consumer
products, such as gasoline (Source: NIEHS)
Let’s Apply

By ESA/Hubble (Own work) [Share
What is in a Star?
Astronomers use diverse spectroscopic techniques to investigate
the composition of stars and other celestial objects, such as gal-
axies and nebulae. Spectroscopic data provide information not
only about the chemical composition of these objects, but also about their temperature, density,
distance, and even their motion. Let us explore how this can be done.
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/blackbody.html
Blackbody Radiation
Stars, as many hot solids, emit EM radiation in a continuous range of wavelengths

(l). However, the intensity of the radiation at each specific l is a function of tem-
perature (T). The EM spectrum of stars can
be modeled by assuming that they behave
as perfect radiation emitters or absorbers
(blackbody objects). The interactive tool
that can be accessed in this page simulates
the intensity of the EM radiation emitted
by a black body as a function of wavelength
at different temperatures.
• Set the temperature in the simulation

to that of a light bulb. What type of CLICK TO PLAY
EM radiation is mostly produced by this object?
• How does the nature of the EM radiation produced by a hot object changes
when a) increasing its temperature and b) decreasing its temperature?
• How will the color of a hot object change as its temperature increases?
• How would the change in the EM radiation produced with increasing tempera-
ture affect the elements and compounds in the object’s surroundings?
• The area under the intensity vs. wavelength curve is a measure of the total ener-
gy produced by the object. Estimate the fraction of the total
energy emitted by the Sun that is in the form of visible light.
Share and discuss your ideas with a classmate, and clearly jus-
tify your reasoning.
TRIFID NEBULA
NASA
Solar Spectrum
Our sun’s EM spectrum as measured 2.5

UV Visible Infrared
from Earth is similar to that of a
black body object with a surface tem- 2.0 Sunlight at Top of Atmosphere
perature close to 5500 oC. However,
its fine structure varies depending on 1.5
Intensity
5500 oC Blackbody Spectrum
the altitude where it is measured (see
1.0
the figure).
0.5
Radiation at Sea Level
• How would you explain the

presence of absorption “dips”in 0
the solar spectrum measured at 250 750 1250 1750 2250
Wavelength (nm)
the top of the atmosphere?
• How would you explain the presence of deeper and wider absorption dips in the solar
spectrum measured at sea level?
Stellar Spectra
Chemical elements in a star’s photosphere absorb specific radiation. The “dips” in their spec-
tra as measured at the top of our planet’s atmo-
sphere can then be used to detect their presence
in the star. Additionally, the shape of the spectra
is indicative of the star’s temperature. Consider
the spectra from two different stars.
• Use the blackbody radiation simulation

from the previous page to try to reproduce
the basic shape of each of these spectra and
estimate the temperature of each star.
• The following table lists the wavelengths
associated with major absorption lines for different types of atoms and ions. Use this
information to speculate about the chemical composition of each star.
Atom/Ion l (nm) Atom/Ion l (nm)

Ca+ 393.5, 396.8 Li 670.8
He+ 420, 541.2 Mg 518.3
H 410.2, 434.0, 486.1, 656.3 Na 588.9
Fe 425, 527 Ne 439, 618
Let’s Apply
The Water Case
Water (H2O) is certainly one of the most important chemical compounds for life in our planet. Its
physical and chemical properties have a crucial influence on environmental phenomena, as well
as in the anatomy and physiology of living organisms. In particular, the manner in which water
molecules interact with EM radiation influences from our planet’s temperature to our ability to see
the world. Consider the following spectrum of liquid water in a wide range of wavelengths.
106
Absorbance (1/cm)
104
102
100
10–2
UV IR MW
10–4
10 102 103 104 105 106 107 108 109

Wavelength(nm)
EM Absorption
Analyze the absorption spectrum for water:
• What type of EM radiations are mostly absorbed by water molecules? What types of
radiations go through this liquid without much being absorbed?
• How would you explain that the spectrum shows such wide absorption bands?
• How would you use the data to explain why water is a clear liquid with a bluish tint?
• How would our ability to do observations of celestial objects be affected if water were to
strongly absorb EM radiation at all wavelengths?
• How might the nature of the EM radiation absorbed and not absorbed by water have
influenced the evolution of organs to detect light (e.g., eyes) in living organisms?
Greenhouse Gas
CLICK TO PLAY
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/blackbody.html
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M1/vibrations.html
Most of the sunlight that reaches Earth’s tropo-
Bending Vibration Stretching Vibration
sphere is in the form of IR radiation and visible
light. The surface of the planet absorbs part of this
radiation, heats up, and re-emits radiation at dif-
ferent wavelengths. Water in the atmosphere ab-
sorbs IR radiation, mostly at wavenumbers corre-
sponding to the bending and stretching vibrational 1595 cm-1 3756 cm-1
transitions shown on the image.

• Use the interactive simulation for blackbody radiation (click on the image
to the right), together with all of the information provided so far, to deter-
mine whether water molecules will absorb more (or less) radiation coming
from the Sun than radiation re-emitted by the surface of our planet.
• Calculate the energy (in kJ/mol) needed to induce the bending and stretching transi-
tions shown on the image.
• If water molecules in the atmosphere absorb incoming and outgoing IR radiation, where
does that energy go? How should that affect the temperature of the atmosphere?
Microwave Oven
A microwave oven works by generating EM radiation with

a wavelength close to 12 cm in a closed cavity that reflects
that type of radiation.
• Locate this type of radiation on the EM spectrum of

water on the previous page. Determine whether EM
absorption for this l is low or high relative to the absorption at other wavelengths.
• Calculate the amount of energy (in kJ/mol) of this radiation. What type of molecular
transition would be induced if water molecules were to absorb this energy?
In the liquid phase, interactions between water molecules strongly affect each other’s proper-
ties and behavior, thus, absorption of microwave radiation occurs over a range of wavelengths
rather than at specific values. Once a water molecule interacts with MW radiation, the effect
propagates to neighboring molecules via interparticle interactions.
• How would you explain that food with a high water content heats up when exposed to
microwave radiation?
• Would you expect this effect to be stronger or weaker in frozen food?
100
Looking for
Patterns
Experiments based on the analysis of light-matter interactions such as those de-
U2: MODULE 2
scribed in Module 1 of Unit 2 have facilitated the determination of the composi-
tion and structure of the particles of matter. This knowledge is of central impor-
tance in understanding the physical and chemical properties of substances in our
world. In particular, how atoms are bonded to each other in molecules, or how
ions are arranged around each other in ionic networks, will affect the distribution
of electric charge in each particular system. Charge distribution in turn influences
the nature and strength of the interactions among molecules or ions in the system
and with other particles in their surroundings. Thus, the determination or predic-
tion of atom connectivity in the particles of matter is a cru-
cial step in the process of inferring a substance’s properties.
Chemical scientists have developed a variety of strate-
gies, experimental and theoretical, to determine atom or ion
connectivity in molecular and ionic compounds. Spectro-
scopic techniques have been an invaluable analytical tool in
completing this task. However, the analysis of experimental Why do carbon atoms
form FOUR bonds?
data is greatly simplified by using atomic and molecular models
of matter that help us predict many aspects of atom connectivity. Some of these
models have been derived from the recognition of regularities in the bonding be-
havior of different types of atoms and from patterns in the distribution of their
electrons in different energy states. Knowing how to apply this information in
predicting atom connectivity is a critical skill in chemical thinking.
THE CHALLENGE Amazing Carbon

Carbon-based compounds are among the most abundant and diverse in our
world. Most molecules in our body are made of these types of atoms.
• Carbon atoms have the capacity to form four bonds with other atoms of
the same or a different type. What determines the bonding capacity of
carbon atoms? Why is this capacity different for other types of atoms?
to answer questions similar to those posed in the challenge. In particular, the
central goal of Module 2 is to help you understand how to use experimental
spectroscopic data, together with information about atomic composition and
electron configurations, to infer atom connectivity in molecular compounds.
Covalent Bonding
Molecular compounds are chemical substances made up of independent particles
called molecules. The idea that molecules are in turn comprised of atoms con-
nected to each other and arranged in particular geometries in space has been very
useful in explaining and predicting the physical and chemical properties of chemi- Figure 2.14 The bond length is
cal substances. But, what holds atoms together in a molecule? Let us analyze it. defined as the distance at which
the average electron-electron
A useful way of modeling bonding between atoms in molecular systems is and proton-proton repulsive
forces (red arrows) are balanced
based on the analysis of the electrostatic interactions between electrons and pro- by the average electron-proton
attractive forces (black arrows).
tons of the atoms that form the “bond” (electrostatic model). As shown in Figure
2.14 the basic idea is that when two atoms get in close proximity of each
other, the electrostatic attraction between electrons located between the BOND LENGTH
atoms and the protons in each of the atomic nuclei leads to a net at-
tractive force between the two atoms. As the atoms get closer together,
the strength of the attractive interaction increases until reaching a point
in which repulsive interactions between charges of the same type be-
gin to dominate. There is an equilibrium distance at which attractive
forces between electrons and protons are balanced by proton-proton
and electron-electron repulsive forces. This equilibrium distance be-
BOND LENGTH
tween the nuclei of the interacting atoms is conventionally defined as
the “bond length” and the energy needed to separate the atoms from this position
to an infinite distance is taken as a measure of the “bond strength” (also called
bond dissociation energy). The bond between two neutral atoms that results from
this dynamic interaction between electrons and protons in the system receives the
name of covalent bond.
Hydrogen Molecule LET’S THINK

In this activity you can find two simulations based on an electrostatic model of bonding between
two hydrogen (H) atoms. In the first simulation, the interacting atoms form a H2 molecule that
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M2/bond2.html
can be dragged across the stage. In the second simulation, the total internal energy (ET) of the
interacting atoms is represented as a function of the distance (r) between them. ET is a measure of
the energy associated with the interaction and movement of the electrons in the system.
• Analyze the formation of a covalent bond between two hydro-

gen atoms using the first simulation. What happens when you
move the atoms close to each other? What happens if you try
to have the nuclei touch each other? How easy is to “break”
the bond?
CLICK TO PLAY
• Use the second simulation to analyze the changes in total

internal energy (ET) when the two atoms are brought closer
to each other. How would you explain the changes in energy
that you observe? How would you explain the dynamic be-
havior of the bond once it is formed? How would you use the
information from the graph to estimate the bond length and
the bond strength for the hydrogen molecule H2?

102 MODULE 2 Looking for Patterns
In the electrostatic model of covalent bonding, the formation of a bond be-

tween two atoms involves a variety of processes that alter the energy of the system.
For example, as the atoms get closer to each other, interactions between electrons
in one atom and protons in another atom pull some electrons toward the region
between the atoms. As electrons in one atom get farther away from that atom’s
nucleus their potential energy increases but their kinetic energy decreases. Addi-
tionally, as some electrons move towards the region between the two atoms other
electrons in each atom can get closer to their nuclei, which reduces their potential
energy. All these changes in the distribution of electric charge in the pair of atoms
lead to a net decrease in the total energy of the system. At even closer distances, the
attractive interactions between electrons in one atom and protons in another atom
dominate and produce a drastic decrease in the total potential energy. However,
if the atoms get too close to each other, repulsion between electric charges of the
same sign confined into a smaller space cause both the kinetic energy of electrons
and the potential energy of all interacting particles to increase. Thus, from the
Figure 2.15 Electron
energetic point of view, there is an optimal distance (bond length) at which the
density map for the hy- energy of the system is a minimum.
drogen molecule (H2).
From the perspective of the quantum mechanical model of the atom, in which
the position and speed of electrons cannot be precisely defined at the
Derivative from Image by Jindrich Kolorenc
same time (Heisenberg’s Uncertainty Principle), covalent bonding may

be explained by looking at changes in the electron density of the partici-
pating atoms. The formation of the covalent bond allows some electrons
to occupy a larger region of the space, which as we have seen decreases
their average kinetic energy; this phenomenon is called electron “delo-
calization.” As some electrons delocalize into the bonding region, the
remaining electrons in each atom can get closer to their atomic nuclei
which lowers their potential energy. According to this model, covalent bonding is
Electron Density
driven by the delocalization of electronic motion between the two bonded atoms
Low High
which causes a redistribution of electron density in the entire system. As we will
see in other modules of this book, electron delocalization plays a central role in the
formation of stable chemical substances.
LET’S THINK Comparing Models
Consider the following simulations of covalent bond formation based on the electrostatic model
of covalent bonding and on the quantum mechanical model of the atom:
• Compare the two models of bond formation and identify

major differences and similarities in their predictions of
electron charge distribution both as the atoms get close
CLICK TO PLAY
to each other and once the bond is formed. Which of the

models predicts more electron delocalization?
• What limitations do you see in each of the two representa-
tions of bond formation between two hydrogen atoms?
Share and discuss your ideas with a classmate, and clearly justify
your reasoning.
Bonding Patterns
Chemical bonds are dynamic entities in which the atomic nuclei and electrons
involved are in constant movement. Atoms in a bond vibrate around their equi-
librium positions at frequencies determined by both their atomic masses and the
bond strength. The bond strength depends on electron distribution between the
bonded atoms. Thus, a molecule made up of more than two atoms will experience
a variety of vibrational motions with frequencies determined by the molecule’s
atomic composition and connectivity.
Given that vibrational states are quantized, different molecules will undergo
vibrational transitions at characteristic frequencies when interacting with EM ra-
diation. In particular, the analysis of infrared (IR) radiation absorption as a func-
tion of wavenumber can give us important information about atom connectivity
in molecular compounds. Let us consider, for example, the IR absorption spec- Figure 2.16 IR absorption
trum (see Figure 2.16) for formaldehyde (CH2O), a chemical compound naturally spectrum for formaldehyde
(CH2O). Click on the image
produced by many living organisms, including ourselves, but that may be highly to observe the different vi-
brational modes of the CH2
toxic when present in low concentrations in the atmosphere. group in this molecule.
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M2/irspec.html
100
2785 cm-1
1165 cm-1
CH2
CH2
Symmetric
Wagging
Stretching
% Transmittance
2850 cm-1
CH2
50 Asymmetric 1485 cm-1 1250 cm-1
Stretching CH2 CH2
Scissoring Rocking
2850 cm-1
CO
Stretching
CLICK TO PLAY
0
3000 2000 1000 500
Wavenumber (cm-1)
As shown in this spectrum, specific types of bonding arrangements, such as a
carbon atom bonded to two hydrogen atoms (CH2), exhibit characteristic vibra-
tions (e.g., stretching, bending) that can be excited at specific frequencies or wave-
numbers. Although the actual location of the absorption band may shift somewhat
from one molecule to another, experimental results indicate that the existence of
an absorption band in a certain range of wavenumbers, or the identification of a
set of bands in specific locations of the spectrum, can be used as reliable cues to
infer the presence of a particular bonding arrangement in a molecule. This infor-
mation, together with experimental data from other analytical techniques such
as combustion analysis and mass spectrometry, is in many cases enough to infer
the molecular structure of a chemical compound. However, to take full advantage
of this information we need to better understand the different types of covalent
bonding that can occur between atoms.
Multiple pieces of experimental evidence suggests that stable covalent bonds

Figure 2.17 Every covalent bond are formed when at least two electrons are delocalized between the bonded atoms.
involving the delocalization of
two electrons is commonly rep- The covalent bond induced by two electrons is often described as a “single bond.”
resented using a single line be-
tween the bonded atoms. Double However, experiments also suggest that covalent bonding between some atoms
and triple bonds are then repre- may involve more than two electrons. In particular, some atoms form bonds in
sented using two or three linking
lines, respectively. which four or six electrons are delocalized; these types of covalent bonds are la-
beled as double and triple bonds, respectively (see Figure 2.17). The presence of
C C C N multiple bonds explains measured differences in the length and strength of bonds
between the same types of atoms. Interestingly, covalent bonding often involves
C C C N pairs of electrons, a phenomenon that we will try to explain later.
The presence of single, double, or triple covalent bonds between a pair of
C C C N atoms in a molecule changes bond strength, thus affecting the energy of the vibra-
tional states that are allowed in the system. The existence of multiple bonds can
then be detected through the analysis of the IR absorption spectrum of the chem-
ical substance. For a given type of vibration, absorption bands associated with
triple bonds tend to appear at higher wavenumbers (higher radiation energy) than
those of double bonds, and these latter bands are located at higher wavenumbers
than those of single bonds. In general, more energy is normally needed to induce
equivalent vibrational transitions involving stronger bonds. However, the energy
required also depends on the mass of the atoms involved in the bond. More ener-
gies is required to induce vibrational transitions in bonds between lighter atoms
which vibrate at higher frequencies.
The analysis of thousands of IR absorption spectra for a variety of known mo-
lecular compounds has allowed chemical scientists to delimit ranges of wavenum-
bers where vibrational absorption bands corresponding to specific bonding ar-
rangements are likely to appear (see Figure 2.18). Although the presence of a given
absorption band does not tell us how many bonds of a specific type are present in
a molecule, IR spectroscopic data is very useful in inferring molecular structure.
Figure 2.18 In general, most rel- C O C O
O H C N C N CH2 C N
evant vibrations involve molecu-
lar stretching and bending. The N H C C C C CH3 C C
location of the corresponding ab- stretch stretch stretch stretch bend stretch
sorption bands in the IR spectrum
can be used to infer how atoms X-H (with X = O, N) C-H Triples Doubles Singles
are connected in a molecule. cm-1
4000 3000 2000 1000
0.8
CH
Transmittance
0.6 C-H bends

stretch
0.4 O-H
stretch
0.2 C-O
stretch
0
3000 2000 1000
Wavenumber (cm-1)
Structure Determination LET’S THINK

The combination of information from infrared absorption spectroscopy (IR), mass spectrometry
(MS), and combustion analysis is very useful in the determination of the molecular structure of
molecular compounds. To assess your ability to use these types of experimental data in chemical
analysis, consider the following problems:
• Combustion analysis of a poison that causes blindness in humans reveals the formula CH4O.
The MS and IR spectra for this substance are shown below. Use this information to propose a
molecular structure that is consistent with the evidence provided.
100
80 0.8
Relative Abundance
Transmittance
60
0.6 C-H
40 C-H bend
0.4 stretch
20 C-O
O-H stretch
0.2 stretch
0
0 10 20 30 40 3000 2000 1000
m/q Wavenumber (cm-1)
• IR/MS breath analysis can be used to explore fat metabolism for people on a diet. Fat me-
tabolism produces a volatile organic compound with the formula C3H6O. The concentration
of this compound in people’s breath is indicative of how much body fat is being consumed
as a result of dieting. The IR and MS spectra of this molecular compound are shown below.
Use this information to propose a molecular structure that is consistent with the evidence
provided.
100
0.8
80
Relative Abundance
0.6
Transmittance
60
0.4
40
C-H
stretch C-C
20
0.2
C=O stretch
stretch
0
10 20 30 40 50 60 3000 2000 1000
HINT: Remember that the MS spectra contains useful information about molecular structure if you
pay attention to the fragmentation pattern. The mass of the most abundant ions formed during frag-
mentation can be used to infer their composition, which combined with IR data can help you figure out
molecular structure.

The analysis of experimental data about the submicroscopic structure of mo-

Figure 2.19 Atoms in molecu-
lar compounds exhibit regular lecular compounds collected by many different means, from combustion analysis
bonding patterns. to IR spectroscopy to mass spectrometry, reveals the existence of bonding patterns
in these types of chemical substances. This means,
certain types of atoms tend to form the same num-
ber of bonds when they combine with other atoms
and the nature of these bonds is similar among
different compounds. Consider, for example, the
set of molecules depicted on Figure 2.19. If you
analyze the bonding patterns of the atoms that
make up these molecules you will notice that, for
example, carbon atoms always form four chemical
bonds with other atoms while oxygen atoms form
only two bonds (where double and triple bonds
account for two or three of those bonds, respec-
tively). It is as if these atoms had a fixed “bonding
capacity” independent of the nature of the atoms
to which they are connected. They may form sin-
gle, double, or triple bonds with different atoms, but the total number of electrons
http://www.chem.arizona.edu/tpp/chemthink/resources/U1_M2/pt.html
that are delocalized during bonding is frequently the same.
LET’S THINK A Periodic Trend?
Consider the molecules depicted in Figure 2.19:
• Analyze the structure of these molecules and identify the apparent “bonding capacity” of each
of the different types of atoms that made up these molecules;
• Locate each of the different types of atoms in the Periodic Table.
Analyze whether there is any relationship between the position
of an atom in the Periodic Table and its bonding capacity. Do
you detect any particular trend?
Share and discuss your ideas with a classmate. CLICK TO DISPLAY
Molecular compounds result from the combination of atoms of nonmetallic

VALENCY elements. The bonding capacity of these types of atoms, also called its “valence,” is
4 3 2 1 0 highly correlated to their location in the Periodic Table (Figure 2.20). For example,
all atoms from the so-called halogen group or family (i.e., F, Cl, Br, I) commonly
have a valence equal to one: they form a single bond when they combine with
other atoms. This common valence for atoms in the same group (column) in the
Periodic Table could somehow be expected given that group arrangements in this
table are based on similarities in chemical reactivity. Simply put, atoms in a given
group tend to chemically combine in the same proportion with atoms in other
groups in the Periodic Table. Atomic properties that vary regularly across a group
(column) or a period (row) in the Periodic Table are called “periodic properties,”
and valence is thus an example of this type of regular behavior. The recognition of
Figure 2.20 Valence of non- periodic properties is of great value in chemical thinking, because they allow us to
metallic atoms. predict the physical and chemical properties of substances.
Atoms of nonmetallic elements tend to exhibit a fixed valence. However, there

are exceptions and we may find molecular compounds that deviate from the ex-
pected patterns. These deviations from the regular periodic trend are more com-
mon in atoms with larger number of electrons in any given group, for example
in sulfur (S) versus oxygen (O) atoms, or in phosphorus (P) versus nitrogen (N)
atoms. Despite the existence of exceptions, the recognition of bonding patterns
greatly simplifies the determination and prediction of the molecular structure of
chemical compounds.
Combining Information LET’S THINK

The recognition of common bonding patterns of the atoms of nonmetallic elements help
us reduce the number of possible options when trying to infer the molecular structure of
a chemical compound based on experimental data. Let us assess your ability to apply this
information in the characterization of the structure of a molecular compound produced by
our own body.
• The analysis of various human secretions reveals the presence of a chemical compound
that seems to have antimicrobial properties. The elemental composition of this com-
pound obtained by combustion analysis is 40.00% C, 6.71% H, and 53.29% O. What
is the empirical formula of this molecular compound?
• Use the information from the mass spectrum of this compound to derive its molecular
formula.
• Use the information from the MS and 100
IR absorption spectra of this com- 80

Relative Abundance
pound , together with your knowl-

edge about common bonding pat- 60
terns, to propose a likely molecular
40
structure for this substance.
• Clearly show how your proposed 20
structure justifies the presence of 0
major absorption bands in the IR 0 10 20 30 40 50 60 70
spectrum. m/q
• Based on your proposed molecular

structure, propose different structures
0.8
for the ions that led to the MS peaks
with more than 10% relative abun- C-H
Transmittance
0.6
dance. stretch
0.4
• Can you think of a different molecu- C-C
lar structure that may produce similar 0.2
O-H C=O C-O
experimental data? What would you stretch stretch stretch
do to decide what is the actual mo-
3000 2000 1000
lecular structure of this compound? Wavenumber (cm-1)

Atomic Patterns
Covalent bonding is driven by the delocalization of some electrons within a bond
between two atoms. Thus, to understand why atoms tend to exhibit a fixed valence,
and why this bonding capacity is a periodic property, we need to explore electron
Diffracted
distributions within atoms. This is not an easy task as we cannot determine with
rays
exact precision where electrons are and how they are moving at any point of time
Derivative from Images from Life Sciences Foundation
inside an atom. Thus, we need to rely on indirect measurements that can help us
X-ray beam
infer electron configurations --this is, how electrons distribute in both space and
energy levels within atoms.
As a first step, we may want to pay attention to the size of different atoms. This
information may be useful in comparing the probability of finding electrons in
certain regions of the space in different atomic systems. According to our current
model of an atom, atomic size is not a well defined quantity because electrons are
constantly moving through empty space and we cannot determine with precision
where they are at all times. However, chemical scientists have devised strategies to
locate the average position of atomic nuclei in molecules and ionic networks (see
Diffraction Pattern
Figure 2.21); this information can then be used to quantify atomic sizes. For ex-
ample, if we define the bond length (d) as the distance between the atomic nuclei
of two bonded atoms, we can assume that this distance should have a value close
to the result of adding the atomic radius (r) of each of the atoms. Thus, by mea-
suring the length of bonds between similar and different types of atoms in many
molecules, we can start building a scale of atomic sizes based on average values.
The set of atomic radii determined following this procedure are called “covalent
d = 2 r(C) = 0.153 nm atomic radii” to distinguish them from values determined by other approaches.
Figure 2.22 includes the values of the covalent atomic radii for several atoms
Figure 2.21 X-ray crystallogra-
phy is commonly used to deter- as determined using X-ray crystallography. As you can see in this figure, atomic
mine bond lengths. Each crystal-
lized substance diffracts X-ray
size also exhibits a periodic trend: the size of the neutral atoms decreases as the
radiation in different ways. The atomic number Z increases within a period and it increases as the atomic number
analysis of the diffraction pat-
tern provides information about increases within a group. This periodic pattern is commonly summarized stating
distances between atoms.
that atomic size increases as we move from right to left across a period (row) and from
top to bottom within a group (column) in the Periodic Table.
Group 1A Group 2A Group 3A Group 6A Group 7A
(1) (2) (13) (16) (17)
Li Be B O F
128 96 84 66 57
Na Mg Al S Cl
166 141 121 105 102
Figure 2.22 Atomic covalent K Ca Ga Se Br

radii in picometers (pm). 203 176 122 120 120
1 pm = 1 x 10-12 m = 1 x 10-3 nm.
The periodic trend in atomic size can be seen more clearly in

Figure 2.23a where we plot the covalent atomic radii as a func- Rb
K
tion of the atomic number (Z) for atoms with up to 38 protons
in the atomic nucleus. This graph elicits a pretty regular pattern Na
in the evolution of the atomic radius as the number of protons Li
and electrons increases. The pattern repeats systematically at val-
Ar Kr
ues of Z where a new period starts. This periodicity suggests the
existence of distinctive regularities in the spatial distribution of Ne
electrons for atoms in the same group of the Periodic Table. He a)
A similar behavior is observed when analyzing the minimum
energy needed to remove an electron from the neutral atoms of
an element in gaseous state. This energy, often called first ioniza-
tion energy (EI) or first ionization potential, induces the follow- He b)
Ne
ing process in a given substance M:
Ar
Kr
M(g) M+(g) + e-
The energy required to ionize the atoms of a substance can be

measured by bombarding a gaseous sample with fast-moving Li Na K Rb
electrons of known kinetic energy and analyzing the amount of
energy that these electrons lose during the collision. These types
of experiments lead to results like those summarized in Figure
2.23b where we show the first ionization energy (in kJ/mol) as a
Figure 2.23 a) Covalent
function of atomic number for atoms with up to 38 protons in the atomic nucleus. atomic radii (in pm) as a func-
tion of atomic number (Z);
In this case, the first ionization energy increases as we move from bottom to top within b) First ionization energy EI
a group (column) and from left to right across a period (row) in the Periodic Table. The (in kJ/mol) as a function of Z.
periodicity of this property is also evident as the same pattern repeats at values of
Z where a new period starts.
Back to Modeling LET’S THINK

The experimental data for the atomic radii and the first ionization energies summarized in Figure
2.23 suggest the existence of some sort of pattern in the spatial and energetic distribution of
electrons within atoms as a function of atomic number. If you had to build a model to explain or
justify the periodic behavior of these two properties:
• How would you explain that atomic radii decreases as we move from left to right within a
period in the Periodic Table even when more electrons are present in the system?
• How would you explain the big jump in atomic radius as we reach values of Z where a new
period begins?
• How would you explain the increase in first ionization energy as the atomic number in-
creases within a period?
• How would you explain the drastic decrease in the first ionization energy as we reach values
of Z where a new period begins?
Share and discuss your results and ideas with a classmate. Build drawings to represent the type of
electron distribution in space and energy levels that would explain the observed behaviors.
At a first level of approximation, we can make sense of the experimental data

for atomic radii and first ionization energy by conceiving electrons as distributed
in “shells” within atoms. A shell defines both a region in space where it is most
likely to find an electron as well as the total energy that such an electron is likely
to have. Thus, for example, electrons with the lowest energy in an atom are likely
to be those that are moving close to the atomic nucleus, occupying the first shell.
Higher energy electrons are more likely to be found farther away from the nucleus,
moving across a volume that corresponds to an outer shell. According to this “shell
model of an atom,” different shells correspond to different quantized energy states
in which several electrons may exist (see Figure 2.24). To explain the observed
periodicity in the behavior of atomic radii and first ionization energy the model
assumes that there is a limit to the number of electrons that can be found in the
same quantum energy state (or the same shell).
ET
H He Li Ne Na
0
First Ionization
Energy
Figure 2.24 Distribution in To better understand the assumptions about atomic structure made in the
energy and space of electrons
in different quantum states ac- shell model, let’s use this model to try to explain the experimental data summa-
cording to the shell model of
the atom. The zero of energy rized in Figure 2.23. The simplest known atom, the hydrogen atom has one single
in this figure corresponds to electron that we can assume occupies the first atomic shell (n = 1). It is followed by
electrons detached from the
atom. the He atom that has one additional electron and proton. To explain the observed
increase in ionization energy EI and the decrease in atomic radius r as we move
from hydrogen to helium in the Periodic Table, we assume that both electrons
in the He atom also occupy its first atomic shell. However, the energy of this
quantized state in a He atom should be lower than in a H atom because a larger
nuclear charge will exert a stronger attractive force on each electron, keeping them
closer to the nucleus and lowering their potential energy. A stronger attractive
force on each electron will reduce the likelihood of these particles moving too far
away from the nucleus, reducing the average atomic size. It also implies that more
energy will be required to remove one of these electrons from the atom.
The sudden increase in atomic radius and decrease in first ionization energy
as we move from helium to lithium can be justified if we assume that only two
electrons can occupy the first atomic shell. Thus, the third electron in a Li atom
is forced to move in a region of the space farther away from the nucleus where its
total energy will be higher (second atomic shell, n = 2). In consequence the size of
the atom increases and the energy required to ionize it is lower. As we move across
a period in the Periodic Table, electrons occupy the second atomic shell until it is
full. Based on the experimental data that we have, that seems to occur when eight Atomic Maximum
electrons are in that state (the next drastic change in atomic size and first ioniza- Shell # of e-
tion energy occurs when Z =11, for the sodium atom). Addition of electrons to
n=1 2
the same shell does not result in a larger atomic size because the more positive
nuclear charge pulls those electrons towards the nucleus; this stronger attractive n=2 8
force is also responsible for the higher ionization energy values. Major changes n=3 8
in this pattern only occur when a shell is full and electrons are forced to occupy n=4 18
a higher energy shell. Thus, the maximum shell occupancy can be inferred from n=5 18
experimental data such as that shown in Figure 2.23. This analysis leads to the re-
sults summarized in the table shown to the right, where different shells have been
n=6 32
assigned the label n = 1, 2, 3,...
The shell model of the atom does a pretty good job at explaining the general
trends in several atomic properties, such as atomic size and first ioniza- Detector
tion energy. However, it provides limited explanation for anomalies or
By Bvcrist (Own work) [Public domain]

Ionization
deviations from the general pattern and fails to account for experimental Energy

X-ray
results for other atomic properties, such as the energy needed to remove photons
EI = h n - Ek
not just one electron but many electrons from a single atom. This mth ion- E=hn Ejected
Electrons
ization energy, where m is the number of electrons that are ejected from E = Ek
an atom, can be measured using an analytical technique called photoelec-
tron spectroscopy (PES). This method relies on the use of several types
of EM radiation, particularly X-rays in those cases in which the goal is to
remove all electrons from an atom. The ionization energy is determined Figure 2.25 In PES, ioniza-
by bombarding atoms with photons of known energy hn and measuring the ki- tion energies are calculated by
taking the difference between
netic energy of the ejected electrons (Figure 2.25). The more weakly the electron the energy of incoming pho-
tons and ejected electrons .
is held to the atom, the more kinetic energy it will have when ejected. Inner shell
electrons (referred to as core electrons) are held much more tightly to the nucleus
so it usually takes high energy x-ray photons to remove them from an atom.
Adjusting the Model LET’S THINK
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M2/pes.html
X-ray PES can be used to determine how many electrons exist in a given energy state in an atom.
These electrons are expected to have similar ionization energies. A plot of number of electrons as
a function of ionization energy is then indicative of the number and distribution of atomic shells.
• Based on your understanding of the shell model of the atom, predict the structure of the
PES spectra for all of the atoms with an atomic number Z ≤ 11. Use the PES spectrum of
Li atoms shown on this page as a guide for your
predictions;
• The interactive tool associated with this activity
CLICK TO PLAY
displays the actual PES spectra for atoms with

Z ≤ 20. Use the tool to verify your predictions;
• Based on your analysis, discuss how you pro-
pose to change the shell model of the atom to
better explain these experimental results.

As you have seen in the previous activity, the results from PES correlate well
with the predictions of the shell model of the atom for atoms with an atomic num-
ber Z up to four. However, for higher values of Z unexpected deviations occur.
Electrons in the second shell, which we assumed could be occupied by a maximum
of eight electrons, seem to be arranged into two “subshells:” one subshell that can
hold up to two electrons and another subshell with a maximum occupancy
Atomic Atomic Maximum of six electrons. This pattern repeats itself for atoms in the third period in the
Shell Subshell # of e- Periodic Table. PES analysis of atoms with a larger atomic number reveals
n=1 s 2 the existence of other subshells, some of them with a maximum capacity of
s 2 10 electrons and others that can be occupied by up to 14 electrons. Based
n=2 on these experimental results, the shell model of an atom can be modified
p 6
to allow for the existence of shells and subshells in which electrons can be
s 2 distributed as shown in the table to the left. In this table, the labels n=1, 2,
n=3 p 6 3,... are used to distinguish one shell from another, while the letters s, p, d,
d 10 and f are used to label subshells with a maximum occupancy of 2, 6, 10, and
s 2 14 electrons, respectively.
The existence of atomic subshells is predicted by the modern quantum
p 6
n=4 mechanical model of an atom. In fact, this model reveals an even more com-
d 10 plex distribution of electrons within atoms. According to this model, sub-
f 14 shells that can accommodate more than two electrons (subshells p, d, f ) are
actually composed by “sub-subshells” each of them with a maximum capacity
of two electrons. These sub-subshells are traditionally called “orbitals” and thus
we say that the s subshell is equivalent to one “s” orbital, the p subshell contains
three “p” orbitals, the d subshell contains five “d” orbitals, while the f subshell is
composed of seven “f ”orbitals. As it was the case for the terms shell and subshells
in the other models that we have discussed, orbitals should not be thought of
as containers where electrons are placed. Rather, orbitals define energy states in
which electrons can exist and the probability densities of finding these electrons in
certain regions of the space. For example, an electron in a 1s orbital is in the lowest
energy state of an atom and it is likely to be found in a spherical region close to the
atomic nucleus. On the other hand, an electron in a 2p orbital will have a higher
energy and will most likely be found farther away from the nucleus. Additionally,
our current model of the atom predicts that the distribution in space of electrons
in 2p states is not the same in all directions (see Figure 2.26).
E d
p
s
Derivative from image by Florian Marquardt (Own work) [Share Alike 3.0]
n=3 3px 3py 3pz

3dxy 3dxz 3dyz 3dx2-y2 3dz2
y x z y z
3s
x z y x y
z y x z x
n=2
2px 2py 2pz
2s
x y z
Figure 2.26 Each of these images represents the probability den-
z x y sity for electrons in atomic orbitals at different energy levels. The
lighter the color in each of these images, the higher the probabil-
n=1 y z x ity of finding the electron in those regions of space. 3D axes are
shown to indicate the particular perspective from which each image
1s is drawn. Notice that probability densities associated with the same
y types of orbital (s, p, d) have similar symmetries.
x
z
Electrons in an atom in its ground state are expected to occupy the lower en-
ergy levels available in the system. For example, in a hydrogen atom the only elec-
tron will be in the 1s energy level. The ground state electron configuration of this
atom is then said to be 1s1, where the superscript is used to represent the number
of electrons in a particular energy level. The electron configurations of subsequent
atoms in the Periodic Table can then be expressed in the following way:
Electron Configuration
Atom
Spectroscopic Notation Noble Gas Notation
He (Z = 2) 1s 2
[He]
Li (Z = 3) 1s 2s
2 1
[He]2s1
Be (Z = 4) 1s22s2 [He]2s2
B (Z = 5) 1s22s22p1 [He]2s22p1
Ne (Z = 10) 1s22s22p6 [Ne]
Na (Z = 11) 1s 2s 2p 3s
2 2 6 1
[Ne]3s1
You may wonder how the relative energy of different atomic orbitals is deter-
mined. How do we know, for example, that the 2s orbitals are lower in
energy than the 2p and thus are filled up first? The answer is provided by 1s
the analysis of experimental data, such as ionization energies from PES, 2s 2p
together with the application of the quantum mechanical model of the 3s 3p
atom. This information leads to the orbital filling sequence summarized
4s 3d 4p
in Figure 2.27. You may have also noticed that electron configurations
in the so-called spectroscopic notation in the table above can be short- 5s 4d 5p
ened by using a noble gas notation. In this latter format, the bracketed 6s 4f 5d 6p
chemical symbol of the noble gas atom that precedes the atom of inter- 7s 5f 6d 7p
est in the Periodic Table is used to represent that part of the electron
configuration that is similar between the two atoms. This part of the electron con- Figure 2.27 Orbital filling se-
quence based on the relative
figuration happens to represent the distribution of electrons in those inner shells energies. Electrons always oc-
cupy the lowest energy levels
that are already full --it describes the distribution of the so-called “core” electrons available.
in an atom.
Patterns in Electron Configurations LET’S THINK

The analysis of the electron configuration of atoms in the same group in the Periodic Table leads
to the identification of interesting and useful patterns.
• Build the electron configurations, using both spectroscopic and noble gas notations, of the
following types of atoms: C, N, O, F, Mg, Al, Si, P, S, Cl, and Ar. You may use the filling
sequence summarized in Figure 2.27 to guide your work.
• Compare the electron configurations of atoms in the same group in the Periodic Table.
What similarities do you observe?
• Compare the electron configurations of atoms in the same period of the Periodic Table.
What similarities do you notice?

Atoms in the same group of the Periodic Table have similar distributions of
electrons in their higher energy states. This can be seen by comparing electron
configurations in the noble gas notation. For example, for the Li atom we have:
[He]2s1 while for the Na atom we have: [Ne]3s1. The orbital occupation is identi-
cal for those energy levels outside the core of each atom. Electrons in these more
external and higher energy orbitals are called “valence” electrons. Thus, according
to our analysis, atoms in the same group of the Periodic Table have similar valence
electron configurations. These similarities are made explicit in Figure 2.27, where
we show the prototypical electron configuration of the valence electrons of atoms
in each of the different groups in the Periodic Table:
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
s1 s2 s d s d s d s d s d s d s d s2d8 s2d9 s2d10 s2p1 s2p2 s2p3 s2p4 s2p5 s2p6
2 1 2 2 2 3 2 4 2 5 2 6 2 7
1
2 [Ar] 4s23d104p2
3
4
5
The periodicity in valence electron configurations greatly simplifies the con-
Figure 2.28 Valence elec-
tron configurations for the struction of full electron configurations for different atoms. Imagine that we want-
germanium atom (Ge) us-
ing noble gas notation.
ed to build the ground state electron configuration for a germanium (Ge, Z = 32)
atom. The first step is to localize the period (n = 4) and group (14) in which this
atom is in the Periodic Table. The second step is to identify the noble gas atom pre-
ceding Ge in the table, in this case argon (Ar, Z = 18), which we can assume will
have a similar electron configuration to that of the core electrons in Ge. The final
step is to add the electron configuration of the 14 remaining electrons, which can
be deduced from the valence electron configuration of the preceding atoms in the
same period as the Ge atom and from the general structure of the valence electron
configuration of those atoms in the same group (s2p2). Thus we have:
Ge : [Ar] 4s23d104p2
According to the information summarized in Figure 2.27, valence electrons oc-

cupy s and p orbitals in the shell with the same label as the period in which the
atom is located (period 4 in the case of the Ge atoms). However, d and f orbitals
from inner shells will be occupied before than the outer p orbitals.
LET’S THINK Predictions
The construction of electron configurations allows us to predict the properties of chemical substances:
• Build the electron configuration of a bromine atom and sketch its expected PES spectrum.
Share and discuss your ideas with a classmate, and justify your reasoning.
Understanding Bonding
Current chemical models of atomic structure allow us to make sense of the physi-
cal and chemical properties of substances. In particular, as we will see in the fol-
lowing paragraphs, they provide a basic explanation to the observed periodicity
in the bonding capacity (valence) of different types of atoms. Understanding how
atoms bond to each other is of central importance for predicting the three dimen-
sional structure of molecules and the nature of the interactions among them.
Explanations and predictions about chemical bonding can be greatly simpli-
fied if we assume that electrons in atoms can be divided into two major groups.
On the one hand we have core electrons that occupy the low energy, inner orbitals
in atoms. These types of electrons are most likely to be found in regions of space
close to the atomic nucleus and thus we can assume they are not significantly
perturbed by the presence of other atoms. On the other hand, we have valence
electrons which occupy the higher energy, outer orbitals and are significantly af-
fected by neighboring particles. A central idea in chemistry is that the formation of
different types of chemical bonds can be understood by paying attention to the properties
of valence electrons in atoms. To illustrate the power of this idea, let us reanalyze the
formation of covalent bonds between atoms of nonmetallic elements.
When two atoms get close to each other, electrostatic interactions between
protons in one atom and valence electrons in the other atom will attract electrons
to the space between the atoms. This electron delocalization changes the distribu-
tion of the valence electrons in each atom and lowers their average energy. Delocal-
ization favors the formation of chemical bonds because the energy of the bonded
particles tends to be lower than that of the isolated atoms. From this perspective,
the more valence electrons are delocalized through bond formation, the lower the Electron Density
energy of the molecule that may form. However, electron delocalization is con-
strained by the number of available unfilled valence orbitals that the delocalized Low High
electrons can occupy.
Electrons that get delocalized during bonding occupy valence
orbitals that are shared by the bonded atoms (bonding orbitals).
From this point of view, they can be thought as belonging to both
atoms. Therefore, for bonding to occur, atoms should have unfilled
By Dvaid Young & James F. Harrison

valence orbitals that can be occupied by the delocalized electrons.
Given that the formation of bonding orbitals lowers the energy of
the system, it is likely that atoms will form as many covalent bonds
as unfilled electron states are available in their valence shells. Let’s
consider, for example, the case of an oxygen atom with an electron
configuration [He]2s22p4. Given that the p subshell has a maxi-
mum occupancy of six electrons, we can expect an oxygen atom
to induce the delocalization of 6 - 4 = 2 electrons when bonding
with other atoms. Oxygen atoms are then likely to form two bonds
when interacting with atoms of other nonmetallic elements. On the other hand, a
Figure 2.29 Electron density
hydrogen atom with an electron configuration 1s1 will likely form one single bond map for the water molecule.
Bonding has a strong effect
because its valence shell (s orbital) can only hold a maximum of two electrons. on the distribution of valence
Therefore, the most stable molecule that can form during the interaction of one electrons in the system.
oxygen atom with hydrogen atoms is H2O, where one O atom is linked by a single
bond to two H atoms (Figure 2.29).
LET’S THINK Predicting Structural Formulas
Based on the electron configurations of these atoms: H, C, N, Cl, and S, predict the structural
formula of the molecules that will form when combining the following pairs of atoms: H and H,
H and C, H and N, C and Cl, S and Cl, and Cl with Cl.
The valence shell of nonmetallic atoms can be occupied by a maximum of two

electrons in the case of hydrogen and by 2 + 6 = 8 electrons for all the other atoms
of nonmetallic elements. According to our model, their bonding capac-
VALENCE ity (valence) will then be given by the numerical difference between the
4 3 2 1 0 maximum occupancy of their valence shell and the actual number of va-
s2p2 s2p3 s2p4 s2p5 sp
2 6 lence electrons in the isolated atom. As a result of covalent bonding, each
atom in a molecule can be thought of as having a full valence shell. Thus,
it is common to say that the most stable structures that are formed when
atoms bond to each other are those in which each atom has a full valence
electron shell. Given that for most nonmetallic atoms a full valence shell
corresponds to eight electrons, this statement is known as the octet rule.
The octet rule is a useful heuristic to predict the structure of molecular
compounds, but it must be applied and interpreted with caution. For ex-
ample, it is common to think that the octet rule implies that atoms bond
to each other because they “want” to get a full valence electron shell. It
is also common to assume that the octet rule is an unbreakable principle
that controls the behavior of all atoms. However, these simplifications and
over-generalizations often lead people astray in explaining or predicting
the properties of many chemical compounds. Atoms do not have wishes
Figure 2.30 The most com- or desires and their behavior is highly influenced by the forces acting on them.
mon valency of these set of
atoms is given by the numeri- Despite regularities in their properties, they may deviate from the regular patterns
cal difference between the
maximum occupancy of their depending on the nature of the particles with which they interact. Thus, rather
valence shell and the actual
number of valence electrons in than blindly applying a rule to solve any type of problem, it is more effective to pay
the isolated atom. attention to the main factors that control chemical bonding. These factors may be
summarized in the following form:
Factor 1. Bonding is a stabilizing process for atoms with unfilled valence or-
bitals because some electrons gain access to lower energy states. In general, the
more electrons occupy those states, the lower the energy of the system and the
greater its stability relative to that of the isolated atoms.
Factor 2. The number of electrons that gain access to lower energy states is con-
strained by the number of unfilled valence orbitals in the bonding atoms. Because
there is a limit to the number of electrons that can exist in a given energy state,
there will be a limit to the number of bonds that an atom can form. Therefore the
bonding capacity of an atom (its valence) will likely be determined by the number
of available unfilled valence orbitals.
If electron delocalization into bonding orbitals lowers the energy of atomic sys-
tems, one may wonder why more bonds are not formed by delocalizing electrons
in the unoccupied higher energy orbitals of the bonded atom. In general this does O
not happen because the energy increase required to place electrons in those states is
larger than the energy reduction coming from electron delocalization. However, in HO S OH
systems involving large nonmetallic atoms the energy cost of promoting electrons
to higher energy states is considerably lower; thus, it is not uncommon for these O
types of atoms to form molecules in which the number of bonds per atom deviates Figure 2.31 Sulfur atoms
from the common patterns. For example, phosphorus frequently exhibits a valence form 6 bonds in molecules
of sulfuric acid (H2SO4).
of 5 instead of 3, and sulfur forms important compounds in which these types of
atoms have a valence of 6 instead of 2 (Figure 2.31).
Breaking the Rules LET’S THINK

Several molecules that play an important role in the metabolism of living organisms exhibit
bonding patterns that deviate from those most commonly observed in chemical compounds.
• Based on your analysis of atomic electron configurations, which of the following stable mol-
ecules are likely to exhibit unusual bonding patterns: O2, N2, CO, CO2, NO, CH4, SO2?
The formation of covalent bonds is driven by the delocalization of electrons

into lower energy bonding orbitals shared by the bonded atoms. As is the case
with all orbitals, a maximum of two electrons can occupy those energy states.
This is why a single covalent bond tends to involve the delocalization of only two
electrons. In general, the formation of a single bond leads to the delocalization of
one electron from each of the participating atoms. However, this does not need
to be the case in all situations and deviations from this behavior may also result in
unusual bonding patterns.
Electron Spin
The limit in electron occupancy of atomic and molecular orbitals has a large im-
pact on the molecular structure of chemical compounds. Experimental data sug-
gest that this phenomenon is due to an intrinsic property of electrons that con-
straints the number of these particles that can simultaneously occupy the N S
exact same region of space. This intrinsic property is called spin and can
be conceptualized as a measure of the rotational motion of an electron
on its own axis. Analyses of the behavior of electrons in the presence of
magnetic fields suggest that an electron spins at a fixed, invariant rate, and
that all electrons spin at the same rate. However, an electron may only
spin in one of two possible directions: it can rotate clockwise (denoted ↑
or with the value +1/2) or counterclockwise (denoted ↓ or with the value
S N
-1/2). This implies that an electron’s spin is a quantized property. Given
that an electron is a charged particle, its spin gives it magnetic properties. -1/2 +1/2
In fact, spinning electrons can be conceptualized as subatomic magnets that will Figure 2.32 Classical repre-
sentation of electron spin.
be subject to forces in the presence of a magnetic field (Figure 2.32).
Wolfang Pauli introduced the idea of electrons having a quantized spin to

make sense of the electron configurations and bonding capacities inferred from
the type of experimental data discussed in this module. In particular, he proposed
that no two electrons with the same properties could occupy the same orbital
simultaneously (The Pauli Exclusion Principle). The only way this could happen
was if each electron had a different spin. Given that electrons can only exist in two
possible spin states, no more than two electrons can simultaneously occupy the
same quantum state described by an orbital.
Pauli exclusion principle implies that electrons with the same spin in an atom
will be found occupying different regions of the space. This helps reduce the po-
tential energy of the system by keeping electrons far from each other and also al-
lowing them to get closer to the nucleus. From this perspective, pairing electrons
with opposite spin into the same orbital has an energy cost. Pauli’s principle also
requires that for two electrons to occupy the same bonding orbital they should
have opposite spins. This means that in order for a covalent bond to form, the
energy needed to pair up the electrons should be smaller than the energy gained
by delocalizing the electrons into the bonding orbital.
Given that delocalization of electrons into bonding orbitals lowers the aver-
Figure 2.33 The molecule of age energy of the interacting atoms, one can expect available bonding orbitals to
nitrogen monoxide is a radi- be filled with as many valence electrons as possible. However, there are situations
cal. Chemical bonds involving
less than two electrons are in which the number of valence electrons may be an odd, rather than an even,
commonly represented with
dashed lines. number and some bonding orbitals may be occupied by one single electron. These
types of chemical species are called radicals and tend to be extremely reactive; they
have unfilled valence orbitals that will induce the delocalization of electrons from
other species. Although radicals are not very stable particles, they play a central
role in the chemistry of the atmosphere and of our own bodies (Figure 2.33).
LET’S THINK Quantum Explanations
The formation of covalent bonds between atoms of nonmetallic elements is largely controlled by
“quantum” phenomena such as energy quantization, electron delocalization, and electron spin.
• Discuss what you understand by each of these concepts. What do they mean to you? How
would you explain each phenomenon in your own words?
• Discuss how each of these phenomena determines or affects the formation of covalent bonds
between atoms of nonmetallic elements.
• Self-assess the extent to which you can use arguments based on these three phenomena to
explain why:
a) It is necessary to invest energy to separate two bonded atoms;
b) Hydrogen gas is made up of H2 molecules while Helium gas is made up of single atoms;
c) It takes more energy to separate the two bonded atoms in a N2 molecule than in a O2
molecule;
d) A chemical compound such as SF6, used as a contrast agent for ultrasound imaging, can be
stable;
e) The chemical species OH formed in our atmosphere is highly reactive.

FACING THE CHALLENGE with oxygen in compounds such as silica (SiO2).

Therefore, although Si atoms have a high bond-
ing capacity, their reactivity with oxygen limits the
Amazing Carbon number of silicon compounds that are stable in
The number of known chemical substances, both contact with our planet’s atmosphere.
natural and synthetic, exceeds 50 million and A third important property of carbon atoms is
continues to grow exponentially. Many of these their ability to covalently bond to each other and
substances are molecular compounds made up of create linear chains or rings of different sizes. This
carbon atoms covalently bonded to other carbon property opens the door for the synthesis of myri-
atoms and to atoms of different nonmetallic ele- ads of different compounds made up of molecules
ments, such as hydrogen, nitrogen, and oxygen. that not only differ in their chemical composition
Among these substances we find the core compo- but in their three dimensional structure. Carbon
nents of living organisms, including atoms’ capacity to form chains partly
proteins and nuclei acids (DNA). depends on its high valence. How-
Why is carbon such a “prolific” ele- ever, atoms such as nitrogen, with
ment? Could it be possible for other a valence equal to three, and oxy-
types of chemical elements to serve gen, with a valence of two, could,
as the basis for life in other planets? in principle, also form chain-like
One of the properties that makes structures. Why does this not hap-
carbon atoms so special is their pen? The reason lies on the relative
bonding capacity. With a valency strength of multiple bonds between
equal to four, carbon atoms have the these different types of atoms.
highest bonding capacity among the Carbon atoms can form single,
atoms of nonmetallic elements. A double, or triple bonds among them-
high valence facilitates the synthesis selves. However, the delocalization
of a larger diversity of compounds in of electrons into single bonds among
which carbon bonds to different par- many C atoms leads to a larger de-
ticles. However, other types of atoms crease in energy than the formation
in the same group as carbon in the of double and triple bonds between
Periodic Table, such as silicon (Si), a few atoms. From this perspective,
have the same valence. Why is it then DNA
the synthesis of chain-like structures
that they do not react to produce as Molecule is energetically favored. On the con-
many different types of compounds trary, a double bond between two
as carbon does? The answer to this question has to oxygen atoms is more energetically favored than
do with the reactivity of carbon and oxygen atoms. the formation of two single bonds with other oxy-
Although carbon atoms react with oxygen at- gen atoms, and a triple bond between two nitrogen
oms to form relatively strong bonds, these bonds atoms leads to a larger energy reduction than the
are similar in strength to the bonds that carbon creation of three single bonds with other N atoms.
atoms form with atoms of other nonmetallic ele- Thus, rather than long chains or rings, oxygen and
ments. In a planet with a high concentration of nitrogen atoms are most stable as diatomic mol-
elemental oxygen in the atmosphere, this prop- ecules, O2 and N2, with double and triple bonds.
erty of the carbon atoms has been critical to the Carbon compounds have other distinctive
development of life. In particular, it has allowed properties that make them unique, particularly in
for the formation of many compounds of carbon the way in which they interact with water. How-
besides CO and CO2. Silicon atoms, on the other ever, to understand these phenomena we first need
hand, form such strong bonds with oxygen atoms to explore the three dimensional geometry of mol-
that most of the silicon in our planet is combined ecules, as discussed in the following module.
Let’s Apply
What is in your Breath?
Breath analysis of mouth air can serve many purposes, from detecting alcohol levels in blood to
monitoring body fat consumption as part of dieting. It is also useful in understanding and treating
mouth diseases, such as halitosis (bad breath). Let’s see what can you infer from experimental data
for mouth air from a patient with this disease.
Potential Structures
Breath analysis of mouth air using GC/MS reveals the presence of three ma-
jor compounds assumed to be responsible for halitosis (bad breath). A compari-
son search in a MS database allows to identify the substances as 1) H2S, 2) CH4S, and
3) C2H6S.
1 1
• Propose a molecular structure for the first two com-

pounds. Justify your decisions based on the electron 2 2
configurations of each of the atoms involved.

3
Share and discuss your ideas with a classmate, and clearly 3

Room Air Mouth Air Saliva
The Third Compound
Based on your previous analysis and the additional spectroscopic information shown below:
• Propose a molecular structure for the third compound, C2H6S.
100 1.0
80 0.8
Relative Abundance
Transmittance
60 0.6
C-H C-H
40 0.4 stretch
bend
20 0.2 C-S
stretch
0
10 20 30 40 50 60 70 3000 2000 1000
Deathly Smells
Chemical compounds responsible for bad breath are the waste products of the anaerobic respi-
ration of tongue bacteria. These organisms not only produce volatile sulfur compounds such as
the three substances analyzed on the previous page, but also chemical compounds responsible
for the bad smell of dead animals. Combustion analysis of one of these substances reveals the
following chemical composition: 54.49% C, 13.72% H, 31.79% N. The MS and IR spectra
of this substance are shown below.
100 1.0

80
NH2 C-H
Relative Abundance
0.8
Transmittance
60
bend bend
0.6
C-C
40 stretch
0.4
20 C-H C-N
0.2 stretch stretch
0
0 20 40 60 80 100 3000 2000 1000
• Determine the empirical and molecular formulas of this chemical compound;

• Assuming that all the atoms in this compound bond to each other according to com-
mon bonding patterns, propose one potential structure for this chemical substance.
Show how your proposed structure could lead to the MS fragmentation pattern and IR
absorption bands in the spectra above.
• Explore whether there are other molecular structures involving the same types and num-
ber of atoms that could generate similar MS and IR spectra.
Mouth Wash
Mouth washes used to prevent bad breath often contain antibacterial agents
such as ClO2. This chemical substance is also used for bleaching wood pulp in
the paper industry and for disinfecting water.
• Based on the ground state electron configurations of the Cl and O atoms,

discuss whether a ClO2 molecule can be expected to exhibit common
bonding patterns. If it does, propose a potential molecular structure. If it
does not, explain how such a molecule may be stable.
• Discuss whether you would expect this chemical substance to be highly
reactive with other chemical species. How would low or high chemical
reactivity be useful for a substance used as an antibacterial agent?
Let’s Apply
A Different Universe
Imagine that you were able to communicate with aliens from a parallel universe. Among the in-
formation that you manage to exchange and translate into our scientific language, there is a table
and some other data for atomic and molecular properties in their universe. Your task is to use the
available evidence to develop a chemical model of the atom in this parallel universe.
Atomic First Ionization Atomic First Ionization

Symbol Z Symbol Z
Radius (pm) Energy (kJ/mol) Radius (pm) Energy (kJ/mol)
A 1 37 1312 W 23 174 509.8
B 2 32 2372.3 X 24 144 553.1
C 3 29 3200 Y 25 136 578.8
D 4 134 520.2 Z 26 127 579.9
E 5 90 700.5 AA 27 125 583.9
F 6 82 800.6 BB 28 124 637.3
G 7 77 1086.5 CC 29 123 665.5
H 8 75 1202.3 DD 30 122 680.4
I 9 73 1413.9 EE 31 121 697.1
J 10 71 1682 FF 32 119 720.2
K 11 69 2080.7 GG 33 118 735.3
L 12 65 2500 HH 34 117 750.2
M 13 154 495.8 II 35 116 759.6
N 14 130 520.7 JJ 36 115 764.3
O 15 118 577.5 KK 37 115 776.4
P 16 111 786.5 LL 38 114 850.2
Q 17 106 870.8 MM 39 110 929.2
R 18 102 999.6 NN 40 109 1205
S 19 99 1251.2 OO 41 108 1451
T 20 ?? ?? PP 42 107 1502
U 21 95 1750 QQ 43 211 403.2
V 22 196 418.8 RR 44 199 475.8
Your Model
Based on the information provided in the table, build a model of the atom in this parallel uni-
verse that can explain the experimental data. CLICK TO USE
• Would a shell model allow you to explain the data?

How many shells would you propose? How would
electrons be distributed in the different shells?

Additional Cues
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M2/pesp.html
Among the data that you receive there are results of PES analysis of some of the chemical ele-
ments in the parallel universe. The information is summarized in the interactive tool associated
with this activity.
• Would you need to introduce the idea of subshells to

better explain this data? Why? How many subshells
would you have to assume in each major shell? How
many electrons would occupy each sub-shell?

CLICK TO PLAY
Bonding Patterns
Atoms in the parallel universe form the following stable molecules: AB, JK, HJ, HK2, AK, JB,
HB2. Based on all of the information that you have:
• How many electrons would you suspect are shared during the formation of a single
covalent bond between two atoms in this Universe?
• Which atoms would you expect to have a similar valence? What would the value of the
bonding capacity be for different groups of atoms?
• What would the equivalent to the “octet rule” be in this other universe?
Predictions
Chemical models allow us to predict the properties of chemical substances. According to your
atomic model:
• How would you organize the different atoms into a “Periodic Table”?
• What would the electron configuration of atom “T” be based on its location in the Peri-
odic Table? (Create your own notation to represent electron configurations).
• Estimate the atomic radius and the first ionization energy of this type of atom.
• What would you expect the valence of atom “T” to be?
• Would you expect element “T” to exist as single atoms or as diatomic molecules?
• Predict the molecular formulas of the compounds formed when element “T” reacts with
elements Q, R, and S.
124
Predicting
Geometry
A central idea in chemistry is that the physical and chemical properties of molecu-
U2: MODULE 3
lar compounds are not only determined by the composition and connectivity be-
tween the atoms that make up their molecules, but also by the way in which these
atoms are distributed in space. Determining or predicting molecular geometry is
thus as important as establishing atomic composition and atom connectivity
in a molecular compound. Fortunately, these three molecular prop-
erties: composition, connectivity, and geometry are not
independent of each other and we can use infor-
mation about the chemical makeup and structure
of molecules to predict their geometry.
As we will discuss in this module, molecular
geometry is determined by the number and dis-
3D-Geometry
tribution of valence electrons in a molecule. Inter- Aspirin
actions between electrons influence how the atoms that Molecule
make up a molecule distribute relative to each other in
space. Therefore, the atomic and molecular models of matter that we have dis-
cussed in previous modules will become essential tools for prediction. Inferences
about molecular geometry are also greatly simplified by the identification of pat-
terns in the types of geometries that emerge from interactions between specific
numbers of valence electrons. The recognition of these patterns is particularly
useful in analyzing the geometry of large molecules with many different atomic
centers.
THE CHALLENGE Molecular Recognition

Many cellular processes in our body depend on the ability of some molecules
to “recognize” the molecular geometry of other molecules.
• How do you think molecular recognition works? How may it be impor-

tant in triggering or hindering important processes within cells?
This module will help you develop the type of chemical thinking that can help
you explain phenomena similar to that described in the challenge. In particular,
the central goal of Module 3 is to help you understand how to predict molecu-
lar geometry based on the analysis of the number and types of valence electron
pairs surrounding different atomic centers in a molecule.
Lewis Structures
The task of predicting molecular geometries is greatly simplified by following a
systematic procedure to derive the molecular structure of any given chemical com-
pound. Such a procedure was first introduced in 1916 by Gilbert Lewis and it is
based on the creation of electron dot diagrams (also called Lewis dot structures).
These diagrams are schematic representations of how valence electrons are likely to
distribute among atoms in a molecule. To understand how to build these electron
dot diagrams, let us start by creating the simplest types of symbolic representations Figure 2.34 Typical steps in the
construction of the Lewis dot
corresponding to isolated atoms. The rules are straightforward: diagrams for isolated atoms.
H C F
1. The atomic nucleus and core electrons of an atom are represented by using the
chemical symbol of the atom, such as H for a hydrogen atom, C for a carbon
atom, or F for a fluorine atom (see Figure 2.34).
2. Each valence electron in a given atom is represented using a dot placed around
the chemical symbol. The dots are placed in specific regions chosen to represent
the different valence orbitals. In the case of a hydrogen atom, in which there
H C F
is only one valence orbital, the dot representing the single valence electron
can be drawn anywhere around the symbol. For other atoms of nonmetallic
elements, it is common to identify the regions on top, below, to the right, and
to the left of a chemical symbol as representations of the four valence orbitals
associated with these types of atoms.
3. Given that pairing electrons with different spins in a single orbital requires
energy, it is assumed that valence electrons will singly occupy empty orbitals
when available. Thus, dots representing valence electrons are drawn in differ-
ent regions around the chemical symbol until there is a need to pair them up
H C F
(for atoms with five or more valence electrons). No more than two electrons
should be drawn in any of the regions representing a single orbital.
Electron Dot Diagrams LET’S THINK

• Build the electron dot diagrams for the following atoms: He, O, N, P, S,
and Ne.
Electron dot diagrams for atoms (Figure 2.34) explicitly show the number of
FF Lone
Electron
unfilled energy states available for bonding. Thus, these representations help us Pair
F F
predict the bonds that an atom will form with other atoms. For example, we
know that fluorine is a chemical element made up of diatomic molecules, F2. The
formation of this type of molecule results from the delocalization of the unpaired
electron in each participating fluorine atom into a bonding orbital shared by both
atoms. Using electron dot diagrams, the F2 molecule can be represented as shown Bonding
in Figure 2.35. The dot diagram is commonly modified to represent each bonding Electron Pair
electron pair as a solid line between the bonded atoms while other pairs of valence
electrons (lone electron pairs) are depicted as pairs of dots. This type of representa- Figure 2.35 Electron dot
diagram and Lewis structure
tion is known as the Lewis structure of the molecule. of the fluorine molecule, F2.
126 MODULE 3 Predicting Geometry
LET’S THINK Diatomic Molecules
As you know, the chemical elements oxygen and nitrogen also exists as homonuclear (composed
of the same type of atoms) diatomic molecules in nature.
• How would you explain the particular Lewis structure of the O2 molecule
•
shown to the side?
Build the Lewis structure of the N2 molecule based on the number of O O
unfilled valence energy states in the nitrogen atoms.
When atoms of nonmetallic elements combine with each other, their valence
electrons are reorganized. The number of covalent bonds that are formed are de-
termined by the total number of electrons that can be delocalized in the available
unfilled orbitals. Once the molecule is formed, the number of valence electrons
around each atom tends to correspond to the number of electrons in the full
Figure 2.36 Construction valence shell of each atom (two electrons for hydrogen; eight electrons for other
of the Lewis structure of
the water molecule, H2O. atoms of nonmetallic elements). We can use these ideas to formulate a set of basic
steps to facilitate the construction of the Lewis structure of most common mol-
H2O
ecules. Let us illustrate their application in building the Lewis structure of the
water molecule, H2O (see Figure 2.36).
1. As a first step, we need to select a central atom from which the molecule will
be built. In general, the central atom tends to be the one with the highest
O bonding capacity (highest valence). If the atoms present in the system have the
same valence, the largest of these atoms will be central; this is the atom most
Central
Atom likely to form additional bonds by delocalizing electrons in higher energy or-
bitals. Small atoms with a valence equal to one, such as H and F, never play
the role of central atoms.
Total # of
valence e-
=2x1+6=8 2. Count the total number of valence electrons in the molecule. This number is
calculated by adding the valence electrons of each atom present in the system.
3. Use as many pairs of electrons as needed to form single bonds between the
H O H central atom and the other atoms in the molecule. Use a solid line to represent
each bonding electron pair.
4. Use the remaining lone electron pairs to fill the valence shell of each atom as
H O H needed. Start with the terminal or outside atoms; place any leftover valence
electrons on the central atom.
LET’S THINK Lewis Structures
• Build the Lewis structure of the following molecules: CH4, H2S, NH3, CCl4, HF.
The outlined steps can be followed to build the Lewis structures of molecules
in which atoms are connected to each other by single bonds. However, in systems
where some atoms are bonded via double or triple bonds, and additional step
should be considered. Let us analyze the case of the molecule of carbon dioxide,
CO2
CO2, as an example:
1. Which is the central atom? Carbon, the atom with the highest valence. C Central Atom
2. How many valence electrons are in the molecule? We have four valence
electrons from carbon and six valence electrons from each oxygen, for a total Total # of
valence e-
= 4 +2 x 6 =16
of 16 valence electrons (or 8 electron pairs).
3. How many initial bonding electron pairs are required? Two pairs of elec-
trons are needed to connect the carbon atom to the two oxygen atoms.
O C O
4. How do we distribute the lone electron pairs left? There are six pairs of elec-
trons left, three of them can be distributed around each oxygen atom.
If we were to stop the construction of the Lewis structure here, the valence shell of
the carbon atom would not be full; there are only four valence electrons surround-
O C O
ing this atom. A more stable structure can be formed by assuming that one of the
lone electron pairs placed on each oxygen atom will be delocalicazed as additional
bonding pairs. Therefore, we need to add the following step to the construction of
the Lewis structure of molecular compounds:
5. If the valence shell of the central atom is not full, delocalize lone electron pairs
from the external atoms into the bonding region to form double or triple
O C O
bonds as needed.
The formation of double bonds between the carbon and the oxygen atoms leads to
maximum electron delocalization in the available valence orbitals. In general, the O C O
most stable structures are those in which each atom forms as many bonds as unfilled
electron states are available in their valence shells (e.g, 2 bonds for O, 4 bonds for C).
Multiple Bonds LET’S THINK

As discussed in the previous unit, many toxic substances contribute to
indoor air pollution. Among them we find, formaldehyde (CH2O), carbon
monoxide (CO), carbon disulfide (CS2), and hydrogen cyanide (HCN).
• Build the Lewis structure of the molecules of each of these compounds.
All the molecules discussed so far contain only one central atom. What do we
do in those systems in which we have more than one atomic center? In these cases
we can apply the set of steps just described to build the structure of the molecule
but center by center. However, the task will require additional information about
the connectivity between different atoms in the system. Results from IR absorp-
tion spectroscopy, for example, are very useful in these situations.
For molecules composed of C, H, N, and O atoms, the task of build-

ing Lewis structures is simplified by recognizing common valence electron
H distributions around bonded atoms (see Figure 2.37). We know, for ex-
ample, that carbon atoms tend to form four bonds with atoms of the same
or different kind. This occurs in four main forms: a) four
C C C C single bonds, b) two single bonds and one double bond,
c) one single bond and one triple bond, and d) two double bonds.
Oxygen atoms are likely to have two lone electron pairs in their
N N N valence shell and to form either two single bonds or one double
bond with different types of atoms. Keeping these types of patterns
in mind is useful in building the molecular structures of complex
Figure 2.37 Common molecules, predicting the value of angles between different bonds
O O
distribution of elec-
tron pairs around H, C, in a molecule, and recognizing potential mistakes in the symbolic
N, and O atoms. representations of chemical substances.
LET’S THINK Larger Molecules
To simplify the identification and representation of more complex molecules, chemical scientists
often use semi-structural formulas that convey partial information about the distribution and
connectivity of atoms in molecules. Consider the following semi-structural formulas for ethanol
and other molecules produced during the metabolism of this substance in our body:
Ethanol - CH3CH2OH Acetaldehyde- CH3CHO Acetic Acid- CH3COOH
• Use these semi-structural formulas, together with the common distribution of valence elec-
trons around the involved atoms, to build the Lewis structures of these three molecules.
Resonance
For some substances, the derivation of the Lewis structure may be not so straight-
O3
forward due to the existence of different ways of arranging valence electrons among
atoms in a molecule. To illustrate this phenomenon, let us consider the case of the
ozone molecule, O3.
1. Which is the central atom? Oxygen, the only option.

Total # of
valence e-
= 3 x 6 =18 2. How many valence electrons are in the molecule? 18 electrons (9 pairs).
3. How many initial bonding electron pairs are required? We need two pairs
of valence electrons to connect the atoms.
? 4. How do we distribute the lone electron pairs left? There are seven pairs of
electrons left. Three of them can be distributed around each of the external
oxygen atoms, while the last pair can be placed on the central atom.
O O O 5. Can multiple bonds be expected among atoms? If the valence shell of each
of the atoms is to be full, a double bond can be expected. But, between which
pair of atoms?
Given the symmetry of the molecule, we may think that it does not matter
which of the two double bonds actually forms. The outcome is the same in both
cases. However, the experimental analysis of the bond length in the O3 molecule
reveals that predictions based on the proposed Lewis structure (Figure 2.38) do
not match the data. In particular, the model predicts the existence of two types of
bonds, one single and one double, with different expected lengths (double bonds
tend to be shorter than single bonds between the same atoms because of a stron-
ger net attraction between bonding electrons and their atomic nuclei). The actual
O O O
experimental results indicate the presence of two identical bonds with a length in-
termediate between that of a single and a double bond between two oxygen atoms:
Bond Type
O-O
Bond Length (pm)
148
O O O
O3 128
Figure 2.38 Resonance
structures of the ozone
O=O 121 molecule.
These experimental data suggest that covalent bonds in the O3 molecule are
intermediate in length between single and double bonds. We may thus think that
rather than forming a double bond between one of the pairs of oxygen atoms, we
should delocalize one single electron in each of the two bonding regions. However,
theoretical calculations suggest that the electron configuration of this molecule is
actually more complex. The two electrons seem to be delocalized across the entire
molecule and cannot be assigned to any of the two bonding regions.
Molecules such as O3, in which some valence electrons are delocalized across
more than one covalent bond are said to exhibit resonance. When electrons get
delocalized their kinetic energy decreases as well as the potential energy of the re-
maining electrons in each atom that can get closer to their atomic nuclei. The net
decrease in total energy stabilizes the molecule. The larger the volume (or number
of bonds) in which electrons can be delocalized, the greater the stabilization.
Given the difficulties representing the actual structure of molecules that exhib- O O O
it resonance, it is common to build each of the Lewis structures that can be drawn
Figure 2.39 Alternate
for the molecule (see Figure 2.38), labeling each of them as a different “resonance representation of an
structure.” However, it should be made clear that none of these representations ozone molecule.
matches the actual molecular structure. Another common approach is to build the
backbone of the molecule and use dashed lines to show the presence of delocalized
electrons across multiple bonds (Figure 2.39).
Resonance Structures LET’S THINK

The combustion of sulfur and sulfur-containing compounds produces two major pollutants:
SO2(g) and SO3(g). Molecules of these compounds exhibit resonance.
• Draw all of the possible resonance structures for each of these molecules.
• Which of these molecules is likely to exhibit more resonance stabilization? Justify your rea-
soning.
NOTE: Sulfur atoms in these molecules exhibit a valence that deviates from common patterns.
Molecular Ions and Radicals

Many important molecular species in our surroundings and inside our own body
are either charged particles (ions) or have unpaired valence electrons (radicals).
In general, their Lewis structures can be built by following the same set of steps
described in the previous sections. We just need to properly count and distribute
the total number of valence electrons present in each system.
In the case of molecular ions, attention should be paid to the total number of
valence electrons when building their Lewis structure. If the species is positively
charged (cation), the total number of valence electrons will be smaller as a result
of the loss of electrons; if the species’ electrical charge is negative (anion), the pres-
ence of additional valence electrons should be taken into account. Consider, for
example, the cases of the H3O+ (hydronium) and the CO32- (carbonate) ions, two
species that play a central role in determining the acidity of aqueous solutions in
both living organisms and the environment. The total number of valence elec-
trons in each of these species can be calculated in the following way:
# valence e- (H3O+) = 3 x 1 + 6 - 1 = 8
# valence e- (CO32-) = 4 + 3 x 6 + 2 = 24
where one valence electron has been subtracted from the normal count in the case
of the H3O+ ion to account for its 1+ charge, while two electrons have been added
to the count for the CO32- ion to reflect the presence of a 2- charge. Using the
above numbers, the corresponding Lewis structures can be built using standard
procedures:
H
H O H
2 2 2
O O O
O C O O C O O C O
Notice the use of brackets to indicate the charge of the ions. As you can see, some
ions can also exhibit resonance structures and, thus, resonance stabilization.
LET’S THINK Other Ions
The following molecular ions, NO2- (nitrite ion) and NO3- (nitrate ion), also play a central role in
many environmental processes, from cloud formation to the destruction of the ozone layer.
• Build the Lewis structures of these ions and analyze whether they can exhibit resonance.
Radical species, also called free radicals, have unpaired valence electrons and
can be neutral or charged particles. In general, they are easily recognizable because O H or OH
they have an odd, rather than an even, number of valence electrons. These chemi-
cal substances are highly reactive due to the presence of unfilled valence orbit-
als in their atoms or molecules. Radicals play an important role in combustion
processes, atmospheric chemistry, and biological processes such as cell signaling
N O
and immune defense. They are also believed to be involved in the development
or NO
of degenerative diseases, such as Parkinson’s and Alzheimer’s, as well as in cancer N O
development and progression.
The Lewis structure of some radicals is pretty simple, such as that of the hy-
droxyl radical OH (see top of Figure 2.40). This species has seven valence electrons O N O
and thus one of the valence orbitals associated with the oxygen atom is unfilled.
The OH radical is produced in the atmosphere through reactions involving water
and oxygen. It is a highly reactive chemical species that reacts with many pollut-
ants in the atmosphere. Inside our body, the hydroxyl radical can cause serious O N O
damage by reacting with nucleic acids and thus inducing mutations.
Another important radical species is nitrogen monoxide, NO, a particle with
11 valence electrons. In this case, the unpaired electron is delocalized in the bond- O N O
ing region between the two atoms (Figure 2.40). This radical is an important
molecule in our body, helping protect organs from damage and controlling vaso-
dilation. However, it is also associated with pathological processes such as multiple
sclerosis and arthritis. O N O
Radical species can also exhibit resonance stabilization. Such is the case of
nitrogen dioxide, NO2, a chemical species with 17 valence electrons which plays or NO2
a major role in urban pollution. This chemical compound is produced during the
combustion of fossil fuels in our cars and is responsible for the reddish-brown haze Figure 2.40 Lewis structures
characteristic of polluted cities. As shown in Figure 2.40, the NO2 molecule has and other common symbolic
representations of various
several resonance structures that represent the delocalization of multiple electrons radical species.
across the entire particle.
Radical Action LET’S THINK

Many free radicals in the atmosphere are produced through the interaction of gaseous
substances with solar UV radiation. UV photons have enough energy to break chemi-
cal bonds and generate radical species. Take, for example, the case of chlorofluoro-
carbon (CFC) molecules such as CCl2F2 which generate the radicals •CClF2 and •Cl
when reaching the stratosphere.
• Build the Lewis structures of the •CClF2 and •Cl radicals.
The •Cl radical in turns reacts with O3 molecules to generate O2 and •ClO particles.
This process is one of the major causes of ozone depletion on our planet.
• Build as many Lewis structures as you can of the •ClO radical in which at least
one of the atoms has a full valence shell. What does the existence of several poten-
tial structures tell you about the stability of this radical?

Molecular Geometry
The Lewis structure of a molecule can be used to infer its three dimensional ge-
ometry by paying attention to the interactions between valence electrons in the
system. Electrons are charged particles that repel each other and repulsive forces
between them will keep them separated as far as possible. On the other hand,
attractive forces between electrons and protons will pull electrons towards the dif-
ferent atomic nuclei in the molecule. In general, we can expect valence electrons
to adopt spatial configurations in which electron-electron repulsions are minimal
and both electron-proton attractions and electron delocalization into bonding re-
gions are maximal. Given that covalent bonding involves the delocalization of one
or more pairs of valence electrons in the space between two atoms, the distribu-
tion of atoms around any atomic center in a molecule will be determined by the
repulsion between all the valence electrons associated with the central atom. The
previous ideas suggest that molecular geometry can be inferred from the Lewis
structure of a molecule by identifying two main things:
O
1. The number of regions, or domains, of high electron density around each
H C O H atomic center in a molecule (see Figure 2.41);
2. The geometrical arrangement in the three dimensional space that will keep
these “electron domains” as far apart as possible.
Figure 2.41 Each of the
encircled areas represents
a different electron do-
main in this Lewis struc- This suggestion is at the core of the so-called Valence Shell Electron Pair Repul-
ture of formic acid (CH2O2). sion (VSEPR) Theory of molecular shape. A central assumption in this theory is
that the most stable spatial distribution of electron domains in a molecule (electron
domain geometry) will determine how its several atomic nuclei arrange in space
(molecular geometry).
LET’S THINK From Structure to Geometry
Consider the following Lewis structures for a set of important molecules in Earth’s atmosphere:
F H
O C O Cl C Cl H C O
F
H
O S O H O H H N H
• How many regions of high electron density (electron domains) do you identify around each
central atom?
• How would you arrange the electron domains around each central atom to minimize re-
pulsions between electrons in different domains? Hint: It may help to think of the electron
domains as inflated balloons with their ends attached to the same point (central atom).
It is important to point out that in the VSEPR theory, an electron domain
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M3/co2.html
represents a region in the space around each atom in a molecule where valence
electrons are likely to be found. This region may not need to correspond to an
orbital and may contain more than two electrons. For example, all the electron
pairs in the bonding region between two atoms, no matter whether they are part
of a single, a double or a triple bond, are thought to belong to the same electron O C O
domain. Although bonding electron pairs also repel each other, electron-proton
interactions will confine them in the region between the two atoms. Thus, they
will be associated with the same electron domain.
As you may have inferred in the previous activity, when an atomic center is
surrounded by two electron domains, such as in the molecule of CO2, the most CLICK TO PLAY
stable configuration is that in which each electron domain forms an angle of 180o
degrees with the other. The electron domain geometry is then said to be “linear.” As Figure 2.42 The mo-
lecular geometry of the
a result of this electron distribution, the nuclei of the three atoms in the CO2 mol- CO2 molecule is linear.
ecule are expected to be on a same line and the molecular geometry (the distribution
of atomic nuclei in space) will be linear as well (see Figure 2.42).
In the case of the molecule of formaldehyde (CH2O, Figure 2.43), the central
atom is surrounded by three electron domains. Electron repulsions are minimized
when the electron domains are in the same plane, close to 120o degrees from each
other. For these molecule we can expect the three angles not to be identical be-
O
cause the electron domain corresponding to the double bond has a higher electron
C
density than the others. Repulsions between electrons in the double bond region
and those in the single bonds are stronger than those between the single bonds
H H
themselves; as a result the angle between the single bonds is smaller. The geometry
of both of the electron domains and the actual molecule is “trigonal planar.”
A molecule such as ozone, O3, is also characterized by the presence of three 121o
electron domains around the central atom. We can thus infer that the electron
domain geometry around this atomic center will be trigonal planar too. However,
one of the electron domains in this case corresponds to a lone electron pair rather
than to a bonding region. Given that there is not an atom in the direction of this 118o
electron domain, the actual geometry of the molecule is different from the electron
Figure 2.43 The mo-
domain geometry. The three atomic nuclei in this system form what is called a
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M3/o3.html
lecular geometry of the
“bent” or “angular” structure. In general, lone electron pairs are less confined than CH2O molecule is trigo-
nal planar.
bonding electron pairs and tend to occupy a larger space. Therefore, the net repul-
sion force that they exert on other electron domains is larger. This effect, together
with the delocalization of additional electrons across the bonding regions in the
ozone molecules, explains the smaller angle (< 120o) in the ozone molecule (see
Figure 2.44).
Electron Domain Molecular
Geometry Geometry
CLICK TO PLAY
Figure 2.44 Electron
O
domain and molecu-
lar geometries of the
O O ozone, O3, molecule.
116.8o
Trigonal Planar Bent or Angular

LET’S THINK From Structure to Geometry
Based on the Lewis structure for the following molecules, ions, and radicals of importance in our
atmosphere: CS2, SO2, SO3 HCN, •NO2, N2O, NO2-, NO3-:
• Infer the electron domain geometry and the molecular geometry of each species;
• Discuss whether the different bond angles in these chemical species would be equal to,
smaller or larger than the bond angles expected for symmetrical molecules with a similar
electron domain geometry.
http://www.chem.arizona.edu/tpp/chemthink/resources/U1_M2/ch4.html
Share and discuss your ideas with a classmate. Clearly justify your reasoning.
For molecules with four equivalent electron domains around an atomic center,
CLICK TO PLAY such as the CH4 (methane) molecule, the most stable configurations corresponds
to a tetrahedral geometry in which electrons domains are 109.5o degrees apart
from each other (see Figure 2.45). As it is the case for all systems in which all of
the electron domains around the atomic center of interest correspond to bonding
electron pairs, the molecular geometry is the same as the electron pair geometry.
However, for chemical species in which one or two of the four electron domains
correspond to lone electron pairs, molecular geometry needs to be inferred from
the actual location of the atomic nuclei.
Figure 2.45 Molecular The ammonia molecule, NH3, is a typical example of a molecule with one
geometry of the meth-
ane, CH4, molecule. atomic center surrounded by four electrons domains, one of which corresponds
to a lone electron pair. As shown in Figure 2.46a, the electron pair geometry is
tetrahedral, but the geometrical shape defined by the atomic nuclei is called “tri-
gonal pyramidal.” The stronger repulsive force between lone and bonding electron
pairs leads to an effective bond angle of 107.8o versus 109.5o in the case of CH4.
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M3/nh3.html
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M3/h2o.html
For the water molecule, H2O, where two of the four electron domains around the
oxygen atom are associated with lone electron pairs (Figure 2.46b), the molecular
geometry is “bent” or “angular” with an even smaller bond angle (104.5o) due to
the larger net repulsive forces exerted by the two lone electron pairs.
a) b)
CLICK TO PLAY
Figure 2.46 Electron do-

main and molecular geom-
etries of the molecules of a)
ammonia, NH3; b) water, H2O.
There are molecules, ions, and radicals with more than four electron domains
around a central atom. In these cases, the most stable electron domain geometries
also correspond to those configurations in which repulsion forces are minimized
while bonding interactions are maximized. For example, for five electron domains
the geometry is “triangular bipyramidal” while for six electron domains the geom-
etry is “octahedral.” Differences between electron domain and molecular geom-
etries will also arise whenever one or more of the electron domains is associated
with lone electron pairs.
From Structure to Geometry LET’S THINK

Based on the Lewis structure for the following molecules, ions, and radicals of importance in our
planet: H2S, •CClF2, CCl3F, PO43-, H3O+, NH4+, SO42-.
• Infer the electron domain geometry and the molecular geometry of each species. Predict
expected deviations in the value of different bond angles.
Figure 2.47 summarizes basic information about electron domain and mo-
lecular geometries for different types of chemical species:
# of Electron Lewis Structure Electron Domain Molecular

Domains (Example) Geometry Geometry
2 O C O
Linear Linear
O
H C H
Trigonal Planar Trigonal Planar
3
O O O Figure 2.47 Electron do-

main and molecular geom-
etries for chemical species
with different numbers of
Trigonal Planar Bent or Angular electron domains around a
central atom. Balloons are
H used to represent the vol-

ume where electrons are
more likely to be found in
H C H
the different domains.
H Tetrahedral Tetrahedral
H N H
4
H
Tetrahedral Trigonal Pyramidal
H O H
Tetrahedral Bent or Angular
The different molecules that we have used to illustrate how to infer electron
domain and molecular geometries from Lewis structures have a single central
atom. However, most molecules of interest have two or more atomic centers. In
these cases, identifying a particular geometrical shape to represent the entire mol-
ecule may not be easy. Moreover, molecules are dynamic systems in which the rela-
tive orientation of one atomic center with respect to another may change pretty
quickly. Therefore, for larger molecules it is common to build and describe their
molecular shape working on one atomic center at a time. This task is greatly sim-
plified by following a systematic procedure to identify molecular geometry and
Figure 2.48 Systematic
(Figure 2.48) and by recognizing the typical geometrical shapes associated with
procedure to infer the mo- common central atoms (e.g., C, O, and N; Figure 2.49).
lecular geometry around
any given atomic center. The following image illustrates a sequence of steps that facilitate the derivation
of the molecular geometry around any given atomic center “A”:
STEP 1 STEP 2 STEP 3 STEP 4
A A A A
Build Lewis structure and Count # Infer Electron Identify Molecular
identify central atom Electron Domains Domain Geometry Geometry
In this particular example, the molecular geometry around the atomic center “A”
is triangular pyramid with an expected bond angle slightly smaller than 109.5o
due to the presence of a lone electron pair. Notice that in this figure we have intro-
duced a new set of symbols to represent a three-dimensional structure in a plane,
the so called “wedge and dash projection.” This type of representation is based on
the use of three types of lines to convey perspective: a) solid lines represent bonds
which are in the plane of the paper, b) dashed wedges symbolize bonds that extend
away from the viewer, and c) bold wedges represent bonds that extend towards the
viewer. While Lewis structures (step 1 in Figure 2.48) explicitly convey informa-
tion about connectivity and number of electron domains, but not molecular ge-
ometry, wedge and dash projections are designed to more clearly represent three-
Figure 2.49 Common ge- dimensional shape (step 4 in Figure 2.48).
ometries around C, N, and Inferences about molecular geometry are also facilitated by recognizing the
O atoms in molecules of
organic compounds. following geometrical patterns in the bonding of C, N, and O atoms:
Carbon (C) Nitrogen (N) Oxygen (O)

~109o
C Tetrahedral N
~108 o
Trigonal Pyramidal
O
~120o
C Trigonal Planar ~105o
N Bent or Angular
C ~180o
C Linear
~118o
Bent or Angular
To illustrate the application of these ideas in the derivation of the molecular

geometry around various atomic centers, let us analyze the molecular geometry of
the simplest amino acid produced by our body, glycine (C2H5NO2 or NH2CH-
2
COOH). Based on its Lewis structure (see Figure 2.50), and applying the basic
ideas discussed on the previous page, we can see that this molecule has four atomic
centers with the following molecular geometries: 1) triangular pyramid; 2) tetra-
hedral, 3) trigonal planar, and 4) bent or angular. The identification of these basic
shapes helps us predict the angles between different bonds across the molecule.
H O ~122 o
Figure 2.50 Analysis of the

molecular geometry around
1 2 3 4
H N C C O H
different atomic centers in the
molecule of glycine. Compare
the Lewis structure with dy-
namic ball-stick representation
~105 o
of the molecule.
~108 H H
o
~109 o
Analyzing Geometries LET’S THINK

Psychoactive drugs are chemical substances that act primarily on our central nervous system,
affecting brain function. Analyze the molecular geometry of the psychoactive drugs most con-
sumed by humans:
• Identify the molecular geometry around each atomic center H H 1

4
in the molecule of ethanol. Predict the expected value of the
H C C O H
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M3/caffeine.html
bond angles marked on its Lewis structure. Make a sketch

of the three-dimensional structure of this molecule.
3 H H 2
CLICK TO PLAY
• Three-dimensional visualizations of molecules using ball-and-
stick or space-filling representations often do not show double
and triple bonds. Their presence has to be inferred from the typi-
cal valence and molecular geometry around each central atom.
Analyze the interactive representation of the molecule of caffeine
shown to the left. Identify the location of the missing double or
triple bonds. Build the Lewis structure of this molecule.
• The image to the right shows a representation of the molecule of

nicotine. In this case, carbon and hydrogen atoms are not explic-
4 1
itly represented. Carbon atoms are assumed to be located at the
junction between two lines or at the end of single lines. The pres-
2
ence of hydrogen atoms can be inferred from the typical valence of 3
each central atom. Identify the location of the missing hydrogens
and predict the value of the selected bond angles.

Chemical scientists have devised multiple types of molecular representations

that help visualize different aspects of a molecule’s shape, composition, and con-
nectivity. Some of these representations have been designed to simplify the writing
or displaying of complex molecular structures. Such is the case of the so-called
“skeletal” or “bond-line” structures in which most or all the carbon and hydrogen
atoms in a molecule are not shown explicitly. This type of short-hand notation
is widely used to represent organic molecules. The basic idea is to use solid lines
to represent the “carbon skeleton” of a molecule, assuming that a carbon atom is
implicitly located at the junction of two lines or at the end of any line, unless a
different type of atom is explicitly represented in the structure. The number of
hydrogens bonded to each carbon atom may be inferred from its typical valence
Figure 2.51 Skeletal struc- (i.e., four bonds). Lines representing bonds are drawn at angles that try to capture
tures of different molecules. the basic geometry around different atomic centers in the molecule. To illustrate
Ball-and-stick representations
shown for comparison. these ideas, consider the skeletal structures of the following common molecules:
O
NH2
OH
H
Butane Butene Ethanol Acetaldehyde Aniline

Notice how hydrogens bonded to atoms different from carbon are explicitly
shown. In some other cases, such as for the molecule of acetaldehyde, one may
choose to highlight the presence of some hydrogens in certain parts of a molecule.
LET’S THINK Skeletal Drawings
• Draw the skeletal structures of the following molecules of importance in our body:
Lactic Acid Methionine Adenine Glucose
• Derive the Lewis structure of these other physiologically important molecules:
Glutamic Acid Arachidonic Acid Adrenaline

FACING THE CHALLENGE mimic those of biological molecules and thus can
trigger or hinder specific cellular processes.
Many biological processes that depend on
Molecular Recognition molecular recognition are commonly described
The existence of any living organism relies on the and explained by using some sort of “lock-and-
coordination of multiple physical and chemical key” model. The basic idea behind this model is
processes. This coordination is achieved at the that molecules that “recognize” each other possess
submicroscopic level, through the interactions of specific complementary geometric shapes that fit
molecules, ions, and free radicals inside, outside, exactly into one another, like a key into a lock.
and within the membranes of living cells. For ex- Although very useful in a first approximation, the
ample, the presence of molecules of one particular lock-and-key model fails to recognize the dynamic
compound, such as adrenaline, near a cell may af- nature of molecules. In particular, it can be ex-
fect the structure of some proteins embedded in its pected that interactions between molecules may
membrane. In turn, structural changes in the com- induce slight changes in their shapes. Therefore,
ponents of the cell membrane may trigger other more than acting as a rigid key in a hard lock, a
molecular processes inside the cell. For a mecha- better analogy would be to think of them as a hand
nism like this to work, it is fitting into an elastic glove.
crucial that the affected pro- Processes based on mo-
teins do not respond in the lecular recognition may
same way to the presence of involve more than two spe-
every molecule in their sur- cific types of molecules with
roundings. Somehow, the complementary shapes. For
interactions between adrena- example, current models
line and the target proteins developed to explain how
should be specific to this set different odors are detected
of substances. by humans propose that
The results of multiple molecules of a single smelly
experiments suggest that By Sarah Harris (Own work) [Generic 3.0] via Openstax substance may activate vari-
the specificity in the interactions between differ- ous types of protein receptors in our nose. Simi-
ent chemical species in biological systems is highly larly, these protein receptors may respond to the
dependant on molecular geometry and composi- presence of more than one type of odor molecule.
tion. This implies that a molecule such as adrena- How is then that “recognition” occurs? In these
line triggers structural changes in specific proteins types of systems, it is believed that every specific
because of its particular shape and composition; molecule will induce different degrees of changes
some characteristic features in its structure lead in a group of protein receptors. It is the specific
to distinctive interactions with the target protein pattern of change generated by a certain type of
molecules. This selective process of interaction be- molecule that results in an specific odor percep-
tween molecular species is often called “molecular tion.
recognition” and plays a central role in the biology Molecular recognition clearly depends on the
of living organisms, from controlling the speed of nature of the interactions between different mol-
chemical reactions within cells, to transferring ner- ecules. These interactions are in turn determined
vous stimuli, to detecting odors in the surround- by the atomic composition, connectivity, and ge-
ings. Understanding these types of processes has ometry of the molecules. As we will discuss it in
been critical in the development of pharmaceuti- the next module, these three factors influence how
cal drugs that mimic the properties and behavior electrons are distributed across a molecule, many
of biological molecules. The idea has been to syn- times creating uneven distributions of charge that
thesize molecules with structures that somehow affect how molecules interact with each other.
Let’s Apply
Functionality
A central idea in chemistry is that the chemical properties of
many molecules are determined by the presence of distinctive H H
arrangements of atoms that tend to behave as a single chemi-
H C C O H
cal entity during a reaction. These distinctive groups of atoms

are called “functional groups” and their properties depend on
their atomic composition, connectivity and geometry. For ex-
ample, the molecules of all alcohols, such as ethanol, include H H Hydroxyl
the so-called “hydroxyl” functional group (-OH): Group
Main Functional Groups
The presence of a given functional group in the molecules that make up a substance is used to
classify it in particular groups. For example, all substances made up of molecules that include
the hydroxyl functional group are classified as “alcohols.” The following table lists other com-
mon functional groups together with the chemical classes of substances that they define. The
table includes the Lewis structure of the functional group, using the symbols “R, R1, R2,...” to
represent other parts of the molecule.
Chemical Functional Lewis Chemical Functional Lewis

Class Group Structure Class Group Structure
O
Ketone Ketone
R1 C R2
Ether Alkoxy R1 O R2
O Amine R1
Aldehyde Aldehyde Amine (R1 and R2 can
R1 C H be H atoms) R N R2
H H
Carboxylic O C C
Carboxyl Aromatic Phenyl R C C H
Acid R1 C O H C C
H H
• Determine the molecular geometry around the atomic centers in each functional group.
Estimate the values of the angles between different bonds in each functional group.
Biological Molecules
Most biologically active molecules include different functional groups in their structure. This
feature enriches their physical and chemical properties.
• For example, this is the Lewis structure

of phenylalanine, an essential amino H 1 H
acid needed by our body to biochemi-
cally synthesize a wide variety of pro-
C C 2 H H O 3
teins. a) Identify the different functional H C C C C C O H
groups present in this molecule; b)

Determine the chemical classes to which C C H N H 4
phenylalanine belongs; c) Estimate the H H H 5
values of the selected bond angles.
• Norepinephrine plays the role of hormone and neurotrans-

mitter in our body. The ball-and-stick representation of
a molecule of this substance is shown to the left. a) Iden-
tify the location of missing double or triple bonds in this
representation; b) Identify the different functional groups
present in this molecule; c) Write the Lewis structure of
this molecule; e) Describe the different molecular geom-
etries of the various atomic centers in this molecule.
• The Lewis structure of the oxaloacetate ion is

shown to the right. Oxaloacetate is produced 2-
during the combustion of glucose (cell respira- 1 O 2 H O
tion) in our body. a) Determine the molecular
geometry around each atomic center in this O C C C C O
molecular ion; b) Draw all possible resonance
forms of this ion; c) Estimate the values of the
4 O H 3
selected bond angles.
• Guaifenesin is a component of common

over-the-counter drugs used as expectorants.
1 A skeletal representation of a guaifenesin
2
molecule is shown to the left. a) Identify the
different functional groups in this molecule;
3 4 b) Describe the different molecular geometries
around central atoms in this molecule; c) Esti-
mate the value of the selected bond angles.
Let’s Apply
Molecular Mimicking
The development of many pharmaceutical drugs focuses on the design of chemical substances that
somewhat resemble or mimic the size, shape, and atomic composition of natural substances used
by our body or by pathogen organisms that we want to eliminate from our system. The molecules
of these drugs can then effectively interact with protein receptors in the living organisms triggering
or inhibiting their function.
Antibacterial Drugs
Sulfanilamide was one of the first commercially available synthetic antibacterial agents. This
chemical substance interferes with the production of folic acid in bacteria, a vital nutrient re-
quired by these organisms to grow. Bacteria produce folic acid using para-amino benzoic acid
(PABA) as the natural substrate. The skeletal structures of sulfanilamide and PABA are below:
• Identify common functional groups between PABA

the PABA and sulfanilamide molecules; Sulfanilamide
• Determine the basic molecular geometry of

these functional groups;
• Explain how you think sulfanilamide may
inhibit the synthesis of folic acid;
• Predict whether the third molecule shown in
the image could also work as an antibacterial
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M3/builder.html
agent. Justify your ideas based on structural
arguments.
Some antibacterials interact with proteins that speed up important chemical reactions in bac-
teria, like the synthesis of cell walls. Proteins are large molecules made by the chemical com-
bination of amino acids such a alanine, a molecular compound with the structural formula
CH3CH(NH2)COOH.
• Write the Lewis structure of alanine and identify its

major functional groups;
• Describe the molecular geometry around each of the
atomic centers in this molecule. Build a sketch of the
three-dimensional shape of this molecule. Use the
interactive tool associated with this activity to verify
your predictions.
CLICK TO PLAY
During the synthesis of the cell walls in bacteria, the proteins that facilitate wall construction
bind to portions of the growing cell membrane made by a couple of bonded alanine mol-
ecules. The Lewis structure of the binding region is shown below, together with a representa-
tion of its molecular geometry using dashes and wedges to show perspective (the symbol R
represents the rest of the molecule):
O
R C
H
O H H O H H O N
C CH3 H

R C N C C N C C O H H
C N C CH3
CH3 CH3 O
H C O
O H
• Analyze the molecular geometry around each atomic center in this binding region of the
bacterial cell membrane and verify that the dash and wedge projection is correct for each
center. If you find representational mistakes, indicate how they need to be corrected.
Two very important groups of antibacterial agents, penicillins and cephalosporins, inhibit the
action of the protein that speeds up the synthesis of the bacterial cell wall. The molecules of
these pharmaceutical drugs bind to the proteins and block their action. Consider the following
skeletal representations of two widely used types of penicillin and cephalosporin:
Penicillin G Cephalexin
• Compare the molecular structure and atomic composition of these two antibacterial
agents to that of the cell binding site (first image on this page) to which cell wall-synthe-
sizing proteins attach. Identify the structural features in these pharmaceutical drugs that
are similar to the binding site (this part of the drug its called the “pharmacophore”).
• Search for the chemical structures of other types of penicillins and cephalosporins
and verify that they have the same pharmacophore that you identified. If they do not,
reevaluate your answer.
144
Inferring Charge
Distribution
The physical and chemical properties of materials, as well as the physical and
U2: MODULE 4
chemical changes that they undergo, are determined by the interactions among
the particles that make up the system at the submicroscopic level. The nature and
strength of these interactions depend, in turn, on the atomic composition and
connectivity of the interacting particles, as well as on their molecular geometry.
These three factors influence how electrons arrange within molecules and how
easily these electrons are affected by the presence of other molecules or
ions in their vicinity. Knowing how to infer charge distribution
in molecules from composition and structural cues is thus a
critical skill in chemical thinking.
The analysis of charge distribution in molecular
systems is of such importance that chemical scientists
have developed a variety of strategies to both qualita-
tively and quantitatively identify regions in a molecule Electrostatic Potential
of low and high electron density. In this module we will Map for N2O
discuss methods that are useful in the analysis of the physical properties of sub-
stances, such as the determination of bond and molecular polarity and the con-
struction of electrostatic potential maps such as that shown in the figure. We will
leave for subsequent course units the discussion of strategies that aid in the pre-
diction of the chemical reactivity of different types of compounds, such as the
identification of oxidation states.
THE CHALLENGE Greenhouse Gases

Gaseous substances that absorb and emit infrared (IR) radiation in a planet’s
atmosphere are called greenhouse gases. Substances such CO2(g) and N2O(g)
are greenhouse gases while N2(g) and O2(g) are not.
• What structural properties of the CO2 and N2O molecules, not present
in N2 and O2, may determine how they interact with IR radiation?
This module will help you develop the type of chemical reasoning that can be
used to explain phenomena similar to that described in the challenge. In particu-
lar, the central goal of Module 4 is to help you understand how to infer charge
distribution in a molecule based on its atomic composition, connectivity, and
three dimensional geometry.
Contrasting Behaviors LET’S THINK

http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M4/hexwat.html
Chemical substances interact with charged objects in different ways. Analyze, for example,
the following movies showing the interactions of liquid hexane C6H14(l) and liquid water
H2O(l) with objects that have been electrically charged by rubbing:
CLICK TO PLAY
CLICK TO PLAY
C6H14(l) H2O(l)
• How would you explain the different behaviors of these two substances?
• How could substances that do not have a net electric charge be attracted to an electri-
cally charged object? How may electric charge be distributed in the molecules of
these types of substances to explain their behavior?
Partial Charges
Experimental results such as the ones illustrated in the previous activity suggest
that electric charge is not evenly distributed in all types of molecules. This allows
us to explain the attractive interaction between some chemical substances and d- d+
electrically charged objects. If we assume, for example, that valence electrons in a
water molecule spend more time in certain regions of the molecule than in others,
the electron density will vary from atom to atom. One average, some regions of
the molecule will have a higher electron density than others and exhibit a partial
negative charge (d-, measured in units of electron charge); other parts of the mol-
ecule where valence electrons spend a lesser amount of time will have a positive
partial charge (d+). Although the molecule as a whole will be neutral (the sum of
all partial charges will be zero), the uneven distribution of charge will affect how
the molecule interacts with other neutral or charged particles.
To illustrate these ideas, imagine that we modeled a water molecule as an el-
lipsoidal particle with positive and negative partial charges on opposite sides of the
+
particle (see Figure 2.52). These electrical charges would have to be identical in
magnitude but opposite in sign for the molecule to be neutral. When a stream of
these molecules passes nearby a positively charged object, we can expect the nega-
tive sides of the molecules to turn towards the object while their positive sides turn
away. Given that the negative sides of the molecules will be closer to the positively
charged object, they will be subject to an electrostatic force of attraction larger in
magnitude than the repulsion exerted on the farther side with the positive partial
charge. The end result will be a net force of attraction on the water molecules that Figure 2.52 Model of the
will deviate them from their initial trajectory (Figure 2.52). attraction between water
molecules and an electri-
cally charged object.
146 MODULE 4 Inferring Charge Distribution
The assumption that valence electrons are unevenly distributed across the mol-
ecules of some substances allow us to explain many of their physical and chemical
properties. But, what causes this unequal distribution of electrons? The answer lies
in the nature of the atoms that are present in the system. Some atoms seem to exert
stronger forces of attraction on electrons than others, increasing the likelihood of
valence electrons in a bond spending more time in the vicinity of those atoms than
in other regions of a molecule. These types of atoms tend to have valence energy
states that are lower in energy than equivalent states in other atoms. The relative
ability of atoms in a molecule to attract valence electrons in their vicinity can be
quantified by analyzing the relative average energy of their unfilled valence energy
states.
LET’S THINK Back to PES
Photoelectron spectroscopy (PES) data for isolated atoms provides informa- ET

tion about the energy needed to remove electrons from different atomic
states (mth ionization energy). The more energy is needed to eject an electron 0
from an atom, the lower the energy of the orbital it occupies. Thus PES data Ionization
Energy
can be used to estimate the average energy of the valence electrons.
Valence electrons in atoms of nonmetallic elements occupy s and p orbit-
als. In a first approximation, the average energy of these valence electrons (EAV) can be calculated
by first multiplying the number of electrons in each of these orbitals (nS and nP) by their associated
ionization energy (IS and IP), and then dividing this result by the total number of valence electrons
(nS + nP) in the system:
nS x IS + nP x IP
EAV =
nS + nP
CLICK TO PLAY
• The interactive tool that you can launch by clicking on the image allows
you to display the PES spectra of different atoms. Using the “dual mode” in
this tool, visually compare the energies of the valence electrons for the fol-
lowing atoms: H, C, N, O, F, S, and Cl. Then, use the relationship shown
above to complete the following table of EAV values for each of these atoms.
Atom H C N O F S Cl
EAV (MJ/mol) 1.31 1.89 2.31 1.59
• What periodic trends do you observe in the previous data?

• When a covalent bond is formed, some valence electrons are delocalized into the bonding
region. If the bonded atoms are of different types, bonding electrons are likely to spend more
time moving in a volume closer to one of the atoms. Based on your previous results for EAV,
discuss which atom is likely to have a negative partial charge when the following covalent
bonds are formed: H-C, H-O, H-Cl, C-N, C-O, C-F, and C-Cl.
• Use all your data to identify a simple way to predict the sign of the partial charges on each of
the atoms in a covalent bond based on their relative positions on the periodic table.
The average energy of the valence electrons in isolated atoms (EAV) as calcu-
lated in the previous activity can be used to predict which atom in a bond is likely
to have a negative or positive partial charge. Based on these types of analyses,
chemical scientists have defined a property of atoms in a bond that allows us to
predict charge distribution in molecules. This property, called electronegativity
(c), is a measure of the decrease in the total energy of an atomic system if a bond-
ing electron were to be localized in the vicinity of a given type of atom. The larger
this decrease in energy, the larger the electronegativity of that type of atom and the
larger the likelihood of finding bonding electrons closer to it. The electronegativity
of an atom can also be thought of as a measure of the probability of finding bond-
ing electrons localized in the vicinity of that atom.
Atomic electronegativities (c) have been estimated using different strategies,
from determining the average energy of valence electrons to calculating the force
between valence electrons and protons in atoms to analyzing the energy required
to break different types of bonds. Figure 2.53 shows electronegativity values com- Figure 2.53 Electronega-
tivities (c) of the different
monly used in predicting charge distribution in chemical systems: elemental atoms.
As you can see in this image, the electronegativity values for the elemental
atoms follow periodic trends: c increases as we move up a group (column) in the
periodic table and as we go from left to right across a period (row). This is the same
pattern followed by the first ionization energy of isolated atoms and opposite to
variations in the average energy of valence electrons (EAV) and in atomic size. Thus,
the most electronegative atoms tend to be those that are the smaller in size and
with the lower valence electron energy states.
The electronegativity of an atom not only provides information about the
likelihood of electrons in a bond to be more or less localized around certain atom.
This quantity also tells us how energetically costly it would be to displace elec-
trons away from that atom. As a consequence, when a chemical bond between
atoms A and B is formed, the partial electric charge that each of them acquires is
determined by both the difference in electronegativities Dc = cA - cB between the
bonded atoms and their average electronegativity cAV = (cA + cB)/2. The first of
these quantities Dc is a measure of the tendency of valence electrons to move to-
wards one of the atoms, while cAV quantifies the average “resistance” in the system
for this to happen. Thus, the partial charge on each atom in a diatomic molecule
can be estimated using the following relationship:
cA - cB Dc
(2.4) dA = = = - dB
cA + cB 2cAV
Given that most atoms of nonmetallic elements have relatively high electro-
negativities, Dc < 2.0 and cAV > 2.0 for covalent bonds. Therefore, partial charges
on bonded atoms will have either small or middle-sized magnitudes (|d| < 0.35)
and bonding electrons will still be largely delocalized between the two atoms.
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M4/pten.html
LET’S THINK Partial Charges
Equation (2.4) can be used to generate a first estimate of the partial charges (d) on atoms linked by a
single bond. These numbers are useful in identifying regions in a molecule with high or low electron
density and in estimating the probabilities of finding bonding electrons in different locations.
• Estimate the partial charges on each of the atoms in the following

bonds: H-C, H-N, H-O, H-F, C-O, C-N, C-F. Atomic electronegativity
values are included in the interactive periodic table to the right.
• Consider a chemical bond between two atoms A-B with partial charges
dA = - dB = -0.2. What is the probability of finding the bonding elec-
CLICK TO PLAY
trons in the vicinity of atom A versus atom B? What partial charge
would atoms A and B have if the likelihood of finding bonding electrons localized around
atom A was four times higher than that of finding them around atom B?
Bond and Molecular Polarity

Differences in electronegativity between bonded atoms lead to an unequal distri-
bution of electron charge density. The existence of positive (d+) and negative (d-)
partial charges separated by a certain distance creates an electric dipole in a bond.
The effect of this electric dipole on its surroundings is determined by the magni-

tude and direction of the associated electric dipole moment ( m ). The magnitude of
d- d+ this quantity results from the product of the magnitude of the partial charge (d) on
the bonded atoms times the distance (d, bond length) between them:

m (2.5) m = |d| x d.
By convention, chemical scientists assign the direction of the electric dipole mo-
ment on a bond from the positive to the negative poles (Figure 2.54) representing
the direction towards which electron density is shifted. The magnitude of a bond’s
dipole moment is said to be a measure of the polarity of the bond. Thus, the larger
the dipole moment the more polar the bond. For diatomic molecules (particles
Figure 2.54 Representa-
made up of only two atoms) the magnitude and direction of the bond dipole
tion of the electric dipole determine the strength of the molecules’ electrostatic interactions with charged
moment associated with a
polar chemical bond. particles and other electric dipoles in the surroundings.
The units of the dipole moment in the International System of Units are Cou-
lomb-meters (C-m). However, it is common to express dipole moments using
the Debye (1 D = 3.335 x 10-30 C-m) as the basic unit. In general, single covalent
bonds have dipole moments that do not exceed the 2 Debyes. For example, the
average dipole moment for a C-H bond is estimated to be close to 0.4 D (weakly
polar), while that for the H-F bond is close to 1.9 D (strongly polar).
Bond Dipoles LET’S THINK

The magnitude of a bond’s dipole moment (m) depends on the partial charge (d) on the bonded
atoms and the bond length (see Equation (2.5)). Based on Equation (2.4) we can thus expect
the value of m to be proportional to the difference in electronegativities Dc between the bonded
atoms. Consider the following molecules of importance in our planet’s atmosphere:
CF4 CO2 N2 CH4 H2O O2 SO2
• Arrange these molecules in order of increasing bond polarity;

• Draw the dipole moment vectors on each of the bonds of these molecules. Given that
dipole moments are vectorial quantities, discuss how you would add the individual bond
dipoles in each molecule to determine the net molecular dipole moment.
The presence of polar bonds in a molecule does not necessarily imply that the
molecule has a net dipole moment itself. The electric dipole moment is a vectorial
quantity and the effects of bond dipoles directed in opposite directions will cancel
each other out. Thus, in analyzing the net polarity of a molecule it is not only im-
portant to analyze the relative magnitude of each bond dipole but to consider their
orientation in space. Molecular polarity strongly depends on molecular geometry.
USEFUL TOOLS magnitude or direction:
To determine the net dipole moment of a mol- R

ecule, the individual dipoles associated with R
each bond in the system need to be added. R
The graphical method is the simplest approach
to sum vectors. To illustrate the application of The vector sum R, or net dipole moment, cor-
this strategy for vector addition let us consider responds to the arrow that goes from the be-
a concrete example: ginning to the end point of the sequence of
added dipoles (black arrows above). As shown
Imagine that you wanted to add three bond in the image, the net result is independent of
dipoles m1, m2, and m3 with magnitudes of 0.5 the order in which the dipoles are sequenced.
D, 1.0 D, and 1.5 D, respectively, and directions
as shown in the image. To
find the vector sum, we This head-to-tail procedure to add vectors can
start by representing the m2 be used with as many bond dipoles as pres-
dipoles by arrows drawn m3 ent in a molecule. However, in many cases the
to scale based on each di- m1 addition has to be made in three dimensional
pole’s magnitude. Then, space. Although vector addition is more diffi-
we draw the arrows in sequence by placing the cult to visualize in these situations, the graphi-
beginning of one of the arrows at the end of cal method can still be applied to generate the
another (head-to-tail), without changing their vector sum.
To illustrate how to qualitatively infer the net dipole moment of a molecule

with more than one bond, let us first consider the case of the CO2 molecule. Each
of the two double bonds in this particle are polar with associated dipole moments
equal in magnitude but with opposite directions:
d- d+ d- Vector Sum
m=0
m=0 As it can be inferred from the symmetry of this molecule, the individual bond
dipoles cancel each other out and the net dipole moment for the CO2 molecule is
equal to zero. The molecule is then said to be “nonpolar.” As this example shows,
the lack of net polarity in a molecular system does not imply that the electric
charge is equally distributed across the molecule; electron density around the car-
bon atom in CO2 is certainly lower than in the vicinity of the oxygen atoms. A
m=0
zero net dipole moment is also characteristic of systems in which charge distribu-
tion is fully symmetrical around an atomic center, such that the contributions of
individual bond dipoles cancel each other out. This is the case of other common
molecules such as SO3 and CH4 (see Figure 2.55). Interactions involving mole-
cules of this type are similar in nature to those of nonpolar particles with no partial
charge on any atom, such as N2 or O2.
The water molecule is a typical example of a “polar” molecule with a non-
Figure 2.55 Dipole mo- zero net dipole moment. In this case, bond dipoles do not cancel each other out
ment addition leads to a
zero net dipole moment because of the bent geometry of the molecule. Rather, they add up to produce a
for SO3 and CH4.
dipole moment with a magnitude close to 1.85 D:
d- Vector Sum
m = 1.85 D
d+ d+
The presence of this net dipole moment has a strong influence on the nature of
m = 0.53 D the interactions between water and other molecules or ions. In general, substances
made up of polar molecules are attracted to charged objects and measurements of
d+ the strength of these interactions can be used to determine their dipole moment.
Polar molecules are made up of atoms with higher electronegativity differences
Dc and tend to be asymmetrical. The presence of atomic centers with lone electron
pairs commonly leads to the existence of a net dipole moment because they create
regions with high electron density (see Figure 2.56). Thus, for example, in the wa-
d- d- ter molecule the presence of the two lone electron pairs associated with the oxygen
atom further increases the electron density around this atom, contributing to this
molecule’s high dipole moment.
Figure 2.56 Ozone (O3) is a
polar molecule despite being The determination of the polarity of molecules with more than one atomic
made up of the same types of center is simplified by analyzing the system center by center. For organic mol-
atoms. Lone pair electrons on
the external atoms of this non- ecules, it is useful to pay attention to the symmetry of the molecule and to the
linear molecule create regions
of high electron density. polarity of the functional groups present in the system. In general, the dipole mo-
ment associated with the C-H bond is so small (Dc~0.4) that hydrocarbon chains
are assumed to be nonpolar for all practical purposes.
Molecular Polarity LET’S THINK
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M4/dipole.html
Consider the following molecules: NO2, N2O, NH3, CH2O, CCl4, and CHCl3.
• Use the interactive tools that you can access on this page
to aid you in drawing and adding the bond dipoles on
each of these molecules; take into account the difference
in electronegativities between atoms to estimate the rela-
tive magnitude of the dipole moments.
• Add the bond dipoles using the graphical method to de-
termine each molecule’s net dipole moment.
NOTE: Bond dipole vectors can be drawn by clicking on the screen

of the interactive tools and dragging the mouse at the same time.
Click on and drag a vector’s arrow head to move it across the screen.
For non-planar molecules you need to carefully think about how to
add vectors in three dimensions.
your reasoning.
CLICK TO PLAY
Electrostatic Potential Maps

The identification of areas in a molecule with different partial charges helps us
predict molecular polarity and the nature of the molecule’s interactions with other
particles. To simplify this task, chemical scientists have developed strategies to
visually represent charge distribution in molecules and ions. One useful approach
is to create the electrostatic potential map of the particles of interest. These types of
representations are built using a standard color scheme to depict areas in a mol-
ecule with different electrostatic potentials.
The electrostatic potential at any point is a measure of the energy required
to place a unit positive charge (e.g., a proton) at that particular point. The more
positively charged the region of the space, the more energy will be needed to add
another positive charge due to repulsive forces between equally charged particles. Figure 2.57 Electro-
static potential map for
Therefore, the electrostatic potential will be high, or very positive, at that loca- the water molecule.
tion. On the contrary, bringing a positive charge to a negatively charged region
of a system will cost little or even generate energy, and the electrostatic potential
will be low or negative. Thus, by calculating the electrostatic potential at differ-
ent points around a molecule we can map the distribution of charge in the
system.
To display electrostatic potential data for a molecule it is common to
use the following coloring conventions: dark blue areas identify regions
with the highest or most positive electrostatic potential (positive partial
charge) while dark red areas correspond to regions with the lowest or most
negative electrostatic potential (negative partial charge). Intermediate poten-
tials are assigned colors according to the standard color spectrum (Figure 2.57).
Electrostatic potential maps allow us to make quick judgments about molecu-

lar polarity and charge distribution in molecules and ions. Compare, for example,
the electrostatic potential maps for the ammonia molecule NH3 and the ammo-
nium ion NH4+:
NH3 NH4+
These potential maps clearly show the uneven distribution of charge in the polar
NH3 molecule, with a negative partial charge in the vicinity of the nitrogen atom,
while the positive electric charge in the NH4+ ion appears to be equally distributed
across the system.
Electrostatic potential maps also help us identify those regions in a molecule
that will determine the nature and strength of its interactions with other particles.
In general, we may expect that positively charged regions (or areas with a high
electrostatic potential) in one particle will be attracted to negatively charged re-
gions (or areas with a low electrostatic potential) in another particle (Figure 2.58).
Figure 2.58 How would you

expect CO2 and H2O mole-
cules to interact among them-
selves and with each other?
LET’S THINK Larger Molecules
Electrostatic potential maps are particularly useful in analyzing the polarity of larger organic mol-
ecules with many atomic centers. Consider the following electrostatic potential maps for important
volatile organic compounds (VOCs) in our atmosphere:
Hexane Acetone Benzene Ethyl

Acetate
C6H14 C3H6O C6H6 C4H8O2
• Analyze the distribution of charge in each of these molecules and identify regions of positive
and negative partial charge. Discuss whether you would expect each of these molecules to be
polar or nonpolar.
FACING THE CHALLENGE the greenhouse effect is smaller because it is pres-

ent in much smaller concentrations. The potential
of a substance to contribute to the greenhouse ef-
Greenhouse Gases fect also depends on its lifetime in the atmosphere.
Our planet receives energy from the Sun, most of This is, the average time it takes for its concentra-
it in the form of visible light. Earth’s surface ab- tions to return to its natural value following an in-
sorbs a large proportion of this energy and releases crease in its concentration in the atmosphere.
it back in the form of infrared radiation. A fraction Measured average temperatures of our plan-
of this IR radiation is in turn absorbed by some et in the past sixty years indicate the presence
gases in our atmosphere (greenhouse gases) and of a warming trend. The term “global warming”
re-emitted back to the surface. Earth’s atmosphere is currently used to refer to the measured in-
normally traps 84% of the solar energy re-emit- crease in the average temperature of the Earth’s
ted by the planet’s surface. near-surface air and oceans
This phenomenon is called since the mid 20th century,
the Greenhouse Effect and and its projected continua-
helps our planet sustain tion. Most experts in earth
an average temperature of and atmospheric sciences
15 C.
o
consider that the increasing
Greenhouse gases are concentrations of atmospher-
chemical substances that ab- ic greenhouse gases caused by
sorb and emit IR radiation. human activities are mostly
This property is determined responsible for this unprec-
by their molecular geometry edented rapid rise in global
and polarity. For a molecule temperatures in recent years.
to absorb IR radiation two Global warming is expected
By Barb Deluisi, NOAA
basic conditions must be to induce climate changes in
met: 1) At least one of the molecule’s modes of our planet with potentially harmful consequences
vibration must lead to changes (oscillations) in its for the environment and human health.
net dipole moment; 2) The energy of the IR pho- Since the beginning of the industrial revolu-
tons interacting with the molecule should match tion human activities have led to a significant
the energy difference between allowed vibrational increase in the concentration of atmospheric
states in the system. The change in the dipole mo- greenhouse gases. Some of these activities include:
ment of the molecule is required because it allows burning of fossil fuels and deforestation that result
the particle to interact with the oscillating electric in higher CO2(g) concentrations; use of CFCs in
field of the IR radiation wave. Therefore, fully refrigeration systems which are released into the
symmetrical molecules with no bond dipoles will environment; agricultural practices based on the
not absorb EM radiation in the IR range and thus use of fertilizers that generate gaseous nitrogen
will not act as greenhouse gases. compounds; livestock and manure management
The primary greenhouse gases in our planet’s that lead to higher methane atmospheric concen-
atmosphere are water vapor (H2O(g)), carbon trations. Overall, existing data reveal increases be-
dioxide (CO2(g)), methane (CH4(g)), and ozone tween 15% to 60% in the concentrations of dif-
(O3(g)). The contribution of a gaseous chemical ferent atmospheric greenhouse gases compared to
substance to the greenhouse effect depends on its pre-industrial values. A significant proportion of
chemical composition and structure, as well as on the current human-induced greenhouse gas emis-
its abundance. For example, although one gram of sions comes from industrialized countries. The
methane traps 25 times more thermal energy than US, for example, contributes with close to 16% of
one gram of carbon dioxide, its contribution to the total annual emissions in the world.
Let’s Apply
Warming Substances
The relatively rapid increase of average near surface temperatures in the past 50 years in our planet
seems to be associated with the presence of greenhouse gases in our atmosphere that can absorb IR
radiation. Understanding the properties of these chemical substances is thus crucial to predict their
warming potential and to make decisions about how to best reduce or control their environmental
effects.
Temperature Changes By Giorgiogp2 (Own work) [Share

http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M4/temp.html
The graph and movie associated with this ac-
tivity (from NOAA and NASA data sources)
summarize information about how average
global and local temperatures in our planet have Temperature Anomaly
changed in the past 120 years. The data shows
the 1880-2007 global mean surface tempera-
ture difference (temperature anomaly) relative
to the average value in the 1951–1980 period.
• What specific trends do you observe in the

average global temperature variations?
Year
• What specific trends do you observe in
average local temperature variations?
• How would you explain that average local tem-
perature changes are not the same across the globe?
CLICK TO PLAY
Active Vibrations
Greenhouse gases are made up of molecules with at least one mode of vibration that leads to
temporal changes (oscillations) in its net dipole moment (IR active vibration modes).
• Which of the following vibration modes for the CO2 molecule are IR active?
CLICK TO PLAY
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M4/co2vib.html
The Methane Case Source: Chemistry at Penn State University
Methane is an important greenhouse gas in our

planet.
• Which of the vibration modes represented

in the image are IR active?
• How would the net dipole moment of the
CH4 molecule change in each of the IR ac-
tive vibrations?

Clearly justify your reasoning.
Greenhouse Gases?
Many pollutants in our atmosphere can act as greenhouse gases.
• Analyze the polarity of these molecules and discuss whether they can absorb IR radiation.
Cl2 SO3 C2H6 SF6
N2O CH2Cl2
Relative Contributions
The following image shows the IR 0.8

CO2
spectra of the main greenhouse gases
in our planet. Each spectrum is scaled H2O
Transmittance
0.6
considering the substance’s concen- N2O

0.4 CH4
tration and global warming potential
C3F8
(GWP). The image also shows Earth’s
0.2 CFCs
emission spectrum (black line).
3500 3000 2500 2000 1500 1000 500

• Analyze the IR spectrum of each
Wavenumber (cm-1)
of the different gases. Identify
which of them can be expected to absorb outgoing IR radiation emitted by our planet.
• Estimate the relative amount of Earth’s IR radiation absorbed by each of the different
gases and arrange them in order of decreasing contribution to the greenhouse effect.
Let’s Apply
More on Functional Groups
The nature and strength of the interactions between organic substances depend on the polarity of
the functional groups present in the interacting molecules.
Functional Group Polarity
Consider the following functional groups:
Chemical Functional Lewis Chemical Functional Lewis

Class Group Structure Class Group Structure
O
Ketone Ketone
R1 C R2
Ether Alkoxy R1 O R2
Carboxylic O Amine R1
Carboxyl Amine (R1 and R2 can
Acid R1 C O H be H atoms) R N R2
• Assign partial charges to the visible C, H, O, and N atoms in these functional groups;
• Determine the relative magnitude and direction of relevant bond dipoles assuming that
R1 and R2 groups represent hydrocarbon chains;
• Determine the direction of the net dipole moment of each functional group.
Consider the electrostatic potential maps of molecules of medical relevance:
Amphetamine Glutamic Acid Tyrosine
• Based on the composition and structure of each molecule, explain the distribution of
charge as implied by the electrostatic potential maps.
Where From?
restrict the possible states (orbitals) in which they
can exist; b) their spin, that constrains the num-
ber of electrons that can occupy the same orbital.
Where To? Zooming into the electronic structure of at-

oms allowed us to explain and predict the bonding
patterns between atoms of nonmetallic elements.
Our analysis showed that covalent bonding is
The central goal of this unit was to help you de- driven by the delocalization of valence electrons
velop ways of thinking that can be used to uncov- into the space between two atom, which lowers
er and predict the atomic and molecular structure the energy of the system. However, the number
of substances. In particular, we have discussed of bonds formed is constrained by the number of
how the careful analysis of the unfilled orbitals in the interacting atoms.
interactions between EM ra-
diation and matter allows us ZOOMING IN
to derive information about ET

both atom connectivity in
1s22s22p4
molecules and electron distri-
bution in these particles. This
information can then be used
to build models to explain O
and predict molecular geometry and polarity. H H
Our analysis of light-matter interactions re-
vealed important properties of molecules, atoms,
and electrons. Of central importance is the fact ZOOMING OUT
that their energy is quantized, this is, it can only
take a set of discrete values that are characteristic How valence electrons distribute around
of each type of system. The quantization of ener- atomic centers in a molecule determines both
gy states in atoms and molecules is clearly mani- its three dimensional geometry and polarity. In
fested in the absorption and emission spectra of general, the most stable configurations are those
chemical substances. These spectra are unique in which electrostatic repulsions between valence
fingerprints that reveal the internal structure of electrons are minimized and attractions between
the particles that make up chemical elements and electrons and protons are maximized. This could
compounds. lead to an uneven distribution of bonding elec-
Experimental results from spectroscopic anal- trons between atoms in a molecule, creating cen-
ysis also show the existence of periodic patterns ters with positive and negative partial charge. As
for important atomic properties such as valence, we will see in the next Unit,
atomic size, and ionization energy. The analysis of the presence of polar bonds
Source: Bessonov & Harauz
these periodic trends has guided the development and of a net dipole mo-
of theoretical models of the electronic structure ment in molecules has
of atoms. In a first approximation, periodic prop- a strong influence on
erties can be explained assuming that electrons in the physical properties of
atoms are arranged in shells and subshells with chemical substances. But
a well defined occupancy. In the quantum me- before we move on, let us
chanical model of the atom, specific electron con- explore if “YOU ARE READY” by assessing your
figurations result from two fundamental proper- ability to apply what you have learned in this
ties of electrons: a) their wave-like properties, that Unit to the analysis of some interesting problems.
158 Are you Ready?
Are You Ready?

An odorant is a substance capable of triggering an olfactory response; odor is the sensation resulting from
stimulation of the olfactory organs. Odors play an important part in our everyday life, from appetite
stimulation to serving as warning signals for disease detection. Several theories of how molecules interact
with protein receptors in olfactory cells are currently under investigation. However, many of them suggest
a strong relationship between type of odor and molecular size, shape, and polarity. Let’s investigate this.
100
Orange Smell
Relative Abundance
80
Elemental analysis of one of the chemi-
cal substances that we associate with 60
the smell of fresh orange juice reveals 40
the following composition: 62.04% C,
10.41% H, 27.55% O. The mass and 20
IR spectra of the substance are shown
0
below. 0 20 40 60 80 100 120
m/q
• Determine the empirical and mo-
lecular formulas for this chemical
compound. 0.8
• Propose a structural formula this
C-H
Transmittance
compound (Hint: Your formula 0.6

should explain the presence of stretch C=O
stretch
peaks at m/q = 29, 43, and 71 in 0.4
C-H C-C
the mass spectrum). bendC-O
0.2
stretch
Share and discuss your results with a
3000 2000 1000
classmate. Clearly justify your reasoning.
Wavenumber (cm-1)
Bitter Poison
HCN is an extremely poisonous and highly volatile liquid with a faint, bitter, almond-like odor that some
people are unable to detect due to a genetic trait. This compound is obtainable from some fruits that have a pit,
such as cherries, apricots, apples, and bitter almonds, from which almond oil and flavoring are made.
• Draw the Lewis structure of HCN and determine its molecular geometry. Assign partial charges to each
atom in the system and sketch each bond dipole. Determine whether this molecule is polar or nonpolar.
• CH3CN is a solvent with a sweet odor that can be metabolized to form HCN when ingested. It is struc-
turally similar to HCN. Draw the Lewis structure of CH3CN and indicate the electron domain and mo-
lecular geometries around each C and N atoms. Analyze bond and molecular polarity for this molecule.
What’s that Smell?

Molecules Molecules Important Factors
with a smell with no smell
Based on the information provided in the table shown to the left:
NH3, H2S, N2, O2,
HBr, HCN CO2, CH4 • Suggest which of the following factors: i) bond polarity, ii) molecu-
lar polarity, or iii) molecular geometry, seems to affect whether a
small molecule will trigger an odor or not.
Important Factors
H
Citronellal is the main component in the mixture of chemical com-
pounds that give citronella oil its distinctive lemon scent. Its Lewis H C H
structure is represented to the right.
C C H3
• Indicate the molecular geometry of each of the encircled atomic
centers;
H C
• Estimate the value of the bond angles marked on the image; H C H
• Draw three dimensional structures of this molecule using:
a) wedge and dash projections; b) skeletal or bond-line structures.
H C H
• Identify and name the functional group that may be responsible H C C H3
for the characteristic odor produced by this substance.
H C H
Share and discuss your ideas with a classmate, and justify your thinking. H C O
Fruity Smell
All the molecules shown to the left have fruity smells.

By Johanna84 (Own Work) [Public domain] via Pixabay
• Compare the chemical composition, molecular ge-

ometry, and charge distribution of these molecules.
What structural factors do they have in common?
Which of these factors may be responsible for their
fruity smell?
160 Are you Ready?
What’s that Smell?

Nutty, Medicinal Smells
Although the relationship between odor and molecular structure is complex,

there is solid evidence that they are interrelated. For example, flat or planar
molecules tend to have nutty, medicinal smells.
• Which of these molecules are likely to be in this category?
H H H H H
N C H C C H C C
H H
H3C C C CH3 C C HO C C CH3
HO H
C N H C C H C C
H H H H H
Justify your answer based on the analysis of their molecular geometry.
Something Fishy
The three compounds that are shown below have a strong “fishy” odor, which is thought to be associated
with the presence of a particular functional group.
H H
H H H H CH3 C C
By Schwarzenarzisse (Own Work) [Public domain] via Pixabay

H C C N C H H3C N CH3 H C C NH2
H H H C C
H H
• Assume that in order to generate that odor, these molecules have to fit into a protein receptor with
the same molecular geometry as their active functional group. What would this geometry be?
• How is charge distributed in each of these molecules? Sketch the associated electrostatic maps.
Your Design
• Based on what you have learned, design three molecules that you think will have a) a nutty, me-
dicinal smell, b) a fishy smell, and c) a fruity smell. Draw the Lewis structure of the molecules and
justify your choices based on the expected composition and geometry of the molecules.
Are You Ready?

The Role of Ions
Olfactory receptors are proteins that bridge through the cell membrane. It has been found that
the structure of these proteins changes dramatically when certain metal ions bind to them. The
charge of the relevant ions can be explored using photoelectron spectroscopy (PES). Imagine
that PES analysis reveals the presence of certain X2+ ions in some type of olfactory receptors. The
spectrum of these ions is shown below. Based on this information:
• What is the electron configuration of this ion?

• What is the identity of element X? (Remember this is the spectrum of the ion X2+, not of
the neutral atom X).
Absorption spectroscopy of the metal-protein system reveals a sharp absorption peak at 244 nm.
• What is the energy (in J) absorbed by each ion (1 photon per ion)?
• What is the energy absorbed by one mole of ions (in kJ/mol)?
Share and discuss your ideas with a classmate. Justify your reasoning and calculations.
162 Are you Ready?
Are You Ready?

The determination of a substance’s identity based on the analysis of its molecular structure is a fundamental
analytical tool in forensic science. Consider, for example, this case described in the San Francisco Chronicle
in May 13, 2001:
In the thick of evening traffic earlier this year, a minivan broke from
the gridlock on Interstate 580, leveled a call box and continued out of
control onto the streets of Livermore. The van struck several parked
cars and pedestrians scattered as it shot through a shopping plaza and
lurched onto a concrete island. Police found the 30-year-old driver
drooling on himself, with a bluish line along his gums, his hands
clenched to the steering wheel. They assumed he was drunk, but the
“beverage” police found in the van wasn’t alcohol.
Formula and Structure 100

Relative Abundance
80
The analysis of the “beverage” found in
this crime scene revealed the presence of 60
a liquid substance with the following el-
emental composition: 53.31% C, 11.19% 40
H, 35.51% O. The mass spectrum of the
substance is shown on this page. 20
0
• Determine the empirical and mo- 0 20 40 60 80 100
lecular formulas of this chemical m/q
compound.
The IR spectrum of the compound is also

shown on this page. 0.8
C-H
Transmittance
bend
• Draw the Lewis structures of at least 0.6
3 compounds with the same chemi-
cal formula that could generate this
O-H C-H C-C
0.4
stretch stretch C-O
type of spectrum.
stretch
0.2
Share and discuss your results with a class-
3000 2000 1000
mate, and clearly justify your reasoning.
Wavenumber (cm ) -1
A Mystery Drink
Molecular Geometry
The illegal drug was identified as “BD” by a forensic lab; the drug is
GHB
also known as “One Comma Four” or “One Four Bee.” This chemi-
cal substance has euphoriant effects in our body, similar to those O H H H
of ethanol. Additionally, BD is transformed into GHB inside cells. H O C C C C O H
GHB is famous because of its narcoleptic effects (date rape drug).
H H H
• Investigate the chemical formula and Lewis structure of BD
and compare them with your results from the previous activity;
• Identify the main functional groups in the BD and GHB mol-
ecules;
Ethanol
• Draw three dimensional structures of BD and GHB using:
a) wedge and dash projections; b) skeletal or bond-line struc-
H H
tures. Provide the electron domain and molecular geometry H C C O H
around each C and O atom in these two molecules.
H H
Share and discuss your results with a classmate, and clearly justify
your reasoning.
Bond and Molecular Polarity
The molecular geometry and polarity of drugs such as ethanol, BD, and GHB
determine how their molecules interact with protein receptors in our body:
• Assign partial charges to each of the different atoms that make up the mol-
ecules of BD and GHB. Sketch the bond dipoles associated with each of the
bonds in these molecules paying attention to their relative magnitude and
direction.
• Discuss whether you would expect these substances to be polar or non
polar.
• The more polar a substance is, the more difficult for it to go through cell
membranes and affect cell functions. Which of these substances, BD or
GHB, can then be expected to be a better narcoleptic?
• How would you explain that ethanol has stronger euphoriant effects (pro-
duce intense excitement) than BD in our body?
Share and discuss your results with a classmate, and clearly justify your reasoning.
164 Are you Ready?
A Mystery Drink
Metal Poisoning?
The presence of a bluish line along the gums of the intoxicated man led the foren-
sic investigators to also consider “metal poisoning.” Forensic scientists commonly
use atomic absorption spectroscopy to detect the presence of metals. Blood analy-
sis using this technique revealed a strong absorption at 188.5 kJ/mol.
• Using the absorption spectra for different metallic elements shown on this
page, determine the most likely identity of the metal in this beverage.
• Write the electron configuration of this metallic element and discuss what
type of substance this is.
Share and discuss your results with a classmate, and clearly justify your reasoning.
Mg
Pb
Hg
Cd
Reflecting Back
It is important that you reflect on the way you approached the work on these assessment activities and self-
evaluate your knowledge and understanding:
• Which of the tasks did you find most difficult? What made it difficult for you? How did you tackle it?
• How did you evaluate each of your answers? How did you know they were correct or incorrect?
Discuss with a classmate those concepts and ideas you have most trouble understanding.

Module 1
P82 & P83: Background image from Microsoft Office; P84: Top right by William Chien (Own work) [NoDerivs 2.0 Generic] https://www.
flickr.com/photos/58935121@N08/14661414636; P85: Fig. 2.1 “Onde electromagnetique” by SuperManu (Own work) [Share Alike 3.0] http://
commons.wikimedia.org/wiki/File:Onde_electromagnetique.svg; P86: Fig. 2.2 “EM spectrumrevised” by Philip Ronan, Gringer (Own work)
[Share Alike 3.0] http://commons.wikimedia.org/wiki/File:EM_spectrumrevised.png, Fig. 2.3 Derivative from image by ADInstruments; P88:
Fig. 2.4 Screenshot of PhET simulation http://phet.colorado.edu/en/simulation/photoelectric; P91: Fig. 2.8 “Co ellipse” by Joseph A. Stroscio
Robert J. Celotta Steven R. Blankenship Frank M. Hess (Own work) [Public domain] http://commons.wikimedia.org/wiki/File:Co_ellipse.gif;
P94: Fig. 2.12 by NASA, Bottom Derivative from images by NASA; P95: Bottom center By Natural Institute of Environmental Health Sciences
(NIEHS); P96: Top Right “Starsinthesky” by European Space Agency (ESA/Hubble) [Share Alike 3.0] http://commons.wikimedia.org/wiki/
File:Starsinthesky.jpg, Bottom left “Trifid Nebula” by NASA.
Module 2
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P102: Fig. 2.15 Derivative from
image by Jindrich Kolorenc http://www.fzu.cz/~kolorenc/qmc/; P108: Fig. 221 Derivative from images from Life Sciences Foundation; P111: Fig.
2.25 “System2” by Bvcrist (talk) (Own work) [Public domain] vhttp://commons.wikimedia.org/wiki/Fitxer:System2.gif; P112: Fig. 2.23 Deriva-
tive from “HAtomOrbitals” by Florian Marquardt (Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/File:HAtomOrbitals.png;
P115: Fig. 2.29 By David Young & James F. Harrison http://server.ccl.net/cca/documents/dyoung/water/.
Module 3
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P139: By Sarah Harris (Own
work) [Generic 3.0] http://cnx.org/content/m32928/latest/?collection=col10677/latest.
Module 4
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P153: Center By Barb Deluisi
at NOAA http://www.esrl.noaa.gov/gmd/outreach/carbon_toolkit/basics.html; P154: Top right “NOAA Land Ocean temperature anomaly” by
Giorgiogp2 (Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/; P155: Top right Source: Chemisty at Penn State University
http://courses.chem.psu.edu/chem210/mol-gallery/methane-vib/methane-vibrations.html; P157: Top left image from Microsoft Office, Bottom
right by Kyrylo Bessenov & George Harauz https://journal.lib.uoguelph.ca/index.php/surg/article/view/1102/1802; P158 & P159: By Johan-
na84 (Own work) [Public domain] via Pixabay http://pixabay.com/en/orange-the-oranges-the-fruit-of-the-207819/; P160 & P161: By Schwar-
zenarzisse (Own work) [Public domain] via Pixabay http://pixabay.com/en/fish-swim-see-fishing-catch-fish-301312/.
General
UNIT 3
How do we
predict
properties?
The core concepts, ideas, and models introduced and dis-
cussed in Unit 1 and Unit 2 can be used to explain and
predict the physical properties of a wide variety of useful
materials in our world. They can also serve as a guide in
the design of chemical substances with specific properties,
from antibiotics to plastics to detergents and soaps. The
central goal of Unit 3 is thus to show you how to use your
knowledge to explain and predict the physical properties of
chemical compounds based on their submicroscopic compo-
sition and structure.
To illustrate the power of the chemical ideas and models that

we have discussed, we will focus our attention on the analysis
and design of useful materials in our world. In particular, we
will try to address these two basic questions:
How can we use structural information to predict physical

properties?
How can we use physical properties to infer structural
characteristics?
166
Chemical Thinking
UNIT 3 MODULES
M1. Analyzing Molecular Structure
Predicting physical properties based on mo-
lecular structure.
M2. Considering Different Scales
Predicting physical properties based on analy-
ses at different molecular scales.
M3. Characterizing Ionic Networks
Predicting physical properties based on ion size
and charge.
167
168
Analyzing
Molecular
Structure
One of the major benefits of chemical thinking is that it allows us to explain and
U3: MODULE 1
predict the physical properties of chemical substances based on the analysis of

their submicroscopic composition and structure. These types of predictions are
greatly facilitated by identifying the types of atoms present in the system. For ex-
ample, if all the atoms that make up a chemical substance belong to nonmetallic
elements, it is likely that the substance is a molecular compound. If we find that the
chemical composition involves a combination of atoms from me-
tallic and nonmetallic elements, the chemical substance is likely
to be an ionic compound. As we will see in this Unit, this initial CO2
classification based on chemical composition is extremely helpful
in deciding what type of chemical principles and models to ap-
ply in explaining or predicting physical properties. For example,
it helps us decide whether we should think of the substance as NaCl
made up of individual molecules or by anions and cations ar-
ranged in a network. This simple distinction determines which
structural factors should be taken into consideration while mak-
ing predictions. Let us then start our discussion by analyzing the factors that influ-
ence the physical properties of molecular compounds.
THE CHALLENGE Liquid Crystals?
Imagine that you wanted to design a new type of material that can have inter-
mediate properties between a liquid and a crystalline solid. For example, you
may want the material to flow as a liquid but still have its molecules arranged
in an ordered fashion to interact with light as a crystal.
• What types of molecular structures could lead to such properties?

• Which molecular characteristics would determine phase behavior?
central goal of Module 1 is to develop your ability to explain and predict the
physical properties of molecular compounds based on the nature and strength
of the intermolecular interactions between their molecules.
Chemical Thinking U3 How do we predict properties? 169
Molecular Compounds
In general, the chemical combination of atoms of nonmetallic elements, such as
C, H, O, and N, results in the formation of individual molecules in which atoms
are connected to each other via covalent bonds. This behavior can be explained by
analyzing the electronegativity c and valence of the atoms involved.
As we discussed it in Unit 2, bond formation is a stabilizing process for atoms
with unfilled valence orbitals because some electrons can occupy lower energy
states. However, the distribution of valence electrons in a bond will depend on
the electronegativity of the participating atoms. In particular, a difference in elec-
tronegativities Dc = cA - cB between bonded atoms A and B will favor an uneven
distribution of electrons (bond polarity), but the magnitude of this effect will
depend on the average electronegativity cAV = (cA + cB)/2 of the system. The larger
the electronegativity of each of the atoms involved, the more energetically costly
for electrons to move away from any of them. Given that atoms of nonmetallic
elements have relatively high electronegativities, the value of cAV tends to be high
(cAV > 2.0) while that of Dc is relatively low (Dc < 2.0) when bonds between
these types of atoms are formed. As a result, the most stable charge distribution is
that in which bonding electrons are delocalized between the two atoms forming Figure 3.1 The physical prop-
the covalent bond. Covalent bonds are said to be highly “directional” because the erties of a molecular com-
pound emerge from the inter-
likelihood of finding the bonding electrons outside the region between the two action of many molecules but
are ultimately determined by
bonded atoms is low. its chemical composition.
Molecules are atomic systems in which atoms are connected to a few other
atoms arranged in well defined directions in space. The high directionality of cova-
lent bonding combined with the constraint in the number of bonds that atoms of
nonmetallic elements can form (their valence) favors the formation of individual
H2O
molecules rather than, for example, large networks of interconnected atoms. The
physical properties of molecular compounds, such as their density, viscosity, heat
capacity, and boiling point, are determined by the nature and strength of the inter-
actions between their molecules. These physical properties are said to emerge from
the dynamic interactions of the myriads of molecules that make up a macroscopic
sample of the substance (Figure 3.1). Consequently, to predict the actual value
of, let’s say, the boiling point of water based on information about its molecular
structure we would have to simulate the behavior of a system composed of the
order of a mole (1023) of H2O molecules. This task would be quite challenging ET
and computationally demanding. However, as we will see in this module, simple 1s22s22p4
chemical models allows us to qualitatively predict the relative values of the physical
properties of a wide variety of molecular compounds.
Intermolecular
Force
d-
O
d+ H H
170 MODULE 1 Analyzing Molecular Structure
LET’S THINK Important Factors?
The stronger the intermolecular forces (IMFs) between the T (oC)

molecules in a compound, the more energy is required to
G
separate molecules from each other. This in turn affects the
value of physical properties such as the boiling and melt-
ing points of the substance. The following representation
100
depicts the boiling and melting points of two molecular
compounds, HCl and H2O:
L
G
• Make a list of all of the composition and structural
0
factors that you think affect the nature and strength of
the IMFs between the molecules that make up each of
these two compounds.
• How would you explain the differences in the melting L
-100 S
and boiling points of these two substances?
S
Share and discuss your results and ideas with a classmate,
and clearly justify your reasoning.
Intermolecular Forces
F
Interactions between the different molecules that make up a substance
arise because molecules contain charged particles, electrons and protons,
Repulsion
that attract or repel each other with forces that vary depending on the
d intermolecular distance (Figure 3.2). The strength of these intermolecu-
lar forces (IMFs), as well as how this strength varies with the distance
between molecules, are affected by factors such as the total number of
Attraction
electrons in the interacting molecules and the distribution of electrons

http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M1/dispersion.html
and atomic nuclei within these particles. Predictions about the relative
strength of IMFs between different types of molecules can thus be simpli-
fied by paying close attention to molecular properties such as bond polar-
ity, molecular polarity, and polarizability (a measure of how easy it is to
Figure 3.2 IMFs between differ- change charge distribution in a system).
ent types of molecules (repre- The distribution of electrons in a molecule is always affected by the presence
sented as red and blue spheres)
of other molecules or ions in their surroundings. Electrons are charged particles
with a small mass and are thus easily accelerated by the action of electric or mag-
CLICK TO PLAY netic forces. In atoms and molecules, electrons are attracted to the protons in the
different atomic nuclei in the system and the effect of external forces
acting on them will vary depending on electron location. For example,
internal or core electrons are likely to be less affected than the more ex-
ternal valence electrons. The extent to which charge distribution in the
atoms or molecules that make up a substance is affected by the pres-
ence of an external charge can be used as a measure of the substance’s
Figure 3.3 Explore how elec- polarizability (see Figure 3.3). The magnitude of the polarizability in atomic and
tron distribution is affected by molecular system can be expected to depend on the number of electrons and the
the presence of another atom
or charged species. volume that these electrons occupy.
Polarizability LET’S THINK

Consider the following pairs of molecules represented as generic neutral particles of different sizes
and with different numbers of protons (p+) and electrons (e–):
8 p+ 8 e– 8 p+ 8 e– 8 p+ 8 e– 12 p+ 12 e– 12 p+ 12 e– 8 p+ 8 e–
• Which of the molecules in each pair is more polarizable? Justify your reasoning.
The polarizability of atoms and molecules is a measure of the ease with which
the electrons and nuclei that make up these particles can be displaced from their
average positions. In general, atomic and molecular polarizability increases with
the number of electrons present in the system and with the size of the space they
may occupy. The more electrons a particles has, the more likely that some of them
will be affected by external forces acting on them. The larger the size of the par-
ticle, the weaker the interactions of the more external electrons with protons in
the nuclei, which facilitates charge redistribution. Given that external electrons are
the ones that contribute the most to the polarizability of molecular systems, the
more exposed these electrons are, the more polarizable the molecule will be. Thus,
molecules with a large surface area, such as those with flat or elongated geometries,
are more polarizable than those with more spherical shapes.
In general, it is useful to think of the net force between different molecules as re-
sulting from three major of contributions: polarizability, molecular polarity, and
bond polarity. For example, part of this force may be attributed to the high po-
larizability of the molecules while another contribution may be associated to the
presence of a strong dipole moment. In the rest of Module 1 we will discuss how to
infer the relative importance of these different contributions based on the analysis
of the composition and structure of the interacting molecules in pure substances.
Analyzing Trends LET’S THINK

Consider the following data:
Molecular Total Boiling Point Heat of Vaporization
Substance Number e– (K) (kJ/mol)
H2 2 20.3 0.904
F2 18 85.0 6.51
C2H6 18 184.6 14.7
• How could you explain these results based on the bond polarity, molecular polarity, and
polarizability of the different molecules?
Share and discuss your results and ideas with a classmate, and justify your reasoning.
Dispersion Forces: When two atoms or molecules approach each other, at-
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M1/polariza.html
tractive interactions between protons in one particle and electrons in the other,
as well as repulsive interactions between electrons in both systems, may “polar-
ize” each of the particles. This means that some parts of each molecule may be-
CLICK TO PLAY come more electron-rich than others, creating zones that acquire a negative partial
charge while other regions may have a positive partial charge (elec-
tron deficient regions). We say that the interacting particles develop
“induced dipole moments.” This uneven distribution of charge is not
permanent and the induced dipole moments will appear and disap-
pear as particles move closer or away from each other, or change their
relative orientation in space (Figure 3.4). However, when two atoms
or molecules interact, the formation of these dynamic dipole mo-
ments results in a net force between particles that may be attractive
or repulsive depending on the distance between them. These types of
intermolecular forces are traditionally called dispersion forces and
Figure 3.4 Dispersion
they are present among any two atoms or molecules. Other common labels used
forces between atoms or to refer to these types of forces include “London dispersion forces” and “induced
molecules result from in-
teractions between instan- dipole-induced dipole interactions.”
taneous dipole moments.
The strength of the dispersion forces between particles tends to be propor-
tional to the product of the polarizabilities of the interacting species. These types
of forces can then be weak in systems composed of small non polarizable particles,
but pretty strong for substances made up of molecules with many electrons and
a large surface area. Dispersion forces are the major contribution to the IMFs
between the atoms and molecules of most substances. As we will see later, con-
tributions from other types of interactions only become important for systems
comprised of small polar molecules. For non polar substances, the magnitude of
the dispersion forces between particles determines many of their physical proper-
ties, such as melting and boiling point, surface tension, and viscosity. The strength
of these interactions can be estimated by measuring the energy needed to evapo-
rate one mole of the liquid substance at a given temperature and pressure (molar
heat of vaporization, Qvap). These types of experimental results indicate that the
strength of dispersion forces typically falls in a range between 0.05 to 40 kJ/mol
for most common substances.
LET’S THINK How Polarizable?
Consider these sets of different types of atoms and mol-

He HF CH4
ecules:
Ne HCl C4H10
• Which of the atoms or molecules in each set would Ar HBr C8H18
be the least polarizable? Which would be the most?
Discuss which compositional and structural factors in atoms and molecules may affect their
polarizability.
• How would you expect the strength of the dispersion forces between molecules vary within
and across these sets of particles?
Analyzing Trends LET’S THINK

Consider the following data:
Molecular Total Boiling Point
Substance Number e– (K)
C4H10 34 261.5
C3H8O 34 280.5
C3H6O 32 184.6
• How could you explain these results based on the bond polarity, molecular polarity, and
polarizability of the different molecules?
Dipole-Dipole Forces: Dispersion interactions between all types of molecules

result from fluctuations in the electron distributions of the interacting particles. d+
However, in the case of polar molecules additional contributions to the IMFs arise d-
from the presence of permanent dipole moments in the system. Polar molecules
are characterized by the presence of electron-rich regions (with a negative par- d+
tial charge) and electron-deficient regions (with a positive partial charge). These
molecules can thus be thought of as assemblies of opposite partial charges that
interact via electrostatic forces with the partial charges on other particles (Figure d-
3.5). These types of interactions, called dipole-dipole forces, cause molecules to
reorient in space as regions with opposite charge are attracted to each other and
regions with similar charge repel each other. These types of IMFs are said to be Figure 3.5 Dipole-Dipole
interactions between HCl
“directional” because their strength depends on the relative orientation of the in- molecules.
teracting particles.
Dipole-dipole forces between polar molecules are an additional
attractive contribution, besides dispersion forces, to the IMFs be-
tween particles of polar molecular compounds. Thus, one can ex- 7
Vapor Pressure (atm)
pect polar molecules to be attracted more strongly to each other than

non polar molecules with similar polarizability (i.e., with equivalent C4H10
5
contributions to IMFs from dispersion forces). For example, acetone
(C3H6O) and isobutane (C4H10) have similar polarizabilities. Howev- m = 2.91 D
3
er, we can expect the IMFs between C3H6O molecules to be stronger
than those between C4H10 molecules due to the dipole-dipole forces
between acetone molecules. This phenomenon can be used to explain 1 C3H6O
why the boiling point of acetone is higher than that of isobutane at
all pressures (Figure 3.6). 250 270 290 310 330
In general, the strength of dipole-dipole forces is proportional Temperature (K)
to the product of the net dipole moment of the interacting particles.
Although interactions between polar molecules can be quite strong
Figure 3.6 Dipole-dipole forces
(5 to 40 kJ/mol), dipole-dipole forces frequently account for less than 20% of the between acetone (C3H6O) mole-
total IMFs between polar molecules. For most substances, polar or non polar, dis- cules reduce the vapor pressure
of this substance compared to
persion forces are the major contributors to intermolecular interactions. that of isobutane (C4H10)
Explaining Trends LET’S THINK

Consider these data:
Molecular Total Boiling Point
Substance Number e– (K)
• How could you explain these results based on
strength of dispersion interactions and dipole- O2 16 90
dipole interactions? CHF3 34 191
• How do total number of electrons and molecular Br2 70 332
polarity seem to affect boiling points? CHCl3 58 334
CCl4 74 350
Clearly justify your reasoning.
d- HF Hydrogen bonding forces: As we have seen in the previous paragraphs, molecular

polarizability and molecular polarity play a central role in determining the strength
d+ of the IMFs between the particles that make up molecular compounds. However,
there are some substances in which bond polarity also contributes to intermolecular
d- interactions. This contribution is particularly important in compounds comprised
of molecules in which hydrogen (H) atoms are covalently bonded to nitrogen (N),
oxygen (O), or fluorine (F) atoms. The differences in electronegativity Dc for the
d+ H-N, H-O, and H-F covalent bonds are large, which leads to large bond dipoles
d- and large partial charges on each of these atoms. Additionally, these different at-
CH3COOH oms are small, particularly hydrogen, which allows the electron-deficient H atoms
in one molecule to get close to the electron-rich N, O, or F atoms in another
d- molecule, increasing the probability of establishing a strong electrostatic interac-
tion between particles (Figure 3.7). This strong interaction is also enhanced by the
d+ presence of lone electron pairs in the valence shell of N, O, and F atoms, which are
attracted towards the positively charged H atoms in their vicinity.
d-
CH3NH2 The strong attractive interaction between a H atom covalently bonded to an
N, O, or F atom in a molecule, and a different N, O, or F atom in a surround-
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M1/hbond.html
ing molecule is called a “hydrogen bond” (or H-bond). It is important to notice
that, despite its name, a “hydrogen bond” is just another contribution to the IMFs
Figure 3.7 Representation between some molecules. A single H-bond can be quite strong (between 10 to 40
of hydrogen bonding inter-
actions (red dotted lines) kJ/mol), but not as a strong as a covalent bond between a H atom and a N, O, or
between different types of
molecules. F atom (from 350 to 570 kJ/mol) in a molecule.
LET’S THINK Hydrogen Bonding?
The interactive tool associated with this activity includes several representations of the molecular
structure of a variety of molecular compounds. CLICK TO PLAY
• Analyze the structure of each of these molecules and predict which

parts of a molecule can form H-bonds with a similar or a different
molecule in the set. Test your predictions by dragging the selected
molecules onto the stage and observing their interactions. Share and
discuss your ideas with a classmate.
Hydrogen bonding is a highly directional and highly local contribution to the

IMFs between molecules. This means that the strength of this type of interaction
strongly depends on the relative orientation of the interacting particles (direction-
ality) and the force is highly localized between specific atoms. Thus, there is a re-
duced number of molecular arrangements in which H-bonding between a pair of
molecules may occur. However, once the interaction takes place it is likely to keep
molecules close to each other for extended periods of time (i.e, until collisions
with other molecules provide enough energy to separate the particles or change
their orientation). Hydrogen bonding may be the most important contribution
to the IMFs between small polar molecules that are not very polarizable. Such is
the case of water, H2O, for which H-bonding accounts for over 70% of the IMFs
between water molecules.
Analyzing Hydrides LET’S THINK

“Hydride” is the generic name given to all compounds that result from the combination of
hydrogen with other elements. Many of these compounds are vital to life in our planet or have
industrial applications. The following graph depicts the boiling points of the different sets of
hydrides formed by the reaction of hydrogen with non metallic elements.
• Explain the trends in the variation

100 H2O
of the boiling points for hydrides
formed with elements of the same Lines connect hydrides
periodic group or family. Justify of elements in the same
periodic family.
all deviations from these trends
Temperature (oC)
based on your analysis of differ- 0 H2Te

H2Se
ent contributions to the IMFs NH3 H2S SbH3
between molecules.
• Explain the trends in the variation SnH4
AsH3
of the boiling points for hydrides
-100 PH3
GeH4
formed with elements in the same SiH4
row in the periodic table.
CH4
Share and discuss your results and
ideas with a classmate, and justify your 2 3 4 5
reasoning. Period
Hydrogen bonding interactions are of central importance

in biological systems. For example, the biological activ-
ity of proteins and nucleic acids (e.g., DNA)
depends on its three dimensional structure Figure 3.8 The helical
structure of DNA is sus-
(Figure 3.8). As we will see in the next mod- tained by H-bonding inter-
actions (red dashed lines).
ule, the molecular geometry of these large
molecules strongly depends on H-bonding
between atoms within the same molecule.
Your Turn
The central concepts and ideas about molecular structure and intermolecular forces discussed up to
this point should have helped you develop the basic knowledge and skills that are needed to explain
and predict the properties of molecular compounds, and even to design substances with desired prop-
erties. To test your ability to apply chemical thinking in this area, we have designed a set of challenges
based on two very important groups of substances for life in our planet:
Carbon Compounds
Are you Ready to Face these Challenges?
Carbon Compounds
Among all the known chemical elements, carbon is the most multifaceted. Carbon atoms chemi-
cally combine with other carbon atoms, or with atoms of other nonmetallic elements, to form a
wide variety of stable chemical compounds. This versatility is due in part to the high valence of
the carbon atoms which can combine with other four atoms of the same or different types to
form linear, ramified, or cyclical molecules. The physical properties of carbon compounds
are determined by the polarizability and polarity of their molecules. As we have seen in
this module, these factors affect the strength of intermolecular forces. Critical informa-
tion about molecular polarizability and polarity can be inferred by paying close at-
tention to the size, shape, and chemical functionality of the molecules that make up a
carbon compound. Keep these ideas in mind when facing the following challenges.
Phase Change
Hexane (C6H14) is a common liquid solvent that boils at 341 K.
• What chemical substances are present in the bubbles of boiling hexane?
Family Matters
Linear alkanes, alcohols, and ketones are commonly used as reactants to synthesize many useful prod-
ucts and as solvents in labs and industries. The graph depicts the boiling points for three different com-
pounds in each of these families of substances.
200
Alkanes
• How would you explain the trend in boiling 160 Ketones
points within a family and across families? Alcohols
• Select a set of compounds with similar boiling 120

points across families; write their chemical for- 80
Tb (oC)
mulas and draw their molecular structures. Based

40
on these data, derive an empirical rule to predict
when the contribution of dispersion forces to 0
IMFs is likely to overcome the contributions from
–40
molecular polarity and from hydrogen bonding.
3 5 7
Clearly justify your reasoning. # of Carbons
Amines
Amine are carbon compounds that con-

Amine Dipole Boiling Point
tain a nitrogen atom bonded to hydrogen Moment (D) (oC)
atoms and carbon atoms. The table shows
chemical formula, dipole moment, and CH3NH2 1.6 –7
boiling points of three different amines. CH3NHCH3 1.0 9
(CH3)3N 0.6 3
• Build a reasonable explanation for
the relative boiling points of these substances.
Cycloalkanes
Cycloalkanes are carbon compounds characterized by the presence of
one or more rings of carbon atoms in their molecular structure. The
shape of their molecules affects the physical properties of these types of
compounds. Consider, for example, the boiling points, densities (r), and
viscosities (h; measured in centipoises, cP) of the following compounds:
Linear Alkanes Cycloalkanes

Tb (oC) r (g/ml) h (cP) Tb (oC) r (g/mL) h (cP)
C5H12 36 0.63 0.24 C5H10 49 0.75 0.42
C6H14 65 0.66 0.29 C6H12 81 0.78 1.02
C8H18 126 0.70 0.54 C8H18 149 0.83 2.1
• How would you explain the differences in property values for linear
alkanes and cycloalkanes with the same number of carbons?
• Estimate the values of the different properties for heptane (C7H16)
and cycloheptane (C7H14).
Aromatic Compounds
Linear Boiling Point Aromatic Boiling Point
An aromatic compound is a Alkane (oC) Compound (oC)
hydrocarbon with alternating
single and double bonds between C5H12 36 C6H6 80
carbon atoms forming rings. C6H14 65 C7H8 111
• Build a reasonable explanation for the higher boiling points of

aromatic compounds versus those of linear alkanes with similar
numbers of electrons.
Given that carbon atoms can form covalent bonds with other carbon atoms
in different directions, molecules of carbon compounds may not be linear and be
comprised by several “branches” of carbon chains. The presence of these branches
or ramifications affects the strength of the IMFs between particles.
Structural Isomers
Chemical compounds made up of molecules with the same molecular formula but
different atom connectivity are called structural isomers. The following table lists
some of the physical properties of different isomers of pentane (C5H12):
Let’s Think
Isomer Tb (oC) r (g/mL)
n-pentane 36 0.63
isopentane 27.7 0.62
neopentane 9.5 0.59
• How would you justify the observed changes in the values of the boiling point
and density for these substances? What seems to be the effect of branching on
the physical properties of these carbon compounds?
Lubricants
Liquid alkanes are commonly used as lubricants, both in the automotive and the
cosmetic industries. In general, lubricants are expected to have high viscosities and
low volatilities. Analyze the molecular structure of the following isomers of decane
(C10H22):
• Which of these isomers will work best as a lubricant?
Interactions in Mixtures
Dispersion forces, dipole-dipole interactions, and hydrogen bonding are the major
contributions to the IMFs between molecules in pure chemical compounds. How-
ever, when different types of substances are in contact with each other in a mixture
additional types of interactions may arise. The nature of these interactions may be
inferred by carefully analyzing the nature of the interacting particles. For example,
when a non polar substance interacts with a polar compound we can expect the
permanent partial charges on the polar molecules to induce a temporary dipole
moment on the molecules of the non polar species. The polarization of the non
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M1/benz.html
polar molecules will cause a net attractive force between particles as a result of a
dipole-induced dipole interaction. Similarly, if a non polar substance interacts
with an ionic compound, the positive and negative ions in this latter system will
polarize the non polar molecules leading to attractive ion-induced dipole interac-
tions. If the ionic compound was to interact with a polar substance, the attraction CLICK TO PLAY
between particles will be the result of ion-dipole forces. The strength of all these
types of interactions will depend on the specific composition and structure of the
interacting particles. The table at the bottom of this page presents prototypical
ranges of strength (measured as energy needed to separate particles) for common
chemical substances. Notice that these energies are far smaller than those needed
to break covalent bonds between atoms in a molecule (~300-500 kJ/mol).
The strength of the interactions between different types of particles affects the
Figure 3.9 There is a net
extent to which substances mix with each other. In general, the random move- attraction between ben-
ment of different types of particles leads to mixing, particularly if the interactions zene molecules and water
molecules. Why is benzene
between molecules of different types are as strong as the interactions between mol- not soluble in water then?
ecules of the same type. However, if the molecules of a substance interact more
strongly with each other than with the particles of a different substance, mixing
will be less likely to occur, particularly at low temperatures. Mixing could also be
hindered if there are many more ways in which the particles of one substance can
interact with each other than with the particles of the other substance. In general,
segregation or immiscibility of molecular compounds is more likely to be observed
in systems in which the mixed particles exhibit large differences in molecular size,
composition, and structure (Figure 3.9).
Intermolecular Forces in Mixtures
Ion-Dipole Dipole-Dipole, H-bonding Dipole-Dipole

(4-600 kJ/mol) (10-40 kJ/mol) (5-25 kJ/mol)
Ion-Induced Dipole Dipole-Induced Dipole Induced Dipole-Induced Dipole

(3-15 kJ/mol) (2-10 kJ/mol) (0.05-40 kJ/mol)
We can qualitatively predict whether two substances will mix or not with each
other by constructing potential energy-configurations diagrams such as those we
used in Unit 1 to analyze phase transitions. To predict solubility, we want to com-
Ep pare the relative potential energy and the available number of molecular configu-
H2O-CH3OH System
rations for the mixed and the unmixed states of the two components. Consider,
for example, a mixture of methanol (CH3OH) and water (H2O). In this case,
interactions between CH3OH molecules and H2O molecules are rather similar
to those between the water and the methanol molecules themselves. This suggests
that the potential energy of the mixed state is similar to that of the unmixed state
(see Figure 3.10). Given that the two types of molecules do not differ much in size
or in the nature of their intermolecular interactions, we can predict that random
Unmixed Mixed motion will lead to the formation of the mixture (there are many more molecular
configurations in the mixed state than in the unmixed state). This type of behavior
# of Configurations is typical of systems involving molecules that are similar in size, composition, and
structure. That is why it is common to say that “like dissolves like” as random
Figure 3.10 Potential en- molecular motions lead to mixing in these types of systems.
ergy-configurations diagram
for the CH3OH-H2O system. Making judgements about the relative potential energy and the number of
available molecular configurations of the mixed and the unmixed states is not
always easy. However, paying attention to these two factors is critical in explaining
and predicting the mutual solubility of substances at different temperatures.
LET’S THINK Mutual Solubility

Consider the following potential energy-configurations diagrams for two different pairs of sub-
stances: Water-Sugar and Water-Hexane.
Ep Ep
H2O-C12H22O11 H2O-CH3CH2CH2CH2CH2CH3
Unmixed Mixed Mixed Unmixed
# of Configurations # of Configurations
• Analyze each diagram and predict whether each pair of substances can be expected to mix
or not when they get in contact with each other.
• Predict the effect of increasing or decreasing the temperature on the mutual solubility of
each pair of substances.
• Discuss how you would expect a change in pressure to affect the mutual solubility of these
substances.
Your Turn
Important systems in our planet, including the atmosphere, hydrosphere, lithosphere, and biosphere
are mixtures of compounds that contain oxygen as a component. Oxygen gas, for example is the sec-
ond most abundant substance in the atmosphere and water is the most abundant liquid on Earth. The
following challenges have been designed to test your ability to apply chemical thinking to predict and
explain the properties of Oxygen Compounds and their Mixtures.
Are you Ready to Face these Challenges?
Oxygen Compounds
Oxygen is a highly reactive nonmetallic element. It exists in the form of O2(g) in our
atmosphere (20.8% of air’s volume) but it readily reacts with many substances leading
to the formation of both molecular and ionic compounds. In consequence, oxygen
atoms in the Earth’s crust account for almost half of its total mass. Given that oxygen
atoms comprise most of the mass in water, these elemental atoms also account for
most of the mass of both the hydrosphere and most living organisms. All major types
of structural compounds in living organisms, such as proteins, carbohydrates, lipids,
and nucleic acids are made up of molecules with oxygen atoms that have a strong
impact on the nature of the intermolecular interactions.
Let’s Think Polluting Oxides
Oxygen reacts with nonmetallic elements

such as nitrogen and sulfur to form molecu-
Atmospheric Components lar oxides that act as atmospheric pollutants:
The table lists the normal boiling points of

major components of our atmosphere: NO2
NO SO2
Substance Tb (K)
N2 77.4
Ar 87.3 N2O SO3
O2 90.2
• How would you explain these results? • Arrange these substances in order of
• Based on this data, estimate the normal increasing normal boiling point as pre-
boiling for ozone, O3, an allotropic dicted based on IMF strength.
form of oxygen.
Share and discuss your results and ideas with
Share and discuss your results and ideas with a classmate, and clearly justify your reason-
a classmate, and justify your reasoning. ing.
Water, H2O, is the most abundant molecular compound of oxygen on our

planet and it is a vital substance for all known forms of life. The molecular com-
position and structure of this chemical compound are responsible for physical
properties that are unexpected in substances made up of small particles.
Heat Capacity
Water helps regulate the temperature of the lower layer of our atmosphere, the
troposphere. This is due to its high “heat capacity.” The specific heat capacity
Let’s Think is a measure of the amount of energy
required to change the temperature of Substance Heat Capacity
1.0 g of substance by 1 C. Consider the
o (J/(g oC))
specific heat capacities listed in this table: H O(l) 4.184
2
• How would you explain the dif-

H O(g)
2
2.0
ferences in heat capacities for these CH3CH2OH(l) 2.44
substances (the letters within pa- C6H6(l) 1.67
rentheses, l and g, indicate whether
the substance is in the liquid or gas state, respectively)?
• How can H2O(l) help regulate the temperature of the troposphere?
• What would be the environmental impact of water having a smaller
Earth
NASA heat capacity?
Density Wonders A Linear Molecule?

http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M1/water.html
Water is one of the few chemical substances Imagine for a second, that the water
known to have a solid phase (ice) that is less molecule was linear and not bent.
dense than its liquid phase.
• How would this change the
• Analyze the molecular dynamics simulation strength of the different contri-
for the melting of butions (i.e., dispersion, dipole-
CLICK TO PLAY
ice associated with dipole, and H-bonding) to the
this activity. Use IMFs between water molecules?
your observations, • What would be the impact of
together with your this change on a) the physical
knowledge of IMFs, properties of water, b) Earth’s
to explain why ice climate, and d) life in our
is less dense than planet?
liquid water.
© Roy Tasker, VisChem Project.
Share and discuss your ideas with a
Share and discuss your ideas with a classmate. classmate.
Intermolecular forces between the molecules of a liquid substance are responsible for a phenomenon
By PD (Own Work) [Share Alike 3.0]

known as surface tension. Interactions between molecules at the liquid surface allow

it to resist the action of external forces as revealed, for example, in the ability of some
insects to walk on water surfaces without sinking. The surface tension is a measure
of the force per unit length needed to extend the surface of the liquid and separate
its molecules. Thus, it is typically measured in dynes/cm (force/length). Liquid wa-
ter has a large surface tension compared to other liquids (72.8 dynes/cm at 20 oC).
Surface Tension
The surface tensions of different liquid alcohols measured at 20 oC are shown in the table:
Let’s Think • How would you explain the large dif-

Surface
ference in the surface tension of these
Substance Tension
liquids compared to that of liquid water?
(dynes/cm)
• How would you explain the trend in the
CH3OH(l) 22.4
variation of the surface tension as the
molecular length increases? CH3CH2OH(l) 22.1
• How would you expect the surface ten- CH3CH2CH2OH(l) 23.6
sion of these liquids to vary when chang-
CH3CH2CH2CH2OH(l) 24.3
ing the temperature?
Water-Alcohol Mixtures Ep
H2O-CH3CH2CH2OH
The potential energy-configuration diagram for a mixtures of water and
propanol (CH3CH2CH2OH) is shown to the right.
• Would you expect water and propanol to mix?

• How would an increase in temperature affect the solubility of
propanol in water?
Unmixed Mixed
Spectroscopic analysis of the surface of mixtures of water with propanol
reveals that propanol molecules tend to accumulate at the surface of the # of Configurations
liquid mixture, adopting configurations like those shown in the image.
• Explain this phenomenon based on the comparison of the poten-

tial energy and number of molecular configurations for a state in
which propanol molecules are at the surface and another state in
which they are homogeneously distributed in the solution.
• Discuss how the presence of propanol molecules at the liquid sur-
face may affect the surface tension of the solution.

Given that water is the most abundant chemical compound in liv-

ing organisms, the way in which other substances interact with water has
ByDiliff (Own Work) [Generic 2.5]

a crucial impact on the anatomy and physiology of plants and animals.

Whether a substance dissolves or not in water, or the extent to which it
dissolves, is thus many times a question of life or death.
Gas Solubility
The main atmospheric gaseous components N2 and O2dissolve only

slightly in water, but enough to sustain aquatic life.
• If the solubility of O2 in H2O at 20 oC is close to 9 mg/L, would the

solubilities of N2 be lower or higher?
• Represent in a potential energy-configuration diagram for the two
states of the O2-H2O system shown to the right.
• Use the diagram to predict the effect of temperature on O2 solubility.
It is common to refer to chemical substances as hydrophilic or as hydrophobic, depending on the

degree to which their particles are attracted to water molecules. In general, hydrophilic molecules tend
to be polar and IMFs between these types of molecules and water molecules are as strong as the interac-
tions between the particles that make up each substance. Thus, hydrophilic substances dissolve more
easily in water. Hydrophobic molecules tend to be non polar and interactions between these types of
molecules and water molecules are much weaker than those that hold water or the hydrophobic sub-
stance together. In consequence, hydrophobic substances tend to segregate from water.
Solubility Patterns Drug Distribution
The table lists information for the solubil- The movement of a drug from the blood stream
ity in water of chloromethanes, many of into the body’s tissue depends on its solubility in
which are important ground water pol- water and in non polar lipids (which make up
lutants. cell membranes). Consider these common drugs:
Amphetamine
Sol (g/L) Sol (g/L) C9H13N
CH4 0.024 CHCl3 8.0
CH3Cl 5.3 CCl4 0.80
Ephedrine
CH2Cl2 13. C10H15NO
Methamphetamine
• How would you justify these data C10H15N
based on IMF type and strength? • Arrange these drugs in order of increasing
hydrophilicity or solubility in blood.
HINT: m(CH3Cl)= 1.92 D;
m(CH2Cl2)=1.60 D; m(CHCl3)= 1.04 D. Share and discuss ideas with a classmate.
FACING THE CHALLENGE than those wave components oscillating in a per-

pendicular plane; the material is then said to be
birefringent. Birefringence can lead to multicol-
Liquid Crystals ored images when liquid crystals are examined
It is common for people to think that all substanc- under polarized white light (this is, light in which
es can only exist in the three traditional states of the electric field is confined to oscillate in a single
plane). Electromagnetic waves of different colors
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M1/lc.html
matter: gas, liquid, and solid. However, there are
some chemical compounds that exhibit a wider have different wavelengths and their speed will be
range of phase behaviors. For example, some sub- affected in distinctive ways by the material. They
stances may exist in states that have intermediate will thus emerge with different polarization direc-
properties between those of a liquid and a solid tions and will lead to different colors when analyzed
crystal. These “liquid crystal” phases may flow like through a polar-
CLICK TO PLAY
a liquid but refract light like a crystal. As it can be izing filter (see
expected from the ideas discussed in this module, slide show). This
this type of behavior is mostly determined by the procedure can be
particular geometry and polarity of the molecules used to identify
that make up the substance. the presence of
Many chemical compounds that exhibit liquid diverse ordering
crystalline behavior are composed of polar mol- domains in a liquid crystal or how this ordering
ecules with cylindrical geometry. IMFs between changes with temperature.
these types of particles cause them to align along a The ability of liquid crystals to change the
common direction (called the director). Molecules direction of the electric oscillations in polarized
thus acquire orientational order although they still light has been exploited in the design of the liquid
may be located at random positions with respect crystal displays (LCD) used for computer, televi-
to each other (po- sion, and cellular phone screens. In these types of
sitional disorder). devices, a thin layer of liquid crystal is placed be-
In this type of state tween two transparent electrodes and two polariz-
of matter molecules ing filters. The filters are arranged to ensure that in
can freely flow (like the absence of liquid crystal polarized light passing
the particles in a through one of the filters will be blocked by the oth-
liquid) along the er. However, when the liquid crystal is introduced,
Solid Liquid Crystal Liquid
director axis, but the change induced in the polarization direction
movement in other directions will be highly re- allows light to go through both filters. Given that
stricted (like particles in a solid crystal). molecules of liquid crystals are polar, their orienta-
Molecular ordering in liquid crystalline phases tion in space can be changed by charging the elec-
does not tend to extend over an entire macroscopic trodes and
sample of the material. Most commonly, orienta- applying Polarizer
tional ordering along a given director only extends an electric
over a region or domain that is a few micrometers field. This
By Mingxia Gu
wide. However, a macroscopic sample of the liquid change

Electrode
crystal will be comprised of many ordered domains in ori-
with directors pointing in different directions. entation
Liquid crystalline phases have very interesting is used
and useful optical properties. For example, when to con- Analyzer
Field Off Field On
light interacts with a liquid crystal, the electro- trol the
magnetic waves oscillating in a plane parallel to amount of light that goes through the filters and
the molecular director travel at a different speed create regions with different tonalities.
Let’s Apply Glycerol
Fatty Acid
Fat Chemistry
Most substances identified as “fats” belong to a
group of chemical compounds called “triglycerides.”
These compounds can be thought as resulting from
the combination of glycerol (an alcohol) with fatty

acids (carboxylic acids) and thus are characterized Ester
by the presence of the “ester” functional group. Group Triglyceride
Chain Length
The properties of any specific type of fat are determined by the composition and structure of
the fatty acid chains that make up its molecules. Below, you can see the structure of three com-
mon fatty acids:
Lauric Acid C12H24O2
Palmitic Acid C16H32O2
Stearic Acid C18H36O2
• Which of the following fats would you expect to have the lowest melting point, the one
with molecules made up of three lauric acid chains (glycerol trilaureate), three palmitic
acid chains (glycerol tripalmitate), or three stearic acid chains (glycerol tristearate)?
The fatty acid chains that make up molecules of fat

can differ not only in length but also in the number
of double bonds between carbon atoms present in the
system. When the chains contain only single bonds
between carbon atoms they are said to be “saturated”
(each carbon atom is bonded to as many hydrogen Saturated
atoms as possible). When there is one or more double
bonds present in a chain it is said to be “unsaturated.”
The presence of double bonds alters the molecular ge-
ometry of molecules of fat, changing the strength of
their IMFs.
Unsaturated
Cis and Trans Fats
The geometry of a molecule of fat is affected by the presence of double bonds, or unsatura-
tions, in its hydrocarbon chains. The geometry depends on how the four atoms or groups of
atoms linked to the double bonded carbons are placed with respect each other. There are two
possible configurations called “cis,” when the two hydrogen atoms are bonded on the same
side of the molecule, and “trans” when the two hydrogen atoms are bonded on opposite sides:
Cis Trans
Configuration Configuration

• How would you expect the presence of double bond (unsaturations) to affect the
melting point of fats? Would you predict saturated fats to have a higher or lower
melting point than unsaturated fats?
• Which types of unsaturated fats would you expect to have a lower melting
point, fats made up of unsaturated molecules in a cis configuration (cis fats) or
fats constituted by unsaturated fatty chains with trans configuration (trans fats)?
Unsaturated Fats
Consider the line structures of these four unsaturated fatty acids:
Arachidonic Acid Linoleic Acid Linolenic Acid Palmitoleic Acid

C20H32O2 C18H32O2 C18H32O2 C16H30O2
• What types of unsaturations (cis or trans) are present in each of these molecules?
• If you had to design a fat with the lowest melting point possible using a combination
of at least two of these fatty acids to synthesize a triglyceride, which of them would you
choose? Which two fatty acids would choose to produce a fat with the highest melting
point possible?
Let’s Apply
Organofluorines
Organofluorines are chemical compounds made up of molecules that contain fluo-
rine atoms bonded to carbon atoms. The chlorofluorocarbons(CFCs) involved in
the destruction of the ozone layer of our planet are typical examples of these types of
compounds. However, organofluorines have a wide range of applications including
refrigerants (A, C, D), pharmaceuticals (B, H, I), and surface active materials (G, F).
A
Perfluorocarbons
Chemical compounds made up of only carbon and fluorine atoms are known B
as perfluorocarbons (PFC). These are non polar substances with interest-
ing properties. The table lists the boiling points of some perfluorocarbons
compared to those of hydrocarbons (HC) with the same number of elec-
C
trons (isoelectronic) and similar molecular geometry (each fluorine atom is
replaced by a –CH3 group):
PFC Tb (oC) HC Tb (oC) D

CF4 -128 C5H12 10
C2F6 -78 C8H18 107
C3F8 -37 C11H24 194 E
• How would you explain the lower boiling points of the perfluorocar-
bons compared to those of their isoelectronic hydrocarbons? F
• Would you expect perfluorocarbons to be more or less soluble in water
than hydrocarbons? G
Perfluorodecalin (C10F18) is a nonpolar cycloperfluorcarbon used to make H

“artificial blood” given its ability to dissolve large amounts
of oxygen (O2). In fact, it would be possible to breath
when submerged in a pool of this compound.
I
• How do you explain that perfluorodecalin dissolves
much larger amounts of O2 and CO2, two non polar
gases, than an equivalent hydrocarbon?
Share and discuss your ideas with a classmate, and clearly Mouse and fish
breathing under
justify your reasoning. C10F8.
Water Repellent?
By BASF (Own work) [NoDerivs 3.0]
Some textiles are frequently treated with organofluorines to make

them more hydrophobic. A layer of the fluorine compound reduces
the ability of the fibers to absorb water.
• Build a reasonable explanation to justify why some organo-

fluorine compounds may reduce water absorption by textiles.
Share and discuss your ideas with a classmate. Don’t forget to clearly justify your reasoning.

Fluorinated Drugs
In recent years, chemical scientists have discovered that substituting
one or more hydrogen atoms in the molecular structure of some
drugs many times enhances the pharmaceutical effects of these sub-
stances. One property that is frequently altered by the presence of
fluorine atoms is the capacity of the drug to dissolve and diffuse
across cellular membranes made up of non polar lipid chains.
The graph shows

measurements of 160
differences in the
relative solubility in 120
octanol versus wa- Atorvastatin
# of pairs
ter for 293 pairs of 80 (Lipitor)

molecules that only Reduces blood
differ by the pres- 40 cholesterol
ence of one fluo-
rine atom. Positive 0
values of the dif- - 0 + D
ference D indicate
that the fluorinated compound dissolves in octanol (versus water) to
a larger extent than the nonfluorinated substance.
• According to these data, how should we expect the presence

of fluorine atoms in drug molecules to most frequently affect
their ability to diffuse through cellular membranes?
• How would you explain the change introduced by fluorine
atoms in the ability of drugs to diffuse through cellular mem-
branes? Fluoxetine
(Prozac)
Share and discuss your ideas with a classmate, and clearly justify Used to treat
your reasoning. depression
190
Considering
Different Scales
Many important substances in our surroundings and inside our own bodies are
U3: MODULE 2
made up of large molecules comprised of hundreds or thousands of atoms (mac-

romolecules). These types of substances include common synthetic ma-
terials such as plastics and polymeric fibers as well as natural substances
such as carbohydrates, proteins, and nucleic acids. The molecules
that make up these materials are so big that atoms in one region
of a molecule may interact with atoms in a distant region of
the same molecule as the chain of atoms that form the back-
bone of the molecule bends over upon itself. Thus, the physical
properties of these types of substances do not only depend on
the nature of the intermolecular interactions between molecules
but also on the nature of the interactions between atoms within the Hemoglobin
Macromolecule
same molecule (intramolecular interactions).
To better understand and be able to predict the properties of chemical sub-
stances made up of macromolecules we need to explore how interactions acting at
different scales between particles in a system determine its behavior. We also need
to discuss how these different interactions will affect the global shape of macro-
molecules.
THE CHALLENGE Smart Materials
Imagine that you wanted to design materials made up of macromolecules that

can change their shape or assemble into larger and more complex units by
simply changing the temperature, pressure, moisture level, or nature of the
solvent in which they are dissolved.
• What types of molecular composition and structure could lead to such

behavior?
This module will help you develop the type of chemical reasoning that is used
to answer questions similar to that posed in the challenge. In particular, the central
goal of Module 2 is to develop your ability to explain and predict the physical
properties of macromolecular compounds based on the analysis of their com-
position and structure at different scales, and on the nature of intramolecular
and intermolecular interactions in the system.
Polymers
Polymers are a common type of materials made up of macromolecules. These mac-
romolecules are formed by repeated linking of the same type of molecule (called
a monomer) through covalent bonds. Many types of molecules can be used as
monomers to produce different polymers. The following table summarizes the
basic composition and structural features of some monomers commonly used to
produce well known synthetic polymers:
Monomer Polymer Polymer Chain
Structural Formula Molecular Structure
Ethylene Polyethylene
Vinyl Chloride Polyvinyl chloride (PVC)
Tetrafluoroethylene Teflon
Notice that brackets are used in the structural formula of a polymer to enclose the
basic structural unit that is repeated in the molecule. The subindex “n” indicates
that this unit is repeated multiple times within a single polymeric chain.
The linking of monomers during the synthesis of a polymer often leads to
macromolecular chains with different lengths. Nevertheless, chemists have devel-
oped strategies to control the average chain length of the polymers they synthesize.
Certain monomers, or mixtures of monomers, can be used to form ramified struc-
tures in which smaller chains branch out from a central chain (Figure 3.11). The
physical and chemical properties of a polymeric material are determined by both Figure 3.11 Different
the chemical composition and structure of the monomers that form the macro- ways of representing
branched polymer chains.
molecule, and the actual length and shape of the macromolecular chains.
Different Scales LET’S THINK

The properties of polymers are determined by composition and structural features at the mono-
meric scale and at the chain scale.
• How would you expect the composition of a monomer to affect the properties of a polymer?
• How would you expect the length and shape of polymeric chains to affect such properties?
192 MODULE 2 Considering Different Scales
The prediction of the physical properties of polymers is facilitated by analyz-

ing their composition and structure at different scales. We can begin such analysis
by paying attention to the chemical nature of the basic units that make up the
macromolecules (monomeric scale). The presence of specific functional groups in
the polymeric chains affects how molecules of the material interact with each other
and with the molecules of other substances. For example, some functional groups
may help produce a more hydrophobic polymer while others may facilitate the
dissolution of the polymer in water.
LET’S THINK
http://www.chem.arizona.edu/tpp/chemthink/MW/PolymerWater.jnlp
Functionality
Consider three solid surfaces made with the types of poly-

meric molecules shown in the image:
• Which of the surfaces are likely to be wetted by water

(H2O molecules will stick to them), and which ones
are likely to be dissolved by water (H2O molecules
will be able to separate the chains)? Click on the
image to open interactive simulations that may help
guide your thinking.
• What would happen if we use acetone (CH3COCH3)
or hexane (C6H14) instead of water?
Share and discuss your results and ideas with a classmate,

and justify your reasoning.
[Generic 3.0] via Wikimedia Commons
The composition and structure of the repeating units in the molecules of a

By GYassineMrabetTalk (Own Work)
polymer have a strong impact on its physical properties because the same features
are repeated multiple times along each polymeric chain. Consider, for example, the
structure of Nylon 6-6 in Figure 3.12. This polymer is produced by the reaction
of an amine and a carboxylic acid and its molecular structure includes multiple
amide groups (–CO–NH–) that can interact via hydrogen bonding with similar
groups in other nylon chains. Although a single hydrogen bond is a relatively weak
Figure 3.12 Hydrogen bond-
ing interactions between poly- interaction, the multiple hydrogen bonds formed between chains give nylon a
meric chains of Nylon 6-6.
high mechanical strength and good resistance to high temperatures.
LET’S THINK Kevlar
Kevlar is a high strength polymeric material with many appli-

cations, from producing bicycle tires to body armor. Its mo-
lecular structure is represented in the image.
• How would you explain the high strength of this material?

• Why is this material stronger than nylon 6-6?

At a larger scale, we can pay attention to the molecular architecture of the

macromolecules without considering their actual chemical composition. Factors
such as the length of the macromolecules and the presence of branching chains
stemming out from the main polymeric chains will affect the shape that polymer
chains adopt and how these chains interact with themselves and with other chains.
These factors in turn determine how close polymeric chains can get to each other,
how strongly they interact, or how easily they will be able to slide over each other.
Chain length and branching are thus used in polymer synthesis to control mate-
rial properties such as melting point, density, flexibility, elasticity, viscosity, and
thermoplasticity (how soft or hard the polymer becomes by changing the tem-
perature).
Length and Branching LET’S THINK
http://www.chem.arizona.edu/tpp/chemthink/MW/PolymerBranch.jnlp
http://www.chem.arizona.edu/tpp/chemthink/MW/PolymerLength.jnlp
Consider three different types of polymeric materials made up of molecules with different lengths
CLICK TO
and degrees of ramification (branching) as shown in the images.
CLICK
PLAYTO PLAY
B
C
• Predict how the following properties of the three types of polymeric materials will differ:
Melting point, density, flexibility, elasticity, and viscosity. In which case will the value of each
of these properties be higher or lower? Click on images B and C above to open interactive
simulations that may help guide your thinking.
To qualitatively predict differences in physical properties of polymeric ma-

terials made up of molecules with different lengths and degrees of ramification,
we need to pay close attention to how these macromolecules might interact with
each other. For example, longer molecules should have more points of interaction
with neighboring molecules than shorter molecules; they can also be expected to
have more conformations in which they can get tangled up in each other. These
phenomena are likely to result in harder materials with higher melting points. On
the other hand, polymers made up of linear molecules that can get closer to each
other than materials comprised of branched molecules are likely to have higher
densities. The presence of short branches facilitates the ability of molecules to
slide over each other, thus decreasing the viscosity of the material. However, the
presence of long branches may lead to chain entanglement, increasing polymer
viscosity. These types of structure-property relationships are exploited by chem-
ists to produce many of the different polymers in our surroundings. For example, Figure 3.13 Polymers, such as
HDPE and LDPE, used to make com-
plastic bags are commonly made using low density polyethylene (LDPE) which is mercial products are identified by
an specific recycling symbol.
made up of molecules with a higher degree of branching than those present in high
density polyethylene (HDPE) used to make water and milk jugs (Figure 3.13).
The properties of a polymeric material can also be changed by adding other

substances that affect the way in which polymeric chains interact with each other.
In fact, most commercial plastics are mixtures of one or more polymers with many
different types of additives that help make them softer, more rigid, more resistant
to high temperatures, etc. For example, to make a polymer softer it is common to
add substances made up of smaller molecules that can embed themselves between
the chains of polymers, spacing them apart and facilitating the chains sliding over
each other (Figure 3.14). These types of substances are called plasticizers.
Other types of additives may increase the strength of the interactions between
polymer chains and make the material more rigid. For example, some of these
Figure 3.14 Phtalates, with the substances are made up of polar or charged molecules that interact strongly with
general structural formula shown
above, are commonly used as neighboring polymer chains, linking
plasticizers. However, their use
is controversial because of their them to each other. Other additives
potential carcinogenic effects. may actually chemically react with the
polymer chains forming covalent bonds
that connect the chains to each other
permanently. These types of additives
are known as cross-linking agents and
are widely used in industry. Vulcanized
rubber, for example, is cross-linked us-
Figure 3.15 Vulcanized rub- ing sulfur as cross-linking agent (Fig-
ber is made up of polyisoprene
chains (in blue and green) cross- ure 3.15). Interestingly, sulfur atoms
linked with sulfur (in black). also build cross-links between protein
chains inside our body.
LET’S THINK Cross-linking
Consider the following polymer and potential-cross linking agent:
Poly vinylalcohol
(PVA)
Boric Acid
• Discuss how boric acid could act as a cross-linking agent between PVA chains. Build submi-
croscopic representations of the interactions between molecules of these two types of sub-
stances.
• PVA is a water-soluble polymer with adhesive properties. How would you expect the proper-
ties of a PVA aqueous solution to change when adding boric acid?
Proteins
Among the various polymeric substances that are present in our bodies, proteins Carboxyl
are the most abundant and the ones that have more diversified functions. Proteins Amine
are natural polymers made up of macromolecules that result from the combina-
tion of smaller molecules (monomers) called amino acids. Molecules of amino
acids contain an amine group (–NH2), a carboxylic acid group (–COOH), and Side
a side-chain (–R) with a composition and structure that varies between different Chain
amino acids (Figure 3.16a). All of the different proteins inside our body (over
100,000 types) result from the combination of only twenty different amino acids.
These molecules combine to form single chains (polypeptides) through a chemical
reaction in which the amine group of one amino acid reacts with the carboxylic Peptide
group of another amino acid, forming a covalent bond (peptide bond; Figure Bond
3.16b) and releasing water in the process.
Figure 3.16 a) Basic struc-
Every type of protein is made up of polypeptide chains that have a unique tural formula of an amino
sequence of amino acids. This specific sequence is known as the primary structure acid; b) Peptide bond.
of the protein and characterizes the macromolecule at the monomeric scale (Figure
3.17). The primary structure has two main parts: a) the backbone of the molecule
characterized by the presence of peptide bonds, and b) the collection of side chains
that result from the bonding of different amino acids.
Backbone
Side Chains
The chemical composition and molecular geometry of the backbone and side
chains in a polypeptide determine the three dimensional structure that it will take. Figure 3.17 Section of the
primary structure of an hy-
A polypeptide chain can fold upon itself and interactions between different parts pothetical polypeptide.
of the backbone can force the molecule to adopt particular structures.
Multiple Interactions LET’S THINK

Consider the schematic representation of a single polypeptide
shown in the figure. The image represents two different sections of
the polypeptide that are approaching each other.
• Analyze bond polarity along the two sections of the poly-

peptide’s backbone. Assign partial charges (d+ and d–) to the
different atoms and identify the types of interactions (e.g., dis-
persion forces) that exist between the two depicted sections of
the backbone (assume that the side chains are non polar).
• Build a schematic representation of the most stable conforma-
tion that this region of the polypeptide is likely to adopt.
In general, the stronger type of intramolecular interaction between different

parts of the same polypeptide is hydrogen bonding. Hydrogen bonds are weaker
a) a-Helix than actual covalent bonds between atoms and can more easily be broken or dis-
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M2/prosec.html
turbed. However, there are so many points along the backbone of a polypeptide
where these types of interactions can be established, that their collective effect adds
up and hydrogen bonding strongly influences the nature of the three-dimensional
structure that the macromolecules adopt. H-bonding between different parts of a
polypeptide generates regions with particular geometric shapes. The specific na-
ture of these conformations constitutes the secondary structure of the protein.
The secondary structure of a protein describes the three-dimensional architec-
CLICK TO PLAY
ture of local sections of the polypeptide chains, at a scale involving tens of mono-
b) b-Sheet meric units (amino acids). The most common secondary structures that emerge
from intramolecular interactions are alpha helices (Figure 3.18a) and beta sheets
(Figure 3.18b). In an alpha helix (a-helix), a section of the polypeptide chain is
coiled like a spring. The backbone of the polymeric chain forms the inner part of
the coil while the side chains extend outward from the coil. In a beta sheet (b-
sheet), different sections of a polypeptide chain are aligned side-by-side forming
a pleated sheet. These two types of structural conformations are stabilized by the
presence of hydrogen bonds between amine (>N-H) and carbonyl (>C=O) groups
along the molecule’s backbone. It is common to use “ribbon diagrams” as those
Figure 3.18 Common sec-
ondary structures in proteins shown in Figure 3.18 to represent or highlight the presence of a-helix and b-
a) a-helix; b) b-sheet. Click
on the images to display dy- sheet structures. The ribbon shows the overall path and organization of the protein
namic representations. backbone in three dimensions, at a scale in which the specific amino acid sequence
(primary structure) is not described.
LET’S THINK In Our Skin
The different architectures of a-helices and b-sheets give them specific structural characteristics:
a. The average distance between amine (>N-H) and carbonyl (>C=O) groups interacting via
hydrogen bonding is smaller in a-helices than in b-sheets;
b. Polypeptides in b-sheets are more stretched than in a-helices;
c. b-sheets can stack on top of each other while a-helices can align with each other, bound
together by multiple interactions.
[Public domain] via Pixabay
By Hans (Own Work)
Some proteins, such as a-keratin, present in mammalian skin, are

made of polypeptides with a-helical structure. Other proteins, like
b-keratin, a component of reptilian skin, consists of stacked b-sheets.
• Discuss how the secondary structure of these proteins may relate to the macroscopic
physical properties of mammalian and reptilian skins.
The properties and function of proteins depend on their structure beyond the
secondary scale. Overall polypeptide structure is determined by how secondary
elements, a-helices and b-sheets, arrange with respect to each other in space. In
some cases, several polypeptides assemble in a group to form the actual protein
that perform particular functions inside living organisms.
FACING THE CHALLENGE ical properties, this is, the shape of their macro-
molecules changes in response to the presence of
specific ions or molecules in their surroundings.
Smart Materials For example, polymers can be chemically designed
Chemical scientists have been able to develop ma- to exist as extended chains in acidic solutions but
terials that have properties that can be changed in to contract into a coiled state in more basic en-
a controlled fashion by modifying external factors vironments. These properties can be useful in the
such as temperature, acidity, moisture, and electric design of, for example, pharmaceutical capsules
or magnetic fields. Although the chemical compo- that transport drugs to specific tissues in our body,
sition and structure of such materials is actually where the polymeric vessels breaks apart in re-
varied, many of these substances are polymers that sponse to the specific chemical composition of the
can change their shape, size, color, electrical and surroundings.
thermal conductivity quite dramatically. In recent years, the development of smart ma-
Shape-memory polymers, for example, are terials has also taken advantage of the ability of
materials that have the ability to return to their some polymers to self-assemble. Self-assembly in
exact original shape after suffering a large defor- this case refers to a process in which a disordered
mation. These types of polymers can “remember” molecular system forms an organized structure
two or three different shapes, and the transition or pattern. The molecular assemblies (also called
between these shapes can be induced by changing supra-molecular structures) that are formed re-
variables such as temperature, electric or magnetic sult from the different intermolecular interactions
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M2/smem.html
field, type of light, or the nature of the solvent in among the polymeric chains themselves, without
which the material is immersed. any external intervention. Molecular self-assembly
Thermo-responsive shape-memory polymers has become an important approach to materials
have a visible, temporary form and a stored per- development in modern nanotechnology.
manent form. These polymers are first processed One critical advantage of developing nano-
to receive structured smart materials through self-assembly is
their per- that this process tends to be reversible. This means
CLICK TO PLAY
manent that molecular assemblies can be formed or de-

s h a p e . stroyed by simply changing the appropriate envi-
Then, the ronmental conditions (e.g., temperature, acidity).
polymers Scientific and technological research in this area
are de- promises to generate a wide variety of innovative
formed to By Mariëlle Leenders via YouTube materials, from smart fluids for fire-fighting, smart
http://www.chem.arizona.edu/tpp/chemthink/MW/design.jnlp
give them their temporary shape. This can be done gels for the cleaning up of oil spills, and smart sur-
by heating up the sample, deforming it, and cool- faces that can act as biological sensors.
ing it down. The permanent shape is now stored To better understand the properties and be-
while the sample shows the temporary shape. havior of self-assembling molecular systems, we
Heating up the polymer above certain temperature invite you to use
induces a transition back to its permanent shape. the interactive
CLICK TO PLAY
Some shape-memory polymers are light acti- simulation that

vated (photoactive). Electromagnetic radiation of you can launch
certain frequency may induce the formation of by clicking on
cross-links between polymer chains while other this image. This
type of radiations may break these cross-links. The computational
material can then be rapidly switched between a tool will chal-
flexible and a rigid state. lenge you to design the supra-molecular assemblies
Other types of polymers have chemo-mechan- that make up a smart material.
Let’s Apply
Polymeric Materials
The physical properties of polymeric materials depend on molecular characteristics such as chain
length, degree of branching, and functionality. The properties of these materials also are affected by
the presence of additives such as plasticizers and cross-linking agents. Let us explore your ability to
use this knowledge to select or design polymers with specific properties.
Melting Point
Imagine that you have to select a polymeric material with the highest melting point possible
among these three choices:
[ ] [n
] [ ]
n n
Polyester Polyamide Polypropylene
• Which of these substances would you select? Assume that you are comparing samples of
each material with similar molar mass.
Tacticity
Tacticity refers to the orderliness of a succession of re- Isotactic

peating units in a polymer chain. For example, chains of
polypropylene (–[CH2–CH(CH3)]n–) tend to adopt two
different conformations: Isotactic (–CH3 groups placed
in the same position with respect to other atoms) and
Atactic (–CH3 groups placed randomly along the chain). Atactic
• If you were to compare samples of isotactic and

atactic polypropylene: Which sample would you
expect to be more rigid? Which one would you
expect to have a lower density?
Mechanical Processes
The properties of polymeric materials can also be changed by ap-

plying mechanical tensions that force polymer chain to take new
arrangements. For example, in the production of fibers and films
it is common to force the polymer through a nozzle (extrusion).
As a result of this process, polymer chains partially align in paral-
lel directions. Similar structural changes can be induced by blow
molding or stretching a polymer.

• How would you expect material properties such as melting
point, density, and flexibility to change as a result of the
extrusion process?
your reasoning.
Cross-Linking Design
Computer simulations have become a very useful tool in the design of new materi-
als. In particular, molecular dynamics simulations allow us to explore the effect of
composition and structural features on the static and dynamic properties of materials.
The interactive simulation associated with this activity can be used, for example, to
explore the qualitative properties of good non reacting cross-linking agents for a given
http://www.chem.arizona.edu/tpp/chemthink/MW/Crosslinking.jnlp
type of polymer.
• Click on the image to launch

the simulation. Use this tool
to design molecules that could
CLICK TO PLAY
act as cross-linking agents for

the specific type of polymer
included in the simulation. Your
cross-linking agent should work
in a wide range of temperatures.
Remember to be systematic in
the exploration of relevant vari-
ables that may affect the proper-
ties of your system.
• Based on the results of your investigation, describe the basic characteristics of
the most effective non reactive cross-linking agent for this type of polymer.
Let’s Apply Folding
Protein Folding
When protein molecules are synthesized inside a cell, they Unfolding
exist as unfolded polypeptides or random chains. How-
ever, intermolecular interactions with surrounding water molecules and intramolecular interac-
tions between amino acid residues lead the macromolecules to “fold” into the conformation that is
most stable in that environment. The particular three-dimensional structure that protein molecules
adopt as result of folding is essential to their function. Changes in the temperature, salt concentra-
tion, or acidity of the surroundings may cause proteins to unfold and become inactive.
Intramolecular Interactions
Consider this schematic representation of a segment of a folded protein:
• Identify the main types of interaction

forces present between the side chains
shown in the figure.
• Arrange these interaction forces from
strongest to weakest.
• Explain why the protein is folded in
this particular way. Why are the side
chains arranged as shown in the figure.
Intermolecular Interactions
Proteins are surrounded by water or by lipids in cell membranes.
• How you would expect

this section of a protein
to fold when immersed
in a) water; b) lipid (oil).
Consider the nature of the
IMFs in each case.
Share and discuss your ideas

with a classmate.
Composition and Solvent Effects
The folding properties of protein molecules can be explored and analyzed using mo-
lecular dynamics simulations. For example, the interactive modeling tool associated
with this activity will allow you to explore the effect of both protein and solvent com-
position on protein folding.
http://www.chem.arizona.edu/tpp/chemthink/MW/folding.jnlp
• Click on the image to launch the simulation. Use this tool to explore the effects
of changing the solvent and
the types of amino acids on

CLICK TO PLAY
protein folding. Remember to
control the variables that you
change (one at a time) and to
record your observations in a
systematic way.
• Based on the results of your
exploration, discuss how the
hydrophilicity and hydrophobicity of sections of a polypeptide can influence
folding of polypeptides surrounded by water or by lipids in cell membranes.
Temperature and Salinity Effects
Molecular dynamics simulations can also be used to explore the effect of temperature
http://www.chem.arizona.edu/tpp/chemthink/MW/foldingSalt.jnlp
and salinity on protein folding.
• Click on the image to launch the simulation. Use this tool to explore the effects
of changing the temperature
and the salinity of the solvent
on protein folding. Remember
CLICK TO PLAY
to control the variables that

you change (one at a time) and
to record your observations in
a systematic way.
• Based on the results of your
exploration, discuss how
temperature and salinity may influence folding of polypeptides surrounded by
water or by lipids in cell membranes.
202
Characterizing
Ionic Networks
Knowledge about the atomic composition of a chemical compound allows us to
U3: MODULE 3
make inferences about its submicroscopic structure as well as about its general
physical properties. We have seen, for example, that if all of the atoms that make
up a chemical substance belong to nonmetallic elements, it is like-
ly that the substance is a molecular compound. Similarly, if the
chemical composition involves a combination of atoms from
metallic and nonmetallic elements, the chemical substance
is likely to be an ionic compound such as sodium chloride
(NaCl). These latter types of substances have physi-
cal properties that often are quite different from those
associated with molecular compounds: All aqueous USGS
solutions of water soluble ionic compounds conduct Sodium Chloride

electricity while most aqueous solutions of molecular Ionic Network
compounds do not. Most ionic compounds exist as rigid solids at room tem-
perature, while molecular compounds are present as solids, liquids, and gases in
our surroundings. These differences result from the characteristic submicroscopic
structure of these two classes of substances. In particular, ionic compounds are
made up of ions arranged into crystalline networks and not by atoms covalently
bonded as independent molecules. As we will discuss it in this module, this struc-
tural feature gives ionic compounds their distinctive behavior.
THE CHALLENGE Skeletal Structures
Most skeletal structures in animals are mixtures of ionic compounds and pro-
teins. These include skeletons, teeth, and shells.
• What would be the evolutionary advantage of these mixed skeletal

structures over those made of only proteins?
central goal of Module 3 is to develop your ability to explain and predict the
physical properties of ionic compounds based on the charge and size of the ions
present in the system.
Electron Transfer
Binary ionic compounds, substances made up of two different types of atoms, re-
sult from the combination of atoms of metallic elements, such as Mg, with atoms
http://www.chem.arizona.edu/tpp/chemthink/resources/U2_M4/pten.html
of nonmetallic elements such O. This type of chemical combination leads to the
formation of monoatomic cations (e.g., Mg2+) and anions (e.g., O2-) that arrange
into crystalline ionic networks (e.g., MgO). As it was the case in our analysis of the
structure and properties of molecular compounds, this behavior can be explained
CLICK TO PLAY
by analyzing the electronegativity c of the atoms involved.
Atoms of metallic and nonmetallic elements have rather different electronega-
tivities. The electronegativities of metallic elements tend to be low, while non-
metallic elements have the higher electronegativities in the periodic table (Figure
3.19). Remember that the electronegativity of an atom can be thought as a mea-
sure of the probability of finding bonding electrons localized in the atom’s vicinity.
When atoms of metallic and nonmetallic elements interact, the valence electrons Figure 3.19 Click on the
of the metallic elements are attracted towards the atomic nuclei of the nonmetallic image to open an interactive
periodic table listing the elec-
elements. The energy of the system decreases as valence electrons of the metallic tronegativity of the elements.
atoms get closer to the nonmetallic atoms. How the valence electrons actually re-
distribute between the two interacting particles depends on the value of both the
difference in electronegativities Dc = cA - cB and the average electronegativity cAV
= (cA + cB)/2 of the atoms involved. The larger the value of Dc, the more likely for
valence electrons to relocate closer to the more electronegative atom. The lower the
value of cAV the easier for this process to occur.
Given that for most pairs of metallic and nonmetallic atoms Dc is large (Dc
> 2.0) and cAV has an intermediate value (1.5 < cAV < 3.0), the most stable state
when these types of atoms interact is that in which valence electrons of the me-
tallic atom are transferred to the nonmetallic atom. In this process, the metallic
atoms gain positive charge and become cations while the nonmetallic atoms gain
negative charge and become anions. Strong electrostatic interactions among these
anions and cations leads to the formation of an ionic network.
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M3/ionic.html
Ionic Networks LET’S THINK
Electrostatic interactions between the anions and cations that result from the transfer of valence
electrons from metallic atoms to nonmetallic atoms lead to the formation of an ionic network
instead of independent molecules. Why does this happen?
• Click on the image to launch a molecular dynamics simulation of the reaction between
metallic and nonmetallic atoms. Select an initial number of atoms of each type and ana-
lyze what happens as the atoms react and ions are formed.
CLICK TO PLAY
• Based on your observations, explain why an ionic network

is formed in this case rather than a collection of indepen-
dent molecules.
• Analyze what happens to the ionic network as you increase
the temperature.
204 MODULE 3 Characterizing Ionic Networks
CLICK TO PLAY The net charge that atoms of metals and nonmetals are likely to acquire when
they react with each other can be inferred from the analysis of the electron con-
figurations of the isolated atoms. In general, the valence electrons of atoms of me-
tallic elements occupy orbitals with a higher energy than the unoccupied valence
orbitals in the atoms of nonmetallic elements (Figure 3.20). Thus, when these
different types of atoms interact, electrostatic forces between charge particles are
likely to induce the transfer of valence electrons from higher energy states in the
metallic atoms to the available lower energy states in the nonmetallic atoms. The
Figure 3.20 Use the photoelec- number of electrons that are transferred is then determined by both the number
tron spectroscopy tool to com-
pare the energy of valence or- of valence electrons in the metallic element and the number of unoccupied valence
bitals in, for example, Na and Cl.
orbitals in the nonmetallic element.
LET’S THINK What charge?
Atoms in the same group of the periodic table have similar valence electron configurations:
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
s1 s2 s d s d s d s d s d s d s d s2d8 s2d9 s2d10 s2p1 s2p2 s2p3 s2p4 s2p5 s2p6
2 1 2 2 2 3 2 4 2 5 2 6 2 7
1
2
3
4
• What charges would the metallic atoms in groups 1, 2, and 13 will likely acquire when react-
ing with non metallic atoms in groups a) 15, b) 16, and c) 17?
• What charge will the nonmetallic atoms acquire as a result of these interactions?
In general, we can expect atoms of nonmetallic elements to acquire a nega-

tive charge equal in magnitude to the number of electrons they
can accept in the unoccupied orbitals in their valence shell. Ac-
cepting more electrons into higher energy states would have
too high an energy cost. The resulting anions will then have an
electron configuration similar to that of the nearest noble gas
element in the same period in the periodic table (Figure 3.21).
On the other hand, the behavior of atoms of metallic elements
depends on the number of valence electrons in these particles.
Atoms of elements in the first two groups in the periodic table,
also known as alkali metals (Group 1) and alkaline earth metals
(Group 2), consistently lose all the electrons in their valence
shell, thus becoming cations with +1 and +2 charges, respec-
Figure 3.21 Atoms of nonme- tively. These cations have an electron configuration similar to
tallic elements tend to gain elec- that of the nearest noble gas element in the previous period in the periodic table
trons while atoms of metallic el-
ements tend to lose them when (Figure 3.21). Core electrons are not transferred during these interactions as they
they interact with each other.
occupy rather low energy states in atoms of metallic elements.
Predicting the charges that atoms of transition metals (Groups 3 through 12

in the periodic table) acquire when reacting with nonmetallic elements is not as
straightforward as for Groups 1 and 2 in the periodic table. Transition metal ele-
ments have electrons in the d-subshell that can also be transferred to the nonmetal
atoms during a chemical reaction. However, the actual number of electrons that
the transition metal atoms lose depends on the conditions of the reaction. Figure
3.22 summarizes the electric charges most commonly associated with transition Figure 3.22 Common
ionic charges of stable
metal cations: transition metal cations.
Common Ion
By Felix Wan (Own Work) [Share Alike 3.0]

Ion Charges (+)
Less Common Ion

Atomic Number
Given the different charges that transition metal cations can take, it is common
to use roman numerals (e.g., I, II) to indicate the type of cation present in a given
ionic compound. Thus, we may have copper(I) chloride (CuCl) or copper(II) chlo-
ride (CuCl2). Similarly, you may see references to Fe(III) or Ti(II) compounds to
indicate classes of substances composed of a specific type of ion (i.e., Fe3+ or Ti2+).
Group 13 LET’S THINK

Metallic elements in Group 13 of the periodic table (e.g., Al, Ga, In) tend to form stable cations
with charges +1 or +3 when reacting with nonmetallic elements:
• How would you explain this behavior based on the analysis of the valence electron configu-
ration of this set of elements?
No matter what ions are formed during the reaction of metallic and nonme-
tallic elements, the ionic network that is formed has no net charge. Cations (+)
and anions (-) combine in ratios that ensure charge neutrality. If the network was
not neutral, it would keep attracting ions. For example, in the reaction of chlorine
gas, Cl2(g), with metallic sodium, Na(s), chloride anions with a -1 charge (Cl-)
and sodium cations with a +1 charge (Na+) are formed. These ions arrange into a
network comprised on Na+ and Cl- ions in a 1 to 1 (1:1) ratio. The formula unit
of this ionic compound, NaCl, represents the proportion in which the ions com-
bine. When Cl2(g) reacts with Mg(s), Cl- and Mg2+ ions are formed. In this case,
electrical neutrality is achieved when these ions combine in a 2:1 ratio (MgCl2, Figure 3.23 The for-
magnesium chloride). What would you then expect to happen when aluminum mula unit for aluminum
oxide is Al2O3. Why?
metal, Al(s), and oxygen gas, O2(g), combine (Figure 3.23)?
LET’S THINK Formula Units
Metallic and nonmetallic elements tend to react in well defined ratios to produce ionic compounds.
The ratio in which the ions combine is determined by the condition of electrical neutrality.
• Predict the formula unit of the ionic compounds that result from the combination of the fol-
lowing elemental substances:
a) K(s) + F2(g) b) Mg(s) + O2(g) c) Na(s) + S8(s) d) Ca(s) + N2(g)
Hint: During the reaction, each substance will generate stable monoatomic ions with a charge that
can be predicted by analyzing the number of valence electrons present in the neutral atoms.
Assuming that valence electrons from atoms of metallic elements are fully
transferred to atoms of nonmetallic elements in the formation of ionic compounds
d = - 0.8 works well in predicting many physical properties of this kind of substances. How-
ever, experimental results suggests that valence electrons are never fully transferred
from one type of atom to another. A more accurate model would depict these
valence electrons as more likely to be located in the vicinity of the nonmetallic
atoms but still partially associated with the metallic atoms. The higher the
electronegativity difference Dc and the lower the value of cAV for the interact-
ing atoms, the higher the probability of finding those electrons in the vicinity
of the nonmetallic atoms. Consider, for example, the case of NaCl for which Dc
d = + 0.8 = 2.1 and cAV = 1.95. Experimental measurements of the dipole moment of NaCl
ion pairs in the gas phase suggests that the partial charge d on the chlorine atoms
is close to d = -0.8 instead of d = -1 as it would be expected if the transfer of the
Figure 3.24 Electrostatic single valence electron from the sodium atom to the chlorine atoms was complete.
potential map for a NaCl
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M3/ionc.html
ion pair in the gas phase. Based on these results we can estimate that the bond in NaCl has an 80% ionic
character, which indicates that the valence electrons from the Na atoms remain
associated to these particles to some extent (Figure 3.24).
LET’S THINK Ionic Character
Chemists have devised ways to estimate the percent ionic character of a bond based on the electro-
negativity difference between the atoms involved. In general, when this percentage is larger than
50% the binary compound is best described as an ionic compound (otherwise, the compound is
best modeled as a molecular compound with polar bonds).
CLICK TO PLAY
• Use the interactive tool associated with this activity to explore the ionic
character of the following bonds: C-O, K-Cl, O-H, Cs-F, H-F, Li-Br.
• Based on your analysis, what value of Dc could be taken as a rough
estimate of the boundary between polar covalent and ionic bonding.
Ionic Networks
a) NaCl
Attractive and repulsive interactions between cations and anions in an ionic com-
pound force these charged particles to take well-ordered, three-dimensional ar-
rangements. Ions are packed close together into a repeating array called a crystal
lattice. However, the particular structure of the crystal lattice depends on factors
such as the charge and the size of the ions. For example, in sodium chloride, NaCl,
each type of ion in the lattice is surrounded by six ions of the opposite charge.
CLICK TO PLAY
These six ions are arranged on the corners of an imaginary octahedron with an ion
of opposite charge in its center. In turn, ions with the same charge are arranged
into what is called a face centered cubic (FCC) packing in which ions occupy the b) CsCl
corners and center of each of the faces of a large set of stacked imaginary cubes
(Figure 3.25a). On the other hand, in the crystal lattice structure of cesium chlo-
ride, CsCl, ions of the same charge occupy only the corners of stacked imaginary
cubes, with ions of the opposite charge located at the center of each of theses cubes
(body centered cubic (BCC) packing; Figure 3.25b). In general, ionic compounds
adopt a crystalline structure in which the potential energy due to ion interactions
has a minimum value.
The structure of crystalline ionic solids can be Figure 3.25 Crystal lattice
structures of a) NaCl an b)
more easily described by identifying the size, shape, CsCl. Click on each image
and composition of the simplest repeating unit in the to display a more dynamic
representation
system (Figure 3.26). This structural unit is called a
“unit cell” and the entire structure of the lattice can
be generated by multiplying and stacking copies of
the unit cell in different directions. The ratio of cat-
ions to anions present within the unit cell of an ionic
solid determines the formula unit of the compound. CsCl
Figure 3.26 Unit cells of
NaCl and CsCl. The ratio of
anions to cations in the unit
cell is 1:1 in both cases.
NaCl
Structure-Properties LET’S THINK

The submicroscopic composition and structure of ionic compounds determine many of their phys-
ical properties. For example, ionic compounds are shattered when struck.
• How would you explain this phenomenon based on the submicroscopic composition and
structure of ionic compounds?
• Which compositional and structural factors may affect how easily an ionic compounds is
shattered when struck?
Many physical properties of ionic compounds are determined by the charge

and the size of the ions in the network. These two factors influence the magnitude
of the repulsive and attractive electrostatic forces between particles in the system.
Attractive interactions between anions and cations tend to be pretty strong; sepa-
rating these charged particles typically requires energy investments between 400
and 4000 kJ/mol. However, repulsion between ions of the same charge are also
strong. Thus, the presence of impurities in the crystal lattice of an ionic compound
or the application of a force that deforms the crystalline network may force equally
charged ions close together, destabilizing the solid structure. In general, the analy-
sis of differences in the size and charge of the ions that make up a set of a ionic
compounds allows us to qualitatively predict the relative values of physical proper-
ties such as melting and boiling points, and water solubility.
LET’S THINK Ion Size and Charge
http://www.chem.arizona.edu/tpp/chemthink/MW/ionic.jnlp
The molecular dynamics simulation associated with this activity can be used to explore the ef-
fect of ion size and charge on the physical properties of ionic compounds.
• Launch the simulation by clicking on the image.

Use this interactive tool to explore how changing
CLICK TO PLAY
a) the charge and b) the size of the ions that make
up the ionic network may affect the melting and
the boiling temperature of these types of systems.
• Based on your results and knowledge about the
nature of the electrostatic interactions between
charged particles, explain the observed effects of
ion charge and size on the physical properties of ionic networks.
The magnitude of the electrostatic forces between cations and anions in an

ionic network is determined by Coulomb’s law:
(3.1) F = K q1q2 / r2
r where q1 and q2 are the electric charges of the interacting ions and r is the dis-
tance between these two particles (Figure 3.27); Coulomb’s constant K is equal to
8.988 x 109 Nm2/C2 when expressed in SI units. According to this relationship,
-+ the higher the ion charges and the smaller the ion sizes, the larger the electrostatic
force between particles. Given that physical properties such as melting points de-
pend on the force required to separate the particles that make up a system, we can
expect these properties to follow somewhat regular trends with varying ion charges
and sizes in a set of ionic compounds. However, other factors such as the distribu-
Figure 3.27 The distance
(r) between charged par- tion of ions in the lattice (e.g., FCC vs. BCC structure) or the ionic character of
ticles is measured from
center to center. the bonds may also affect the properties of the system, leading to deviations from
predictions made based solely on ion size and charge. In general, the properties of
a crystalline solid material depend on the composition and structure of the par-
ticles that make up the system, as well as on their three-dimensional arrangement.
The size and charge of monoatomic anions and Group 1 Group 2 Group 13 Group 16 Group 17
cations depend on the number of valence electrons
lost or gained by the neutral atoms. Losing valence
By Popnose (Own Work) [Share Alike 3.0] via Wikimedia Commons

electrons results in positive ions with a smaller radius
as the lost electrons are taken from the most external
orbitals. Additionally, the net repulsion force on the
remaining electrons decreases, facilitating their get-
ting closer to the atomic nucleus. Cations are thus
smaller than the associated neutral atom. On the
other hand, gaining electrons results in negatively
charged ions with a larger radius; the additional
electrons are located in outer orbitals and the net
repulsion between electrons in the system increases.
Anions are then larger than the associated neutral
atom. As shown in Figure 3.28, although anions and
cations have different sizes than the neutral atoms,
their sizes follow a periodic trend. For particles with
electric charges of the same type, either positive or negative, ion size increases as Figure 3.28 Comparative radii
(in picometers; 1 pm = 1 x10-12 m)
we move from right to left within a period and from top to bottom within a group of neutral atoms and associated
anions or cations.
in the periodic table.
Property Trends LET’S THINK

Based on a comparative analysis of the charge and size of the ions that make up the ionic com-
pounds in each of the following sets of substances:
a) NaCl, NaBr, NaF b) CaO, NaCl, MgO c) KF, RbF, NaF
• Arrange each of the substances in a set in order of increasing melting point.
Consider the boiling points of the following ionic compounds: CaO (2850 oC), BaO (2000 oC),
MgO (3600 oC), BeO (3900 oC).
• How would you justify the differences in boiling points?
The graph shows the heat of fusion (energy re-

quired to melt the solid at its melting point) in
kJ/mol for different sets of ionic compounds:
• How could you explain the various trends in

the behavior of the heat of fusion represented in
this graph?
• How would you expect the heat of vaporization
for these same sets of substances to vary?
Share and discuss your results and ideas with a class-

mate, and clearly justify your reasoning.
Water Solubility
Some ionic compounds are highly soluble in water; others are not. Aqueous solu-
tions of soluble ionic compounds conduct electricity, which makes them different
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M3/solu.html
from most aqueous solutions of soluble molecular compounds. This phenomenon

CLICK TO PLAY can be explained if we assume that the ionic network breaks apart during the
dissolution process and ions can move freely through the solution. Soluble ionic
compounds are then said to be “strong electrolytes” as they seem to dissociate
completely into free ions when immersed in water (Figure 3.29). Sodium chloride,
NaCl(s), is a typical example of a strong electrolyte and its dissolution in water can
be represented using the following chemical equation:
NaCl(s) + H2O(l) Na+(aq) + Cl-(aq)
where the symbols Na+(aq) and Cl-(aq) are used to represent the separated ions
in aqueous solution. Solutions of slightly soluble ionic compounds, such as zinc
Figure 3.29 Click on the im-
age to start the animation of sulfide ZnS(s), barely conduct electricity. This behavior suggests that in these cases
an ionic compound dissolving only a small fraction of the ions goes into the solution. Slightly soluble ionic com-
in water. Notice that interac-
tions between ions and water pounds are classified as “weak electrolytes” as most of the ionic network remains
molecules constrain molecu-
lar motion. intact when these types of substances are immersed in water.
The solubility of ionic compounds in water is determined by several compet-
ing factors. For example, the degree of dissolution will depend on the relative
strength of the interactions between ions in the network and between ions and
surrounding water molecules. If ions interact weakly with each other and more
strongly with water molecules they may separate. However, strong interactions
between ions and water molecules may reduce the number of configurations that
such molecules can adopt, reducing the likelihood that random motion will lead
to the dissolution of the ionic solid.
LET’S THINK Dissolves or not?
http://www.chem.arizona.edu/tpp/chemthink/MW/ionicsolution.jnlp
The molecular dynamics simulation associated with this activity can be used to ex-
plore the effect of ion charge on the solubility of ionic compounds in water.
• Launch the simulation by clicking on the im- CLICK TO PLAY

age. Use this interactive tool to explore how
changing the charge of the ions that make up
the ionic network may affect the solubility of
these types of compounds in water at a constant
temperature.
• Explore how changes in temperature may affect
the solubility of ionic compounds in water.
• Based on your results and knowledge about the nature of the electrostatic
interactions between ions and dipolar molecules, explain the observed effects
of ion charge on solubility.
For an ionic compound to be soluble in water, at least one of the following

conditions needs to be met:
• The net interactions between ions and water molecules should be stronger
than the net interactions between the ions themselves. Thus, the dissolution
process results in a state with a lower potential energy.
• The number of configurations that the ions and the water molecules can
adopt when mixed is larger than the total number of configurations that
they can have if they do not mix. Under these conditions, random particle
motions are likely to result in dissolution.
By Taxman (Own Work) [Public domain]

If both of these conditions are satisfied, the ionic compound is likely to be soluble

at all temperatures. If only one of these conditions is met, the outcome will de-
pend on which competing factors (i.e., strength of interactions versus number of
configurations) is dominant. In these cases, the solubility of the ionic compound
is likely to vary significantly with temperature. Finally, if none of these conditions
are satisfied, the ionic compound will be rather insoluble.
In general, conditions that favor the solubility of ionic compounds tend to be
dominant when these substances are made up of ions with small electric charges Figure 3.30 The organization
of solvent molecules around
(e.g., +1, -1). This is mostly because ions with small charges do not strongly con- around ions (or other mole-
cules) is known as “solvation.”
strain the configurations that surrounding water molecules can adopt, facilitating
the dissolution process (Figure 3.30). The larger the charge of the ions, the larger
the ion-dipole interactions, and the larger the probability that molecular move-
ments will be constrained in the vicinity of those ions. The lower the number of
configurations that water molecules can adopt, the lower the likelihood that ran-
dom motions will lead to the formation of such a state.
Solubility Trends LET’S THINK

Consider the following potential energy-configurations diagrams for the dissolution of three dif-
ferent ionic compounds: NaCl(s), CaCl2(s), and ZnS(s).
Ep NaCl(s) Soluble Ep CaCl2(s) Soluble ZnS(s) Insoluble

Ep
CaCl2(s) + H2O(l) Zn2+(aq) + S2-(aq)
Na+(aq) + Cl-(aq)
NaCl(s) + H2O(l)
Ca2+(aq) + 2Cl-(aq) ZnS(s) + H2O(l)
# of Configurations # of Configurations # of Configurations
• Use these diagrams to explain the solubility in water of each of these substances. Describe
what may be happening at the molecular level in each of these systems.
• Discuss how changes in temperature may affect the solubility of each these compounds.
Consider the following examples of ionic compounds soluble and insoluble in water:
Soluble: NaCl, MgBr2, K2S, CaI2, NaF, AlCl3
Insoluble: MgO, ZnS, Al2O3, FeS, CrS, Ni2O3
• Use this data to derive a simple rule to predict the solubility of ionic compounds based on
ion charges.
In general, ionic compound made up of ions Am+ and Bn- in which both
m and n are larger than one are likely to be insoluble in water. Although this
solubility rule works well in many cases, there are important exceptions.
For example, the ionic compounds MgF2, AgCl, PbCl2, are insoluble in water.
These exceptions result from the influence of other factors that also affect solubil-
ity such as the size of the ions, the degree of ionic character of the bond between
ions, and the particular distribution of the ions in the crystal lattice. The following
table summarizes the experimental solubility trends for ionic compounds made
up of different types of ions. As you can see, there are only a few exceptions to the
above solubility rule.
Soluble Ionic Compounds Important Exceptions (Insoluble Compounds)

F- Fluorides of alkaline earth metal ions (e.g., Mg2+, Ca2+) and Pb2+
Cl- Chlorides of Ag+, Hg22+, and Pb2+
Most compounds
Br- Bromides of Ag+, Hg22+, and Pb2+
containing
these anions I- Iodides of Ag+, Hg22+, and Pb2+
are soluble NO3- None
SO 4
2-
Sulfates of Sr2+, Ba2+, Hg22+, and Pb2+
Insoluble Ionic Compounds Important Exceptions (Soluble Compounds)
S2- Sulfides of NH4+, the alkali metal cations (e.g., Na+, K+), and alka-
Most compounds line earth metal ions (e.g., Mg2+)
containing OH- Hydroxides of the alkali metal cations and NH4+, Ca2+, Sr2+, and Ba2+
these anions CO32- Carbonates of NH4+ and the alkali metal cations
are insoluble
PO43- Phosphates of NH4+ and the alkali metal cations
LET’S THINK Size Effects
Ion size affects the solubility of ionic compounds in diverse ways. Based on Coulomb’s Law as
expressed in Eq. 3.1, larger ions can be expected to interact less strongly among them, which may
facilitate their separation. However, they may also interact less strongly with water molecules, which
reduces the probability of the ions being taken away but also reduces the constraining effect on the
configurations that water molecules can adopt. Consider the potential energy configurations dia-
grams for NaCl(s), NaBr(s), and NaI(s):
Ep NaCl(s) Soluble Ep NaBr(s) Soluble NaI(s) Soluble

Ep
NaI(s) + H2O(l)
NaBr(s) + H2O(l)
Na+(aq) + Cl-(aq)
Na+(aq) + Br-(aq) Na+(aq) + I-(aq)

NaCl(s) + H2O(l)
# of Configurations # of Configurations # of Configurations
• Use the diagrams to analyze the effect the ion size on solubility. Explain the observed behav-
iors based on the effect of ion size on interactions and available configurations for the par-
ticles that make up this set of substances.
Polyatomic Ions
Not all ionic compounds are made up of monoatomic ions (made up of a single
atom). There are also molecular ions ( made up of several atoms covalently bond-
ed). These types of charged particles are known as polyatomic ions and they can be
cations or anions. Among the most common polyatomic ions we find:
Hydroxide Nitrate Carbonate

Ion Ion Ion
OH - NO3- CO32-
Sulfate Phosphate Ammonium

Ion Ion Ion
SO42- PO43- NH4+
Ionic compounds made up of one or more types of polyatomic ions have a

similar submicroscopic structure to that of compounds made up of monoatomic
ions: cations and anions in these types of substances are arranged into an electro-
neutral ionic network in which ions with a certain charge tend to be surrounded Figure 3.31 Ammonium
by particles with the opposite charge (Figure 3.31). The physical properties of chloride, NH4Cl, is made up
of ammonium polyatomic
these types of compounds can also be qualitatively inferred by analyzing the charge cations NH4+ and chloride
monoatomic anions Cl-.
and size of the ions that make up the system.
Dissolves or not? LET’S THINK

Consider the following ionic compounds:
Barium Sulfate Magnesium Nitrate Calcium Phosphate

Ammonium Nitrate Calcium Carbonate
• Write the formula unit of each of these ionic compounds (remember that the ionic lattice
should be electroneutral);
• Predict the solubility in water of these different ionic compounds based on the analysis of
ion charge.
Chemical substances that include polyatomic ions in their structure are very
common in our surroundings and have a variety of uses and applications. For ex-
ample, soluble ionic compounds such as ammonium nitrate (NH4NO3) and mag-
nesium nitrate (Mg(NO3)2)are important fertilizers. Insoluble ionic compounds
such as calcium carbonate (CaCO3) and calcium phosphate (Ca3(PO4)2) serve as
structural components in living things. In the section “Facing the Challenge” you
can learn more about the structure and properties of these types of substances.
Ionic compounds are used in many different ways in daily life, and in chemis-
try laboratories and industries. Many pharmaceutical drugs, for example, are sold
as ionic compounds (also called salts) that are easier to administer and tend to be
more chemically stable. In chemical synthesis, ionic compounds are used to intro-
duce desired anions or cations into a reaction mixture. Anions and cations cannot
be stored in isolation from each other. Consequently, when a specific type of ion is
needed to carry out a chemical process, an ionic compound that includes such an
ion in its structure needs to be selected. It is thus critical to learn to identify ionic
compounds that will be soluble under the reaction conditions and will generate
the targeted anions or cations.
LET’S THINK Choosing the Right Salt
Imagine that you work in a laboratory and have access to the following chemical compounds:
CCl4, CoCl2, CuCl2, NaCl, NH4Cl, ZnCl2, CF4, NaF, KBr, CO2, Na2CO3, CaCO3,
CuCO3, Na3PO4, AlPO4, KCN, CH3COONa, KOH, NaOH, NH4OH, CH3OH,
Al(NO3)3, Cu(NO3)2, NaNO3, Zn(NO3)2, NH4NO3, Na2SO4, CaSO4, Na2S, CuS
• Basic aqueous solutions contain higher concentrations of hydroxide ions OH– than pure wa-
ter. Which substances in the list could you choose to prepare basic solutions?
• Solutions containing carbonate ions CO32- ions are slightly basic. Select the substance in the
list that would be best to use to prepare these types of solutions. Give the name and formula
of another compound not included in the list that you could buy to prepare these types of
solutions.
• Electrochemical cells are devices that transform chemi-
By Hey Paul (Own Work) [Generic 2.0]

cal energy into electrical energy. A typical electro-
chemical cell can be prepared by preparing two aque-
via Flickr Commons

ous solutions, one containing Cu2+ ions and the other
containing Zn2+ ions. Which salts in the list could be
used for this purpose?
• Electrolysis is a process in which an electric current is
used to produce a chemical reaction. Aqueous solu-
tions containing nitrate ions NO3– are commonly used
to allow the transfer of charge through an electrolytic cell. Which chemical compounds in the
list could be used for such purpose?
• Imagine that you needed to prepare aqueous solutions that conduct electricity. Identify all of
the strong electrolytes in the list and represent the ions that they generate when dissolved in
water.
• Identify all the substances in the list that generate polyatomic ions when dissolved in water.
• Imagine that you wanted to prepare two aqueous solutions of soluble ionic compounds that
when mixed produce an insoluble salt that precipitates. Identify at least three different pairs
of solutions that are likely to show this behavior.
FACING THE CHALLENGE tween these two components is critical to bone’s

resilience and strength.
Other structural elements of living organisms,
Skeletons and Shells such as exoskeletons, are also based on composite
The material that makes up our bones is quite ex- materials that combine molecular and ionic com-
traordinary. It can resist a load of one tonne with- pounds at the nanoscale level. For example, the
out fracturing and it is elastic enough to recover its shells of mollusks result from the combination of a
shape when subject to small deformations. These complex protein, conchiolin, and calcium carbon-
properties result from the combination of two main ate (CaCO3) crystals. As it was the case for bones,
types of components: flexible fibers of collagen, a the proteins form a matrix on which the crystals of
type of protein, and brittle crystals of the calcium the ionic compound nucleate and grow.
mineral hydroxyapatite (Ca10(PO4)6(OH)2). The Most shell forming organisms seemed to have
macromolecular compound gives bones their elas- emerged during the Cambrian period. The sudden
ticity while the ionic substance makes them hard. appearance of shells has been related to changes in
Around 30% of bone material is composed of ocean chemistry that allowed stable calcium com-
collagen, a fibrous protein also present in our skin pounds to precipitate into a shell. However, given
and tendons. Collagen fibers are made of three in- that the development of exoskeletons coincides
tertwined polypeptide chains of about 1000 amino with the time in which animals started burrowing
acids per chain. On the other hand, close to 70% to avoid predation, it is possible that the formation
of a bone is made of hydroxyapatite, a crystalline of skeletons was favored by an increased evolution-
ionic compound mainly made of calcium phos- ary pressure from predators.
phate, but which also includes calcium carbonate, Ocean chemistry controls the composition of
calcium fluoride, and calcium hydroxide. mollusks shells. Calcium carbonate has two main
Bone is a composite natural material whose crystalline forms, calcite and aragonite. This lat-
properties depend intimately on its nanoscale ter form tends to be more stable when the oceans
structure. Collagen spontaneously forms fibers of contain a higher proportion of magnesium than
intertwined polypetides on which tiny hydroxy- calcium ions. Existing data suggest that the form
apatite crystals (10-50 nanometers in length) grow of CaCO3 present in the exoskeleton of a given
(see figure). Both the size and the orientation species reflects ocean composition at the time that
the species first evolved a calcified skeleton, and
Collagen
not the current composition of the environment
triple helix in which the animals develop. However, current
10 nm
ocean chemistry determines the amount of CaCO3
that deposits onto the protein matrix.
Hydroxyapatite The exoskeletons of insects do not include
crystals
ionic compounds
Source: Nature
500 nm
in their structure.
Bone-forming
osteoblast cell They are made of
Bone-marrow
stem cell Extracellular
the macromolecular
bone matrix compound chitin,
a polymer of a N-
100 mm
acetylglucosamine
(see figure), embedded in a protein matrix. Chi-
tin is also an important component of the exo-
skeletons of crustaceans (e.g., crabs, lobsters, and
of the ionic crystals are dictated by the collagen shrimps), which also include proteins and calcium
matrix, and the precise structural relationship be- carbonate in their nanostructure.
Let’s Apply
“Green” Solvents
Many solvents commonly used by the chemical industry are volatile organic compounds (VOCs)
that contribute to atmospheric pollution. In recent years, ionic compounds that are liquid at room
temperature (ionic liquids) have been introduced as “greener” alternatives due to its low volatility.
These types of liquids have also been described as designer solvents because their properties can be
adjusted to suit the requirements of a particular process. Let us explore the type of thinking involved
in designing these types of materials.
Melting Points
Common ionic compounds have melting points above K+ NH4+

100 oC and thus are solid a room temperature. How-
ever, the melting temperature depends on the com- Cl- 776 oC 338 oC
position and structure of the ions that make up the
substance. Consider the melting points of the ionic NO3- 334 oC 170 oC
compounds that result from the combination of the CH3COO- 292 oC 112 oC
anions and cations shown in the table:
• Explain the relative melting points of these ionic substances based on the analysis of
the characteristics of the ions involved.
• Make hypotheses about the general structural characteristics of ionic compounds
that could be liquid at room temperature.
Ionic Liquids
Cl-
Ionic liquids are compounds made up of carbon-based molec-
ular cations and diverse types of anions. These substances have
melting points near ambient temperature (up to 100 oC). The Br-
first room-temperature ionic liquid, ethylammonium nitrate
(C2H5)NH3+NO3- was discovered in 1914 and melts at 12 oC.
• Imagine that you wanted to synthesize ionic liquids based CF3SO3-

on the combination of ethylammonium cations and the anions
shown to the right. Which of these new substances would you
expect to have the highest and the lowest melting points?
BF4-
Side Chains
One of the most studied ionic liquids is 1-Butyl-

3-methylimidazolium hexafluorophosphate, also
known as BMIM-PF6. This compound melts at 6.4
o
C. Imagine that you wanted to design new ionic liquids based on
this compound by simply changing the structure of the side chain at-
tached to the ring. These are some possibilities:

• How would you expect the melting point of the new compound to be in com-
parison to that of BMIM-PF6? Lower or Higher?
Melting Trends
The graph to the right shows the variation

250
of the melting point for a set of ionic liquids
200
made up of cations that differ from each other
Temperature (oC)
150
only on the length of a hydrocarbon side chain
(similar to the example discussed above). 100
50
• How would you explain the variation in 0

2 4 6 8 10 12 14 16 18 20
the melting temperature with increasing -50
number of carbons in the side chain? -100
Number of Carbons
Why would the melting point first de-
crease and then increase with longer side
chains?
Unique Properties
Ionic liquids such as BMIM-PF6 have unique properties. How do you explain them?
• These types of substances have very low volatilities. Why?

• These liquids dissolve non polar substances, such as CO2. Why?
Let’s Apply
[Generic 2.0] via Flickr Commons

By Palge Powers (Own Work)
Pigments and Paints
Some ionic compounds are used as pigments in the production of paints. These
pigments tend to be insoluble in water and can be prepared by mixing aqueous
solutions containing free anions and cations that combine with each other to
form an insoluble compound that precipitates from solution.
Mixing Components
Pigment Color
The table to the right lists the formula units of some solid pig- Formula Unit
ments as well as their colors. Imagine that you wanted to prepare BaSO4 White
these pigments using some of these solid ionic compounds avail-
PbI2 Yellow
able in your lab:
Fe(OH)3 Brown
BaCl2, CaCO3, CaCl2, CdCl2, FeCl3, Fe(NO3)3, K2CO3, KI, KNO3,
CdS Yellow
NaOH, Na2S, ZnS, Na2SO4, PbCl2, PbCO3
• Propose a strategy to produce each of the pigments included in the table. You need to de-
scribe what substances you would use and how you would combine them.
• In each case, build a submicroscopic representation that illustrates how the product will be
formed by combination of the initial materials.
Producing Paints
Pigments like the ones described in the previous activity

may be used to produce paints. The solid pigment can be Solvent
ground into a powder and dispersed in a solvent to facili- Hexane
tate their application. However, small grains of the ionic
compound tend to agglomerate when added to a solvent.
This can be avoided by adding additives (also called ve- Binder
hicles or binders) that not only help disperse the pigment Linseed Oil
grains throughout the solvent but also bind the pigment
to the painted surface when the solvent evaporates. Con-
sider the solvent and binder represented to the right:
• Discuss how the binder may help disperse the pig-

ment particles in the solvent. Clearly justify your
reasoning based on IMFs between particles.
Where From?
conduct electricity.
With this third unit of the course we close
our analysis of how chemical models and ideas are
Where To? used to describe, explain, and predict the physical

properties of the wide variety of substances in our
surroundings. Our path started by zooming into
the submicroscopic world of atoms, molecules,
The central goal of this unit was to help you devel- and ions to better understand their composi-
op ways of thinking that are used to explain and tion and structure. In this unit we have shown
predict the physical properties of chemical com- you how we can use that knowledge and way of
pounds based on their thinking to make sense of the material world that
submicroscopic com- surrounds us and to design substances that can
position and struc- improve our way of living.
Source: Bessonov & Harauz
ture. In particular, we
have discussed how ZOOMING IN
the analysis of the
chemical nature of
the atoms that make
up a substance is use-
ful in predict- ing whether the material is
likely to be molecular or ionic. Classifying sub- OUR PATH
stances in this way is rather helpful as it allows us
to identify which composition and structural fac- ET
tors, such as polarizability, molecular polarity, or
1s22s22p4
ion charge and size are more likely to determine
the physical properties of a chemical system.
As you may imagine, the chemical models O
for different types of substances discussed in this H H
unit have limitations. The boundaries between ZOOMING OUT
covalent and ionic substances are somewhat dif-
fuse. Thus, we may find materials that have mixed
properties between ionic and covalent. Instead of By Martina Rathgens
(Own Work)
thinking of chemical bonding as sharply divided d-
[Generic 2.0]
via Flickr Commons
into different types (covalent versus ionic), many d+
times is more useful to think of different types of
chemical bonding as simply modeling different
degrees of delocalization of the valence electrons
present in a system. Thus, ionic bonding de-
scribes cases in which electrons get highly local- The knowledge and ways of thinking de-
ized in the more electronegative atoms that make veloped in the first three units of this textbook
up a substance; while covalent bonding describes will be critical in our exploration of the chemi-
systems in which valence electrons become de- cal behavior of substances, the central focus of all
localized in the space between two atoms. There subsequent units. But before we move on, let us
are also systems in which valence electrons are explore if “YOU ARE READY” by assessing your
delocalized amonng all atoms in the system. This ability to apply what you have learned in this unit
behavior leads to metallic substances that can to the analysis of some interesting problems.
Are You Ready?

Imagine that you work for a consulting agency specialized in providing advice to chemical industries and
companies involved in materials design and production. Your central task is to provide the best possible
advice to different companies and justify your suggestions based on your chemical knowledge.
Solvents
An industry specialized in the production of organic solvents for chemical

synthesis is interested in designing three light weight hydrocarbons with the
same number of carbons but different boiling points.
• Which three molecular structures would you propose for these hydro-
carbons? Arrange them in order of increasing boiling points.
Share and discuss your results with a classmate, and justify your reasoning.
Fertilizers
Nitrates are mainly produced for Lubricants

use as fertilizers. They tend to be
highly soluble and biodegrad- A company that produces lubri-
able compounds. The four most cants is interested in selecting an
commonly used nitrates are the inexpensive material with high
ammonium, sodium, potassium, viscosity. These are the molecu-
and calcium salts. Assuming the lar structures of the cheapest op-
cost per kilogram of each of these tions:
compounds is similar:
• Which of them do you rec-
• Rank the four options from ommend to select?
least to most economical
sources of nitrate ions? Share and discuss your results
with a classmate, and clearly jus-
By M stone (Own Work) [Share Alike 3.0]
Share and discuss your ideas with tify your reasoning.

a classmate, and clearly justify

your reasoning.
Materials Design
Molecular Cages
A pharmaceutical company is seeking to deliver nonpolar drugs in aque-

ous solution by trapping them inside molecular cages like the one depicted
to the right (cyclodextrine). When added to water, these molecular cages
dissolve very well while keeping the nonpolar drug inside the cavity.
• How would you explain this behavior? R

R
R
Side View
http://www.chem.arizona.edu/tpp/chemthink/resources/U3_M4/peptide.html
Polypeptide Design
A pharmaceutical company is experimenting with a new set of drugs based

on polypeptide chains. They are interested in designing a polypeptide that
will have a coiled section and an uncoiled section when dissolved in water. CLICK TO PLAY
• Click on the image shown at right to launch an interactive tool that

will allow you to build polypeptide chains. What type of structure
would you propose to synthesize to accomplish the desired goals?
Desiccants
A company is interested in producing two types of solid desiccants (sub-

stances that absorb the water in their surroundings). The goal is to produce
two substances that are solid at standard conditions, are soluble in water, and
have different melting points, both above 400 oC.
• List your ideas about the structural differences you can introduce to
produce the desired properties.
• Draw a structural representation for each compound that you propose
to synthesize.
Materials Design
Strong Fibers
A manufacturer of bullet proof vests is interested in producing fibers that are as stiff as glass, as
strong as steel, and as heat resistant as asbestos.
• Which of the following polymers would you suggest they use?
Justify your answer based on the analysis of the likely arrangement and interactions between poly-
mer chains in each of these materials.
Greases
A manufacturer of electric motor lubricants is interested in developing a new type of grease prod-
ucts with varying degrees of solubility in water. Lubricating grease, as soaps, tends to be composed
of ionic compounds made up of fatty acid anions and alkali metal cations (e.g., Li+, Na+, K+).
• Which types of cations would you suggest they use to make the most insoluble grease? And
the most soluble?
Salting Roads
The addition of soluble ionic compounds to liquid water lowers its freezing point. This effect is
used in cold cities during the winter to melt ice and snow on the streets. The salts are more effective
the more ions they generate in solution per mole of compound added.
• If asked for advice, which of the following ionic compounds would you recommend to use
for salting roads: AlCl3, CaCl2, CaO, Ca(CH3COO)2, KCl, NaCl, MgCl2 ?
• What other considerations would you take into account in making your recommendation?
Are You Ready?

Antifreeze
Soluble molecular compounds also lower the freezing point of water when dissolved in this liquid.
Molecular compounds are preferred over ionic compounds in the preparation of antifreeze liquids
used in cars to prevent water in the cooling system from freezing. The following images represent the
molecular structures of compounds commonly used as antifreeze:
Methanol Ethylene Glycol Propylene Glycol Glycerol
• Rank these substances in order of increasing melting point and solubility in water. Discuss
how these information may be useful in selecting the best antifreeze.
Diapers
Sodium polyacrylate -[CH2-CH(COONa)-]n is a wa-

ter “super absorbent” polymer used in the production
of diapers. This cross-linked polymer can absorb more
COO- COO- COO- COO-
than 200 times its mass in tap water. Water absorption Na+ Na+ Na+
in this system is the result of diffusion and attractive in-
teractions between water molecules and the negatively Na+ COO- Na+ COO- Na+COO- NaCOO-
+
charged polymer chains. In this process, sodium ions COO- COO- COO- COO-
are displaced and the polymer network swells.
• A diaper manufacturer is interested in changing

the absorption capacity of the polyacrylate by
replacing the sodium ions Na+ in this ionic polymer by other cations such as Li+, K+, NH4+,
Mg2+, and Ca2+. Which of these substitutions can be expected to increase the absorption
capacity of the polymer? Which of them will decrease it?
Are You Ready? Na+
Commercial soaps are mixtures of ionic compounds typically made up of monoat-

omic cations, such as Na+ and K+, and organic polyatomic anions derived from fatty
acids. These negatively charged molecular ions are characterized by the presence of
hydrocarbon chains which are 12 to 18 carbon atoms long. You can apply the ideas
discussed in this Unit to explain the behavior of these types of materials and predict
their physical properties.
Hard or Soft
How hard (solid, insoluble) or soft (liquid, soluble) a soap is depends on the nature of the
anions and cations present in the system. Analyze how each of the following factors may affect
the hardness or softness of soaps:
• The nature of the cations. For example, many soaps are ionic compounds made up of
Na+ ions. How will the properties of these types of soaps differ from those made up of
Li+ or K+ ions?
• The length of the hydrocarbon chain. Many soaps are made up of a mixture of anions
such as the laureate ion (C12), the myristate ion (C14), and the stearate ion (C18). How
will the proportion in which these different ions are present affect the properties of the
soap?
• The degree of unsaturation of the hydrocarbon chain. For example, soaps may include
different proportions of stearate ions (saturated) and oleate ions (monounsaturated).
How would you make a soap softer or harder by varying the proportion of these two
types of ions present in the system?
Hard Water
Hard water is water with a high concentration of Mg2+ and Ca2+

ions coming from the dissolution of ionic compounds (minerals)
in the ground. Soaps tend to be less soluble in hard water than in
regular water and they form a white precipitate
By Bbypnda (Own Work) [Sahre Alike 3.0]
(soap scum) instead of producing foam.

• How you would explain the behavior of

soaps in hard water?

Soaps and Detergents

Surprising Properties Monolayer
CLICK TO PLAY
When soaps dissolve in water the
http://www.chem.arizona.edu/tpp/chemthink/MW/soap.jnlp
ions tend to self-assemble into dif-
ferent structures such as those illus-
trated in the image.
Micelle
• Click on the image to launch
a molecular dynamics simula-
tions that will allow you to
build a simple particulate
model of a submicroscopic
sample of mixture of soap and
water. Analyze how the nature
of the self-assembled structures
that are formed depends on a)
the strength of the interactions
between hydrocarbon chains in
the fatty acid anions and b) the temperature of the system.
The self-assembled structures present in soapy water give the solution particular properties, such
as the ability to dissolve nonpolar materials (e.g., grease).
• Discuss how nonpolar materials can be “dissolved” in soapy water. What role do self-as-
sembled structures such as micelles may play in this process?
Self-assembled structures are also responsible for the formation of bubbles

in soapy water. A soap bubble is made of air encapsulated by a thin layer of
water trapped between two monolayers of fatty acid anions.
• The formation of a soap monolayer on the surface of water reduces

the energy needed to “distend” the surface of the liquid. It is said that
the presence of soap molecules reduces the surface tension (measure of the force per unit
length needed to increase the surface area) of the system. How would you explain this
phenomenon?
• The presence of soap particles on the liquid layer of a bubble stabilizes the bubble (it pre-
vents it from expanding too much or collapsing). How would you explain this behavior?
(Hint: Consider what should happen to the surface tension of those regions of the liquid
layer that expand or contract).
Are You Ready?

Designing Soaps
A soap making company wants to produce aromatic bar soaps, some softer than others. The fol-
lowing table shows the common percent composition of fatty acids in the natural oils that the
company plans to buy to make the soaps:
Oil Saturated Unsaturated

C12 C14 C16 C18 C18 C18
Lauric Myristic Palmitic Stearic Oleic Linoleic
Coconut 44-52 13-19 8-11 1-3 5-8 0-1
Olive - 0.1-1 7-16 1-3 65-80 4-10
Palm - 0.5-2 32-45 2-7 38-52 5-11
Soya Bean - - 7-11 2-6 22-34 43-56
• Which of these oils would you recommend to buy to make hard soaps? Which oil would
you recommend to use to produce the soft soaps?
Detergents
Detergents contain chemical substances with a structure similar to that of fatty acids. Their mol-
ecules are said to be “amphiphilic” as they contain a region which interacts more strongly with
water (hydrophilic) than other regions (hydrophobic). The following images depict the structures
of two common detergents.
• Compare the molecular structure of these detergents. Identify the hydrophobic and hydro-
philic regions in each molecule. Discuss why detergents behave similarly to soaps.

Module 1
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P166 & P167: Background
center by Kyrylo Bessenov & George Harauz https://journal.lib.uoguelph.ca/index.php/surg/article/view/1102/1802; P183: Top right “Waterstri-
derEnWiki” by PD (Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/File:WaterstriderEnWiki.jpg; P184: Top right “Georgia
Aquarium - Giant Grouper edit” by Diliff (Own work, Edited by Fir0002) [Generic 2.5] http://commons.wikimedia.org/wiki/File:Georgia_
Aquarium_-_Giant_Grouper_edit.jpg; P185: Bottom right By Mingxia Gu http://www.personal.kent.edu/~mgu/LCD/tn.htm; P191: Top right
By BASF -The Chemical Company (Own work) [NoDervs 3.0].
Module 2
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P192: Fig. 3.13 “Nylon-3D-
h bond” by GYassineMrabetTalk (Own work) [Generic 3.0] http://commons.wikimedia.org/wiki/File:Nylon-3D-h_bond.png; P196: Bot-
tom right By Hans (Own Work) [Public domain] via Pixabay; P197: Center left By Mariëlle Leenders via YouTube https://www.youtube.com/
watch?v=EikQOrLyc-A;
Module 3
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P202: Top right By USGS http://
schools-wikipedia.org/images/165/16537.jpg.htm; P205: Fig. 3.24 “Transition metal oxidation states 2” Derivative of image from Felix Wan (Own
work)[Share Alike 3.0] http://commons.wikimedia.org/wiki/File:Transition_metal_oxidation_states_2.png; P209: Fig. 3.30 “Atomic & ionic radii”
by Popnose (Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/File:Atomic_%26_ionic_radii.svg; P211: Fig. 3.32 “Na+H2O” by
Taxman (Own work) [Public domain] http://commons.wikimedia.org/wiki/File:Na%2BH2O.svg; P214: Middel right “Chemicals” by Hey Paul
(Own Work) [Generic 2.0] https://www.flickr.com/photos/heypaul/2288311/in/album-72157601506935860/; P215: Bottom left Source: Nature
http://www.nature.com/nature/journal/v412/n6846/fig_tab/412491a0_F1.html; P218: Upper right “Lead Iodide” by Palge Powers (Own Work)
[Generic 2.0] https://www.flickr.com/photos/paigggeyy/5533819494/in/photolist-9r1gJW-b2WjD2-4A3PGy; P224: Bottom right “Hard Water
Calcification” by Bbypnda (Own work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/File:Hard_Water_Calcification.jpg
General
UNIT 4
How do we
characterize
chemical
processes?
The diversity of materials in our world is the consequence of a
long history of chemical activity in our planet. Chemical process-
es involving elementary substances and simple chemical com-
pounds in the primitive Earth are thought to be the precursors
for the natural synthesis of the millions of different substances
that can now be found in our surroundings.
Chemical scientists have learned to induce and manipulate

chemical process for a variety of purposes, from synthesizing new
substances to controlling the formation of unwanted pollutants
in our environment. Chemical thinking in this area relies on the
knowledge about the composition and structure of matter that we
discussed in the first three Units of this book.
In this Unit we will begin our analysis of powerful ways of thinking about
chemical processes. In particular, the central goal of Unit 4 is to help you
understand how to model and characterize chemical reactions. To illustrate
these ideas, we will again focus our attention on Earth’s atmosphere, trying to
answer questions such as:
How do substances react? What drivesschemical reactions?

What amounts of substance and energy are involved in chemical reactions? Ozone Hole
NASA
228
Chemical Thinking
UNIT 4 MODULES
M1. Modeling Chemical Reactions

Identifying factors that affect chemical
processes.
M2. Understanding Proportions
Determining the amount of substance
produced or consumed.
M3. Tracking Chemical Energy
Predicting the amount of energy released
or absorbed.
229
230
Modeling
Chemical
Reactions
Chemical knowledge and ways of thinking are not only useful in separating, de-
U4: MODULE 1
tecting, identifying, or quantifying the amount of different substances in our sur-

roundings. Chemical thinking is equally powerful in monitoring and controlling
changes in the chemical nature of the components of a system of
interest. It allows us, for example, to reduce the amounts of pol-
By Mike Walker and Theodore Gray

lutants that escape through exhaust pipes in cars or to gener-
ate a wide variety of products from the basic components of
petroleum. It opens the door for the production of new phar-
maceutical drugs or for the design of devices that can capture
the carbon dioxide produced in combustion processes. In gen-
eral, chemical thinking gives us the power to induce or hinder
chemical transformations and to synthesize new substances. Nylon Synthesis
Our knowledge about chemical processes is based on the systematic
experimental study of the chemical reactions that can occur between two or more
substances. However, thinking in this area is also guided by theoretical models
developed to explain why and how reactions happen and to predict the outcome
of such processes. As we will discuss in this module, the most powerful models of
chemical reactions are based on the atomic-molecular theory of matter.
THE CHALLENGE Ozone Issues

Ozone (O3) is a chemical substance involved in important chemical reactions
in our atmosphere. The speed at which these reactions occur many times
depends on the amount of sunlight:
• How can light affect the speed of a chemical reaction?

• Would you expect this effect to depend on radiation wavelength?
central goal of Module 1 is to help you understand how to think of chemical
reactions using the atomic-molecular model of matter.
Chemical Thinking U4 How do we characterize chemical processes? 231
Chemical Change
Many materials in our surroundings are in constant change. We see ice melt and
liquid water evaporate in our oceans; we observe sugar dissolving in our coffee,
By Nickel Eisen (Own work) [Generic 2.0]

iron corroding in fences, trees burning, glass breaking, and LCD screens glowing.

All these changes are detectable because there are properties of matter, such as
color or phase, that vary. However, the submicroscopic origin of such changes may
be diverse. For example, when water boils a gas is produced. Analysis of this system
indicates that such a gas has the same chemical composition and molecular struc-
ture as liquid water. We therefore think of this process as a simple physical change.
When we burn a piece of paper a gas is also produced. Yet, chemical analysis in this
case indicates that the gas has a different chemical composition than the original
paper or the surrounding air. The gas is actually a mixture of several components, Figure 4.1 Color change
in autumn leaves is the re-
mainly CO2(g) and H2O(g). Therefore, we think of this process as a chemical sult of chemical changes.
change. In general, the formation of one or more new chemical substances with a
distinct composition are indications that a chemical process has occurred (Figure
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M1/reactions.html
4.1).
Distinctive Features LET’S THINK

The movies linked to the images below show four different chemical reactions. In all of these pro-
cesses at least one new substance is produced.
• Compare and contrast each of these chemical reactions.

Identify main differences and similarities among them.
• If you did not know that these processes involve chemical
changes, what distinctive properties or behaviors could you
use to decide whether a chemical change has occurred?
• How would it be useful to know whether a process involves a
chemical change?
CLICK TO PLAY
Distinguishing physical from chemical changes is frequently not easy. How

do we know, for example, whether putting sugar in our coffee involves just one
substance dissolving into another or an actual chemical reaction between different
components? The reality is that to make these judgments we frequently need to
have access to analytical tools that allows us to monitor the chemical composition
of the system of interest. Chemical scientists, however, have analyzed thousands of
chemical reactions looking for patterns of behavior that can be used as a guide in
deciding what may happen when different types of substances interact with each
other. This knowledge is not only useful in making decisions about how to best
synthesize a given chemical compound, but also in monitoring and controlling
chemical processes in our surroundings. The factors that we should consider in-
clude: chemical composition and structure of the interacting substances, tempera-
ture and pressure of the surroundings, rate at which the process occurs, amount of
energy that is involved in the process, and changes in physical properties such as
color, state of matter, or electrical conductivity.
232 MODULE 1 Modeling Chemical Reactions
Experimental analysis of a wide variety of chemical reactions has revealed basic

common features of chemical processes:
A
Combustion • Chemical reactions may involve one or more initial substances, called the re-
Reaction actants.
• As a result of a chemical reaction new chemical substances with different
[Share Alike 2.5] via Wikimedia Commons
By Einar Helland Berger (Own work)
chemical composition are formed, called the products.

• Reactants combine to form products in specific definite proportions. For ex-
ample, H2(g) always combines with O2(g) in a 2 to 1 (2:1) ratio when forming
H2O(l).
• When chemical reactions occur in closed environments, the total mass of the
system before and after the process remains constant (mass is conserved).
• Chemical processes always lead to a net transfer of energy between the system
in which the reactions takes place and its surroundings. There are chemical
B
processes that result in a net absorption of energy from the surroundings (en-
Acid-Base
dothermic reactions); there are chemical processes that result in a net release of
Reaction
energy from the system to the surroundings (exothermic reactions).
• Chemical reactions occur at varying speeds. The speed or rate of chemical
[Generic 2.0] via Flickr Commons
processes depends on the chemical nature of the reactants, but also on factors
By Kate Ter Haar (Own work)
such as temperature, pressure, and concentration of the reacting species.

• Some chemical reactions go to completion. This is, the reactants are fully
transformed into products when combined in the proper proportion. How-
ever, there are many other chemical systems in which the final state (called the
chemical equilibrium state) involves the presence of constant amounts of both
reactants and products (Figure 4.2). The relative proportion of reactants to
Figure 4.2 A) Combus- products at equilibrium depends on factors such as the temperature and pres-
tion reactions typically go
to completion; B) Reaction sure of the system.
involving acidic and ba-
sic substances frequently
reach an equilibrium state.
These basic experimental facts about chemical reactions define the core phe-
nomena that any successful theory about chemical processes should be able to
explain. Throughout this Unit we will explore how the atomic-molecular model of
matter can help us face such challenge.
LET’S THINK Your Ideas
The atomic-molecular model of matter assumes that all substances are made up submicroscopic
particles (atoms, ions, or molecules) in constant movement and interaction.
• Discuss how this model could be used to explain the following facts:
Mass is conserved in chemical processes in closed systems.
Chemical processes always result in energy transfer.
The speed of chemical reactions depends on temperature.
Not all chemical reactions go to completion.
Share and discuss your ideas with a classmate. You are expected to generate plausible explanations
based on the interaction of particles at the submicroscopic level.
Basic Assumptions
The common features associated with chemical reactions can be explained using
the atomic-molecular model of matter. These explanations are based on the set of
fundamental assumptions that we will discuss in this section.
Assumption 1. Chemical reactions are processes in which the particles that

make up the reactants are rearranged. As a result of these rearrangements,
substances with a different chemical composition are formed.
The atomic rearrangements that occur in a chemical reaction typically involve

the breaking of chemical bonds in the reacting particles, and the formation of new
chemical bonds between atoms in the system. However, there are cases in which
the change is only due to either bond breaking or bond forming. For example,
atoms of type A and type B in a mixture may react to form molecules AB by cova- BEFORE
lently bonding to each other.
The changes in the atomic composition of the particles involved in a chemical
process are frequently represented using a “chemical equation.” In these types of
representations, the chemical formulas of all of the reactants are added on the left
hand side of the equation while the chemical formulas of all of the products are
added on the right hand side. The representations of reactants and products are
then linked by an arrow that indicates the direction of the process. Thus, for the
reaction described above, we would have:
A + B AB
Reactants Products
Chemical equations indicate the minimal proportion in which the particles

involved in the process react or are produced, rather than the total amounts of
particles present before and after the reaction. Thus, for example, the chemical
equation for the process depicted in Figure 4.3 is:
2 H2 + O2 2 H2O and not 2 H2 + 2 O2 2 H2O + O2
Stoichiometric Coefficients
AFTER
The chemical equation for this reaction indicates that hydrogen and oxygen mol-
ecules react in a ratio of 2 to 1 to produce 2 water molecules. The numbers used
to represent the proportion in which chemical species react or are produced in a
Figure 4.3 Submicro-
chemical equation are called the stoichiometric coefficients. scopic representation
of the reaction be-
The idea that chemical processes involve the rearrangement of atoms or ions in tween hydrogen and
a system allows us to explain two crucial facts about these types of processes. On oxygen to form water.
the one hand, we can understand why chemical reactions lead to the formation
of new substances, or to net changes in the amounts of some of the substances
present in a closed system: atomic rearrangements generate new types of submi-
croscopic structures. On the other hand, we can explain why the total mass is
conserved in chemical reactions that occur in closed systems. No matter how the
atoms rearrange during the process, we should end with the same number of each
type of atom as we had before the reaction started.
LET’S THINK Reactions with Oxygen
Oxygen gas in our atmosphere reacts with many chemical substances on Earth. We take advan-
tage of some of these reactions to generate energy through the combustion of different types of
fuels. However, some of the products of these processes are major air pollutants.
• Natural gas, composed mainly by methane (CH4), is used to power some vehicles. Use the
following submicroscopic representation of the reaction between CH4 and O2 molecules to
derive the corresponding chemical equation.
• The high temperatures in combustion engines induce the reaction between nitrogen and
oxygen in the air and produce nitrogen monoxide, a well-known pollutant. Use the follow-
ing submicroscopic representation of this process to derive its chemical equation.
It is common for chemical reactions to occur under conditions in which one of the reactants is in
excess. In these cases, the formation of the products will be limited or constrained by the reactant
present in the smallest proportion. This substance is called the “limiting reactant.”
• Natural gas contains small amounts of sulfur compounds. When burned, they produce the
pollutant SO2 that further reacts with oxygen in the atmosphere to produce another harm-
ful substance. Consider the system below: What is the chemical equation that represents this
process? Which substance is acting as limiting reactant in this particular case?
• The incomplete combustion of substances such as carbon (C) and ethane (C2H6) produces
carbon monoxide (CO), a toxic pollutant. Write the chemical equation that corresponds to
each of these processes, complete each of the following submicroscopic representations, and
identify the limiting reactant in each case.
? ?
Assumption 2. Rearrangement of atoms during a chemical reaction involves

A
electron redistribution among different atoms. As a result of this process, the
internal potential energy of particles in the system changes. Endothermic
Ep Process
The formation of new types of molecules or ions during a chemical reaction
is accompanied by changes in charge distribution. Some atoms may lose electrons
and others may gain them; some atoms in a molecule will become more electro- 2 O3
positive and others will gain a negative partial charge. All these changes will alter
the internal potential energy Ep of the particles in the system, defined as the energy Energy Absorbed
associated with the internal interactions and movement of the electrons that make 3 O2
up such particles. The above assumption allows us to explain why chemical reac-
tions always involve transfer of energy from or towards the surroundings. Reactants Products
The changes in internal potential energy during a chemical process are often Reaction Path
represented using energy diagrams. In these types of representations, the internal
potential energy of particles is depicted along the reaction path. This reaction path
may be conceived as the sequence of atomic rearrangements that take place as B
reactants become products. Therefore, the reaction path starts with those particles Exothermic
identified as the reactants and ends with the particles that make up the products. Process
Figure 4.4 illustrates the initial and final states in the energy diagram for two dif- Ep
ferent types of reactions.
The energy diagram in Figure 4.4A corresponds to the reaction between oxy-
gen molecules, O2, to form ozone molecules, O3, in our atmosphere. Experiments 2 H2 + O2
indicate that for this reaction to occur a net amount of energy needs to be supplied
to the system (the process is endothermic). This result suggests that the internal Energy Released
potential energy of the O3 molecules, the products, is higher than that of the O2 2 H2O
molecules, the reactants. The external energy provided in the form of light or heat
Reactants Products
is transformed into internal energy of the ozone molecules during the chemical
reaction. On the other hand, the reaction between H2 and O2 molecules to form Reaction Path
H2O is known to release energy (the process is exothermic). We can explain this
Figure 4.4 A) Energy
behavior by assuming that the internal potential energy of the water molecules diagram for the reaction:
3O2 --> 2O3. B) Energy
is lower than that of the hydrogen and oxygen molecules (Figure 4.4B). In this diagram for the reaction:
situation, the internal potential energy of the reactants is transformed into kinetic 2H2+ O2 --> 2H2O.
energy (thermal energy) during the chemical process.
Energy Diagrams LET’S THINK

The combustion of propane (C3H8) in our stoves as well as the production of glucose (C6H12O6)
in plants are processes involving important air components (O2, CO2, and H2O).
• Write the chemical equations that depict the minimal proportion in which molecules react
during the combustion of C3H8 in stoves and during the production of C6H12O6 in plants.
• Based on your experience and knowledge about these two processes, sketch their corre-
sponding energy diagrams clearly indicating the relative internal potential energy of reac-
tants and products.
• Classify each of these processes as endothermic or exothermic.
Assumption 3. For a chemical reaction to occur, particles of the different re-

actants must collide. The more collisions per unit time, the faster the process.
The atoms, ions, and molecules that make up chemical substances are in con-
stant movement and interaction. Thus, they can be expected to collide with each
other on a regular basis. These collisions may result in rearrangement of atoms
under the proper conditions. Given that the frequency of collisions will depend on
particle speed and the space available for particles to move, the above assumption
implies that the speed or rate of a chemical reaction should depend on factors such
More as temperature, pressure, and concentration of particles in the system.
Effective
Assumption 4. For a chemical reaction to occur, colliding particles must be
oriented in a manner that allows reacting groups to interact effectively.
The particles that make up chemical substances can be expected to move,

vibrate, and rotate in random ways. Thus, when these particles collide, they are
likely to do it in random relative orientations. Given that molecules have particu-
lar geometries and charge distributions, some collisions will be more effective than
others in inducing rearrangement of atoms and electrons. Take, for example, the
Less two different collisions between NO and O3 molecules represented in Figure 4.5.
Effective These two molecules react in our atmosphere to produce molecules of O2 and the
pollutant NO2. Given the structure of NO2 molecules, collisions in which the
nitrogen atom in the NO molecule is oriented towards the O3 molecule are more
Figure 4.5 More or likely to lead to the formation of NO2 and O2.
less effective collisions
in the reaction of NO Mixtures of molecules made up of two or more atoms can collide in many
and O3 molecules.
different relative orientations or configurations. The higher the fraction of rela-
tive orientations that lead to effective collisions (configuration effectiveness),
the faster the chemical process can be expected to be. Thus, in general, the fewer
the number of particles that need to interact to generate the products and the sim-
pler the composition and structure of such particles, the faster the process.
LET’S THINK Effective Configurations?

Reactants Products Reactants Products
Consider the three pairs of chemical processes repre-
sented in the images.
• Which of the processes in each pair can be

expected to be faster assuming equal conditions
of temperature, pressure, and concentration of
particles in the system?
HINT: Determine which mixture of reactants is likely to

have a larger fraction of effective versus ineffective con-
figurations during collisions between reacting particles.

clearly justify your reasoning.
Assumption 5. For a chemical reaction to occur, colliding particles must have

enough energy to reach a transition state that leads to the formation of the
new products.
Transition
State
Chemical reactions involve the rearrangement of atoms and electrons in a
system. However, an initial supply of energy is frequently required to trigger such Ep O
N O O
O
process. For example, energy may be needed to separate bonded atoms in a mol- Ea
ecule to the point where their attraction is weak enough for one of the atoms to
detach or to bond to a different nearby atom. The initial energy that needs to be NO + O3
supplied, called the activation energy Ea, increases the internal potential energy of
the reacting particles and makes them reach an unstable state from which atomic
rearrangements are more likely to happen. This unstable state is known as the NO2 + O2
“transition state” and represents a high-energy intermediate step in the transfor-
Reactants Products
mation from reactants to products. This step, as well as the associated activation
energy Ea, can be represented in an energy diagram as shown in Figure 4.6. The Reaction Path
shape of such energy diagram suggests that the activation energy may be thought
as an energetic barrier that needs to be overcome for particles to react. Figure 4.6 Energy dia-
gram for the reaction
The activation energy needed to reach the transition state is frequently sup- between NO and O3
depicting the transition
plied by collisions among reacting particles. Thus, the higher the kinetic energy of state for this process.
the colliding particles, the greater the chance of them reaching such a state. At any
given temperature, some particles in a system will have enough kinetic energy to
overcome the activation barrier. However, the fraction of particles that reacts
will depend on the value of the temperature T and the activation energy Ea
(Figure 4.7). The existence of an activation energy barrier allows us to explain
why different chemical processes occur at different rates. The value of the acti-
vation energy Ea depends on the chemical nature of the reacting species as well
as on the presence of agents that may facilitate their interactions (called cata-
lysts). In general, the smaller the value of Ea, the larger the fraction of particles
with enough kinetic energy to overcome the activation barrier and the faster the
chemical reaction will be. For some mixtures of reactants, the activation energy Figure 4.7 The fraction
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M1/activation.html
of collisions with energy
is so small that the average kinetic energy of their particles at room temperature higher than Ea increases
is enough to produce collisions that take most particles over the barrier. In other with increasing T.
cases, energy needs to be supplied by external means using heat or light sources.
A Simple Model LET’S THINK

The molecular dynamics simulation linked to the image shown to
CLICK TO PLAY
the right is based on a simple model for a chemical reaction of the

generic type A + B --> AB. In this simulation, the average rate of the
reaction can be inferred by observing how the percentage of atoms of
type A in the system (%A) changes as a function of time.
• Predict how you expect the speed of the reaction to change with a) increasing temperature,
b) increasing initial concentration of reactants, c) increasing activation energy.
• Use the simulation to verify your predictions. Make sure to properly control variables and to
derive your conclusions based on repeated observations under similar conditions.
Let us take a moment to summarize the core ideas about reaction rates dis-
cussed up to this point. Assumptions 3, 4, and 5 introduced in previous paragraphs
imply that the rate of a chemical reaction is determined by four main factors at the
Ep submicroscopic level: 1) the frequency of collisions, 2) the kinetic energy of the
colliding particles, 3) the activation energy, and 4) the configuration effectiveness
(the fraction of all possible collisions between reacting species in which particles
N2O2+ O2 meet at effective orientations for the reaction). The first two factors may be altered
by changing variables such as the temperature, pressure, or the initial concentra-
2 NO + O2
tion of the reactants; in general, increasing the value of any of these properties
tends to increase the rate of reaction, particularly if reactants are in the gas phase.
The last two factors in the list depend on the chemical composition and structure
2 NO2
of the reacting species and on the presence of other substances that may facilitate
Reactants Products
(catalysts) or hinder (inhibitors) interactions between particles. Any structural fac-
tors that facilitate the formation of the transition state or lower its internal po-
Reaction Path tential energy (lower Ea) will lead to higher reaction rates. The more complex the
reaction mixture is (number, type, size, geometry, and distribution of particles),
Figure 4.8 Energy dia- the fewer the expected fraction of effective configurations that can lead to new
gram for the reaction:
2NO + O2 --> 2NO2, in- products and the lower the reaction rate.
volving the formation of The rate of a chemical process also depends on the sequence of events that lead
an intermediate species.
to the transformation of reactants into products. Although some reactions may
involve a single transition state, many others follow a more complex path involv-
ing the formation of short-lived intermediate species and several transition states.
For example, in the reaction of NO with O2, the first step is the formation of the
intermediate N2O2 that reacts with O2 to produce NO2 (Figure 4.8).
LET’S THINK Reaction Rates
The energy diagrams shown to the right correspond Ep Ep

to the reactions A + B --> AB and
D + E --> DE. Both processes have the same activa-
tion energy Ea. Ea
A+B Ea DE
• If we assume that T, P, and the initial concen-
trations of all of the reactants in these two pro- AB D+E
cesses are the same. Which of these reactions
would you expect to be faster? Reaction Path Reaction Path
It is common to think that exothermic reactions are faster than endothermic

reactions. Most chemical processes that we notice in our environment, such as
burning and explosions, are exothermic and tend to occur very rapidly. However,
these reactions do not occur at constant temperature. Many exothermic processes
are fast because the energy that they generate dramatically increases the tempera-
ture of the reaction mixture, which accelerates the transformation of reactants into
products. On the other hand, the net absorption of energy associated with endo-
thermic processes causes a temperature decrease, which lowers the reaction rate.
But when exothermic or endothermic reactions are carried out ensuring constant
temperature throughout the process, the net release or absorption of energy does
not have an influence on the speed of the reaction.
Assumption 6. As reactants interact to generate products in a chemical reac-

tion, particles of the products may chemically interact with each other and re-
generate particles of the reactants. The final state of the system is determined
by the balance between these two opposite processes.
Particles of the products formed during a chemical reaction may interact with
themselves and rearrange to regenerate particles of the reactants. The probability of
Ep
Ea (A->B)
this event (backward process) depends on the same types of factors that affect the
rate of formation of the products (forward process): the temperature and pressure
of the system, the concentration of the products, and the activation energy and
configuration effectiveness of the reaction between products.
To illustrate these ideas, let us consider a simple reaction in which molecules A Ea (B->A)
of type A (reactants) undergo atomic rearrangements that lead to molecules of
type B (isomerization reaction). At constant temperature, the initial rate of trans-
formation of A into B will depend on both the concentration of A molecules and
the value of the activation energy Ea(A-->B) represented in the energy diagram in B
Figure 4.9. As the reaction proceeds, molecules of type B may transform back into
molecules of type A at a rate determined by the concentration of B particles and Reactants Products
the activation energy Ea(B-->A) (Figure 4.9). Given that the reaction starts with a Reaction Path
higher concentration of A than B particles, the initial rate of the forward process
(A --> B) should be higher than the rate of the backward process (B-->A). Howev-
er, as A is consumed and B is produced, the forward process will slow down while Figure 4.9 Energy dia-
gram for the isomeriza-
the backward process will speed up. Eventually these two processes will occur at tion reactions A --> B and
B --> A showing the activa-
the same rate and no changes will be observed in the net amounts of molecules of tion energy for each process.
types A and B in the system (on average, the same number of molecules of each
type will be produced and consumed at any given time). When this occurs, we say
that the system has reached chemical equilibrium.
Chemical Equilibrium LET’S THINK
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M1/equilibrium.html
Imagine that you had a container with 1 mole of molecules of type A
t(s) A (mol) B (mol)
and 0 molecules of type B. If you knew that 60% of the A molecules
transform into B molecules every second and 30% of B molecules 0 1 0
transform back into A molecules in the same period of time: A->B 1 x 0.6 = 0.6 -->
B->A <-- 0
• What would the number of moles of A and B molecules in the 1 0.4 0.6
container be when the system reaches chemical equilibrium? A->B 0.4 x 0.6 = 0.24 ->
HINT: Complete and extend the table shown to the right to keep B->A <- 0.6 x 0.3 = 0.18
track of the moles of molecules of each type as a function of time. 2 0.34 0.66
A->B ? ->
The interactive tool linked to the image can be used to explore the effect
B->A <- ?
of changing the probabilities of the A --> B and B --> A processes on
3 ? ?
the relative amount of products and reactants at chemical equilibrium.
CLICK TO PLAY
• Use the simulation to find a general relationship between the prob-

abilities of the forward and backward processes and the relative
amounts of reactants and products at equilibrium.
As you may have noticed in the previous activity, the ratio of the concentra-
tions of products to reactants at chemical equilibrium, which is a measure of the
extent of the chemical reaction, is determined by the ratio of the probabilities of
the forward and backward processes. The larger the probability of reactants trans-
forming into products, and the lower the chance for products transforming back
into reactants, the larger the reaction extent when the equilibrium state is reached.
Given that the probabilities of the forward and backward processes depend on
both the values of the activation energy and the configuration effectiveness associ-
A+B C+D ated with each of these processes (as implied by core Assumptions 4 and 5 previ-
ously discussed), we can qualitatively predict what types of chemical reactions can
be expected to attain larger extents (or be more product-favored).
Given that chemical reac- The relative values of the activation energies for the forward and backward
tions involve forward and
backward processes, it processes in a chemical reaction depend on the relative internal potential energy of
is common to represent
them using chemical equa- reactants and products. For example, when products have lower internal potential
tions with a double arrow, energies than reactants (exothermic processes), the height of the activation barrier
particularly in those cases
where it is known that the for the forward process is lower than the corresponding value for the backward
process does not go to
completion. process (Figure 4.9). This feature favors the conversion of reactants into products
(product-favored). The opposite behavior is characteristic of endothermic process-
es (reactant-favored). Therefore, from the energetic point of view, exothermic pro-
cesses are more likely to reach larger reaction extents than endothermic processes
(in fact, many exothermic processes practically go to completion). However, we
should also analyze the effect of configuration effectiveness on the rate of the for-
ward and backward processes. The probability of two or more particles colliding in
an effective configuration is lower in systems involving more complex molecules or
more complex reaction mixtures. Thus, the relative complexity of the reactant and
the product mixtures may also affect the reaction extent.
LET’S THINK Reaction Extent
The energy diagrams for two important atmospheric reactions are shown below. One corresponds
to the reaction between gaseous nitrogen and oxygen to form nitrogen monoxide. The other repre-
sents the reaction between solid carbon and gaseous oxygen to form carbon monoxide.
• Analyze whether the forward or the back-

ward processes for each of these reactions Ep Ep
can be expected to be more probable based
on the analysis of the corresponding
a) activation energies, and b) configura-
2 NO
tion effectiveness.
• Discuss which of these reactions is likely 2 C + O2
N2 + O2
to be more product-favored.
2 CO
Share and discuss you ideas with a classmate, Reaction Path Reaction Path
and justify your reasoning.
The six modeling assumptions about chemical reactions introduced in this

module define the core ideas used by chemical scientists to make sense of chemical
change in our world. These assumptions will guide many of our discussions in the
following modules and Units of this book.
FACING THE CHALLENGE mation. UV-B radiation, which can be harmful to

the skin
and is
Stratospheric Ozone the main
Ozone (O3) is an important component of our c a u s e
Altitude (km)
planet’s atmosphere. This substance is naturally of sun-
produced in a chemical reaction that involves mo- burn, is
lecular oxygen (O2) and is activated by UV radia- screened
tion: UV photons induce the splitting of O2 mol- out with
ecules, generating free oxygen atoms that bind to Ozone Concentration (DU/km)
close to
other oxygen molecules and produce ozone. Once 95% ef-
formed, ozone molecules may also be split by UV fectiveness in the process of oxygen regeneration.
radiation and regenerate molecular oxygen. This However, most UV-A reaches our planet’s sur-
cycle of ozone formation and decomposition oc- face and, although less harmful, it can potentially
curs mainly in the stratosphere of our planet, in a cause genetic damages. Modern sunscreen lotions
region from about 10 to 50 km above Earth’s sur- include a mixture of chemical substances that ab-
face. About 90% of the ozone in the atmosphere sorb UV-A and UV-B radiation.
is contained in this “layer,” in concentrations that The oxygen-ozone cycle has been disrupted in
range from 2 to 8 ppm. Compared to other major recent years by the presence of chemical substances
components of the atmosphere, the total amount that create alternative reaction paths for the de-
of O3 in the stratosphere is actually rather small. If composition of O3 molecules. In particular, chlo-
all of the ozone in this region were compressed to rofluorocarbons (CFCs) used for several years as
the pressure of air at sea level, it would form a layer foaming agents and refrigerants have been shown
no more than 3 mm thick. to be particularly damaging to the ozone layer.
The decomposition of O2 and O3 molecules in CFCs are highly stable compounds capable of sur-
the oxygen-ozone cycle involves the absorption of viving the rise to the stratosphere, where Cl radi-
energy (activation energy) in the form of UV radicals are generated by the action of UV light. CFCs
ation. An equivalent amount of energy is released take fifteen years on average to reach the strato-
in the form of heat when O2 and O3 molecules sphere, and they can remain in the atmosphere for
reform. Thus, the cycle leads to the transformation up to one hundred years. The Cl radicals that they
of high-energy UV radiation into thermal energy generate react with ozone molecules and each of
that is dispersed into the atmosphere. This chemi- them can break down over 100,000 O3 molecules.
cal process is vitally important for life in our plan- Concerns about the thinning of the ozone
et because it absorbs harmful UV radiation that layer arose in the 1970’s but atmospheric concen-
could alter the structure of biological molecules trations were not systematically monitored until
and induce cellular mutations. the 1980’s. Major seasonal declines have been ob-
UV radiation is com- served, particularly around
monly classified into three the north and south poles
main categories based on its (ozone hole). The interna-
wavelength: UV-A (400–315 tional community signed a
nm), UV-B (315–280 nm), treaty in 1987 (the Montreal
and UV-C (280–100 nm). protocol) that sharply lim-
UV-C radiation, which has ited the use of CFCs. As a
the highest energy and is the result of these international
most harmful to living organ- efforts, the depletion of the
isms, is entirely screened out ozone layer has slowed down
in the process of ozone for- Click to show projections of O3 concen- in recent years.
trations if CFCs had not been banned.
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M1/ozone.html
Let’s Apply
The Ozone Layer
Stratospheric ozone screens out much of the Sun’s harmful UV radiation that reaches our planet.
The protection against high energy radiation offered by the ozone layer is the result of a set of
chemical reactions that occur at different speeds and to different extents in our atmosphere. Let us
investigate some of them.
Ozone Formation
Ozone is formed naturally in the stratosphere through this chemical reaction:
3 O2 2 O3
The activation energy Ea for the forward process in this reaction is 498.5 kJ/mol and
there is a net absorption of 143 kJ of energy per mole of O3 produced.
• Build the energy diagram for this chemical reaction taking into account the
relative values of Ea and the energy absorbed in the process;
• Discuss whether you would expect this reaction to be product-favored or
reactant-favored based on the analysis of the activation energies and configura-
tion effectiveness of the forward and backward processes.
Basic Steps O radical = O
The formation of ozone actually occurs in two

steps, as shown in the image. The first step has Step UV
an activation energy (Ea) of 498.5 kJ/mol and 1 Light
absorbs 498 kJ/mol of energy (net). The acti-
vation energy for the second step is very small
(~0) and it releases 106 kJ of energy (net) per
mole of O3 formed. Step
2
• Build the energy diagram for this chemi-
cal reaction taking into account the
relative values of Ea and the net energy Overall
absorbed and released in each step.
3 O2 2 O3
Light Activation
The formation of ozone in the atmosphere is said to be photo activated rather than ther-
mally activated. This means that the activation energy required to start the reaction is
provided in the form of electromagnetic radiation.
• Given the information provided in the previous activities, what is the maximum
wavelength of the electromagnetic radiation that will initiate the process of O3
formation by activating O2 molecules?

Share and discuss your ideas with a classmate. Clearly show and explain your calculations.
Close to 3 x108 tons of ozone naturally form and decom-

pose every day in the stratosphere. Ozone decomposition UV
is naturally activated by UV radiation with wavelengths Light
around 280 nm (UV-B radiation). This process is repre-
sented in the figure. Some pollutants in the stratosphere,
such as chlorofluorocarbons (CFCs), create alternative
paths for ozone destruction and upset the natural balance.
Ozone Destruction
Chlorofluorocarbons
(CFCs) are the main Natural Alternative
source of Cl• radicals in
the atmosphere. These Ep Ea = 17 kJ/mol
Ep Ea = 2.1 kJ/mol
radicals create an al- Ea = 0.4 kJ/mol
ternative reaction path O• + O3 Cl• + O3 161 kJ/mol
for ozone destruction.
Consider the energy 391 kJ/mol ClO + O2
+ O• 230 kJ/mol
diagrams for the natural
destruction of ozone by
O• radicals and for the 2 O2 2 O2 + Cl•
alternative reaction in- Reaction Path Reaction Path
duced by Cl• radicals.
• Which of these two reactions paths is faster?

• Which of these two reaction paths is more product-favored?
• Cl• radicals in the alternative reaction path are present at the beginning and at the
end of the process. What are the consequences of this regeneration of Cl• radicals
on the ozone layer?
Let’s Apply
Nitrogen Oxides
Nitrogen oxides, such as NO, NO2 and N2O4, are prominent air pollutants. These molecular com-
pounds tend to form in reactions involving nitrogen, oxygen, and ozone at the high temperatures
that are characteristic of internal combustion engines in cars and in thermal power stations.
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M1/no.html
NO formation
Atmospheric nitrogen and oxygen react to form nitrogen monoxide in an endothermic reac-
tion that absorbs 90.2 kJ of energy per mole of NO formed. Experimental data suggest that the
decomposition NO back into N2 and O2 has an activation energy close to 300 kJ/mol.
CLICK TO PLAY
• Click on the image to launch a simulation for the formation of
NO. Select appropriate relative values for the activation energy
and the internal potential energy of reactants and products.
Run the simulation at different temperatures and observe what
happens. How does the apparent kinetic energy of reactants
and products differ? How do you explain this behavior?
NO2 Dimerization
Nitrogen dioxide is a reddish-brown toxic gas with a sharp,

biting odor. This pollutant is responsible for the orange
haze present in many big cities. NO2 molecules react with
each other at low temperature to produce N2O4. A submi-
croscopic representation of the initial state of this process
in a certain system is shown in the image to the right.
• Draw the final state of the reaction assuming it goes Ep

to completion. Ea = 1.2 kJ/mol
The energy diagram for the dimerization of NO2 into

N2O4 is shown on this page. 2 NO2
57.2 kJ/mol
• Compare the probabilities of the forward and back-
ward processes based on the corresponding activa-
tion energies and configuration effectiveness. N2O4
Reaction Path
Chemical Equilibrium
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M1/n2o4.html
The dimerization of NO2 into N2O4 is a typical example of a chemi- CLICK TO PLAY
cal reaction that does not go to completion at most common tem-
peratures. The concentration of both species at chemical equilibrium
depends on factors such as temperature, pressure, volume of the con-
tainer, and initial number of molecules. The interactive simulation
linked to the image shown to the right will allow you to explore the
properties of this chemical process at a constant temperature (10 oC).
• Launch the interactive tool. Before running the simulation (selecting the “on” button),

predict whether you would expect a higher concentration of reactants or products when
chemical equilibrium is reached. Use the energy diagram shown on the previous page to
guide your thinking. Run the simulation and analyze the outcome.
• Turn the simulation off and choose a different number of NO2 molecules in the initial
state. Predict changes that you would expect to see in the relative concentrations of
reactants and products at chemical equilibrium. Base your predictions on your analysis
of changes in the rates of the forward (2 NO2 --> N2O4) and backward (N2O4 --> 2 NO2)
processes. Run the simulation and analyze the outcome.
• Predict the effect of varying the volume of the system on the relative concentrations of
reactants and products at chemical equilibrium. Base your predictions on your analysis
of changes in the rates of the forward and backward processes. Run the simulation and
analyze the outcome.
Smog
Photochemical smog is a type of air pollution in the troposphere of our planet produced when
sunlight acts upon motor vehicle exhaust gases to form harmful substances such as ozone (O3).
For example, nitrogen dioxide reacts with atmospheric oxygen in the presence of light to pro-
duce ozone and nitrogen monoxide.
• The image shows a submicroscopic representation of the products

of the reaction between NO2 and O2 in a certain location. Assuming
that the reaction went to completion, draw a microscopic represen-
tation of the system before the reaction started. Write the balanced
chemical equation for the process and identify the limiting reactant.
• The reaction between NO2 and O2 is photo activated by electromag-
netic radiation with a wavelength shorter than
390 nm. Estimate the activation energy (in kJ/mol) for this process.
• The backward process (reaction between NO and O3) is known to
have an activation energy close to 106 kJ/mol. Use this data to estimate the net amount
of energy absorbed or released in the formation of tropospheric ozone.
246
Understanding
Proportions
The ability to induce and control chemical processes depends on knowledge about
U4: MODULE 2
the proportion in which different substances react. This under-

standing is critical to, for example, create reaction mixtures
in which the amount of product is maximized or to con-
trol the formation of undesired byproducts during fuel
combustion. Understanding the proportions in which
different chemical compounds react and are produced
By EPA
also allows us to predict the maximum amount of
product that will be generated from any mass of reac-
tants that we have. This knowledge has been extremely
valuable in the design of the industrial processes that pro-
duce the many synthetic substances that have revolution-
ized our way of life.
Calculations about the amounts of reactants and products
that are involved in a chemical reaction are simplified when the process goes to
completion. This is, when the conversion of reactants into products is close to
100% because the probability of the forward process is much larger than the prob-
ability of the backward process during a chemical reaction. In this module we will
focus our attention on such highly product-favored processes. The study of react-
ing mixtures that reach a state in which reactants and products coexist in chemical
equilibrium will be considered in Units 5 and 6 of this book.
THE CHALLENGE Carbon Footprint

The term “carbon footprint” refers to the quantity of greenhouse gases emitted
by a defined population, system, or activity. The word “carbon” is used because
the most common greenhouse gas is carbon dioxide.
• How would you calculate the carbon footprint associated with, for ex-
ample, using a stove? What information would you need for this task?
tral goal of Module 2 is to help you understand how to predict the amounts of
reactants and products involved in a chemical reaction.
Tracking Atoms
The identification of the proportion in which different particles chemically react
to form new products is facilitated by representing atomic rearrangements using
chemical equations (Assumption 1 in the previous module). However, these sym-
bolic representations should be carefully built to ensure that each of the participat-
REACTANTS
ing species is properly represented and that all the atoms involved in the process
are accounted for. Consider, for example, the following representation of the reac-
tion between carbon atoms and oxygen molecules to form carbon monoxide:
C + O2 CO
Although the above symbolic representation includes the correct chemical formula
for each species, it fails to represent the actual proportion in which particles re-
act. As written, the chemical equation does not account for all the oxygen atoms
involved in the process. Therefore, we said that the chemical equation is not “bal-
anced.” Given the composition of the oxygen molecules, we can expect that each
O2 particle will react with two carbon atoms and yield two CO molecules. The
balanced chemical equation should thus be represented as:
2 C + O2 2 CO
As shown in the above chemical equation, we use stoichiometric coefficients

to indicate the minimum number of each type of particle in the reactants and
products needed to ensure conservation of the total number of each type of atom
in the system. Identifying the right stoichiometric coefficients requires keeping
close track of the different types of atoms that make up reactants and products.
In chemical reactions that involve reactants made up of molecules with many
atoms of the same type, such as C or H atoms, it is often convenient to begin
balancing the chemical equation by identifying the different numbers of product
molecules that can form with such numbers of atoms. For example, in the reaction
of propane (C3H8) with oxygen (O2), carbon dioxide (CO2) and water (H2O) are
produced:
C3H8 + O2 CO2 + H2O
Given the number of C and H atoms in a propane molecule, we can expect 3 mol-
ecules of CO2 and 4 molecules of H2O (4 x 2 = 8 H atoms) to be formed.
C3H8 + O2 3 CO2 + 4 H2O PRODUCTS
The numbers of C and H atoms in this chemical equation are the same before
Figure 4.10 Balanc-
and after the process, but not the number of O atoms. The production of three ing chemical equations
CO2 molecules and four H2O molecules requires the involvement of 3 x 2 + 4 x is often facilitated by
building submicrosco-
1 = 10 oxygen atoms which have to be supplied by five O2 molecules (5 x 2 = 10 pic representations of
the process of interest.
O atoms). Therefore, the balanced chemical equation for this process should be
written as (Figure 4.10):
C3H8 + 5 O2 3 CO2 + 4 H2O

248 MODULE 2 Understanding Proportions
LET’S THINK Balancing Chemical Equations
Consider the following chemical equations of important chemical processes in our atmosphere:
CO + O2 CO2
NO + CO N2 + CO2
C2H6O + O2 CO2 + H2O
• Balance each of these chemical equations to ensure conservation of each type of atom in-
volved in the process.
To this point we have used chemical equations to indicate the proportions in

which particles of different substances react or are produced in a chemical reac-
tion. However, it is also common to use chemical equations to represent reactions
in terms of actual amounts of reactants and products measured in moles. In these
cases, the states of matter of the substances involved are represented using the
following symbols: (s) for solid, (l) for liquid, (g) for gas, and (aq) for aqueous
solution. For example, the combustion of octane (C8H18, the main component of
gasoline) in the engines of our cars would be represented as:
2 C8H18(l) + 25 O2(g) 16 CO2(g) + 18 H2O(g)

Substance M (g/mol) This chemical equation packs large amounts of information. It not only tells
C8H18 114.2 us the states of matter of reactants and products. It establishes that 2 moles of
C8H18 molecules react with 25 moles of O2 molecules to produce 16 moles of CO2
O2 32.00
and 18 moles of H2O molecules. Given that we can calculate the molar masses (M
CO2 44.01 in g/mol) of each of these chemical compounds, the chemical equation can also
H2O 18.01 be used to derive the proportions in terms of mass in which the substances react:
2 mol C8H18 + 25 mol O2 16 mol CO2 + 18 mol H2O
228.4 g C8H18(l) + 800.0 g O2(g) 704.2 g CO2(g) + 324.2 g H2O(g)
The above information is critical in determining the amounts of reactants that

need to be combined to maximize the amounts of products in a chemical process.
It also helps us in predicting the amounts of products generated using specific
amounts of reactants.
LET’S THINK Mass Proportions
Nitric acid (HNO3) may be formed in the atmosphere in a process involving these substances:
NO2 + H2O + O2 HNO3
• Determine the mass proportions in which substances react in this process.

Amounts of Substance
Calculations of the amounts of reactants and products involved in chemical reac-

tions that go to completion are facilitated by following systematic procedures.
However, what procedure to use depends on the type of question that we want to
answer and on the nature of the information that is available. In general, there are
two major types of problems we may want to solve. In some cases we may be in-
terested in determining how much mass of a reactant is needed to produce certain
amount of product, or to react with another substance. In other situations we may
want to predict how much product will be formed given certain initial amounts of
reactants. All these types of problems are referred to as “stoichiometry problems.”
Let us analyze how to best approach these types of challenges.
A. Determining amounts of reactants.
No matter what type of stoichiometry problem we are facing, the first step
towards its solution is to identify the balanced chemical equation that represents
the chemical reaction of interest. Imagine, for example, that we want to produce
ethanol biofuel (C2H6O) by fermentation of glucose (C6H12O6) (Figure 4.11). The
balanced chemical equation that represents this important industrial process can Substance M (g/mol)
be written as:
C6H12O6 180.2
C6H12O6(s) 2 C2H6O(l) + 2 CO2(g) C2H6O 46.07
CO2 44.01
Given this chemical equation, how can we calculate what mass of glucose should
be used per every kilogram (1000 g) of ethanol that we want to produce? The
above equation indicates the mole proportions in which glucose reacts and ethanol
is produced. To take advantage of this information, we need to identify how many
moles (n) of ethanol we want to generate. To determine this quantity we can use
the relationship n = m/M, where m is the mass that we have and M is the molar
mass of the substance of interest. Equivalently, we can apply this conversion factor:
1 mol C2H6O
By ARS (Own work) [Public domain]

1000 g C2H6O x = 21.71 mol C2H6O
46.07 g C2H6O

Once the number of moles of the desired product are identified, we can use the
chemical equation to infer the moles of reactant that we need. In this case we
know that every mole of C6H12O6 produces 2 moles of C2H6O. Thus, we require:
1 mol C6H12O6
21.71 mol C2H6O x = 10.85 mol C6H12O6 Figure 4.11 Production
2 mol C2H6O of ethanol biofuel in the
US has almost quadru-
pled in the past 10 years.
This number of moles of glucose can be expressed in grams of the substance by
multiplying by its molar mass:
180.2 g C6H12O6
10.85 mol C6H12O6 x = 1955. g C6H12O6
1 mol C6H12O6
The general strategy to calculate the mass of a reactant needed to generate a

given mass of product is summarized in the following diagram:
Divide by Use Mole Ratios Multiply by

Mass Moles Moles Mass
Molar Mass Balanced Molar Mass
Product Product
Product Chemical Equation
Reactant Reactant
Reactant
LET’S THINK Nitric Acid
Nitric acid (HNO3) is one of the main chemical species associated with an atmospheric phenom-
enon known as “acid rain.” Although HNO3 may be produced in different ways, one of the main
paths involves the following substances:
NO2(g) + H2O(l) HNO3(aq) + NO(g)
Average concentrations of HNO3 in a big city such as Los Angeles are close to 1 mg (1 mg = 1 x
10-6 g) per m3.
• Determine the concentration of NO2 in mg/m3 that is involved in the production of HNO3 in
this environment.
Share and discuss your ideas with a classmate, and clearly show your calculations.
B. Predicting amounts of products.
Predictions about the maximum amount of product that can be formed in

a chemical reaction (also called the theoretical yield of the reaction) can be made
following a procedure similar to that described in the previous section. However,
these problems require that we pay close attention to the relative mole proportions
in which different reactants are present in the system. In particular, we need to
determine which reactants are in excess and which of them will act as the limiting
reactant.
Calculations of theoretical yields are simplified in chemical processes involv-
ing a single reactant (e.g., decomposition reactions) or in situations where all of
the reactants except one are known to be in excess in the system. In such cases,
identification of the limiting reactant is quite easy. Imagine, for example, that
you were interested in estimating the maximum mass of CO2(g) produced every
time that 1 kg of octane (C8H18) is burned in a combustion engine. These types of
calculations are at the base of the determination of the carbon footprint of many
human activities. Let us assume that the corresponding chemical reaction:
2 C8H18(l) + 25 O2(g) 16 CO2(g) + 18 H2O(g)
takes place under conditions of excess oxygen gas in the engine. Therefore, we
know that C8H18 is the limiting reactant. With this information at hand, we may
want to calculate the number of moles of this substance involved in the process:
1 mol C8H18
1000 g C8H18 x = 8.757 mol C8H18
114.2 g C8H18
Once the moles of the limiting reactant are known, we can use the chemical Substance M (g/mol)
equation (mole ratios) to calculate the maximum number of moles of CO2 that
can be produced. These moles of product can then be transformed into mass of the C8H18 114.2
same substance by multiplying by its molar mass: O2 32.00
CO2 44.01
16 mol CO2 44.01 g CO2
8.757 mol C8H18 x x = 3083. g CO2 H2O 18.01
2 mol C8H18 1 mol CO2
Notice that we performed the transformation of moles of reactant into grams of

product in a single step using two consecutive conversion factors. The above re-
sult indicates that a maximum of 3.083 kg of CO2 are produced per kg of octane
burned. This number is known as the CO2 emission factor for the fuel.
The overall strategy that allows us to predict amount of product based on the
amount of the limiting reactant is summarized in the following diagram:
Divide by Use Mole Ratios Multiply by

Mass Moles Moles Mass
Molar Mass Balanced Molar Mass
Reactant Reactant
Reactant Chemical Equation
Product Product
Product
This general procedure can be applied to predict amounts of products in any

chemical reaction once we have a clear idea of which reactant will be fully con-
sumed during the process (the limiting reactant). Sometimes the amount of
a reactant present in a system may be known in terms of volume rather than
mass. For example, as volume of a liquid or a gas. If the limiting reactant is a
liquid, we can use its density (r) to calculate the equivalent mass of substance:
m = r x V. If the limiting reactant is a gas, we can estimate the number of moles
(n) of reactant by assuming ideal gas behavior: n = PV/(RT).
CO2 Emission Factors LET’S THINK

The comparison of the CO2 emission factors (kilograms of CO2 produced per kilogram of burned
fuel) of different types of fuels is useful in making evaluations about their environmental impact:
• Determine the CO2 emission factors of methane, CH4(g), and ethanol, C2H6O(l), two fuels
currently used as alternatives to gasoline;
• The CO2 emission factor of gasoline is close to 3.2 kg CO2 per kg of fuel. What percent
reduction or increase in CO2 production is associated with using CH4(g) or C2H6O(l) instead
of gasoline?
• Discuss whether these results suggest that CH4(g) and C2H6O(l) are better fuel choices than
gasoline from an environmental perspective. What other factors would you need to consider
to make a better evaluation?
When we are uncertain about which reactants are in excess and which species
is the limiting reactant in a chemical process, we need to take systematic steps to
identify them. Let us consider the following example. Hydrogen gas, H2(g), is seen
by many as one of the most important alternative energy sources of this century.
Modern methods of hydrogen production involve the reaction of hydrocarbons,
Substance M (g/mol) such as ethane (C2H6), with water steam at high temperatures:
C2H6 30.07
C2H6(g) + 2 H2O(g) 2 CO(g) + 5 H2(g)
H2O 18.01
CO 28.01 Imagine that we had a tank with a mixture of 500. g of each reactant. Which
H2 2.016 substance is the limiting reactant? How much hydrogen gas will be produced?
To answer these types of questions, we first need to calculate the number of moles
of each reactant in the system:
1 mol C2H6
500. g C2H6 x = 16.63 mol C2H6
30.07 g C2H6
REACTANTS
1 mol H2O
500. g H2O x = 27.76 mol H2O
18.01 g H2O
Once the number of moles of reactants are known, we can compare the propor-
tion in which reactants are present in the system (actual ratio) to the proportion
in which they react according to the chemical equation (stoichiometric ratio). To
make this comparison, we calculate the corresponding mole ratios:
Actual Ratio Stoichiometric Ratio

27.76 mol H2O H2O 2 mol H2O H2O
= 1.669 = 2
16.63 mol C2H6 C2H6 1 mol C2H6 C2H6
The above stoichiometric ratio indicates that two moles of water require one
mole of ethane to react completely. However, the actual ratio of reactants in our
container is smaller, which suggests that there is not enough H2O to react with the
C2H6 present in the system. Therefore, H2O is the limiting reactant (Figure 4.12).
In general, if the actual ratio is smaller than the stoichiometric ratio, the substance
placed in the top part of the ratio (numerator) is the limiting reactant. If the ac-
tual ratio is greater than the stoichiometric ratio, then the substance placed in the
numerator is in excess and the other reactant limits the reaction. If the actual ratio
and the stoichiometric ratio are the same, reactants are present in stoichiometric
proportions and both substances will be completely used up during the reaction.
PRODUCTS All calculations about the amount of product formed during a chemical reac-
tion should be based on the amount of limiting reactant in the system. Once this
Figure 4.12 Submi-
substance is consumed, no more product can be formed. Thus, the maximum
croscopic represen- amount of hydrogen that can be produced in our example problem results to be:
tation of the reaction
mixture analyzed in
this page.
5 mol H2 2.016 g H2
27.76 mol H2O x x = 139.9 g H2
2 mol H2O 1 mol H2
Biohydrogen LET’S THINK

In the search for renewable chemical paths to produce hydrogen gas for fuel consumption,
chemical scientists have found ways to use carbohydrates extracted from wood residues (cellulosic
materials) to produce H2(g) in a process involving the following substances:
C6H10O5(s) + H2O(l) H2(g) + CO2(g)
• What mass of hydrogen can be produced in a reactor containing a mixture of 1 kg of each

reactant?
Share and discuss your ideas with a classmate, show your calculations, and justify your reasoning.
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M2/combustion.html
An Interesting Application
The types of calculations discussed in this module are critical in making decisions CLICK TO PLAY
about how to create reactions mixtures that maximize yields or that minimize
By Nrbelex (Own work) [Saher Alike 3.0]

undesirable by-products. As an example of the importance of stoichiometric cal-

culations, let us analyze a problem of critical importance in modern societies: the
combustion of fuels in car engines (Figure 4.13).
Most transportation vehicles depend on the energy supplied by chemical reac-
tions involving mixtures of air and different types of fuels. The performance of a
vehicle’s internal combustion engine, as well as the amount of diverse pollutants
that result from the chemical reactions that take place in the combustion cham-
Figure 4.13 Click
bers, depend to a great extent on the so-called air-fuel ratio (AFR) at which the on the image to ob-
engine is run. The AFR is the mass ratio of air to fuel present in an internal com- serve the intake and
combustion of fuel
bustion engine. Maximum production of energy and lower amounts of pollutants inside an engine.
are often associated with air-fuel mixtures in which reactants are supplied in the
right stoichiometric proportions.
O2 Needs LET’S THINK

To calculate the AFR of a fuel, we need to determine the mass of oxygen gas that should be pres-
ent in the engine per unit mass of fuel. Consider the case of octane fuel (C8H18):
2 C8H18(l) + 25 O2(g) 16 CO2(g) + 18 H2O(g)
• How many moles of O2(g) are needed to react completely with 1.000 g of C8H18(l)? How
many grams of oxygen is this?
Share and discuss your ideas with a classmate. Show your calculations and justify your reasoning.
The mass of oxygen needed per gram of fuel can be used to calculate the mass
of air that should be present in the engine to fully burn the fuel. Air is a mixture
of close to 79% N2(g) and 21% O2(g) by number of moles (or 76.7% N2(g) and
23.3% O2(g) by mass). This information, together with the molar masses of N2
and O2, is all that we need to determine the stoichiometric AFR of the fuel.
LET’S THINK Stoichiometric AFR
Based on the number of moles or the mass of O2 needed to completely burn 1.000 g of C8H18 that
you calculated in the previous activity:
• Determine the number of moles of air that you will have to inject into an internal combustion
engine per gram of octane in the system;
• Determine the mass of air that you will have to inject. This number corresponds to the stoi-
chiometric AFR for octane.
Share and discuss you ideas with a classmate, and clearly outline your calculations.
An internal combustion engine does not necessarily run at the stoichiometric

AFR all of the time. Sometimes there may be less air than is needed to fully burn
the fuel injected into the combustion chamber (lower AFR); the engine is said to
be “burning rich.” It may also happen that the combustion chamber has more air
than is required under stoichiometric conditions (higher AFR); the engine is then
“burning lean.” Car engines are run at the stoichiometric AFR (14.7 for gasoline)
only under light load conditions. Under high load conditions, or when the car is
accelerating, rich mixtures (lower AFR) are frequently used to prevent detonations
and overheating.
LET’S THINK Exhaust Gases
The gases emitted into the environment as a result of the combustion of fuels are known as exhaust
gases. The composition of these gaseous mixtures depends on the AFR at which the combus-
tion engine is run. Changes in the composition of the exhaust gases are frequently represented by
plotting the %Mol (or %Volume) of each of the different substances in the exhaust mixture as a
function of the AFR.
• Using a graph such as that shown to the right, make a quali-

Stoichiometric
tative plot of the expected %Mol of a) C8H18, b) O2, and Ratio
c) CO2 in the exhaust gases as a function of AFR. RICH LEAN
HINT: Analyze which substance is expected to be the limiting reac-

tant at different AFR values and predict how its concentration will
%MOL
affect the formation of products and the consumption of reactants.
The combustion of fuels such as octane may lead to the formation

of pollutants such as CO(g):
2 C8H18(l) + 17 O2(g) 16 CO(g) + 18 H2O(g) AFR
• How would you expect the %Mol of CO in the exhaust gases to change as a function of AFR?
Share and discuss you ideas with a classmate, and justify your reasoning.
FACING THE CHALLENGE are determined using stoichiometric calculations

similar to those discussed in this module. In gen-
eral, these calculations are facilitated if we know
Carbon Footprint the %mass of carbon in the fuel of interest. If we
The term “carbon footprint” often refers to the do, then we can infer how much CO2 will be pro-
amount of carbon dioxide (usually in tonnes) be- duced per kilogram of fuel:
ing emitted by a defined population, system, or
activity. We can thus estimate the carbon footprint 44.01 g CO2
mass CO2 = %mass C x
of a person, a production system, a factory, or an 12.01 g C
entire coun-
try. These This relationship indicates that the CO2 emis-
calculations sion factor of a fuel increases with the %mass of
Gas
may take 7 tonnes
carbon it contains. In general, this percentage in-
into ac- Road Trip
creases with molecular size and degree of unsatura-
count only 2 tonnes tion (number of double or triple bonds between
the direct carbons). This phenomenon is illustrated in the
Flight
emissions LA-London following table where we show the CO2 emission
associ- 1 tonne factors (expressed in kg of CO2 per liter) of three
ated with Electricity liquid hydrocarbons and three common liquid fos-
1.1 tonnes
the system sil fuels:
of inter-
est, such as the amount of CO2 generated in the Compound CO2
or Emission Factor
chemical transformation of corn starch into etha- Fuel (kg/L)
nol. However, many times it is convenient to also
Hexane (C6H14) 2.00
consider the less direct emissions associated with
a given process, such as the CO2 emitted as part Octane (C8H18) 2.15
of corn crop production or the transportation of Decane (C10H22) 2.25
ethanol fuel from its production centers. Gasoline 2.35
Carbon footprint calculations require detailed Kerosene 2.58
information about the different materials and pro- Diesel 2.69
cesses involved in a given activity. These calcula-
tions are often facilitated by knowledge of the so- Although calculations of carbon footprints are
called CO2 emission factors (or emission intensity) part of the determination of the so-called Ecologi-
of all potential sources. These factors express the cal Footprint (measure of human’s demand on the
average emission rate of CO2 from a given source Earth’s ecosystem), the carbon component in this
relative to the intensity of a specific activity: latter environmental index takes a slightly differ-
ent approach. In the Ecological Footprint, the
mass of CO2 emitted amount of CO2 produced by a source or activity
CO2 emission factor =
quantity of activity is translated into the amount of productive land
and sea area required to sequester such emissions.
The “quantity of activity” in this relationship can This result tells us how CO2 emissions compare
be expressed in diverse ways, such as liters of gas with other human demands, such as need for food
burned, gallons of gasoline consumed, distance sources and amount of agricultural land taken to
traveled, or megajoules of energy produced. build cities and roads. Nowadays, the carbon foot-
CO2 emission factors are frequently used to print is close to 54% of humanity’s overall Eco-
compare the environmental impact of different fu- logical Footprint and constitutes its most rapidly
els or activities. In the case of fuels, these factors growing component.
Let’s Apply
CO2 Emissions
Many of our daily activities result, directly or indirectly, in the emission of CO2 into the environ-
ment. We burn gasoline in our cars; we combust propane in our stoves and natural gas in our
heating systems. We use electricity that is largely generated by burning coal in power plants and
we live in houses and cities built with cement produced in a process in which CO2 is also formed.
Personal Contributions
The table shown to the right includes data for the average
consumption of oil, coal, and natural gas per person per year
in the US. Use this information to:
Amount
• Calculate the mass of CO2 (in tonnes) produced per (person/year)
person per year in the US. Although oil, coal, and Oil 3.5 m3
natural gas are mixtures of many different substances,
Gas 2125 m3
to simplify the calculations assume that oil is mostly
made of heptane (C7H16), natural gas is made of meth- Coal 3.2 tonne
ane (CH4), and that the mass percentage of carbon in Additional Data
the coal we use is close to 90%. Thus, the following r(Oil) ~ 0.8 kg/L
chemical equations may be used to solve the problem: V(Gas) ~ 22.4 L/mol
at STP
C7H16(l) + O2(g) CO2(g) + H2O(g) 1 m3 = 1000 L
CH4(g) + O2(g) CO2(g) + H2O(g) 1 tonne = 1000 kg
C(s) + O2(g) CO2(g)
Using a Cell Phone
The carbon footprint of having and using a cell phone is close to 50 kg of CO2 per
year. If we assume that the energy needed to produce and make the cell phone work
comes from burning coal (90% carbon):
• What is the associated mass of coal (in kg) consumed per cell phone per year?
Share and discuss your ideas with a classmate, and show your calculations.
Cement Production
Many industrial processes emit large quantities of CO2 as a result of diverse chemical processes.
The world cement industry, for example, emits close to 9 x 1011 kg CO2 per year. This number
amounts to 5% of the total CO2 emissions worldwide. Half of these gas emissions result from
the decomposition of limestone (CaCO3) into lime (CaO) in a reaction known as calcination:
CaCO3(s) CaO(s) + CO2(g)
• What mass of CaCO3(s) is being consumed to produce cement every year in the world?
• What is the CO2 emission coefficient for the calcination of CaCO3(s) (kilograms of CO2

per kg of cement produced)?
Share and discuss your ideas with a classmate, and clearly explain your reasoning.
Abrasives
Silicon carbide (SiC) is a extremely hard chemical compound widely used as an abra-
sive (materials used for grinding and polishing). This substance is produced by the
reaction of silicon dioxide (SiO2) and carbon (C):
SiO2(s) + C(s) SiC(s) + CO(g)
CO2(g) emissions from this process are calculated assuming that the CO(g) produced
reacts with O2(g): 2 CO(g) + O2(g) 2 CO2(g). Close to 1 x 105 tons of CO2 are
produced through this process every year in the US.
• Consider a mixture of 1 kg SiO2(s) and 0.6 kg C(s). Which species would be

the limiting reactant in this reaction mixture?
• What would be the theoretical yield of CO2(g) in the above reaction mixture?
Share and discuss your ideas with a classmate, and clearly explain your reasoning.
Capturing CO2
Cars are the second largest source of greenhouse gases in the US. A single car spews
out around 5000 kg of CO2 every year. Close to 40% of this CO2 may be captured by
a mix of potassium hydroxide (KOH) and water dispersed within the ceramic wool
support of a CO2 exhaust filter:
CO2(g) + KOH(aq) KHCO3(aq)
• What mass of KOH (in kg) is required to keep the filter working every year?
Let’s Apply
Hydrogen Fuel
Hydrogen is considered one of the most promising alternative sources of energy of the future. Hy-
drogen reacts with oxygen in a strongly product-favored exothermic reaction that generates water
as the only product. From this perspective, hydrogen is one of the cleanest fuels.
Hydrogen Production
One of the most common methods of hydrogen production is steam reforming of

methane gas:
CH4(g) + H2O(g) CO(g) + H2(g)
• Balance the above chemical equation;

• Determine the mass of methane gas, CH4(g), that should be used to produce
1 kg of H2(g).
Share and discuss your ideas with a classmate, and clearly show your calculations.
Renewable Options
The aqueous-phase reforming process allows the gen- US Hydrogen

eration of hydrogen from biomass-derived compounds Refueling Stations
such as sugars and sugar alcohols. An example of this 2008
process is the reaction between glycerol (C3H8O3) and
water vapor at temperatures above 150 oC:
C3H8O3(l) + H2O(g) CO2(g) + H2(g)
• Balance this chemical equation;

• Identify the limiting reactant in a mixture of
500. g of glycerol and 250. g of water;
• Determine the theoretical yield of H2(g) in the
By EERE
above reaction mixture.

clearly show your calculations.
Air-Fuel Ratio (AFR)
Hydrogen gas reacts with oxygen gas to produce water as represented in the following
chemical equation:
2 H2(g) + O2(g) 2 H2O(g)
• Calculate how many grams of O2(g) are needed to react completely with 1.000 g of
H2(g);
• Use the result of the previous calculation to determine the stoichiometric AFR for
hydrogen fuel (grams of air needed per gram of H2(g)). Assume that air is a mixture

of 79% N2(g) and 21% O2(g) by mole (or 76.7% N2(g) and 23.3% O2(g) by mass);
• Compare the stoichiometric AFRs of hydrogen and gasoline (14.7). Use this result,
together with the fact that gasoline is a liquid and hydrogen is a gas at STP, to dis-
cuss potential differences in the design of combustion engines that use these fuels.
Share and discuss your ideas with a classmate, and show and explain your calculations.
Exhaust Gases
Initial (grams)
The table shown to the right includes the mass H2(g) O2(g)
composition of four different samples of air-fuel
mixtures injected into a hydrogen fuel engine. S1 0.07560 1.200
S2 0.09469 1.000
• Calculate the AFR of each of the mixtures; S3 0.1008 0.800
• Predict the expected number of moles and S4 0.1134 0.600
the mass of H2(g), O2(g), and H2O(g) after
the reaction goes to completion; Stoichiometric
Ratio
• Calculate the %Mol of H2, O2, and H2O
in the final mixtures; RICH LEAN
• Plot on the same graph (see image to the

right) the %Mol of H2, O2, and H2O as a
%MOL
function of AFR;
• Identify the reaction mixture (S1, S2, S3, or
S4) that corresponds to each of the submi-
croscopic representations shown below.
AFR
260
Tracking
Energy
Based on the six fundamental assumptions about chemical processes introduced in
U4: MODULE 3
the first module of this Unit, the characterization of a chemical reaction requires
the identification of the atomic rearrangements that occur
during the process, an understanding of the proportion in
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which substances react, the analysis of the net energy ab-
By Sebastian Ritter (Own work)

sorbed or released as a result of the reaction, and the de-
termination of the rate and extent of the chemical pro-
cess. Our discussions in the previous module focused
on issues related to the characterization of reactants and
products and the proportions in which they react. Thus,
in this module we shift our attention towards the topic of
energy transfer in chemical reactions. In particular, we will
try understand the mechanism that leads to the release or absorption of energy at
the submicroscopic level. Understanding energy transfer in chemical processes is
crucial for predicting and controlling reaction rate and extent, topics that will be
discussed in subsequent Units of this textbook.
Transfer of energy between a system and its surroundings during a chemical
process is of critical importance at many levels in our planet. It is through that
mechanism that living organisms generate the energy that they need to survive and
that modern societies produce the energy that powers the industrialized world.
THE CHALLENGE Food Energy
If you have ever been on a diet, you may have heard expressions such as these:
“fats are compact forms of energy storage,” or “gram per gram, fats hold more
energy than carbohydrates.”
• How do you interpret these statements? Do chemical substances actually

contain energy in them? How is that energy held?
Module 3 will help you develop the type of chemical reasoning that is used
tral goal of Module 3 is to help you understand how to estimate the net energy
absorbed or released during a chemical reaction based on the nature of the
chemical bonds in the molecules of reactants and products.
Bond Energy
The exchange of energy in the forms of heat or light between a system and its sur-
roundings is a common phenomenon during a chemical change. Whether energy EXOTHERMIC
is absorbed or released during the process can often be determined by analyzing
how the temperature of the surroundings changes. Chemical reactions that release
thermal energy to the surroundings (exothermic processes) cause the temperature Surroundings
to increase. On the contrary, chemical reactions that absorb thermal energy (endo-
System
thermic processes) cause the temperature of the surroundings to decrease (Figure Tsurr
4.14). Given that during an exothermic process the system loses energy in the
Heat
form of heat (q), the energy lost is frequently represented as a negative number
(e.g., q = –40 kJ/mol). For endothermic processes, the energy absorbed is indi-
cated using positive quantities (e.g., q = +30 kJ/mol).
Combustion reactions in which oxygen gas, O2(g), reacts with a fuel such
as methane gas, CH4(g), are prototypical examples of exothermic processes.
q<0
For example, the combustion of one mole of methane releases close to 802 kJ
(q = –802 kJ/mol) at 25 oC and 1 atm of pressure. The decomposition of stable ENDOTHERMIC
chemical compounds, such as H2O(g), into elementary substances is frequently an
endothermic process [e.g., q = +242 kJ/mol for the decomposition of H2O(l) into
H2(g) and O2(g)]. How do we explain these different behaviors? We have already Surroundings
discussed that the rearrangement of atoms during a chemical reaction involves
System
electron redistribution among different atoms. As a result of this process, the inter- Tsurr
nal potential energy of particles in the system changes (Assumption 2 in Module 1
of this Unit). If the internal potential energy of the products is lower than the in-
Heat
ternal potential energy of the reactants, energy will be released to the surroundings
(exothermic process). On the contrary, if the products have a higher internal po-
tential energy than the reactants, energy has been absorbed (endothermic process).
In order for atomic rearrangements and electron charge redistribution to occur q>0
during a chemical reaction, chemical bonds between some atoms need to be bro- Figure 4.14 Energy
ken and new chemical bonds need to be formed. It is through the process of bond transfer during exo-
thermic and endother-
breaking and bond formation that the internal potential energy of the reactants in mic processes.
the system is transformed into thermal energy during exothermic processes. Bond
breaking and bond formation also lead to the transformation of thermal energy
into internal potential energy of the particles that make up the reaction products
during endothermic processes.
Give or Take? LET’S THINK

During a chemical reactions some chemical bonds may be broken while new chemical bonds
between different atoms may be formed?
• Does it take energy to break a chemical bond?

• Is energy released when a chemical bond is broken?
• Does it take energy to form a chemical bond between two atoms?
• Is energy released when a chemical bond is formed?
262 MODULE 3 Tracking Energy
As we discussed in Module 2 of Unit 2 of this textbook, the formation of a

chemical bond between two atoms is a stabilizing process in which the energy
of the interacting atoms decreases. The delocalization of valence electrons in the
bonding region in covalent bonding or the transfer of valence electrons from one
CLICK TO PLAY atom to another in ionic bonding lead to more stable states with a lower energy.
This is illustrated in Figure 4.15 where the total potential energy (Ep) of a pair of
interacting hydrogen atoms is plotted as a function of the dis-
tance (r) between their nuclei (traditionally, the value of Ep in
0 these types of graphs also includes the internal kinetic energy of
the electrons that make up each atom).
-100
Two atoms separated a certain distance r will attract each
Ep (kJ/mol)
-200 other due to the presence of dispersion forces between them.

As they move towards each other, their potential energy will de-
-300 crease and their kinetic energy will increase. This process will
-400 continue until repulsive forces between atoms begin to domi-
Bond Length nate and the potential energy increases. There is then an equi-
-500 librium distance (bond length) at which the potential energy
100 200
r (pm) is a minimum and a chemical bond may be formed. However,
Figure 4.15 Change in in order for bonding to occur the kinetic energy gained by the
the potential energy (Ep)
of two interacting hydro- atoms as they moved towards each other needs to be dissipated (transferred to
gen atoms as a function other particles); this normally occurs by collision with surrounding particles. If the
of the distance r be-
tween their nuclei. kinetic energy was not dissipated, interactions between the bonding atoms would
not be strong enough to hold them together. Thus, the formation of a chemical
bond generates thermal energy that is transferred to the surroundings. From this
perspective, bond formation is an exothermic process.
While forming a chemical bond between two atoms releases energy to the
surroundings, breaking a chemical bond requires a supply of energy (endothermic
process). In order for two bonded atoms to separate, they need to acquire enough
kinetic energy to overcome the attractive forces that hold them together. The en-
ergy required to separate a pair of bonded atoms in a molecule is known as the
bond dissociation energy and its value depends on the types of atoms involved in
the bond as well as on the nature and distribution of surrounding atoms in the
molecule. The bond dissociation energy is also a measure of the energy that will be
http://www.chem.arizona.edu/tpp/chemthink/MW/bondenergy.jnlp
released when that same bond is formed.
LET’S THINK Bond Formation
We can use a molecular dynamics simulation to explore the effect of bond formation on the
temperature of a system.
CLICK TO PLAY
• Click on the image to launch the simulation of the dimer-

ization reaction 2A –> A2. Use the simulation to analyze
the effect of changing the bond dissociation energy on the
temperature of the system as the reaction progresses.

The dissociation energy of different types of bonds can be measured using a va-
riety of experimental techniques. For example, spectroscopic methods rely on the
identification of the wavelength of EM radiation that is needed to break an spe-
cific bond. Given that the dissociation energy of a bond depends on the particular
molecular environment, the energy required to break, for example, a first C–H
bond in a methane molecule (CH4) may be slightly different than that needed to
separate a second hydrogen atom, or to break a C–H bond in a molecule of eth-
ane (C2H6). However, by assembling a large amount of experimental information
for each type of bond, a consistent set of average bond dissociation energies can
be obtained. As we will see in the following pages, these average values, typically
called bond energies (BE) and expressed in kJ/mol, are very useful in estimating
the amount of energy absorbed or released in different chemical processes.
It is common to consider the dissociation energy of a chemical bond as a mea-
sure of “bond strength.” The stronger the bond, the larger the amount of energy
required to break the bond. This implies that the stronger the bond, the lower (or
more negative) its potential energy (Figure 4.16). This may sound counterintui-
tive because in common life we associate “strength” with the ability to do work or
transfer energy. Thus, one may think that stronger bonds contain or hold more Figure 4.16 Variation of
the potential energy Ep for
energy than weaker bonds. However, this is not the case. Bond strength is not a different types of bonds
as a function of distance
measure of either the energy contained in a bond or the energy holding the atoms between atoms. Stronger
together; rather, it is a measure of the energy that needs to be invested to break the bonds have deeper poten-
tial energy wells (larger BE).
bond (or that was be released when the bond was formed.)
C-O Bond C-H Bond O-H Bond
0 0 0
-100 -100 -100

Ep (kJ/mol)
Ep (kJ/mol)
Ep (kJ/mol)
-200 -200 -200
-300 -300 -300
-400 -400 -400
-500 -500 -500

100 200 r (pm) 100 200 r (pm) 100 200 r (pm)
BE = 360 kJ/mol BE = 414 kJ/mol BE = 464 kJ/mol
Energy Needed to Break the Bond

Smaller Larger
Energy Released when the Bond is Formed
Multiple Bonds LET’S THINK

Carbon atoms typically form double and single bonds with other carbon atoms:
• Sketch how you expect the potential energy Ep of two carbon atoms linked by a) a single
bond (C–C), b) a double bond (C=C), and c) a triple bond (C≡C) to change as a function of
distance r between the nuclei.
• Discuss which type of bond, single, double or triple, will require more energy to break and
which type will generate more energy when formed.
Heat of Reaction
Bond energies can be used to estimate the net amount of energy absorbed or re-
leased during a chemical process. This quantity is called the heat of reaction and is
often represented using the symbol DHrxn. A common procedure to estimate the
heat of reaction is based on the idea that the value of DHrxn should result from
the balance of the energy absorbed in the breaking of bonds in the reactants and
the energy released during the formation of bonds in the products of the reaction.
Given that by convention we assign a negative value to energy that is released by
the system, we can then write:
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M3/rocket.html
DHrxn = S (BE bonds broken) – S (BE bonds formed)
where the symbol S is used to indicate sum over all of the bond energies of the
CLICK TO PLAY bonds broken or formed during the chemical process.
Let us illustrate the application of the above relationship by estimating the
heat of reaction for the combustion of one mole of methane gas in a combustion
engine (Figure 4.17):
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g)
The chemical equation for this reaction at the molecular level can be represented
in the following way using structural formulas:
Figure 4.17 Testing of a

CH4-based rocket by NASA.
+ +
The analysis of the above representations reveals that, no matter how the re-
action actually proceeds, the total combustion of 1 mole of CH4(g) will require
breaking 4 moles of C–H bonds and 2 moles of O=O and forming 2 moles of
C=O bonds and 4 moles of O–H bonds. Thus, using the associated bond energies
listed in the tables at the bottom of this page we can estimate the value of DHrxn:
DHrxn = 4 BE(C–H) + 2 BE(O=O) - 2 BE(C=O) - 4 BE(O–H)
DHrxn = 4 x 414 + 2 x 498 – 2 x 799 - 4 x 464 = –802 kJ
The estimated value compares very well with the actual experimental result, –802.3
kJ, despite the fact that we used average bond dissociation energies. In general,
larger deviations may be expected when working with larger molecules.
Bond BE (kJ/mol) Bond BE (kJ/mol) Bond BE (kJ/mol) Bond BE (kJ/mol)

H–H 436 C–Cl 339 C–S 259 N=O 607
C–H 414 C–N 305 N–H 389 O–H 464
C–C 347 C=N 615 N–N 163 O–O 142
C=C 611 C–O 360 N≡N 946 O=O 498
C≡C 737 C=O 736* N–O 201 S–H 368
*799 in CO 2
Energy exchanges during a chemical reaction such as the combustion of

CH4(g) can be more easily visualized using energy diagrams. Knowledge about
bond energies allows us to estimate the internal potential energy Ep of reactants
and products relative to a state in which all of the atoms are far apart and not
bonded to any other atom (the internal potential energy of such a state is taken to
be zero). For example, if one mole of free carbon atoms combined with 4 moles
of free hydrogen atoms to form one mole of CH4 molecules, four moles of C–H
bonds would be formed and the potential energy of the system would decrease by
4 x BE(C–H) = 4 x 414 =1656 kJ. Thus we could assign an internal potential en-
ergy of Ep = –1656 kJ to a mole of CH4 molecules (this implies we need to supply
+1656 kJ to break 1 mol of CH4 molecules into free atoms). Following a similar
procedure we can calculate the potential energy of each reactant and product, and
build the following types of energy diagrams:
Ep Free Atoms Ep Free Atoms
C+H+H+H+H+O+O+O+O C+H+H+H+H+O+O+O+O
0 0
+996 kJ
+1656 kJ +2652 kJ
-1598 kJ -3454 kJ
-1000 -1856 kJ -2000
2 O2
CH4 + 2 O2 DHrxn
CH4 CO2
CO2 + 2 H2O
-2000 2 H2O -4000
Reactants Products Reactants Products
Reaction Path Reaction Path

The first energy diagram shows the energy needed to break all of the bonds
in each of the reactants and the energy released during the formation of all of the
chemical bonds in each of the products. The energy diagram to the right depicts
the total energy absorbed (bond breaking) and released (bond formation) during
the reaction. As shown in this latter diagram, the internal potential energy of the
products (–3454 kJ) is lower than that of the reactants (–2652 kJ) and the dif-
ference between these two potential energies is equal to the heat of the reaction:
DHrxn= –3454 – (–2652) = –802 kJ.
H2O Decomposition LET’S THINK

In the search for new sources of energy, chemical scientists have explored the decomposition of
water vapor at high temperatures to produce hydrogen gas. This endothermic process requires a
supply of +241.8 kJ per mole of water decomposed.
• Write the balanced chemical equation for this process and represent the reaction using struc-
tural formulas for reactants and products;
• Estimate the heat of reaction DHrxn using bond energies and compare your result with the
experimental value;
• Build an energy diagram representing energy exchanges during the reaction;
• Explain what happens to the energy absorbed during the process.
When predicting heats of reaction it is important to pay attention to the types

and number of chemical bonds in both reactants and products. If molecules of the
reactants contain very strong bonds, more energy will be required to break such
bonds which increases the energy input. However, the final outcome also depends
on the number and strength of the new bonds that are formed. This implies that
we cannot assign a specific value to the energy stored in a given amount of a
chemical substance. The amount of potential energy that will be transformed into
thermal energy during an exothermic process will vary depending on the nature of
each reactant and product. Thus, it is somewhat misleading to talk about certain
compounds “storing” more energy than others, as the amount of energy that can
be extracted from a given substance depends on the nature of both the substances
with which it reacts and the products that they form.
LET’S THINK Ethanol Fuel
Ethanol, C2H6O, is now used as an alternative or as a supplementary fuel in many vehicles. An

approximate energy diagram for the combustion of one mole of ethanol in the presence of O2 is
shown below:
Ep Free Atoms
C+C+H+H+H+H+H+H+O+O+O+O+O+O+O
• Estimate the heat of reaction per
mole of C2H6O burned; 0
+1494 kJ
• The potential energy of ethanol -3196 kJ
molecules is the lowest in this 3 O2 -2784 kJ
system. How is then possible -2000
+3241 kJ
that this reaction is exothermic?
3 H2O
• Where does the energy released C2H6O 2 CO2
in this process come from? -4000
Reactants Products
Share and discuss your ideas with a
classmate. Reaction Path
LET’S THINK Oxidation Effects
Organic compounds made up of molecules that contain fewer hydrogen atoms and more oxygen
atoms per carbon atom are said to be more “oxidized.” Consider the following set of molecules
represented in increasing order of oxidation:
Methane, CH4 Methanol, CH4O Formaldehyde, CH2O Formic Acid, CH2O2
• Estimate DHrxn for the combustion of one mole of the last three compounds;
• Build energy diagrams for each of the reactions and explain the overall trend in the value of
the heat of reaction with increasing degree of oxidation. Share and discuss your ideas with
a classmate, and clearly justify your reasoning.
FACING THE CHALLENGE Foods with a high carbohydrate content in-

clude fruits, breads, pastas, rice, and cereals. The
carbohydrates in these foods are typically disac-
Food Energy charide or polysaccharides that should be decom-
Living organisms need to ingest or absorb chemi- posed into monosaccharide units, such as glucose
cal substances from their surroundings to survive. and fructose, to generate energy during cellular
We eat food that contains chemical compounds respiration (the process in which these substances
such as carbohydrates, lipids, and proteins. Plants react with the oxygen that we breath). However,
absorb carbon dioxide and water from the atmo- most living organisms cannot metabolize all types
sphere and the ground. In some cases, these sub- of carbohydrates. Most humans, for example, can
stances may directly be used to produce energy by metabolize dissacharides such as sucrose and lac-
acting as reactants in exothermic metabolic reac- tose, and polyssacharides such as starch. However,
tions. In other cases, the absorbed compounds are we cannot metabolize cellulose, another polyssa-
used to produce other substances that will be the charide, while termites can.
ones involved in processes that release energy. Fats, also called lipids in medical
Carbohydrates are the main source of energy and biochemical contexts, con-
for the human body. These organic compounds stitute another set of chemi-
are made up of molecules in which carbon, hy- cal compounds that can be
drogen, and oxygen are typically combined in the used to generate energy by
ratio: Cx(H2O)y, where x and y are whole numbers our bodies. Foods with a
that differ depending on the nature of the car- high fat content include natural
bohydrate. Most carbohydrate molecules can be oils (e.g., corn, olive), nuts, milk,
thought as monomers, dimer, trimers, or polymers cheese, and chocolate. As we have seen
build from basic units called saccharides. For ex- before, most substances identified as fats belong
ample, sucrose (C12H22O11), the main component to a group of chemical compounds called triglyc-
of table sugar is a disaccharide that results from erides. These compounds can be thought of as
the combination of two smaller carbohydrate resulting from the combination of glycerol with
molecules (monosaccharides), glucose and fruc- fatty acids. The metabolism of fats in our bodies
tose (both with the molecular formula C6H12O6). involves breaking down triglyceride molecules into
Starch, on the other hand, is a polysaccharide con- free fatty acids that are then used to resynthesize
sisting of many glucose molecules joined together lipids that are stored in adipose tissue. In general,
forming polymeric chains. fats are not used as primary reactants in energy
producing processes unless carbohydrates are not
Glucose Fructose available. This may occur under conditions of star-
vation, fasting, dieting, or untreated diabetes.
The amount of energy released during the
combustion of a given mass of carbohydrates or
fats is often expressed using the nutritional, or
uppercase “C” Calories (Cal) as unit of measure-
ment. One Calorie is equivalent to 1000 lowercase
Sucrose “c” calories or to one kilocalorie (1 Cal = 1000 cal
= 1 kcal). Given that 1 cal = 4.184 J, one nutri-
tional Calorie is equivalent to 4184 J. The num-
ber of Calories that our body needs to produce to
maintain its normal functions depends on factors
such as gender, weight, height, age, and degree of
physical activity.
Let’s Apply
Food Choices
There are a variety of chemical compounds that react with oxygen or other substances to generate
the energy used by living organisms to survive. Let us explore their energetic properties.
Lipids vs. Carbohydrates
Most of the energy used by our body is

supplied by the reaction of carbohydrates
and lipids with oxygen during cellular res-
piration. The most common carbohydrate
is glucose. Most lipids result from the com-
bination of fatty acids, such as oleic acid.
• Write the balanced chemical equa-

tions that represent the reactions of Glucose Oleic Acid
one mole of glucose and one mole of
oleic acid with oxygen to produce carbon dioxide and water;
• Predict which of these reactions will produce more energy per mole of glucose or oleic
acid burned;
• Verify your prediction by estimating the amount of energy produced in each reaction
using bond energies;
• It is common to express the energy produced during fuel combustion in amount of en-
ergy per unit mass (energy density in kJ/g or Cal/g). Determine and compare the energy
density, in Cal/g, for these two substances. Discuss why this quantity may be more use-
ful for purposes of fuel analysis and evaluation than its equivalent in Cal/mol.
• Based on your previous results, discuss the meaning and veracity of the following state-
ments: “fats are compact forms of energy storage,” and “gram per gram, fats hold more
energy than carbohydrates.”
• Lipids are stored as adipose tissue in our bodies. These
Female Male
lipids work as “food storage” that may be used to gener-
ate energy in the absence of adequate levels of glucose in Athlete 16-20% 6-13%
our blood. Using the information provided in the table Fit 21-24% 14-17%
(% of body fat for different individuals), estimate how Average 25-31% 18-25%
much your weight would change if your body used glu- Obese 32%+ 25%+
cose instead of lipids as storage material capable of sup-
plying an equivalent amount of energy. Discuss why the accumulation of fat provides an
evolutionary advantage over the accumulation of glucose or starch in our bodies.

Anaerobic Respiration
Some microorganisms obtain energy from reactions in which oxygen is not involved. Such is
the case of acetogenic bacteria which produce acetates as a product of anaerobic respiration.
For example, some of them rely on the following reaction:
CO2 + H2 CH3COOH + H2O
• Balance this chemical equation and estimate the amount of energy generated per mole
of acetic acid (CH3COOH) that is produced.
• Build an energy diagram that represents the relative internal potential energy of reac-

tants and products and the different energy exchanges during the reaction.
Other types of microorganisms, called methanogenic, obtain energy by degrading organic

compounds and producing methane. For example:
CH3OH CH4 + H2O + CO2
• Balance this chemical equation and estimate the amount of energy generated per mole
of methanol (CH3OH) consumed.
• Build an energy diagram that represents the relative internal potential energy of reac-
tants and products and the different energy exchanges during the reaction.
Share and discuss your ideas with a classmate, and clearly describe your calculations.
Fermentation Glucose
Some microorganisms and animal cells can produce energy via fer-
mentation. Depending on the microorganism and the environmen-
tal conditions, glucose (C6H12O6) may be transformed into different
substances such as lactic acid (C3H6O3) and ethanol (C2H6O):
C6H12O6 2 C3H6O3
C6H12O6 C3H6O3 + C2H6O + CO2
• Predict which of these processes will generate more energy

based solely on the composition and structure of the molecules Lactic Acid
involved;
• Explain why the combustion of glucose in the presence of O2
produces much more energy than any of these two processes;
• Estimate the energy produced by each of these reactions using
Ethanol
bond energies. Simplify your calculations by identifying the
minimum number of bonds that need to be broken and formed
in the transformation of reactants into products.
Let’s Apply
Explosives
Explosive materials are made up of chemical substances that undergo very fast decomposition re-
actions in which large amounts of energy are released. This energy increases the temperature and
pressure of produced or adjacent gases which expand very rapidly.
Nitroglycerin
One of the most well known explosives is nitroglycerin, an ex-

plosive liquid used as active ingredient in the manufacture of
dynamite. The molecules of this chemical compound undergo
the following decomposition reaction:
C3H5N3O9 CO2 + H2O + N2 + O2
• Balance the above chemical equation;

• Estimate the amount of energy released during the de-
composition of one mole of nitroglycerin.
• Build an energy diagram to represent the relative inter-
nal potential energy of reactants and products and the
energy exchanges associated with this reaction
C-4
C-4 is a common demoli-

tion explosive made up of Ep Free Atoms
3C + 6H + 6N + 6O
cyclonite (C3H6N6O6), also
known as RDX. 0
(-2838 kJ) (-2784 kJ)

(-3126 kJ)
• According to this en- 3 N2 3 H2O
-4000 3 CO
ergy diagram, the Ep of
cyclonite is lower than
that of each of the de- (-7239 kJ)
composition products. -8000 C3H6N6O6
Is this process endo- Reactants Products
thermic? Estimate DHrxn
for the reaction.
Reaction Path
Where From?
through molecular collisions. On the other hand,
the temperature and pressure at which the reac-
tion is carried out, as well as the nature of the
Where To? solvent in which the process takes place will in-
fluence its rate and extent.
As we have seen in this Unit, there are a va-
riety of chemical process that go to completion.
The central goal of this unit was to introduce the This is, the reactants are, for all practical pur-
basic assumptions and strategies used by chemi- poses, fully transformed into products. These
cal scientists to characterize chemical reactions. very product-favored processes typically involve
In particular, we discussed how a model based on reactants with higher internal potential energies
the idea that chemical reactions involve molecular than the products that are formed, and reactant
collisions and atomic rearrangements can be used mixtures in which the probability of molecules
to explain core experimental observations such as colliding in effective ways to induce a transforma-
the formation of new substances, the absorption tion is much higher than that in the mixture of
or release of energy during the process, and the products. When reactions go to completion, the
effect of temperature on the rate of reaction. prediction of the amount of products that will
A central idea to keep in mind is that chemi- be formed or of the net amount of energy that
cal systems and pro- will be exchanged during the process is greatly
cesses are highly dy- simplified. For example, to predict mass amounts
namic and not only we only need to pay attention to the proportion
the conversion of in which substances react as expressed in the bal-
reactants into prod- anced chemical equation, and to identify the lim-
ucts can occur, but iting reactant for the process. Predictions about
also the conversion heat of reaction can be made by using bond en-
of products into re- ergies and by paying attention to the number
actants. Thus, chemi- By NASA and types of chemical bonds that are broken and
cal reactions tend to reach an equilibrium state formed during the process.
in which the rate of conversion of reactants into In the following Unit of the textbook we will
products (forward process) is equal to the rate of focus our attention on the study of chemical pro-
conversion of products into reactants (backward cesses that do not necessarily go to completion.
process). The extent to which reactants may be In particular, we will try to identify composition
transformed into products thus depends on fac- and structural factors that may be used to qualita-
tors that affect the likelihood of the forward and tively predict reaction extent, as
backward processes. well as experimental mea-
Our analysis showed that in order to under- surements that can be
stand, predict, and control the rate and extent of made to actually quan-
a chemical process we need to pay attention to tify the extent of reac-
internal and external factors in a chemical system. tion. Similarly, we will
On the one hand, the chemical composition and discuss the different ave-
structure of reactants and products will affect the nues that can be followed
energy cost (activation energy) of reaching a tran- to predict reaction rates.
sition state from which the transformation can However, before we move on, let us explore if
occur. Composition and structural factors will “YOU ARE READY” to do so by assessing your
also influence the ratio of effective configurations ability to apply what you have learned in this unit
that are likely to induce atomic rearrangements to the analysis of some interesting problems.
272 Are you Ready?
Are You Ready?

A propellant is a material that produces pressurized gas that can be used to provide thrust to an object, such
as a bullet, a rocket, or a space shuttle. Common chemical propellants are mixtures of chemical compounds
that produce large amounts of gases and energy when they react.
Spontaneous Ignition
Hypergolic propellants are combinations of substances that ignite spontaneously on contact

with each other and thus do not require an ignition source. A good example of this type of
propellant is the mixture of hydrazine (N2H4), identified as the fuel, and dinitrogen tetroxide
(N2O4), identified as the oxidizer, used for rocket propulsion. These two substance react ac-
cording with the following chemical equation:
N2H4(l) + N2O4(g) N2(g) + H2O(g)

• Complete the missing states in each of the following submicroscopic representations of
the reaction. Identify the limiting reactant in each case.
The mixture ratio of a propellant is defined as the ratio of oxidizer mass to fuel mass. The so-
called “optimum” mixture ratio produces the highest performance under specific conditions:
• If the optimum mixture ratio for the N2O4 (oxidizer)/ N2H4 (fuel) propellant in a
rocket engine on the surface of our planet is 1.08. Which substance acts as the limiting
reactant under such conditions?
• What total volume of gases will be produced by a 250 L tank of hydrazine (r = 1.02 g/
mL) supplied to a rocket engine at the optimum mixture ratio? Assume STP conditions
and that the gases behave ideally (i.e., PV = nRT can be used to make estimations).
Share and discuss your results with a classmate, and show and explain your calculations.
By NASA
Propellants
Energy Exchanges
Given the reaction between N2H4 and N2O4,
• Estimate the amount of energy absorbed or released per mole of dinitrogen

tetroxide (N2O4) consumed;
• Build the energy diagram for the reaction showing the relative internal poten-
tial energy of reactants and products;
N2H4
The reaction between N2H4 and N2O4 seems to occur in two steps. The first step
leads to the formation of nitrogen monoxide (NO) as an intermediate species:
N2H4 + N2O4 N2 + H2O + NO

• Estimate the energy absorbed or released during this process.
In the second step, the intermediate species is consumed: N2O4
N2H4 + NO N2 + H2O

• Estimate the energy absorbed or released during this process.
The activation energy for the first step of the reaction has been determined to be close
to 110 kJ/mol; the activation energy for the second step is about 165 kJ/mol.
• Use all the information that you have to build an energy diagram that rep-
resents the two steps of the reaction and the different energy exchanges that NO
occur at various stages during this chemical process;
• Determine which of the steps of the reaction will be the slowest based on the
values of the corresponding activation energies;
• Discuss whether you would expect the overall reaction to be product-favored
based on both the relative internal potential energies of reactants and prod-
ucts, and the configuration effectiveness of the reactant and product mixtures.
• Analyze how changing the pressure at which the reaction is performed may
affect the rate and extent of the chemical reaction. HINT: Analyze the effect of
increasing pressure on the rate of the forward and backward processes.
274 Are you Ready?
Propellants
RP-1
The main component of propellant RP-1 is a highly refined form of kerosene, a mix-
ture of hydrocarbons. This propellant has been used in the first-stage boosters of many
space missions. The average chemical composition of RP-1 is close to that of dodecane,
C12H26. This material is usually burned in the presence of liquid oxygen (O2) or using a
85% aqueous solution of hydrogen peroxide (H2O2):
C12H26(l) + O2(l) CO2(g) + H2O(g)
C12H26(l) + H2O2(aq) CO2(g) + H2O(g)
• Balance these chemical equations;

• If the optimum mixture ratio for the O2 (oxidizer)/ C12H26 (fuel) propellant in
a rocket engine on the surface of our planet is 2.28. Which substance acts as the
limiting reactant under such conditions?
• If the optimum mixture ratio for the H2O2 (oxidizer)/ C12H26 (fuel) propellant in
a rocket engine on the surface of our planet is 7.84. Which substance acts as the
limiting reactant under such conditions?
• What would be the pressure of the gases generated by a 200 L tank of kerosene
(r = 0.8 g/mL) supplied to a rocket engine at the optimum mixture ratio when
using a) liquid oxygen and b) hydrogen peroxide? Assume STP conditions and
that the gases behave ideally (i.e., PV = nRT can be used to make estimations).
Share and discuss your results with a classmate, and clearly show your calculations.
Energy Exchanges H2O2
Given the reactions between kerosene and oxygen

and kerosene and hydrogen peroxide:
• Estimate the amount of energy absorbed or re-

leased per mole of kerosene (C12H26) consumed;
• Build the energy diagram for each of the reac-
tions showing the relative internal potential
energy of reactants and products;
C12H26
justify your reasoning and calculations.
By NASA
Are You Ready?

Aerozine 50
The propellant Aerozine 50 is a 50/50 mixture of hydrazine (N2H4) and di-

N2H4 methylhydrazine (C2H8N2). This fuel has been used for interplanetary probes
and spacecraft propulsion systems. The fuel is combined with either dinitro-
gen tetroxide or liquid oxygen, depending on whether spontaneous ignition is
needed (N2O4) or not (O2). Consider the energy diagram for the reaction of
C2H8N2 with O2:
• Estimate Ep Free Atoms

the heat of 2C + 8H + 2N + 8O
the reaction 0 Reactants
(-946 kJ)
between
N2
C2H8N2 and
(-1992 kJ)
O2 based on -2000 4 O2
the rela-
(-3196 kJ)
tive internal 2 CO2 (-3712 kJ)
potential -4000
(-4035 kJ)
4 H2O
energy of C2H8N2
Products
C2H8N2 reactants and
products. Reaction Path
Reaction Extent
Consider the reaction between dimethylhydrazine and oxygen:
C2H8N2 + 4 O2 2 CO2 + 4 H2O + N2
• Sketch an energy diagram representing the overall internal potential energy of reactants and
products. Based on the diagram, discuss whether the reaction is more likely to be product-favored
than reactant favored;
• Analyze the reactant and product mixtures. Discuss whether the reaction is more likely to be
product-favored than reactant favored based on the expected configuration effectiveness of each
of the mixtures.
• Discuss how increasing the pressure of the system would affect the extent of the reaction. HINT:
Analyze the effect of a pressure change on the rate of the forward and backward processes.

276 Are you Ready?
Are You Ready?

Ammonia, NH3, is one of the most important industrial chemical substances. It is widely used in the pro-
duction of fertilizers, pharmaceuticals, refrigerants, explosives, and cleaning agents. It ranks as one of the
ten top chemicals substances produced annually in the world.
Synthesis
Most industrial ammonia is produced by combining N2(g) and H2(g):

N2 + O2
N2(g) + H2(g) NH3(g) inlet

• Complete the missing states in each of the following submicroscopic rep-
resentations of the reaction. Identify the limiting reactant in each case.
Heat
Exchanger
Recycled
Unreacted
N2 + O2
Share and discuss your results with a classmate. Clearly justify your reasoning.
Reactant Supply
Refrigeration
Nitrogen for the synthesis of ammonia is obtained by sepa- Unit
Source: ChemPRIME
rating this elementary substance from air by liquefaction. If

approximately 100 million tonnes (1 tonne = 1000 kg) of am-
monia are produced annually worldwide.
• How many tonnes of N2 are extracted from air each year?

• How many tonnes of H2 are required every year?
Liquid
Share and discuss your results with a classmate, and clearly NH3
The Quest for Ammonia

Energy Exchange
The optimization of the industrial production of ammonia requires a good understanding

of energy transfer during the process:
• Estimate the heat of reaction for the production of ammonia in kJ/mol of NH3
formed and determine whether the reaction is exothermic or endothermic;
• Build an energy diagram to represent the relative internal potential energy of reac-
tants and products, as well as the different energy exchanges that occur during the
process.
Gas
Compressor Share and discuss your ideas with a classmate, and justify your reasoning.
Forward and Backwards

Heat The activation energy (Ea) for the transformation of
Exchanger N2(g) and H2(g) into NH3(g) is close to 320 kJ/mol.
• Estimate the value of the activation energy for

the decomposition of NH3(g) into N2(g) and
H2(g);
• Build the energy diagram for the reaction in-
cluding the location of the transition state;
• Discuss whether the configuration effectiveness
Catalyst
(ratio of collisions with the proper orienta-
(400-500 oC)
tion to induce atomic rearrangements) of the
reactant mixture can be expected to be larger or
smaller than that for the products. Consider a
reactant mixture in which all species are present
in the required stoichiometric proportions.
Heating • Compare the relative rates of the forward
Unit (ammonia synthesis) and backward (ammonia
decomposition) reaction and discuss whether
one can expect the synthesis reaction to go to
completion.
Preheated
Feed Gases Share and discuss your ideas with a classmate, and
(130-300 atm) justify your reasoning.
278 Are you Ready?
The Quest for Ammonia

Reaction Extent
We can use molecular dynamics simulations to explore the effect of different variables, such
as temperature, pressure, and concentration on reaction extent for the synthesis of ammonia.
http://www.chem.arizona.edu/tpp/chemthink/resources/U4_M3/nh3.html
• Based on the information you have derived for the synthesis of NH3(g) from N2(g) and
H2(g), predict the effect of increasing pressure (or decreasing volume) on the extent of
the chemical reaction. HINT: Analyze whether the rate of the forward and backward pro-
cesses will be more or less affected by the change.
• Click on the image to launch a molecular dynamics simulation for the synthesis of
ammonia. Verify your predictions by explor-
ing the effect on the % of ammonia produced
CLICK TO PLAY
(equilibrium concentration) of changing the
volume of the system at constant temperature
and initial amount of reactants.
• Predict the effect of increasing the concen-
tration of the reactants on the extent of the
chemical reaction. Justify your prediction
based on the analysis of changes in the forward and backward rates of reaction.
• Verify your predictions using the simulation to explore the effect on the % of ammonia
produced of using different initial concentrations of N2 and H2.
• Use the simulation to explore the effect on the % of ammonia produced of changing
the temperature at constant volume and initial amounts of reactants. Build a reason-
able explanation to justify the observed behavior.
Share and discuss your ideas and results with a classmate.
Reaction Conditions
The actual production of ammonia is based on the so-called Haber process in which a cata-
lyst, such as iron powder, is used to reduce the activation energy and increase the rate of reac-
tion. The synthesis is performed at temperatures close to 500 oC and pressures of about 200
atm. Under these conditions, the % of ammonia produced is about 15%.
• What would be the advantage of running the process at 500 oC and not at lower tem-
peratures where the reaction extent is expected to be larger?
• What would be the advantage of running the reaction at high pressures?
Share and discuss your ideas and results with a classmate.


Module 1
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P228 & P229: Background
“Ozone Hole” by NASA; P230: Top right By Theodore Gray http://www.theodoregray.com/PeriodicTable/PopularScience/2006/05/1/image1.
jpg; P231: Fig. 4.1 “Kaiserstuhl - Herbst - Rebblatt im Gegenlicht” by Nickel Eisen (Own work) [Generic 2.0] http://commons.wikimedia.org/
wiki/File:Kaiserstuhl_-_Herbst_-_Rebblatt_im_Gegenlicht.jpg; P232: Fig. 4.2a “Et baal” by Einar Helland Berger (Own work) [Share Alike 2.5]
http://commons.wikimedia.org/wiki/File:Et_baal.jpg, Fig. 4.2b “Chemical Reaction” by Kate Ter Haar (Own work) [Generic 2.0] https://www.
flickr.com/photos/katerha/5703151566/in/set-72157626499173551
Module 2
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P246: Top right “Diesel-smoke”
by EPA [Public domain] http://commons.wikimedia.org/wiki/File:Diesel-smoke.jpg; P249: Fig 4.11 “Ethanol plant” by Agriculture Research
Services [Public domain] http://commons.wikimedia.org/wiki/File:Ethanol_plant.jpg; P253: Fig 4.13 “Colorized car engine” by Nrbelex (Own
work) [Share Alike 3.0] http://commons.wikimedia.org/wiki/File:Colorized_car_engine.jpg; P258: Bottom right “Hydrogen station pump” by
EERE Office of Energy Efficiency and Renewable Energy(Public domain) http://commons.wikimedia.org/wiki/File:Hydrogen_station_pump.jpg
Module 3
Most of the images in this module have been generated by the authors (Own work). Other attributions include, P260: Top right “Streichholz” by
Sebastian Ritter (Rise0011)(Own work) [Share Alike 2.5] http://commons.wikimedia.org/wiki/File:Streichholz.jpg; P271: Top left “Ozone Hole”
by NASA; P272 & P273: Background by NASA; P274 & P275: Background by NASA; P276 & P277: Background derivative from image from
ChemPRIME http://wiki.chemprime.chemeddl.org/index.php/File:Haber_Process_Diagram.gif
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Chemical Thinking I

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Chemical

U2. How do we determine structure? 82

U3. How do we predict properties? 166

U4. How do we characterize chemical processes? 228

The central goal of this Unit is to help you under-

What is it made of?

M1. Searching for Differences

THE CHALLENGE Extracting Oxygen

• How would you separate oxygen from other air components?

Choosing Properties LET’S THINK

Air is a mixture of many substances, including nitrogen, oxygen, carbon diox-

Temperature Mass Viscosity

Good differentiating characteristics are properties that do not depend on the

USEFUL TOOLS transformed into degrees Kelvin using the

The transformation of a pure substance from one phase to another at constant

Changing Phases LET’S THINK

By Mysid (Own work) [CCA: Public domain] via Wikimedia Commons

• Predict how temperature will change as a function of time. Keep in mind

By Flanker, penubag (Own work) [CCA: Public domain]

via Wikimedia Commons

USEFUL TOOLS gy invested in applying a force of one new-

The temperatures at which a substance undergoes a phase transition depend on the

The Case of Water LET’S THINK

The following tables include experimental information about the tempera-

Liquid-Gas Liquid-Solid Solid-Gas

on the image to launch a graphing tool and use it to

In a pressure-temperature phase diagram like that shown in Figure 1.5, the

LET’S THINK Comparing Phase Behavior

0.01 100 374 -78 -57 0 31

• Identify the stable phase of each substance at 1 atm and 40 oC.

The liquid-gas transition line in a pressure-temperature phase diagram is also

Filtration: This technique is based on the mechanical separa-

By Ahanix1989 (Own work) [CCA: Public

domain] via Wikimedia Commons

Crystallization: In this strategy, the formation of a solid phase is induced

Distillation: This technique is used to separate substances in a liquid mixture tak-

the liquid mixture is heated up in a flask. When the boiling point of

LET’S THINK Distilled Spirits

• What would you expect

By Deglr6328 (Own Work) [CCA: Share Alike 3.0]

via Wikimedia Commons

Venus Earth Mars

As you can see, the at-

matter from one planet to

ASSESS WHAT YOU KNOW

Answer the following questions based

• What is the state of matter of water and carbon dioxide at day

“fractions” (mixtures that consist of compounds with similar boiling

A rich fuel mixture containing the 10.0

The mixture is at an initial tempera-

• Identify a differentiating char-

Substance Tm(oC) Tb (oC) Substance Tm(oC) Tb (oC)

ASSESS WHAT YOU KNOW

• What is the minimum number of distillation plates or trays,

Materialscientist(talk)) [CCA: Share Alike 3.0]

THE CHALLENGE Clouds

• How do you think clouds form?

• Based on what you know, how would you “model”

Share and discuss your ideas with one of your classmates.

Particulate Model of Matter

By Heron (Own work) [CCA: Public domain]

via Wikimedia Commons

Assumption 1. Any macroscopic sample of a substance is composed of an ex-

Relative Size LET’S THINK