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Basic Concepts in Chemistry

Chemical Nomenclature

Chemical nomenclature is the term given to the naming of


compounds. Chemists use specific rules and "conventions" to
name different compounds. This section is designed to help you
review some of those rules and conventions.

Oxidation and Reduction


Forming Ionic Compounds
Arrangement of Atoms
Naming Ionic Compounds
Naming Binary Molecular Compounds
Naming Inorganic Acids
Naming Compounds

Oxidation and Reduction


When forming compounds, it is important to know something
about the way atoms will react with each other. One of the most
important manners in which atoms and/or molecules react with
each other is the oxidation/reduction reaction.
Oxidation/Reduction reactions are the processes of losing and
gaining electrons respectively. Just remember, "LEO the lion
saysGER:" Lose Electrons Oxidation, Gain Electrons Reduction.
Oxidation numbers are assigned to atoms and compounds as a
way to tell scientists where the electrons are in a reaction. It is
often referred to as the "charge" on the atom or compound. The
oxidation number is assigned according to a standard set of rules.
They are as follows:
1. An atom of a pure element has an oxidation number of zero.
2. For single atoms in an ion, their oxidation number is equal to
their charge.
3. Fluorine is always -1 in compounds.
4. Cl, Br, and I are always -1 in compounds except when they
are combined with O or F.
5. H is normally +1 and O is normally -2.
6. The oxidation number of a compound is equal to the sum of
the oxidation numbers for each atom in the compound.

Forming Ionic Compounds

Knowing the oxidation number of a compound is very important when discussing


ionic compounds. Ionic compounds are combinations of positive and negative ions.
They are generally formed when nonmetals and metals bond. To determine which
substance is formed, we must use the charges of the ions involved. To make a
neutral molecule, the positive charge of the cation (positively-charged ion) must
equal the negative charge of the anion (negatively-charged ion). In order to create a
neutral charged molecule, you must combine the atoms in certain proportions.
Scientists use subscripts to identify how many of each atom makes up the
molecule. For example, when combining magnesium and nitrogen we know that
the magnesium ion has a "+2" charge and the nitrogen ion has a "-3" charge. To
cancel these charges, we must have three magnesium atoms for every two nitrogen
atoms:
3Mg2+ + 2N3- --> Mg3N2
Knowledge of the charges of ions is crucial to knowing the formulas of the
compounds formed.
alkalis (1st column elements) form "+1" ions such as
Na+ and Li+
alkaline earth metals (2nd column elements) form "2+" ions
such as Mg2+ and Ba2+
halogens (7th column elements) form "-1" ions such as
Cl- and IOther common ions are listed in the table below:
Positive ions (cations)
1+

Negative ions (anions)


1-

+
4

ammonium (NH )

acetate (C2H3O2-)

copper(I) (Cu+)

azide (N3-)

hydrogen (H+)

chlorate (ClO3-)

silver (Ag+)

cyanide (CN-)
dihydrogen phosphate (H2PO4-)

2+

hydride (H-)

cadmium (Cd2+)

bicarbonate (HCO3-)

cobalt(II) (Co2+)

hydroxide (OH-)

copper(II) (Cu2+)

nitrate (NO3-)

iron (Fe2+)

nitrite (NO2-)

lead (Pb2+)

perchlorate (ClO4-)

manganese(II) (Mn2+)

permanganate (MnO4-)

mercury(I) (Hg22+)

thiocyanate(SCN-)

mercury(II) (Hg2+)
nickel (Ni2+)
2+

2-

tin (Sn )

carbonate (CO32-)

zinc (Zn2+)

chromate (CrO42-)
dichromate (Cr2O72-)

3+

hydrogen phosphate (HPO42-)

aluminum (Al3+)

oxide (O2-)

chromium(III) (Cr3+)

peroxide (O22-)

iron(III) (Fe3+)

sulfate (SO42-)
sulfide (S2-)
sulfite (SO32-)
3nitride (N3-)
phosphate (PO43-)
phosphide (P3-)

Naming Ionic Compounds


The outline below provides the rules for naming ionic compounds:

Positive Ions
1. Monatomic cations (a single atom with a positive charge)
take the name of the element plus the word "ion"
Examples:
o Na+ = sodium ion
o Zn+2 = zinc ion
2. If an element can form more than one (1) positive ion, the
charge is indicated by the Roman numeral in parentheses
followed by the word "ion"
Examples:
o Fe2+ = iron(II) ion
o Fe3+ = iron (III) ion
Negative Ions
1. Monatomic anions (a single atom with a negative charge)
change their ending to "-ide"
Examples:
o O2- = oxide ion

o Cl- = chloride ion


2. Oxoanions (negatively charged polyatomic ions which
contain O) end in "-ate". However, if there is more than one
oxyanion for a specific element then the endings are:
Two less oxygen
than the most One less oxygen
common starts than the most
THE MOST COMMON
with "hypo-"
common ends
OXOANION ENDS WITH "-ATE"
and ends with "- with "-ite"
ite"

ClO- =
hypochlorite

One more
oxygen than
the most
common starts
with "per-" and
ends with "ate"

Most common
Most common
oxyanions with oxyanions with
four oxygens
three oxygens
o
ClO2
o
SO
o
NO
4
=
2=
3 =
chlorite
sulfate
nitrate
ClO4- =
o
NO2o
PO4
o
ClO perchlorate
= nitrite
3=
3 =
o
SO3
phosphate
chlorate
2= sulfite
o
CrO
o
CO
22=
=
4
3
chromate
carbonate

3.
4. Polyatomic anions (a negatively charged ion containing more
than one type of element) often add a hydrogen atom; in
this case, the anion's name either adds "hydrogen-" or "bi-"
to the beginning
Example:
CO32- becomes HCO3"Carbonate" becomes either "Hydrogen Carbonate" or
"Bicarbonate"
5. When combining cations and anions into an ionic compound,
you always put the cation name first and then the anion
name (the molecular formulas are also written in this order
as well.)
Examples:
o Na+ + Cl- --> NaCl
sodium + chloride --> sodium chloride
o Cu2+ + SO42- -->CuSO4
copper(II) + sulfate --> copper(II) sulfate

o Al3+ + 3NO3- --> Al(NO3)3


aluminum + nitrate --> aluminum nitrate
Arrangement of Atoms
In naming ions, it is important to consider "isomers." Isomers are compounds with
the same molecular formula, but different arrangements of atoms. Thus, it is
important to include some signal within the name of the ion that identifies which
arrangement you are talking about. There are three main types of classification,
geometric, optical and structural isomers.
1. Geometric isomers refers to which side of the ion atoms
lie. The prefixes used to distinguish geometric isomers
are cismeaning substituents lie on the same side of the ion
and trans meaning they lie on opposite sides. Below is a
diagram to help you remember.

2. Optical isomers differ in the arrangement of four groups


around a chiral carbon. These two isomers are differentiated
asL and D.

3. Structural isomers differentiate between the placement of


two chlorine atoms around a hexagonal carbon ring. These
three isomers are identified as o, m, and p. Once again we
have given you a few clues to help your memory.

A pop-up nomenclature calculator is available for help when naming compounds


and for practice problems.
Naming Binary Molecular Compounds
Molecular compounds are formed from the covalent bonding
between non-metallic elements. The nomenclature for these
compounds is described in the following set of rules.
1. The more positive atom is written first (the atom which is the
furthest to the left and to the bottom of the periodic table)
2. The more negative second atom has an "-ide" ending.
3. Each prefix indicates the number of each atom present in
the compound.
Number of Atoms

Prefix

Number of Atoms

mono

di

hepta

tri

octa

tetra

nona

penta

10

deca

4.

Prefix
hexa

Examples:
CO2 = carbon dioxide
P4S10 = tetraphosphorus decasulfide
Naming Inorganic Acids
1. Binary acids (H plus a nonmetal element) are acids that
dissociate into hydrogen atoms and anions in water. Acids
that only release one hydrogen atom are known
as monoprotic. Those acids that release more than one
hydrogen atom are called polyproticacids. When naming
these binary acids, you merely add "hydro-" (denoting the
presence of a hydrogen atom) to the beginning and "-ic acid"
to the end of the anion name.

Examples:
HCl = hydrochloric acid
HBr = hydrobromic acid
2. Ternary acids (also called oxoacids, are formed by hydrogen
plus another element plus oxygen) are based on the name of
the anion. In this case, the -ate, and -ite suffixes for the
anion are replaced with -ic and -ous respectively. The new
anion name is then followed by the word "acid." The chart
below depicts the changes in nomenclature.
Anion name

Acid name

hypo___ite

hypo___ous acid

___ite

___ous acid

___ate

___ic acid

per___ate

per___ic acid

3.

Example:
ClO4- to HClO4 => perchlorate to perchloric acid
ClO- to HClO => hypochlorite to hypochlorous acid
Naming Compounds
A detailed treatise on naming organic compounds is beyond the
scope of these materials, but some basics are presented. The
wise chemistry student should consider memorizing the prefixes
of the first ten organic compounds:
Number of Carbons

Prefix

meth-

eth-

prop-

but-

pent-

hex-

hept-

oct-

non-

10

dec-

There are four basic types of organic hydrocarbons, those


chemicals with only carbon and hydrogen:
1. Single bonds (alkane): suffix is "ane", formula CnH2n+2
2. Double bonds (alkene): suffix is "ene", formula CnH2n
3. Triple bonds (alkyne): suffix is "yne", formula CnH2n-2
4. Cyclic compounds: use prefix "cyclo"

So, for example, an organic compound with the formula "C 6H14" would be
recognized as an alkane with six carbons, so its name is "hexane".

Examples:
N2O4 = dinitrogen tetraoxide
S2F10 = disulfur decafluoride
Practice Problems
Find the formulas of the following molecules:
1.
2.
3.
4.
5.
6.
7.

aluminum fluoride
carbon tetrachloride
strontium nitrate
sodium bisulfate
iron(III) oxide
mercury(II) nitrate
sodium sulfite

8.
9.
10.
11.
12.
13.
14.

ammonium dichromate
magnesium acetate
zinc hydroxide
nitric acid
hypochlorous acid
phosphoric acid
aluminum nitrate

A solution set is available for viewing.


Write the names of the following molecules:
1.
2.
3.
4.
5.
6.
7.

CaCO3
SCl2
Li2CrO4
NaSCN
KClO3
Ca(C2H3O2)2
K2Cr2O7

8.
9.
10.
11.
12.
13.
14.

Mg3(PO4)2
Ba(NO2)2
Hg2Cl2
NaHCO3
H2S
H2SO3
SO3

A solution set is available for viewing.

Atomic Structure

An atom is the smallest building block of matter. Atoms are made


of neutrons, protons and electrons. The nucleus of an atom is extremely small in
comparison to the atom. If an atom was the size of the Houston Astrodome, then
its nucleus would be the size of a pea.

Introduction to the Periodic Table


Charges in the Atom
Atomic Models and the Quantum Numbers
Determining Electron Configuration

Introduction to the Periodic Table


Scientists use the Periodic Table in order to find out important
information about various elements. Created by Dmitri Mendeleev
(1834-1907), the periodic table orders all known elements in
accordance to their similarities. When Mendeleev began grouping
elements, he noticed the Law of Chemical Periodicity. This law
states, "the properties of the elements are periodic functions of
atomic number." The periodic table is a chart that categorizes
elements by "groups" and "periods." All elements are ordered by
their atomic number. The atomic number is the number of
protons per atom. In a neutral atom, the number of electrons
equals the number of protons. The periodic table represents
neutral atoms. The atomic number is typically located above the
element symbol. Beneath the element symbol is the atomic
mass. Atomic mass is measured in Atomic Mass Units where 1
amu = (1/12) mass of carbon measured in grams. The atomic
mass number is equal to the number of protons plus neutrons,
which provides the average weight of all isotopes of any given
element. This number is typically found beneath the element
symbol. Atoms with the same atomic number, but different mass
numbers are called isotopes. Below is a diagram of a typical cells
on the periodic table.

There are two main classifications in the periodic table, "groups" and "periods."
Groups are the vertical columns that include elements with similar chemical and
physical properties. Periods are the horizontal rows. Going from left to right on the
periodic table, you will find metals, then metalloids, and finally nonmetals. The
4th, 5th, and 6th periods are called the transition metals. These elements are all
metals and can be found pure in nature. They are known for their beauty and
durability. The transition metals include two periods known as the lanthanides and

the actinides, which are located at the very bottom of the periodic table. The chart
below gives a brief description of each group in the periodic table.

Group
1A

Group
2A

Group
3A
Group
4A
Group
5A
Group
6A
Group
7A
Group
8A

Known as Alkali Metals


Very reactive
Never found free in nature
React readily with water
Known as Alkaline earth elements
All are metals
Occur only in compounds
React with oxygen in the general formula EO (where O is oxygen
and E is Group 2A element)
Metalloids
Includes Aluminum (the most abundant metal in the earth)
Forms oxygen compounds with a X2O3 formula
Includes metals and nonmetals
Go from nonmetals at the top of the column to metals at the
bottom
All oxygen form compounds with a XO2 formula

All elements form an oxygen or sulfur compound with E 2O3 or


E2S3 formulas

Includes oxygen, one of the most abundant elements.


Generally, oxygen compound formulas within this group are
EO2 and EO3

Elements combine violently with alkali metals to form salts


Called halogens, which mean "salt forming"
Are all highly reactive
Least reactive group
All elements are gases
Not very abundant on earth
Given the name noble gas because they are not very reactive

Charges in the Atom


The charges in the atom are crucial in understanding how the
atom works. An electron has a negative charge, a proton has a
positive charge and a neutron has no charge. Electrons and
protons have the same magnitude of charge. Like charges repel,
so protons repel one another as do electrons. Opposite charges
attract which causes the electrons to be attracted to the protons.
As the electrons and protons grow farther apart, the forces they
exert on each other decrease.
Atomic Models and the Quantum Numbers
There are different models of the structure of the atom. One of
the first models was created by Niels Bohr, a Danish physicist.
He proposed a model in which electrons circle the nucleus in
"orbits" around the nucleus, much in the same way as planets

orbit the sun. Each orbit represents an energy level which can be
determined using equations generated by Planck and others
discussed in more detail below. The Bohr model was later proven
to be incorrect, but provides a useful model for building an
explanation.
The "accepted" model is the quantum model. In the quantum model, we state that
the electron cannot be found precisely, but we can predict the probability, or
likelihood, of an electron being at some location in the atom. You should be
familiar with quantum numbers, a series of three numbers used to describe the
location of some object (like an electron) in three-dimensional space:
1. n: the principal quantum number, an integer value (1, 2, 3...)
that is used to describe the quantum level, or shell, in which
an electron resides. The principal quantum number is the
primary number used to determine the amount of energy in
an atom. Using one of the first important equations in atomic
structure (developed by Niels Bohr), we can calculate the
amount of energy in an atom with an electron at some value
of n:
Rhc
En = -

n2

2. where:
R = Rydberg constant, a value of 1.097 X 107 m-1
c = speed of light, 3.00 X 108 m/s
h = Planck's constant, 6.63 X 10 -34 J-s
n = principal quantum number, no unit
3. For example, how much energy does one electron with a principal quantum
number of n= 2 have?
Rhc
En = -

n2

or

(1.097x107 m-1 (6.63x10-34 Js)(3.0x108 ms-1)

En = = 5.5x10

22
-19

4. You might ask, well, who cares? In addition to the importance of knowing
how much energy is in an atom (a very important characteristic!), we can
also derive, or calculate, other information from this energy value. For
example, can we see this energy? The table below suggests that we can. For

example, suppose that an electron starts at the n=3 level (we'll call this the
excited state) and it falls down to n=1 (the ground state). We can calculate
the change in energy using the equation:
1
E = hv = RH

n i2

1
-

nf2

5. Where:
E = change in energy (Joules)
h = Planck's constant with a value of 6.63 x 10 -34 (J-s)
is frequency (s-1)
RH is the Rydberg constant with a value of 2.18 x 10 -18J.
ni is the initial quantum number
nf is the final quantum number
6. Using the equation below, we can calculate the wavelength and the
frequency of the energy. The wavelength and the frequency give us
information about how we might "see" the energy:
v = c

7. Where:
= the frequency of radiation (s-1)
= the wavelength (m)
c = the speed of light with a value of 3.00 x 108 m/s in a
vacuum
Speed of light =
Rydberg constant =
Planck's constant =
Excited
Ground
Excited state
Ground state

state, n =
state, n =
energy (J)
energy (J)
E =
=
(nm) =

3.00E+08
2.18E-18
6.63E-34
3
2
2.42222E-19
5.45E-19
-3.02778E-19
4.56678E+14
656.92

4
2
1.363E-19
5.45E-19
-4.09E-19
6.165E+14
486.61

5
2
8.72E-20
5.45E-19
-4.58E-19
6.905E+14
434.47

8. l ("el", not the number 1): the azimuthal quantum number, a


number that specifies a sublevel, or subshell, in an orbital.
The value of the azimuthal quantum number is always one
less than the principal quantum number n. For example, if
n=1, then "el"=0. If n=3, then l can have three values: 0,1,
and 2. The values of l are typically not identified as "0, 1, 2,
and 3" but are more commonly called by their historic

names, "s, p, d, and f", respectively. Since the quantum


numbers were discovered through the study of light and
lines on an electromagnetic spectra, chemists identified the
lines by their quality:sharp, principal, diffuse
and fundamental. The table below shows the relationship:
Value of l

Subshell designation

9. m: the magnetic quantum number. Each subshell is


composed of one or more orbitals. In the study of light, it
was discovered that additional lines appeared in the spectra
produced when light was emitted in a magnetic field. The
magnetic quantum number has values between -l and +l.
When l =1, for example, m can have three values: -1, 0, and
+1. Because you know from the chart above that the
subshell designation for l =1 is "p", you now know that the p
orbital has three components. In your study of chemistry,
you will be presented with px, py, and pz. Notice how the
subscripts are related to a three-dimensional coordinate
system, x, y, and z. The chart below shows a summary of the
quantum numbers:
Principal
Quantum
Number (n)

Azimuthal
Quantum
Number (l)

Subshell
Designation

Magnetic
Quantum
Number (m)

Number of
orbitals in
subshell

1s

0
1

2s
2p

0
-1 0 +1

1
3

0
1
2

3s
3p
3d

0
-1 0 +1
-2 -1 0 +1 +2

1
3
5

0
1
2
3

4s
4p
4d
4f

0
-1 0 +1
-2 -1 0 +1 +2
-3 -2 -1 0 +1
+2 +3

1
3
5
7

Chemists care about where electrons are in an atom or a


molecule. In the early models, we believed that electrons move
like billiard balls, and followed the rules of classical physics. The

graphic below attempts to show that earlier models thought that


we could identify the exact path, position, velocity, etc. of an
electron or electrons in an atom:

A more accurate picture is that the electron(s) reside in a "cloud" that surrounds the
nucleus of the atom. This concept is shown in the graphic below:

Chemists are interested in predicting the probability that the electron will be at
some particular part of this cloud. The cloud is better known as an orbital, and
comes in several different types, or shapes. Atomic orbitals are known as s, p, d,
and f orbitals. Each type of atomic orbital has certain characteristics, such as shape.
For example, as the graphic below shows, an s orbital is spherical in shape:

On this graph, the horizontal (x) axis represents the distance from the nucleus in
units of a0, or atomic units. The value of a0 is 0.0529 nanometers (nm). The vertical
(y) axis represents the probability density. What you should notice is that as the
electron moves farther away from the nucleus, the probability of its being found at
that distance decreases. In other words, the electron prefers to hang around close to
the nucleus.
The three graphics below show some other orbitals. The first graph (top left) is of a
"2s" orbital. Each "s" orbital can hold two electrons in its cloud. Notice how there
is a relatively high probability of an electron being near the nucleus, then some
space where the probability is close to zero, then the probability increases
substantially at some distance from the nucleus. The graphic at the top right shows
a "2p" atomic orbital. Orbitals that are "p" orbitals can hold up to six (6) electrons
in their cloud. Notice its "dumbbell" or "figure of eight" shape. At the bottom left is
a "3s" orbital. Again, notice its spherical shape. Finally, at the bottom right, is a
"3p" orbital.

Determining Electron Configuration


One of the skills you will need to learn to succeed in freshman
chemistry is being able to determine the electron configuration of
an atom. An electron configuration is basically an account of how
many electrons there are, and in what orbitals they reside under
"normal" conditions. For example, the element hydrogen (H) has
one electron. We know this because its atomic number is one (1),
and the atomic number tells you the number of electrons. Where
does this electron go? The one electron of hydrogen goes into the

lowest energy state it possibly can, which means it will start at


"level" one and goes into "s" orbitals first. We say that hydrogen
has a "[1s1]" electron configuration. Looking at the next element
on the Periodic Table --helium, or He -- we see it has an atomic
number of two, so two electrons. Since " s" orbitals can hold up to
two electrons, helium has an electron configuration of "[1s2]".
What about larger atoms? Let's look at carbon, with an atomic number of 6. Where
do its 6 electrons go?
First two: 1s2
Next two: 2s2
Last two: 2p2
We can therefore say that carbon has the electron configuration of "[1s 22s22p2]".
The table below shows the subshells, the number of orbitals, and the maximum
number of electrons allowed:
Subshell

Number of Orbitals

Maximum Number
of Electrons

10

14

The Abridged (shortened) Periodic Table below shows the electron


configurations of the elements. Notice for space reasons we
sometimes leave off a portion of the electron configuration. For
example, look at argon (Ar), element 18. The table below shows
its electron configuration as "[3s23p6]" (remembering that "p"
orbitals can hold up to six (6) electrons). Its actual electron
configuration is:
Ar = [1s22s22p63s23p6]
Sometimes you will see the notation: "[Ne]3s 23p6", which means to include
everything that is in neon (Ne, 10) plus the stuff in the "3"-level orbitals.

Periodic Table

Electron Configurations
Periodic Trends in Electron Configurations
Periodic Trends in Oxidation Numbers
Periodic Trends in Radii
Periodic Trends in Ionization Energy
Periodic Trends in Electron Affinity
Periodic Trends in Electronegativity

Electron Configurations
The Bohr theory for a hydrogen-like atom or ion (an atom or ion containing a nucleus and
only one electron, e.g., H, He+, Li2+and Be3+) gives the energy of the electron in a given
electron shell as E being inversely proportional to n2 and the radius of the shell as r being
directly proportional to n2 where n is the principal quantum number. For a hydrogen-like
electron system, the energies of the subshells depend only on the principal quantum number
1s < 2s = 2p <3s = 3p = 3d < 4s = 4p = 4d = 4f < ...
However, for a multielectron atom or ion (an atom or ion containing a nucleus and more than
one electron), the energies of the subshells are no longer the same because of the various
electron-electron interactions and generally follow the order
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f 5d <
6p < 7s < 5f 6d < 7p < ...

Each s subshell contains one s orbital, each p subshell contains three p orbitals, each d
subshell contains five d orbtials, each f subshell contains seven f orbitals, etc., and each
orbital can be assigned a maximum of two electrons. The lowest energy state (the ground
state) of an atom or ion is the one in which all electrons are assigned to the lowest available
orbitals. For example, using the above filling order we would write the electron configuration
for the 10 electrons in neon as
Ne 1s2 2s2 2p6
and the 40 electrons in zirconium as
Zr 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d2
Example Problem: Write the electron configuration for the ground state of an atom of arsenic
(Z = 33).
Answer: For the 33 electrons
As 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p3
Note that the sum of the numbers of electrons in each subshell is equal to the total number of
electrons present in the atom or ion.
Note that there are some discrepancies between the predicted configurations based on the
above general filling order and the observed electron configurationsparticularly for the
transition (d-block) elements and the inner transition (f-block) elements. We will not concern
ourselves with these in this review.

Periodic Trends in Electron Configurations


The arrangement of the atoms in the standard periodic table is based on the electron
configurations. The atoms in a periodic table family or group (a vertical column of elements)
will all have the same valence (outer) electron configurations with respect to the subshells
involved. For example, all of the halogens in Group 17 will have the ns2 np5 configuration
only the values of the principal quantum number change. These outer configurations are
summarized in the figure.

Periodic Trends in Oxidation Numbers


Most atoms do not have completely filled subshells and will gain, lose, or share electrons
with other atoms to complete these subshells. For example, the metals in Groups 1 and 2
readily form positively charged ions (cations) resulting from the loss of thensx electrons
Na(1s2 2s2 2p6 3s1) Na+(1s2 2s2 2p6) + eCa(1s2 2s2 2p6 3s2 3p6 4s2) Ca2+(1s2 2s2 2p6 3s2 3p6) + 2 eThe nonmetals in Groups 13-17 form negatively charged ions (anions) resulting from the
gaining electrons to completely fill thenp subshell
O(1s2 2s2 2p4) + 2 e- O2-(1s2 2s2 2p6)
Br(1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5) + e- Br-(1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6)
For ions, the oxidation number is equal to the charge on the ion.
In compounds where electrons are shared, the nonmetals can also be assigned positive
oxidation numbers corresponding to the loss of the npx and the nsx electrons. For example, in
various compounds of sulfur, S (1s2 2s2 2p6 3s2 3p4), sulfur is often considered to have a +4
oxidation number from the loss of the 3p4 electrons and a +6 oxidation number from the
additional loss of the 3s2 electrons.
To predict the oxidation number of the transition and inner transition elements is a little more
tricky. Even though we would write the configuration of vanadium based on the filling order
as
V 1s2 2s2 2p6 3s2 3p6 4s2 3d3

we must rewrite the configuration as


V 1s2 2s2 2p6 3s2 3p6 3d3 4s2
with the electron occupancy placed in order by increasing principal quantum number which
represents the order of removing electrons. The first electrons that are removed are from the
greatest principal quantum number
V2+ 1s2 2s2 2p6 3s2 3p6 3d3
followed by some or all of the electrons in any partially filled subshell
V5+ 1s2 2s2 2p6 3s2 3p6
Because some of the subshells for transition and inner transition metals are close in energy,
there are often several different possible oxidation numbers.

Periodic Trends in Radii


In going down a family of elements, both the nuclear charges and principal quantum numbers
increase as the atomic numbers increase. As the nuclear charges increase, the atomic radii are
predicted to be smaller because of the greater positive electrical charges of the nuclei
attracting the electrons. From the relationship that r is directly proportional to n2, we would
predict that the atomic radii should increase as the principal quantum numbers increase.
These are opposing effects as the atomic numbers increase. The greater effect is from the
increasing principal quantum numberhowever, the predicted increases are not as large as
expected because some of the increase is offset by the increasing nuclear charge. The general
trend is that atomic radii increase within a family with increasing atomic number.
In going across a period (a horizontal row) in the periodic table, the valence electrons of the
elements all have the same principal quantum number and so we would predict no change in
the radii from a change in the value of n. However, the nuclear charges increase as the atomic
numbers increase and this effect tends to decrease the size of the atoms. The general trend is
that atomic radii decrease within a period with increasing atomic number. The radii of
elements that follow the transition or inner transition elements are similar to those directly

above them in the periodic table family because of the effect of the additional number of
elements in these longer periods offsetting the increased value of the principal quantum
number.

All of the following trends in atomic properties are directly related to the trends in atomic
radii.

Periodic Trends in Ionization Energy


The first ionization energy (ionization potential) is the energy change for the removal of the
least tightly bound electron for a gaseous atom
Na(g) Na+(g) + eIonization energies are always endothermic.
Because Coulombs law (E is inversely proportional to r) predicts that it is easier to remove
an electron from a large atom than from a small atom, the ionization energy is predicted to
decrease within a family with increasing atomic number because the size increases and is
predicted to increase across a period with increasing atomic number because the size
decreases.

Periodic Trends in Electron Affinity


The electron affinity is the energy change for the addition of one electron to a gaseous atom
Cl(g) + e- Cl-(g)
Values of electron affinities can be either endothermic or exothermic. If the electron
configuration is stable before the process, e.g., ns2 or ns2 np6, then the process is
endothermic and if the configuration ns2 np3, the process is not as exothermic as expected.
Excluding these exceptions, the general trend for the exothermic process based on Coulombs
law (E is inversely proportional to r) predicts that the electron affinity will decrease within a
family with increasing atomic number because the atoms increase in size and will increase
across a period with increasing atomic number because the atoms decrease in size.

Periodic Trends of Electronegativity


Electronegativity is the ability of an atom in a covalent bond to attract electrons to itself
and is related to the ionization energy and electron affinity of the atom. There are several
different methods of assigning numerical values for this property, but the general trends are
that the electronegativity decreases within a family with increasing atomic number and
increases across a period with increasing atomic number.

Try It Out
1. Write the complete electron configuration for B, P, Ti, Ge, and U.
2. Predict the oxidation numbers for the elements in question #1.
3. Choose the larger atom in each pair: Mg, Ca; Be, F; Cl, Br; S, Cl.
4. Choose the element with the greater ionization energy in each pair: Mg, Ca; Be, F; Cl, Br;
S, Cl.
5. Choose the element with the greater electron affinity in each pair: Be, F; Cl, Br; S, Cl.
6. Choose the more electronegative element in each pair: Mg, Ca; Be, F; Cl, Br; S, Cl.
Lewis Diagrams and Structures

What is a Lewis Diagram?

What is a Lewis Structure?


How to Build a Lewis Structure
Lewis Structures and Polyatomic Ions
Lewis Structures and Resonance Structures
Lewis Structures for Electron-rich Compounds
Lewis Structures for Electron-poor Compounds

What is a Lewis Diagram?


Lewis diagrams, also called electron-dot diagrams, are used to
represent paired and unpaired valence (outer shell) electrons in
an atom. For example, the Lewis diagrams for hydrogen, helium,
and carbon are

where the symbol represents the element (in this case, hydrogen, helium, and
carbon) and the dots represent the electrons in the outer shell (in this case, one,
two, and four). These diagrams are based on the electron structures learned in the
Atomic Structure and Periodic Table chapters.
What is a Lewis Structure?

The Lewis structure is used to represent the covalent bonding of a molecule or ion.
Covalent bonds are a type of chemical bonding formed by the sharing of electrons
in the valence shells of the atoms. Covalent bonds are stronger than the
electrostatic interactions of ionic bonds, but keep in mind that we are not
considering ionic compounds as we go through this chapter. Most bonding is not
purely covalent, but is polar covalent (unequal sharing) based on electronegativity
differences.
The atoms in a Lewis structure tend to share electrons so that each atom has eight
electrons (the octet rule). The octet rule states that an atom in a molecule will be
stable when there are eight electrons in its outer shell (with the exception of
hydrogen, in which the outer shell is satisfied with two electrons). Lewis structures
display the electrons of the outer shells because these are the ones that participate
in making chemical bonds.
How to Build a Lewis Structure?

For simple molecules, the most effective way to get the correct Lewis structure is
to write the Lewis diagrams for all the atoms involved in the bonding and adding

up the total number of valence electrons that are available for bonding. For
example, oxygen has 6 electrons in the outer shell, which are the pattern of two
lone pairs and two singles. If the electrons are not placed correctly, one could think
that oxygen has three lone pairs (which would not leave any unshared electrons to
form chemical bonds). After adding the four unshared electrons around element
symbol, form electron pairs using the remaining two outer shell electrons.

Incorrect Structure

Correct Structure

are two hydrogen atoms and one oxygen atom. The Lewis
structure of each of these atoms would be as follows:
One good example is the water molecule. Water has the chemical formula of H 2O,
which means there

We can now see that we have eight valence electrons (six from oxygen and one
from each hydrogen). With few exceptions, hydrogen atoms are always placed on
the outside of the molecule, and in this case the central atom would be oxygen.
Each of the two unpaired electrons of the oxygen atom will form a bond with one
of the unpaired electrons of the hydrogen atoms. The bonds formed by the shared
electron pairs can be represented by either two closely places dots between two
element symbols or more commonly by a straight line between element symbols:

Let us try another one.

Example: Write the Lewis structure for methane (CH4).


Answer: Hydrogen atoms are always placed on the outside of the molecule, so
carbon should be the central atom.

After counting the valence electrons, we have a total of 8 [4 from carbon + 4(1
from each hydrogen] = 8.
Each hydrogen atom will be bonded to the carbon atom, using two electrons. The
four bonds represent the eight valence electrons with all octets satisfied, so your
structure is complete.

Example: Write the Lewis structure for carbon dioxide (CO2).


Answer: Carbon is the lesser electronegative atom and should be the central atom.

After counting the valence electrons, we have a total of 16 [4 from carbon + 2(6
from each oxygen)] = 16.
Each oxygen atom has two unshared electrons that can be used to form a bond with
two unshared electrons of the carbon atom, forming a double bond between the
two atoms. The remaining eight electrons will be place on the oxygen atoms, with
two lone pairs on each.

Lewis Structures of Polyatomic Ions


Building the Lewis Structure for a polyatomic ion can be done in
the same way as with other simple molecules, but we have to
consider that we will need to adjust the total number of electrons
for the charge on the polyatomic ion. If the ion has a negative
charge, the number of electrons that is equal to the charge on the
ion should be added to the total number of valence electrons. If
the ion has a positive charge, the number of electrons that is
equal to the charge should be subtracted from the total number
of valence electrons. After writing the structure, the entire
structure should then be placed in brackets with the charge on
the outside of the brackets at the upper right corner.
Example: Write the Lewis structure for the ammonium ion (NH4+).
Answer: Hydrogen atoms are always placed on the outside of the molecule, so
carbon should be the central atom.

After counting the valence electrons, we have a total of 9 [5 from nitrogen + 4(1
from each oxygen)] = 9. The charge of +1 means an electron should be subtracted,
bringing the total electron count to 8.
Each hydrogen atom will be bonded to the nitrogen atom, using two electrons. The
four bonds represent the eight valence electrons with all octets satisfied, so your
structure is complete. (Do not forget your brackets and to put your charge on the
outside of the brackets)

Example: Write the Lewis structure for the hydroxide ion (OH-).
Answer: Since there are only two atoms, we can begin with just a
bond between the two atoms.

After counting the valence electrons, we have a total of 7 [6 from Oxygen + 1 from
each Hydrogen)] = 7. The charge of -1 indicates an extra electron, bringing the
total electron count to 8.
Oxygen will be bonded to the hydrogen, using two electrons. Place the remaining
six electrons as three lone pairs on the oxygen atom. All octets are satisfied, so
your structure is complete. (Do not forget your brackets and to put your charge on
the outside of the brackets)

Lewis Structures for Resonance Structures


The existence of some molecules often involves two or more
structures that are equivalent. Resonance can be shown using
Lewis structures to represent the multiple forms that a molecule
can exist. The molecule is not switching between these forms, but
is rather an average of the multiple forms. This can be seen when
multiple atoms of the same type surround the central atom. When
all lone pairs are placed on the structure, all the atoms may still
not have an octet of electrons. To deal with this problem, the
atoms (primarily in a C, N, or O formula) form double or triple

bonds by moving lone pairs to form a second or third bond


between two atoms. The atom that originally had the lone pair
does not lose its octet because it is sharing its lone pair. Doubleheaded arrows are placed between the multiple structures of the
molecule or ion to show resonance.
Let us look at how to build a nitrate ion (NO 3-).
Nitrogen is the least electronegative atom and should be the central atom.

After counting the valence electrons, we have a total of 23[5 from nitrogen + 3(6
from each oxygen)] = 23. The charge of -1 indicates an extra electron, bringing the
total electron count to 24.
Each oxygen atom will be bonded to the nitrogen atom, using a total of six
electrons. We then place the remaining 18 electrons initially as 9 lone pairs on the
oxygen atoms (3 pairs around each atom).

Although all 24 electrons are represented in the structure (two electrons for each of
the three bonds and 18 for each of the nine lone pairs), the octet for the nitrogen
atom is not satisfied. To satisfy the octet rule for the nitrogen atom, a double bond
needs to be made between the nitrogen and one of the oxygen atoms. Because of
the symmetry of the molecule, it does not matter which oxygen atoms is chosen.
Because there are three different oxygen atoms that could form the double bond,
there will be three different resonance structures showing each oxygen atom with a
double bond to the nitrogen atom. Double-headed arrows will be placed between
these three structures. (Do not forget your brackets and to put your charge on the
outside of the brackets)

Example: What is the Lewis structure for the nitrite ion (NO2)?
Answer: Nitrogen is the least electronegative atom and should be the central atom.

After counting the valence electrons, we have a total of 17 [5 from nitrogen + 2(6
from each oxygen)] = 17. The charge of -1 indicates an extra electron, bringing the
total electron count to 18.
Each oxygen will be bonded to the nitrogen, using two electrons. Place the
remaining 16 electrons initially as nine lone pairs on the oxygen atoms (3 pairs
around each atom) and the nitrogen (one pair).

Although all 18 electrons are represented in the structure (2 electrons for each of
the two bonds and 14 for each of the seven lone pairs), the octet for the nitrogen
atom is not satisfied. To satisfy the octet rule for the nitrogen atom, a double bond
needs to be made between the nitrogen atom and one of the oxygen atoms. Because
of the symmetry of the molecule, it does not matter which oxygen is chosen.
Because there are two different oxygen atoms that could form the double bond,
there will be two different resonance structures showing each oxygen atom with a
double bond to the nitrogen atom. A double-headed arrow will be placed between
these structures. (Do not forget your brackets and to put your charge on the outside
of the brackets)

Lewis Structures for Electron-rich Compounds


Elements with atomic number greater than 13 often form
compounds or polyatomic ions in which there are extra
electrons. For these compounds we proceed as above. Once all of
the octets are satisfied, the extra electrons are assigned to the
central atom either as lone pairs or an increase in the number of
bonds. (Never use multiple bonds with these compoundsyou
already have too many electrons.)

Example: Draw the Lewis structure for phosphorus pentafluoride, PF 5.


Answer: The electronegativity of fluorine is greater than that of
phosphorusso the phosphorus atom is placed in the center of
the molecule.

The total number of electros is 40 [5(7 from each fluorine) + 5 from the
phosphorus] = 40. Using a single bond between the phosphorus atom and each of
the fluorine atoms and filling the remaining electrons to satisfy the octet rule for
the fluorine atoms accounts for all 40 electrons. Note that there are five bonds
around the central atom.

Lewis Structures for Electron-poor Compounds


There is another type of molecule or polyatomic ion in which there
is an electron deficiency of one or more electrons needed to
satisfy the octets of all the atoms. In these cases, the more
electronegative atoms are assigned as many electrons to
complete those octets first and then the deficiency is assigned to
the central atom.

Example: Draw the Lewis structure for boron trifluoride, BF3.


Answer: The electronegativity of fluorine is greater than that of
boronso the boron atom is placed in the center of the molecule.

The total number of electron is 24 [3(7 from each fluorine) + 3 from boron] = 24.
Using a single bond between the boron and each of the fluorine atoms and filling
the remaining electron as lone pairs around the fluorine atoms to satisfy the octets
accounts for all 24 electrons.

The boron atom is two electrons shy of its octet. You may ask about the formation
of a double bond (and even resonance). But, fluorine and boron are not in the list
that can form double bonds (C, N, O, P, S) and so the compound is electron poor.
Try It Out!

Draw the Lewis structure for the following:


1. Hydronium ion (H3O+)
2. Hypochlorite ion (ClO-)
3. Carbonate ion (CO3-2)

4.
5.
6.
7.

Ammonia (NH3)
Hydrogen fluoride (HF)
Ozone (O3)
Xenon difluoride (XeF2)

Chemical Reactions

What is a Chemical Reaction?


Types of Chemical Reactions
Redox Reactions
Nonredox Reactions
Classifying Reactions

What is a Chemical Reaction?


A chemical reaction is a process in which the identity of at least one substance changes.
A chemical equation represents the total chemical change that occurs in a chemical reaction
using symbols and chemical formulas for the substances involved. Reactants are the
substances that are changed and products are the substances that are produced in a chemical
reaction.
The general format for writing a chemical equation is
reactant1 + reactant2 + product1 + product2 +

With the exception of nuclear reactions, the Law of Conservation of Massmatter is neither
created nor destroyed during a chemical reaction is obeyed in ordinary chemical reactions.
For this reason a chemical equation must be balancedthe number of atoms of each element
must be the same on the reactants side of the reaction arrow as on the products side. Details
on balancing chemical equations are found in the units on Stoichiometry and Redox
Reactions.
The general format for writing a chemical equation can be written in a short-hand version as
aA+bB+cC+ dD+
where the lower case letters are the stoichiometric coefficients needed to balance a specific
equation.
The units on Stoichiometry, Redox Reactions, and Acid-Base Chemistry contain additional
background reading, example problems, and information on the topics covered in this unit.

Types of Chemical Reactions


Chemists classify chemical reactions in various ways. Often a major classification is based on
whether or not the reaction involves oxidation-reduction. A reaction may be classified
as redox in which oxidation and reduction occur or nonredox in which there is no oxidation
and reduction occurring.

Redox Reactions
A redox reaction can be recognized by observing whether or not the oxidation numbers of
any of the elements change during the reaction.
Example Problem: Classify the reactions as either redox or nonredox.
(1) 4 Fe(s) + 3 O2(g) 2 Fe2O3(s)
(2) NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
(3) Cl2(g) + H2O(l) HCl(aq) + HClO(aq)
Answer: In equation (1), the iron changes oxidation numbers from 0 to +3 and oxygen
changes from 0 to -2. Equation (1) represents a redox reaction. In equation (2), there is no
change in oxidation numbers for the elements involved: sodium is +1, oxygen is -2, hydrogen
is +1, and chlorine is -1 on both the reactants and products sides. Equation (2) represents a
nonredox reaction. In equation (3), the chlorine changes from 0 to -1 in HCl and to +1 in
HClO. There is no change in the oxidation numbers of hydrogen (+1 in H2O, HCl, and HClO)
and oxygen (-2 in H2O and HClO). Because chlorine is oxidized and reduced, equation (3)
represents a redox reaction.
The reaction described in equation (3) is interesting in that an element in one oxidation state
undergoes both oxidation and reduction. Such a redox process is known as
a disproportionation reaction. The element undergoing disproportionation must have at
least three different oxidation statesthe initial one in the reactant and one higher plus one
lower in the products.

Most simple redox reactions may be classified as combination, decomposition, or single


displacement reactions. In a combinations reaction two reactants react to give a single
product. The general format of the chemical equation is
aA+bB+cC
A special case of a combination reaction in which the reactants are only elements in their
naturally occurring forms and physical states at the temperature and pressure of the reaction
is known as a formation reaction.
Example Problem: Identify which reactions are redox combination reactions.
(4) 6 Li2O(s) + P4O10(g) 4 Li3PO4(s)
(5) CaO(s) + H2O(l) Ca(OH)2(s)
(6) S(s) + 3 F2(g) SF6(g)
(7) ZnS(s) + 2 O2(g) ZnSO4(s)
(8) SO2(g) + Cl2(g) SO2Cl2(g)
Answer: All of the reaction are classified as combination reactions because they involved two
or more reactants producing a single product. However, redox is occurring only in equations
(6), (7), and (8). In equation (6), S is oxidized from 0 to +6 and F is reduced from 0 to -1; in
equation (7), S is oxidized from -2 to +6 and O is reduced from 0 to -2; and in equation (8), S
is oxidized from +4 to +6 and Cl is reduced from 0 to -1.
In a decomposition reaction a single reactant breaks down to give two or more substances.
The general format of the chemical equation is
aAbB+c C+
If the decomposition reaction involves oxidation-reduction, the reaction is often called
an internal redox reaction because the oxidized and reduced elements originate in the same
compound.
Example Problem: Identify which reactions are redox decomposition reactions.
(9) CuSO45H2O(s) CuSO4(s) + 5 H2O(g)
(10) SnCl46H2O(s) SnO2(s) + 4 HCl(g) + 4 H2O(g)
(11) NH4NO2(s) N2(g) + 2 H2O(g)
(12) (NH4)2Cr2O7(s) N2(g) + Cr2O3(s) + 4 H2O(g)
Answer: All of the reactions are classified as decomposition reactions because they involve a
single reactant producing two or more substances. However, redox is occurring only in
equations (11) and (12). In equation (11), the N in NH4+ is oxidized from -3 to 0 and the N in
NO2- is reduced from +3 to 0. In equation (12), the N is oxidized from -3 to 0 and the Cr is
reduced from +6 to +3.
In a single displacement reaction the atoms or ions of one reactant replace the atoms or ions
in another reactant. Single displacement reactions are also known as displacement, single
replacement, and replacement reactions. The general format of the chemical equation is
a A + b BC c AC + d B

Whether or not a redox single displacement reaction occurs will depend on the relative
reducing strengths of A and B.
Example Problem: Identify which reactions are redox single displacement reactions.
(13) 2 Al(s) + Fe2O3(s) 2 Fe(s) + Al2O3(s)
(14) 2 NaI(aq) + Br2(aq) 2 NaBr(aq) + I2(aq)
(15) Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Answer: All three reactions are redox. Both equations (13) and (14) fit the general format of
the single displacement reaction by assigning A as Al, B as Fe, and C as O in equation (13)
and A as Br, B as I, and C as Na in equation (14). To classify equation (15) is a little more
difficult. The reaction has been represented by a net ionic equation in which the anion has
been omitted. If an anion X is added to generate the overall equation, Zn(s) + CuX(aq)
ZnX(aq) + Cu(s), then assigning A as Zn, B as Cu, and C as X shows that this is also a redox
single displacement reaction.
In addition to the single redox reactions described above, a redox reaction may be classified
as a simple redox electron transfer reaction in which the oxidation numbers of ionic
reactants are changed by the direct transfer of electrons from one ion to the othertypically in
aqueous solutions. For example
2 Fe3+(aq) + Sn2+(aq) 2 Fe2+(aq) + Sn4+(aq)
Many redox reactions do not fit into the classifications described above. For example, redox
reactions involving oxygen-containing reactants in aqueous acidic or basic solutions such as
3 Cu(s) + 8 HNO3(aq, dil) 3 Cu(NO3)2(aq) + 2 NO(g) + 4 H2O(l)
Cu(s) + 4 HNO3(aq, conc) Cu(NO3)2(aq) + 2 NO2(g) + 2 H2O(l)
or the combustion of oxygen with more than one element in a reactant
2 CH3OH(g) + 3 O2(g) 2 CO2(g) + 4 H2O(l)
These types of reactions are classified as complex redox reactions.

Nonredox Reactions
There are several classifications of nonredox reactionsincluding combination,
decomposition, single displacement, and double displacement reactions.
The general format of the chemical equation for a nonredox combination reaction is the
same as for a redox combination reaction
aA+bB+cC
However, all reactants and the product must be compounds and no changes in oxidation
numbers of the elements occur. Usually these reactions involve reactants that are acidic and
basic anhydrides.

Example Problem: Identify which reactions are nonredox combination reactions.


(16) 2 Na(s) + Cl2(g) 2 NaCl(s)
(17) SO3(g) + CaO(s) CaSO4(s)
(18) SO2(g) + H2O(l) H2SO3(aq)
Answer: All three equations are combination reactions, but only equations (17) and (18) are
nonredox.
The general format of the chemical equation for a nonredox decomposition reaction is the
same as for a redox decomposition reaction
aAbB+c C+
However, the reactant and all products must be compounds and no changes in oxidation
numbers occur. Quite often one of the products formed will be a gas.
Example Problem: Identify which reactions are nonredox decomposition reactions.
(19) NH4HCO3(s) NH3(g) + CO2(g) + H2O(g)
(20) NH4NO2(s) N2(g) + 2 H2O(g)
(21) CaCO3(s) CaO(s) + CO2(g)
Answer: All three equations are decomposition reactions, but only equations (19) and (21) are
nonredox.
The general format of the chemical equation for a nonredox single displacement reaction is
the same as for a redox single displacement reaction
a A + b BC c AC + d B
However, there are no changes in the oxidation numbers of the elements during the reaction.
Common nonredox single displacement reactions include ligand substitution in complexes
and formation of more stable oxygen-containing compounds from less stable oxygencontaining compounds.
Example Problem: Identify which reactions are nonredox single displacement reactions.
(22) [PtCl4]2-(aq) + 2 NH3(aq) [Pt(NH3)Cl2](s) + 2 Cl-(aq)
(23) Na2CO3(s) + SiO2(s) Na2SiO3(l) + CO2(g)
(24) 2 AgNO3(aq) + Cu(s) Cu(NO3)2(aq) + 2 Ag(s)
Answer: All three equations are single displacement reactions, but only equations (22) and
(23) are nonredox.
Finally, the last classification of nonredox reactions is that of nonredox double
displacement reactions. The general format of the chemical equation is
a AC + b BD c AD + d BC
with no oxidation or reduction of A, B, C, or D occurring. These reactions are also known
as double replacement, partner exchange, and metathesis reactions. Usually one or
more of the products will be a gas, a precipitate, a weak electrolyte, or water. An important

example of a nonredox double displacement reaction is the reaction of an acid with a base
under aqueous conditions.
Example Problem: Identify the nonredox double displacement reactions.
(25) CaCO3(s) + 2 HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
(26) HCl(aq) + KOH(aq) KCl(aq) + H2O(l)
(27) AgNO3(aq) + KCl(aq) AgCl(s) + KNO3(aq)
Answer: All three reactions are nonredox double displacement reactions.

Classifying Reactions
Most experienced chemists can classify a given chemical reaction rather easily and quickly
by inspection of the formulas of the reactants and products in the chemical equation. The
first decision most chemists make is to determine whether or not the reaction involves redox.
Based on this decision, the answers to a few more specific questions will readily lead to the
reaction classification. These specific questions are based on the general formats of the
chemical equations for the different classifications of the reactions described above.
To begin learning what these questions are, you might consider using the online analysis
program that is available athttp://www.xxx.yyy to classify the reactions given in the Example
Problem. The basis of this analysis program is outlined by the flow charts given in Figures
(1) and (2). Please do not memorize this flow chartit is simply a tool to help you learn what
to look for and what questions should be asked as you classify a given reaction.

Figure 1. Flow chart of questions to classify nonredox reactions. (Used by


permission ...)

Figure 2. Flow chart of questions to classify redox reactions. (Used by


permission...)

Example Problem: Classify each reaction.


(28) XeF6(s) XeF4(s) + F2(g)
(29) Zn(s) + 2 AgNO3(aq) Zn(NO3)2(aq) + Ag(s)
(30) H2SO4(aq) + Ba(OH)2 BaSO4(s) + 2 H2O(l)
(31) XeF6(s) + RbF(s) RbXeF7(s)
(32) 2 Cs(s) + I2(g) 2 CsI(s)
Answer: In equation (28), Xe is reduced from +6 to +4 and some of the F is oxidized from -1
to 0. This reaction would be classified as a redox decomposition reaction. In equation (29),
Zn is oxidized from 0 to +2 and Ag is reduced from +1 to 0. One of the reactants is an
element and one of the products is an element. This reaction would be classified as a redox
single displacement reaction. In equation (30), there is no redox occurring. Both reactants are
in the form of aqueous ions, but are not complex ions. This acid-base reaction is classified as
nonredox double displacement. In equation (31), there is no redox occurring. Because there is
one product formed, this reaction is classified as a nonredox combination reaction. In
equation (32), Cs is oxidized from 0 to +1 and I is reduced from 0 to -1. Both reactants are
elements and there is only one product formed. The reaction is classified as a (redox)
formation reaction.

Try It Out
Classify each reaction.
(33) Na2CO3(s) + SiO2(s) Na2SiO3(l) + CO2(g)
(34) 2 Mg(NO3)2(s) 2 Mg(NO2)2(s) + O2(g)
(35) 3 HNO2(aq) 2 NO(g) + NO3-(aq) + H3O+(aq)
(36) BaCO3(s) BaO(s) + CO2(g)
(37) 2 Eu2+(aq) + 2 H+(aq) 2 Eu3+(aq) + H2(g)
(38) [Ag(NH3)2]+(aq) + 2 CN-(aq) [Ag(CN)2]-(aq) + 2 NH3(aq)
(39) MgO(s) + 2 HCl(aq) MgCl2(aq) + H2O(l)
(40) CaO(s) + SO2(g) CaSO3(s)
(41) 2 NO(g) + O2(g) 2 NO2(g)
(42) N2(g) + 2 O2(g) 2 NO2(g)

Stoichiometry

Stoichiometry is simply the math behind chemistry. Given enough


information, one can use stoichiometry to calculate masses,
moles, and percents within a chemical equation.

What is a Chemical Equation


The Mole
Balancing Chemical Equations
Limiting Reagents
Percent Composition
Empirical and Molecular Formulas
Density
Concentrations of Solutions

What is a Chemical Equation?


In chemistry, we use symbols to represent the various chemicals.
Success in chemistry depends upon developing a strong
familiarity with these basic symbols. For example, the symbol
"C"represents an atom of carbon, and "H" represents an atom of
hydrogen. To represent a molecule of table salt, sodium chloride,
we would use the notation "NaCl", where "Na" represents sodium
and "Cl" represents chlorine. We call chlorine "chloride" in this
case because of its connection to sodium. You should have
reviewed naming schemes, or nomenclature, in earlier readings.

A chemical equation is an expression of a chemical process. For example:


AgNO3(aq) + NaCl(aq) ---> AgCl(s) + NaNO3(aq)
In this equation, AgNO3 is mixed with NaCl. The equation shows that
the reactants (AgNO3 and NaCl) react through some process (--->) to form
the products (AgCl and NaNO3). Since they undergo a chemical process, they are
changed fundamentally.
Often chemical equations are written showing the state that each substance is in.
The (s) sign means that the compound is a solid. The (l) sign means the substance
is a liquid. The (aq) sign stands for aqueous in water and means the compound is
dissolved in water. Finally, the (g) sign means that the compound is a gas.
Coefficients are used in all chemical equations to show the relative amounts of
each substance present. This amount can represent either the relative number

of molecules, or the relative number of moles (described below). If no coefficient


is shown, a one (1) is assumed.
On some occasions, a variety of information will be written above or below the
arrows. This information, such as a value for temperature, shows what conditions
need to be present for a reaction to occur. For example, in the graphic below, the
notation above and below the arrows shows that we need a chemical Fe 2O3, a
temperature of 1000 C, and a pressure of 500 atmospheres for this reaction to
occur.
The graphic below works to capture most of the concepts described above:

The Mole
Given the equation above, we can tell the number of moles of
reactants and products. A mole simply represents Avogadro's
number (6.022 x 1023) of molecules. A mole is similar to a term
like a dozen. If you have a dozen carrots, you have twelve of
them. Similarly, if you have a mole of carrots, you have 6.022 x
1023 carrots. In the equation above there are no numbers in front

of the terms, so each coefficient is assumed to be one (1). Thus,


you have the same number of moles of AgNO3, NaCl, AgCl, NaNO3.
Converting between moles and grams of a substance is often important. This
conversion can be easily done when the atomic and/or molecular mass of the
substance(s) are known. Given the atomic or molecular mass of a substance, that
mass in grams makes a mole of the substance. For example, calcium has an atomic
mass of 40 atomic mass units. So, 40 grams of calcium makes one mole, 80 grams
makes two moles, etc.
Balancing Chemical Equations
Sometimes, however, we have to do some work before using the
coefficients of the terms to represent the relative number of
molecules of each compound. This is the case when the equations
are not properly balanced. We will consider the following
equation:
Al + Fe3O4---> Al2O3
+ Fe

Since no coefficients are in front of any of the terms, it is easy to assume that one
(1) mole of Al and one (1) mole of Fe3O4react to form one (1) mole of Al2O3. If this
were the case, the reaction would be quite spectacular: an aluminum atom would
appear out of nowhere, and two (2) iron atoms and one (1) oxygen atom would
magically disappear. We know from the Law of Conservation of Mass (which
states that matter can neither be created nor destroyed) that this simply cannot
occur. We have to make sure that the number of atoms of each particular element in
the reactants equals the number of atoms of that same element in the products. To
do this we have to figure out the relative number of molecules of each term
expressed by the term's coefficient.
Balancing a simple chemical equation is essentially done by trial and error. There
are many different ways and systems of doing this, but for all methods, it is
important to know how to count the number of atoms in an equation. For example
we will look at the following term.
2Fe3O4
This term expresses two (2) molecules of Fe3O4. In each molecule of this substance
there are three (3) Fe atoms. Therefore in two (2) molecules of the substance there
must be six (6) Fe atoms. Similarly there are four (4) oxygen atoms in one (1)

molecule of the substance so there must be eight (8) oxygen atoms in two (2)
molecules.
Now let's try balancing the equation mentioned earlier:
Al + Fe3O4---> Al2O3+ Fe
Developing a strategy can be difficult, but here is one way of approaching a
problem like this.
1. Count the number of each atom on the reactant and on the
product side.
2. Determine a term to balance first. When looking at this
problem, it appears that the oxygen will be the most difficult
to balance so we'll try to balance the oxygen first. The
simplest way to balance the oxygen terms is:
Al + 3 Fe3O4---> 4 Al2O3+ Fe
Be sure to notice that the subscript times the coefficient will give the
number of atoms of that element. On the reactant side, we have a coefficient
of three (3) multiplied by a subscript of four (4), giving 12 oxygen atoms.
On the product side, we have a coefficient of four (4) multiplied by a
subscript of three (3), giving 12 oxygen atoms. Now, the oxygens are
balanced.
3. Choose another term to balance. We'll choose iron, Fe. Since
there are nine (9) iron atoms in the term in which the oxygen
is balanced we add a nine (9) coefficient in front of the Fe.
We now have:
Al +3 Fe3O4---> 4Al2O3+ 9Fe
4. Balance the last term. In this case, since we had eight (8)
aluminum atoms on the product side we need to have eight
(8) on the reactant side so we add an eight (8) in front of the
Al term on the reactant side.
Now, we're done, and the balanced equation is:
8Al + 3Fe3O4 ---> 4Al2O3 + 9 Fe
Limiting Reagents
Sometimes when reactions occur between two or more
substances, one reactant runs out before the other. That is called
the "limiting reagent". Often, it is necessary to identify the
limiting reagent in a problem.
Example: A chemist only has 6.0 grams of C2H2 and an unlimited
supply of oxygen and he desires to produce as much CO2 as

possible. If she uses the equation below, how much oxygen


should she add to the reaction?
2C2H2(g) + 5O2(g) ---> 4CO2(g) + 2 H2O(l)
To solve this problem, it is necessary to determine how much oxygen should be
added if all of the reactants were used up (this is the way to produce the maximum
amount of CO2).
First, we calculate the number of moles of C 2H2 in 6.0 g of C2H2. To be able to
calculate the moles we need to look at a periodic table and see that 1 mole of C
weighs 12.0 g and H weighs 1.0 g. Therefore we know that 1 mole of C 2H2 weighs
26 g (2 12 grams + 2 1 gram).
1 mol C2H2
6.0 g C2H2 x

= 0.25 mol C2H2


(24.0 + 2.0)g C2H2

Then, because there are five (5) molecules of oxygen to every two (2) molecules of
C2H2, we need to multiply the result by 5/2 to get the total molecules of oxygen.
Then we convert to grams to find the amount of oxygen that needs to be added:
5 mol O2
0.25 mol C2H2 x

32.0 g O2
x

2 mol C2H2

= 20 g O2
1 mol O2

Percent Composition
It is possible to calculate the mole ratios (also called mole
fractions) between terms in a chemical equation when given the
percent by mass of products or reactants.
percentage by mass = mass of part/ mass of whole

There are two types of percent composition problems-- problems


in which you are given the formula (or the weight of each part)
and asked to calculate the percentage of each element and
problems in which you are given the percentages and asked to
calculate the formula.
In percent composition problems, there are many possible solutions. It is always
possible to double the answer. For example, CH and C 2H2 have the same
proportions, but they are different compounds. It is standard to give compounds in
their simplest form, where the ratio between the elements is as reduced as it can
be-- called the empirical formula. When calculating the empirical formula from
percent composition, one can convert the percentages to grams. For example, it is
usually the easiest to assume you have 100 g so 54.3% would become 54.3 g. Then
we can convert the masses to moles; this gives us mole ratios. It is necessary to

reduce to whole numbers. A good technique is to divide all the terms by the
smallest number of moles. Then the ratio of the moles can be transferred to write
the empirical formula.
Example: If a compound is 47.3% C (carbon), 10.6% H (hydrogen) and 42.0% S
(sulfur), what is its empirical formula?
To do this problem we need to transfer all of our percents to masses. We assume
that we have 100 g of this substance. Then we convert to moles:
47.3 grams
Carbon:

1 mole
x

1
10.6 grams
Hyrdrogen:

= 3.94 moles
12.01 grams
1 mole

x
1
42.0 grams

Sulfur:

= 10.52 moles
1.008 grams
1 mole

x
1

= 1.310 moles
32.07 grams

Now we try to get an even ratio between the elements so we divide by the number
of moles of sulfur, because it is the smallest number:
3.94
Carbon:

=3
1.310
10.52

Hydrogen:

=8
1.310
1.310

Sulfur:

=1
1.310

So we have: C3H8 S
Example: Figure out the percentage by mass of hydrogen sulfate, H 2SO4.
In this problem we need to first calculate the total mass of the compound by
looking at the periodic table. This gives us:
2(1.008) + 32.07 + 4(16.00) g/mol = 98.09 g/mol
Now, we need to take the weight fraction of each element over the total mass
(which we just found) and multiply by 100 to get a percentage.
2(1.008)
hydrogen:

2.016
=

98.09
32.07
sulfur:

= 0.0206 100 = 2.06%


98.09

= 0.327 100 = 32.7%


98.09

4(16.00)
oxygen:

64.00
=

98.09

= 0.652 100 = 65.2%


98.09

Now, we can check that the percentages add up to 100%


65.2 + 2.06 + 32.7 = 99.96
This is essentially 100 so we know that everything has worked,
and we probably have not made any careless errors.
So the answer is that H2SO4 is made up of 2.06% H, 32.7% S, and
65.2% O by mass.
Empirical Formula and Molecular Formula
While the empirical formula is the simplest form of a compound,
the molecular formula is the form of the term as it would appear
in a chemical equation. The empirical formula and the molecular
formula can be the same, or the molecular formula can be any
positive integer multiple of the empirical formula. Examples of
empirical formulas: AgBr, Na2S, C6H10O5. Examples of molecular
formulas: P2, C2O4, C6H14S2, H2, C3H9.
One can calculate the empirical formula from the masses or percentage
composition of any compound. We have already discussed percent composition in
the section above. If we only have mass, all we are doing is essentially eliminating
the step of converting from percentage to mass.
Example: Calculate the empirical formula for a compound that has 43.7 g P
(phosphorus) and 56.3 grams of oxygen. First we convert to moles:
43.7 grams P

1 mol
x

1
56.3 grams O

= 1.41 moles
30.97 grams
1 mol

x
1

= 3.52 moles
16.00 grams

Next we divide the moles to try to get an even ratio.


1.41
Phosphorus:

= 1.00
1.41
3.52

Oxygen:

= 2.50
1.41

When we divide, we did not get whole numbers so we must multiply by two (2).
The answer = P2O5

Calculating the molecular formula once we have the empirical formula is easy. If
we know the empirical formula of a compound, all we need to do is divide the
molecular mass of the compound by the mass of the empirical formula. It is also
possible to do this with one of the elements in the formula; simply divide the mass
of that element in one mole of compound by the mass of that element in the
empirical formula. The result should always be a natural number.
Example: if we know that the empirical formula of a compound is HCN and we are
told that a 2.016 grams of hydrogen are necessary to make the compound, what is
the molecular formula? In the empirical formula hydrogen weighs 1.008 grams.
Dividing 2.016 by 1.008 we see that the amount of hydrogen needed is twice as
much. Therefore the empirical formula needs to be increased by a factor of two (2).
The answer is:
H2C2N2.
Density
Density refers to the mass per unit volume of a substance. It is a
very common term in chemistry.
Concentrations of Solutions
The concentration of a solution is the "strength" of a solution. A
solution typically refers to the dissolving of some solid substance
in a liquid, such as dissolving salt in water. It is also often
necessary to figure out how much water to add to a solution to
change it to a specific concentration.

The concentration of a solution is typically given in molarity. Molarity is defined


as the number of moles of solute (what is actually dissolved in the solution)
divided by the volume in liters of solution (the total volume of what is dissolved
and what it has been dissolved in).
moles of solute
Molarity =
liters of solution

Molarity is probably the most commonly used term because measuring a volume of
liquid is a fairly easy thing to do.
Example: If 5.00 g of NaOH are dissolved in 5000 mL of water, what is the
molarity of the solution?
One of our first steps is to convert the amount of NaOH given in grams into moles:
5.00g NaOH

1 mole

= 0.125 moles

(22.9 + 16.00 + 1.008)g

Now we simply use the definition of molarity: moles/liters to get the answer
0.125 moles
Molarity =

= 0.025 mol/L
5.00 L of soln

So the molarity (M) of the solution is 0.025 mol/L.


Molality is another common measurement of concentration. Molality is defined as
moles of solute divided by kilograms of solvent(the substance in which it is
dissolved, like water).
moles of solute
Molality =
kg of solvent

Molality is sometimes used in place of molarity at extreme temperatures because


the volume can contract or expand.
Example: If the molality of a solution of C 2H5OH dissolved in water is 1.5 and the
mass of the water is 11.7 kg, figure out how much C 2H5OH must have been added
in grams to the solution.
Our first step is to substitute what we know into the equation. Then we try to solve
for what we don't know: moles of solute. Once we know the moles of solute we
can look at the periodic table and figure out the conversion from moles to grams.
moles solute
Molality =
kg solvent

Now we simply use the definition of molarity: moles/liters to get the answer
moles solute
Molality =
kg solvent
moles solute

mols
1.5

=
kg
moles

1.5

11.7 kg
x 11.7 kg = 17.55 moles

kg
17.55 moles

(2 12.01) + (6 1.008) + 16
x

= 808.5 g C2H5OH
1 moles

It is possible to convert between molarity and molality. The only information


needed is density.
Example: If the molarity of a solution is 0.30 M, calculate the molality of the
solution knowing that the density is 3.25 g/mL.
To do this problem we can assume one (1) liter of solution to make the numbers
easier. We need to get from the molarity units of mol/L to the molality units of
mol/kg. We work the problem as follows, remembering that there are 1000 mL in a
Liter and 1000 grams in a kg. This conversion will only be accurate at small
molarities and molalities.
0.3 mol

1 mL
x

1L

1L
x

3.25 g

1000 g
x

1000 mL

= 0.09 mols / kg
1 kg

It is also possible to calculate colligative properties, such as boiling point


depression, using molality. The equation for temperature depression or expansion
is
T= Kf m
Where:
T is temperature depression (for freezing point) or temperature expansion (for
boiling point) (C)
Kf is the freezing point constant (kg C/mol)
m is molality in mol/kg
Example: If the freezing point of the salt water put on roads is -5.2 C, what is the
molality of the solution? (The Kf for water is 1.86 C/m.)
This is a simple problem where we just plug in numbers into the equation. One
piece of information we do have to know is that water usually freezes at 0 C.
T = Kf * m
T/Kf = m
m = 5.2/1.86
m = 2.8 mols/kg

Practice Problems
1. If only 0.25 molar NaOH and water are available, how much
NaOH needs to be added to make 10 liters of 0.2 M solution of
NaOH?
Check your work

2. If 2.0 moles of sucrose weighing 684 g is put in 1000 g of water and is then
dissolved, what would be the molality of the solution?
Check your work.
3. If you have a 0.25 M solution of benzene with a density of 15 g/L, calculate the
molality of the solution.
Check your work
4. If the density of mercury is 13.534 g/cm3 and you have 62.5 cm3 of mercury,
how many grams, moles, and atoms of mercury do you have? (Mercury has a mass
of 200.6 g/mol.)
Check your work
Acid-Base Chemistry

Water
pH
Definitions of Acids and Bases
Salts
Acid-Base Character
Acid-Base Titrations

Water
We typically talk about acid-base reactions in aqueous-phase
environments -- that is, in the presence of water. The most
fundamental acid-base reaction is the dissociation of water:
H2O

H+ + OH-

In this reaction, water breaks apart to form a hydrogen ion (H +) and a hydroxide
ion (OH-). In pure water, we can define a special equilibrium constant (K w) as
follows:
KW = [H+][OH-] = 1.00x10-14

Where Kw is the equilibrium constant for water at 25 C (unitless)


[H+] is the molar concentration of hydrogen
[OH-] is the molar concentration of hydroxide
An equilibrium constant less than one (1) suggests that the reaction prefers to stay
on the side of the reactants -- in this case, water likes to stay as water. Because
water hardly ionizes, it is a very poor conductor of electricity.
pH
What is of interest in this reading, however, is the acid-base
nature of a substance like water. Water actually behaves both like
an acid and a base. The acidity or basicity of a substance is
defined most typically by the pH value, defined as below:
pH = -log[H+]

At equilibrium, the concentration of H+ is 1.00 10-7, so we can calculate the pH


of water at equilibrium as:
pH = -log[H+]= -log[1.00 10-7] = 7.00
Solutions with a pH of seven (7) are said to be neutral, while those with pH values
below seven (7) are defined as acidic and those above pH of seven (7) as being
basic.
pOH gives us another way to measure the acidity of a solution. It is just the
opposite of pH. A high pOH means the solution is acidic while a low pOH means
the solution is basic.
pOH = -log[OH-]
pH + pOH = 14.00 at 25C
Definitions of acids and bases
Arrhenius
acid: generates [H+] in solution
base: generates [OH-] in solution
normal Arrhenius equation: acid + base
salt + water
example: HCl(aq) + NaOH(aq)
NaCl(aq) + H2O(l)
Brnsted-Lowery:
acid: anything that donates a [H+] (proton donor)
base: anything that accepts a [H+] (proton acceptor)
normal Brnsted-Lowery equation: acid + base
acid +
base

example: HNO2(aq) + H2O(aq)


NO2-(aq)+ H3O+(aq)
Each acid has a conjugate base and each base has
a conjugate acid. These conjugate pairs only differ by
a proton. In this example: NO2- is the conjugate base of the
acid HNO2 and H3O+ is the conjugate acid of the base H2O.
Lewis:
acid: accepts an electron pair
base: donates an electron pair
The advantage of this theory is that many more reactions
can be considered acid-base reactions because they do not
have to occur in solution.
Salts
A salt is formed when an acid and a base are mixed and the acid
releases H+ ions while the base releases OH- ions. This process is
called hydrolysis. The pH of the salt depends on the strengths of
the original acids and bases:
Acid

Base

Salt pH

strong

strong

pH = 7

weak

strong

pH > 7

strong

weak

pH < 7

weak

weak

depends on which is stronger

These salts are acidic or basic due to their acidic or basic ions. When weak acids or
weak bases react with water, they make strong conjugate bases or conjugate acids,
respectively, which determines the pH of the salt.
Acid-Base Character
For a molecule with a H-X bond to be an acid, the hydrogen must
have a positive oxidation number so it can ionize to form a
positive +1 ion. For instance, in sodium hydride (NaH) the
hydrogen has a -1 charge so it is not an acid but it is actually a
base. Molecules like CH4 with nonpolar bonds also cannot be acids
because the H does not ionize. Molecules with strong bonds
(large electronegativity differences), are less likely to be strong
acids because they do not ionize very well. For a molecule with an
X-O-H bond (also called an oxoacid) to be an acid, the hydrogen
must again ionize to form H+. To be a base, the O-H must break off
to form the hydroxide ion (OH-). Both of these happen when
dealing with oxoacids.

Strong Acids: These acids completely ionize in solution so they are always
represented in chemical equations in their ionized form. There are only seven (7)
strong acids:

HCl, HBr, HI, H2SO4, HNO3, HClO3, HClO4


To calculate a pH value, it is easiest to follow the standard "Start, Change,
Equilibrium" process.
Example Problem: Determine the pH of a 0.25 M solution of HBr.
Answer:
Start:
Change:
Equilibrium:

HBr (aq)

H+(aq)
.25 M
0M
-.25
+.25
0
.25
+
pH = -log[H ] = -log(.25) = 0.60

Br-(aq)
0M
+.25
.25

Weak Acids: These are the most common type of acids. They follow the equation:
HA(aq)

H+(aq) + A-(aq)

The equilibrium constant for the dissociation of an acid is known as Ka. The larger
the value of Ka, the stronger the acid.
[H+][A-]
Ka =
[HA]

Example Problem: Determine the pH of 0.30 M acetic acid (HC 2H3O2) with
the Ka of 1.8x10-5.
Answer:
Write an equilibrium equation for the acid:
HC2H3O2
H+ + C2H3O2 Write the equilibrium expression and the Ka value:
[H+][C2H3O2-]
Ka =
= 1.8x10-5
[HC2H3O2]
"Start, Change, Equilibrium":
HC2H3O2
H+
+
C2H3O2 Start:
0.30 M
0M
0M
Change:
-x
+x
+x
Equilibrium:
0.30 - x
x
x
Substitute the variables (disregard the "-x" because it is so small compared to
the 0.30)
and solve for [H+]:
(x)(x)
x2
-5
Ka = 1.8x10 =
=
(.30 - x)
.30
+
-3
x = [H ] = 2.3x10

pH = -log[H+] = 2.64

Strong Bases: Like strong acids, these bases completely ionize in solution and are
always represented in their ionized form in chemical equations. There are only
eight (8) strong bases:
LiOH, NaOH, KOH, RbOH, CsOH, Ca(OH)2, Sr(OH)2, Ba(OH)2
Example Problem: Determine the pH of a 0.010 M solution of Ba(OH) 2.
Answer:

Ba(OH)2(aq)
Start:
.010 M
Change:
-.010
Equilibrium:
0
pOH = -log[OH-] = -log(.010) = 1.70
pH = 14.00 - 1.70 = 12.30

Ba2+(aq)
0M
+.010
.010

+ 2OH-(aq)
0M
+.010
.010

Weak Bases: These follow the equation:


Weak Base + H2O

conjugate acid + OH-

example: NH3 + H2O

NH4+ + OH-

Kb is the base-dissociation constant:


[conjugate acid][OH-]
Kb =
[weak base][H2O]
[NH4+][OH-]
example: Kb =
[NH3[H2O]

Ka x Kb = Kw = 1.00x10-14
To calculate the pH of a weak base, we must follow a very similar "Start, Change,
Equilibrium" process as we did with the weak acid, however we must add a few
steps.
Example Problem: Determine the pH of 0.15 M ammonia (NH 3) with a Kb=1.8x105
.
Answer:
Write the equilibrium equation for the base:
NH3 + H2O
NH4+ + OH Write the equilibrium expression and the Kb value:

[NH4+][OH2-]

= 1.8x10-5

Kb =
[NH3][H2O]
"Start, Change, Equilibrium":

NH3
+
H2O
NH4+ +
OH Start:
0.15 M
-0M
0M
Change:
-x
-+x
+x
Equilibrium:
0.15 - x
-x
x
Substitute the variables (disregard the "-x" because it is so small compared to
the 0.15)
and solve for [OH-]:
(x)(x)
x2
Kb = 1.8x10-5 =
=
(.15 - x)
.15
x = [OH-] = 1.6x10-3 M
pOH = -log[OH-] = 2.80
pH = 14.00 - 2.80 - 11.20

When dealing with weak acids and weak bases, you also might have to deal with
the "common ion effect". This is when you add a salt to a weak acid or base that
contains one of the ions present in the acid or base. To be able to use the same
process to solve for pH when this occurs, all you need to change are your "start"
numbers. Add the molarity of the ion, which comes from the salt, and then solve
the Ka or Kb equation as you did earlier.
Example Problem: Find the pH of a solution formed by dissolving 0.100 mol of
HC2H3O2 with a Ka of 1.8x10-8 and 0.200 mol of NaC2H3O2 in a total volume of
1.00 L.
Answer:
Start:
Change:
Equilibrium:

HC2H3O2(aq)
.10 M
-x
.10 - x

Ka = 1.8x10-8 =

H+(aq)
0M
+x
x
(x)(.20 + x)

(.10 - x)
+

+ C2H3O2-(aq)
.20 M
+x
.20 + x
(x)(.20)
=
(.10)

-9

x = [H ] = -9.0x10
pH = -log(9.0x10-9) = 8.05

Acid-Base Titrations
An acid-base titration is when you add a base to an acid until the
equivalence point is reached which is where the number of moles
of acid equals the number of moles of base. For the titration of a
strong base and a strong acid, this equivalence point is reached
when the pH of the solution is seven (7) as seen on the following
titration curve:

For the titration of a strong base with a weak acid, the equivalence point is reached
when the pH is greater than seven (7). The half equivalence point is when half of
the total amount of base needed to neutralize the acid has been added. It is at this
point where the pH = pKa of the weak acid.

In an acid-base titration, the base will react with the weak acid and form a solution
that contains the weak acid and its conjugate base until the acid is completely gone.
To solve these types of problems, we will use the Ka value of the weak acid and the
molarities in a similar way as we have before. Before demonstrating this way, let
us first examine a short cut, called theHenderson-Hasselbalch Equation. This can
only be used when you have some acid and some conjugate base in your solution.
If you only have acid, then you must do a pure K a problem and if you only have
base (like when the titration is complete) then you must do a K b problem.
[base]
pH = pKa + log
[acid]

Where:
pH is the log of the molar concentration of the hydrogen
pKa is the equilibrium dissociation constant for an acid

[base] is the molar concentration of a basic solution


[acid] is the molar concentration of an acidic solution
Example Problem: 25.0 mL of 0.400 M KOH is added to 100. mL of 0.150 M
benzoic acid, HC7H5O2 (Ka=6.3x10-5). Determine the pH of the solution.
Answer:
Determine where in the titration we are:
0.400 M x 0.025 L = 0.0100 mol KOH added
0.150 M x 0.100 L = 0.0150 mol HC7H5O2 originally
because only 0.100 mol of base has been added, that means the thitration is
not
complete; this means there are two ways to solve this problem: the normal
way
and the way using the Henderson-Hasselbalch Equation.
Normal way:
HC7H5O2 +
OHC7H5O2- + H2O
before reaction:
0.015 mol
0.0100 mol
0 mol
- change:
-0.0100
-0.0100
+0.0100
- after reaction:
0.0050
0
0.0100
-+
[H ][C7H5O2 ]
(x)(0.0100)
Ka =
= 6.3x10-5 =
[HC7H5O2]
0.0050
x = [H+] = 3.2x10-5 M
pH = -log(3.2x10-5) = 4.49
Henderson-Hasselbalch Way:
0.0050 mol
[HC7H5O2] =
= 0.040 M
0.125 L
0.0100 mol
[C7H5O2-] =
= 0.0800 M
0.125 L
[base]
pH = pKa + log
[acid]
0.0800
pH = -log(6.3x10-5) + log
= 4.20 + 0.30 = 4.50
0.0400

This equation is used frequently when trying to find the pH


of buffer solutions. A buffer solution is one that resists changes in
pH upon the addition of small amounts of an acid or a base. They
are made up of a conjugate acid-base pair such as
HC2H3O2/C2H3O2- or NH4+/NH3. They work because the acidic
species neutralize the OH- ions while the basic species neutralize
the H+ ions. The buffer capacity is the amount of acid or base the
buffer can neutralize before the pH begins to change to a
significant degree. This depends on the amount of acid or base in
the buffer. High buffering capacities come from solutions with

high concentrations of the acid and the base and where these
concentrations are similar in value.
Practice weak acid problem:
C6H5COONa is a salt of a weak acid C6H5COOH. A 0.10 M solution of
C6H5COONa has a pH of 8.60.
1. Calculate [OH-] of C6H5COONa
2. Calculate Kb for: C6H5COO- + H2O <---> C6H5COOH + OH3. Calculate Ka for C6H5COOH
See the weak acid solution.
Practice titration problem:
20.00 mL of 0.160 M HC2H3O2 (Ka=1.8x10-5) is titrated with 0.200 M NaOH.
1.
2.
3.
4.

What
What
What
What

is
is
is
is

the
the
the
the

pH
pH
pH
pH

of the solution before the titration begins?


after 8.00 mL of NaOH has been added?
at the equivalence point?
after 20.00 mL of NaOH has been added?

Advanced Concepts in Chemistry


The following topics are more advanced areas of chemistry. In many cases the
advanced topics assume knowledge of some of the basic concepts of chemistry.
Gas Laws
Thermodynamics
Kinetics
Equilibria
Redox Chemistry
Nuclear Chemistry
In addition, we have developed a series of readings in numerical methods in
chemistry. These are advanced readings that are not evaluated in either the pre- or
post-test. Readings include:
Basic Matrix Math
Linear Least Squares
Newton's Method
Integration Techniques

Gas Laws

Gases behave differently from the other two commonly studied states of
matter, solids and liquids, so we have different methods for treating and
understanding how gases behave under certain conditions. Gases, unlike
solids and liquids, have neither fixed volume nor shape. They are molded
entirely by the container in which they are held. We have three variables by
which we measure gases: pressure, volume, and temperature. Pressure is
measured as force per area. The standard SI unit for pressure is the pascal
(Pa). However, atmospheres (atm) and several other units are commonly
used. The table below shows the conversions between these units.
Units of Pressure
1 pascal (Pa)

1 N*m-2 = 1 kg*m-1*s-2

1 atmosphere (atm)

1.01325*105 Pa

1 atmosphere (atm)

760 torr

1 bar

105 Pa

Volume is related between all gases by Avogadro's hypothesis, which


states: Equal volumes of gases at the same temperature and pressure contain
equal numbers of molecules. From this, we derive the molar volume of a gas
(volume/moles of gas). This value, at 1 atm, and 0 C is shown below.
Vm =

= 22.4 L at 0C and 1 atm

Where:
Vm = molar volume, in liters, the volume that one mole of gas occupies
under those conditions
V=volume in liters
n=moles of gas
An equation that chemists call the Ideal Gas Law, shown below, relates the
volume, temperature, and pressure of a gas, considering the amount of gas
present.
PV = nRT
Where:
P=pressure in atm
T=temperature in Kelvins
R is the molar gas constant, where R=0.082058 L atm mol-1 K-1.
The Ideal Gas Law assumes several factors about the molecules of gas. The
volume of the molecules is considered negligible compared to the volume of
the container in which they are held. We also assume that gas molecules
move randomly, and collide in completely elastic collisions. Attractive and
repulsive forces between the molecules are therefore considered negligible.
Example Problem: A gas exerts a pressure of 0.892 atm in a 5.00 L container
at 15C. The density of the gas is 1.22 g/L. What is the molecular mass of
the gas?
Answer:
PV = nRT
T = 273 + 15 = 228
(0.892)(5.00) = n(.0821)(288)
n = 0.189 mol
.189 mol

x
5.00L
x = Molecular Weight = 32.3 g/mol

x grams
= 1.22 g/L
1 mol

We can also use the Ideal Gas Law to quantitatively determine how
changing the pressure, temperature, volume, and number of moles of
substance affects the system. Because the gas constant, R, is the same for all
gases in any situation, if you solve for R in the Ideal Gas Law and then set
two Gas Laws equal to one another, you have the Combined Gas Law:
P1V1

P2V2
=

n1T1

Where:
values with a subscript of "1" refer to initial conditions
values with a subscript of "2" refer to final conditions

n2T2

If you know the initial conditions of a system and want to determine the new
pressure after you increase the volume while keeping the numbers of moles
and the temperature the same, plug in all of the values you know and then
simply solve for the unknown value.
Example Problem: A 25.0 mL sample of gas is enclosed in a flask at 22C. If
the flask was placed in an ice bath at 0C, what would the new gas volume
be if the pressure is held constant?
Answer:
Because the pressure and the number of moles are held constant, we do not
need to represent them in the equation because their values will cancel. So the
combined gas law equation becomes:
V1
V2

=
T1
T2
25.0 mL
V2

=
295 K
273 K
V2 = 23.1 mL

We can apply the Ideal Gas Law to solve several problems. Thus far, we
have considered only gases of one substance, pure gases. We also
understand what happens when several substances are mixed in one
container. According to Dalton's law of partial pressures, we know that the
total pressure exerted on a container by several different gases, is equal to
the sum of the pressures exerted on the container by each gas.
Pt = P1 + P2 + P3 + ...
Where:
Pt=total pressure
P1=partial pressure of gas "1"
P2=partial pressure of gas "2"
and so on
Using the Ideal Gas Law, and comparing the pressure of one gas to the total
pressure, we solve for the mole fraction.
P1

n2 RT/V

n1

=
Pt

=
nt RT/V

= X1
nt

Where:
X1 = mole fraction of gas "1"
And discover that the partial pressure of each the gas in the mixture is equal
to the total pressure multiplied by the mole fraction.
n1
P1 =

Pt = X1Pt
nt

Example Problem: A 10.73 g sample of PCl5 is placed in a 4.00 L flask at


200C.

a) What is the initial pressure of the flask before any reaction takes place?
b) PCl5 dissociates according to the equation: PCl 5(g) --> PCl3(g) + Cl2(g). If
half of the total number of moles of PCl 5(g) dissociates and the observed
pressure is 1.25 atm, what is the partial pressure of Cl 2(g)?
Answer:
1 mol

a) 10.73 g PCl5 x

= 0.05146 mol PCl5


208.5 g

PV = nRT
T = 273 + 200 = 473
P(4.00) = (.05146)(.0821)(473)
P = 0.4996 atm
b)
PCl5
Start:
.05146 mol
Change:
-.02573 mol
Final:
.02573 mol

XCl2 =

PCl3
0 mol
+.02573 mol
.02573 mol
nCl2

Cl2
0 mol
+.02573 mol
.02573 mol
PCl2

=
ntotal

PCl2

1.25 atm

PCl2 = .4167 atm

Ptotal
.02573 mol

=
.07719 mol

As we stated earlier, the shape of a gas is determined entirely by the


container in which the gas is held. Sometimes, however, the container may
have small holes, or leaks. Molecules will flow out of these leaks, in a
process called effusion. Because massive molecules travel slower than
lighter molecules, the rate of effusion is specific to each particular gas. We
use Graham's law to represent the relationship between rates of effusion for
two different molecules. This relationship is equal to the square-root of the
inverse of the molecular masses of the two substances.
r1

1
=

r2

Where:
r1=rate of effusion in molecules per unit time of gas "1"
r2=rate of effusion in molecules per unit time of gas "2"
u1=molecular mass of gas "1"
u2=molecular mass of gas "2"
Previously, we considered only ideal gases, those that fit the assumptions of
the ideal gas law. Gases, however, are never perfectly in the ideal state. All
atoms of every gas have mass and volume. When pressure is low and
temperature is low, gases behave similarly to gases in the ideal state. When
pressure and temperature increase, gases deviate farther from the ideal state.
We have to assume new standards, and consider new variables to account

for these changes. A common equation used to better represent a gas that is
not near ideal conditions is the van der Waals equation, seen below.
n2a

V2

P+

-b

= RT

Where the van der Waals constants are:


a accounts for molecular attraction
b accounts for volume of molecules
The table below shows values for a and b of several different compounds
and elements.
Species

a (dm6 bar mol-2)

b (dm3 mol-1)

Helium

0.034598

0.023733

Hydrogen

0.24646

0.026665

Nitrogen

1.3661

0.038577

Oxygen

1.3820

0.031860

Benzene

18.876

0.11974

Practice Ideal Gas Law Problem:


2.00 g of hydrogen gas and 19.2 g of oxygen gas are placed in a 100.0 L
container. These gases react to form H2O(g). The temperature is 38C at the
end of the reaction.
a) What is the pressure at the conclusion of the reaction?
b) If the temperature was raised to 77 C, what would the new pressure be in
the same container? Ideal gas law solution.
Practice Pressure Problem:
1 mole of oxygen gas and 2 moles of ammonia are placed in a container and
allowed to react at 850C according to the equation:
4 NH3(g) + 5 O2(g) --> 4 NO(g) + 6 H2O(g)

a) If the total pressure in the container is 5.00 atm, what are the partial
pressures for the three gases remaining?
b) Using Graham's Law, what is the ratio of the effusion rates of NH 3(g) to
O2(g)?
Pressure solution.
Chemical Thermodynamics

The scientific discipline that intersects the areas of chemistry and


physic is commonly known as physical chemistry, and it is in that
area that a thorough study of thermodynamics takes place.
Physics concerns itself heavily with the mechanics of events in

nature. Certainly changes in energy -- however measured,


whether it be heat, light, work, etc. -- are clearly physical events
that also have a chemical nature to them. Thermodynamics is the
study of energy changes accompanying physical and chemical
changes. The term itself clearly suggests what is happening -"thermo", from temperature, meaning energy, and "dynamics",
which means the change over time. Thermodynamics can be
roughly encapsulated with these topics:

Heat and Work


Energy
Enthalpy
Entropy
Gibbs Free Energy

Heat and Work


Heat and work are both forms of energy. They are also related
forms, in that one can be transformed into the other. Heat energy
(such as steam engines) can be used to do work (such as pushing
a train down the track). Work can be transformed into heat, such
as might be experienced by rubbing your hands together to warm
them up.

Work and heat can both be described using the same unit of measure. Sometimes
the calorie is the unit of measure, and refers to the amount of heat required to raise
one (1) gram of water one (1) degree Celsius. Heat energy is measured in
kilocalories, or 1000 calories. Typically, we use the SI units of Joules (J) and
kilojoules (kJ). One calorie of heat is equivalent to 4.187 J. You will also encounter
the term specific heat, the heat required to raise one (1) gram of a material one (1)
degree Celsius. Specific heat, given by the symbol "C", is generally defined as:
q
C=
MT

Where:
C = specific heat in cal/g-C
q = heat added in calories,
m = mass in grams
T = rise in temperature of the material in C.
The value of C for water is 1.00 cal/g-C.

The values for specific heat that are reported in the literature are usually listed at a
specific pressure and/or volume, and you need to pay attention to these settings
when using values from textbooks in problems or computer models.
Example Problem: If a 2.34 g substance at 22C with a specific heat of 3.88 cal/gC is heated with 124 cal of energy, what is the new temperature of the substance?
Answer:
q
T =
MC
(124)
T =

= 13.7C
(2.34)(3.88)

new T = 22 + 13.7 = 35.7C

Two other common heat variables are the heat of fusion and the heat of
vaporization. Heat of fusion is the heat required to melt a substance at its melting
temperature, while the heat of vaporization is the heat required to evaporate the
substance at its boiling point.
Chemical work is primarily related to that of expansion. In physics, work is
defined as:
w=df
Where:
w = work, in joules (Nm) (or calories, but we are using primarily SI units)
d = distance in meters
f = opposing force in Newtons (kg*m/s2)
In chemical reactions, work is generally defined as :
w = distance (area pressure)
The value of distance times area is actually the volume. If we imagine a reaction
taking place in a container of some volume, we measure work by pressure times
the change in volume.
w = V P
Where:

V is the change in volume, in liters


If V=0, then no work is done.
Example Problem: Calculate the work that must be done at standard temperature
and pressure (STP is 0C and 1 atm) to make room for the products of the octane
combustion:
2 C8H18 + 25 O2 --> 16 CO2 + 18 H2O
Answer:
Knowing that 25 moles of gas are replaced by 34 moles of gas in this reaction,
we can
calculate a net increase of 9 moles of gas. Knowing the molar volume of an
ideal gas at
STP (22.4 L/mol), the change in volume and the work of expansion can be
calculated
dV = 9 moles 22.4 L/mol = 202 L
The external pressure is 1.0 atm (standard pressure), so the work required is:
w = dV P = 202 L 1.00 atm = 202 l-atm
Using the conversion factor of 1 L-atm = 101 J, the amount of work in joules is:
w = 202 L-atm 101 j/L-atm = 2000 J, or 2kJ of energy

Energy
You might remember the first law of thermodynamics: energy
cannot be created or destroyed. Energy can only change form.
Chemically, that usually means energy is converted to work,
energy in the form of heat moves from one place to another, or
energy is stored up in the constituent chemicals. You have seen
how to calculate work. Heat is defined as that energy that is
transferred as a result of a temperature difference between a
system and its surroundings. Mathematically, we can look at the
change in energy of a system as being a function of both heat and
work:
E = q - w

Where:
E is the change in internal energy of a system
q is the heat flowing into the system
w is the work being done by the system
If q is positive, we say that the reaction is endothermic, that is, heat flows into the
reaction from the outside surroundings. If q is negative, then the reaction is
exothermic, that is, heat is given off to the external surroundings.

You might also remember the terms kinetic energy and potential energy. Kinetic
energy is the energy of motion -- the amount of energy in an object that is moving.
Potential energy is stationary, stored energy. If you think of a ball sitting on the
edge of a table, it has potential energy in the energy possible if it falls off the table.
Potential energy can be transformed into kinetic energy if and when the ball
actually rolls off the table and is in motion. The total energy of the system is
defined as the sum of kinetic and potential energies.
In descriptions of the energy of a system, you will also see the phrase "state
properties". A state property is a quantity whose value is independent of the past
history of the substance. Typical state properties are altitude, pressure, volume,
temperature, and internal energy.
Enthalpy
Enthalpy is an interesting concept: it is defined by its change
rather than a single entity. A state property, the word enthalpy
comes from the Greek "heat inside". If you have a chemical
system that undergoes some kind of change but has a fixed
volume, the heat output is equal to the change in internal energy
(q = E). We will define the enthalpy change, H, of a system as
being equal to its heat output at constant pressure:
dH = q at constant pressure

Where:
H = change in enthalpy
We define enthalpy itself as:
H = E + PV
Where:
H = enthalpy
E = energy of the system
PV = pressure in atm times volume in liters
You will not need to be able to calculate the enthalpy directly; in chemistry, we are
only interested in the change in enthalpy, or H.
H = Hfinal - Hinitial or H = H(products) - H(reactants)
Tables of enthalpies are generally given as H values.

Example Problem: Calculate the H value of the reaction:


HCl + NH3 NH4Cl
(H values for HCl is -92.30; NH3 is -80.29; NH4Cl is -314.4)
Answer:
H = Hproducts - Hreactants
Hproducts = -314.4
Hreactants = -92.30 + (-80.29) = -172.59
H = -314.4 - 172.59 = 141.8

We can also represent enthalpy change with the equation:


H = E + P V
Where:
V is the change in volume, in liters
P is the constant pressure
If you recall, work is defined as P V, so enthalpy changes are simply a reflection
of the amount of energy change (energy going in or
out,endothermic or exothermic), and the amount of work being done by the
reaction. For example, if E = -100 kJ in a certain combustion reaction, but 10 kJ
of work needs to be done to make room for the products, the change in enthalpy is:
H = -100 kJ + 10 kJ = -90 kJ
This is an exothermic reaction (which is expected with combustion), and 90 kJ of
energy is released to the environment. Basically, you get warmer. Notice the
convention used here -- a negative value represents energy coming out of the
system.
You can also determine H for a reaction based on bond dissociation energies.
Breaking bonds requires energy while forming bonds releases energy. In a given
equation, you must determine what kinds of bonds are broken and what kind of
bonds are formed. Use this information to calculate the amount of energy used to
break bonds and the amount used to form bonds. If you subtract the amount to
break bonds from the amount to form bonds, you will have the H for the reaction.
Example Problem: Calculate H for the reaction:
N2 + 3H2 2NH3

(The bond dissociation energy for N-N is 163 kJ/mol; H-H is 436
kJ/mol; N-H is 391 kJ/mol)
Answer:
H = Hproducts - Hreactants
To use the bond dissociation energies, we must determine how many bonds
are in the products and the reactants. In NH 3 there are 3 N-H bonds so in 2 NH3
there are 6 N-H bonds. In N2 there is 1 N-N bond and in 3H2 there are 3 H-H
bonds.
Hproducts = 6(391) = 2346
Hreactants = 163 + 3(436) = 1471
H = 2346 - 1471 = 875

Entropy
Entropy is a measure of the disorder of a system. Take your room
as an example. Left to itself, your room will increase in entropy
(i.e., get messier) if no work (cleaning up) is done to contain the
disorder. Work must be done to keep the entropy of the system
low. Entropy comes from the second law of thermodynamics,
which states that all systems tend to reach a state of equilibrium.
The significance of entropy is that when a spontaneous change
occurs in a system, it will always be found that if the total entropy
change for everything involved is calculated, a positive value will
be obtained. Simply, all spontaneous changes in an isolated
chemical system occur with an increase in entropy. Entropy, like
temperature, pressure, and enthalpy, is also a state property and
is represented in the literature by the symbol "S". Like enthalpy,
you can calculate the change of S (S).
S = Sfinal - S initial or S = S (products) - S (reactants)

Where:
S is change in entropy
Sfinal and Sinitial are the final and initial entropies, respectively
The following table shows the relationship between the state of a substance and its
entropy:
State of substance

Relative Entropy (S)

gas

highest S

aqueous

high S

liquid

medium S

solid

lowest S

Gibbs Free Energy


The free energy of a system, represented by the letter "G", is
defined as the energy of a system that is free to do work at

constant temperature and pressure. Mathematically, it is defined


as:
G = H - TS
Where:
G is the energy (sometimes called the free energy)
H is the enthalpy
T is the temperature
S is the entropy of the system.
You can also calculate the change in G the same way as you calculate the change in
enthalpy or entropy:
G = G(products) - G(reactants)
Where:
G is change in free energy
A pop-up calculator is available to calculate the enthalpy and Gibbs free energy
changes in reactions.
Given a constant temperature and pressure, the direction of any spontaneous
change is toward a lower Gibbs free energy. The graphic below shows that during a
reaction, the amount of free energy decreases until the reaction is at equilibrium. If
the reaction goes towards completion, the free energy minimum occurs very close
to the pure products part of the curve. In other words, the curve moves depending
on the conditions of the reaction.

A table relating all of the state properties summarized above -- enthalpy change,
entropy change, and change in free energy -- is shown below. A spontaneous
reaction is one that occurs without any outside intervention. Processes that are
spontaneous in one direction are non-spontaneous in the reverse direction.
Enthalpy Change

Entropy Change

Spontaneous Reaction?

Exothermic (H < 0)

Increase (S > 0) Yes, G < 0

Exothermic (H < 0)

Decrease (S < 0) Only at low temps, if |T S| < |H|

Endothermic (H > 0) Increase (S > 0) Only at high temps, if T S > H


Endothermic (H > 0) Decrease (S < 0) No, G > 0

Enthalpy Practice Problem: Given the following bond dissociation energies (H-C
is 413 kJ/mol; H-H is 436 kJ/mol; C=C is 614 kJ/mol; C-C is 348 kJ/mol),
determine H for the reaction:
H2C=CH2(g) + H2(g) --> H3C-CH3(g)
Enthalpy solution.
Entropy Practice Problem: Given the following entropy values Al2O3(s) is 51.00
kJ/mol; Al(s) is 28.32 kJ/mol; H2O(g) is 188.7 kJ/mol; H2(g) is 130.6 kJ/mol,
determine S for the reaction:
Al2O3(s) + 3H2(g) --> 2Al(s) + 3H2O(g)

Entropy solution.

Kinetics
Kinetics is the area of chemistry concerned with reaction rates. The rate can be
expressed as:
rate = change in substance/time for change to occur (usually in M/s)
There are several factors that determine the rate of a specific reaction and those are
expressed in the "collision theory" that states that for molecules to react, they must:
1. collide
2. have the right energy
3. have the right geometry
To increase the rate, you must make the above more likely to occur. This is
possible by changing other factors such as:
increasing the surface area (of solids)-this allows for more collisions and
gives more molecules the right geometry
increasing the temperature-this gives more molecules the right energy (also
called the activation energy, Ea)

increasing the concentration (of gases and solutions)-this allows for more
collisions and more correct geometry
using a catalyst-helps molecules achieve the correct geometry by providing
a different way to react

The reaction rate can also be expressed by using a "rate law" and is written as
follows:
For the general reaction: aA + bB + ... ----> gG + hH + .....
the reaction rate can be calculated by:
Reaction rate = k[A]m[B]n ....
Where:
[A], [B], etc. are the concentrations of the reactants
k is the rate constant or rate coefficient, a value dependent on temperature.
m,n, etc. are exponents that correspond to a, b, etc. The concentration is raised to
the power of its coefficient in the balanced equation.
Reaction order is a topic that comes with reaction rates. If you have a reaction in
that A, B, and C are possible reactants, then we can describe the order of the
reaction following this chart:

The order of the reaction is defined as the sum of the exponents of the coefficients.
In general, first order reactions are most commonly seen, but reactions of other
orders are also important. Zero-order reactions -- those for that the change in the
reaction is independent of the concentration of the reaction -- are also possible.
It is possible to determine the order of a reactant, and eventually the reaction rate,
using initial rate information that includes the concentration of the reactants and
the rate at that the product is formed. If you double the concentration of reactant X
and the rate increases by 2a, then the order of reactant X is "a". If you triple the
concentration of reactant Y and the rate increases by 3 b, then the order of Y is "b".
For example, if you have a reaction with one reactant, A, and you double [A] and
the rate doubles, then the rate=k[A]1. If, instead, you double [A] and the rate
quadruples, the rate=k[A]2. If you double [A] and the rate stays the same, then the
rate=k[A]0.

To find the rate constant, k, using initial rate information, just plug in from the
experiment one of the concentrations and rate into the rate law and solve. The units
of k are trickier:
units of k=units of rate/(units of concentration) reaction order
Ex: for 2nd order reaction, k=(M/s)/M2=M-1s-1
Example Problem: Find the rate law and rate constant of A + B --> C using the
following data

When dealing with reaction rates, it is sometimes important to know how to graph
a straight line with the data you have. When graphing concentration versus time,
there are two ways to graph a line. If you have a first order reaction, then the graph
of ln[A] vs. time is a line. If you have a second order reaction, then the graph of 1/
[A] vs. time produces a line.
A quantitative way to examine reaction rates is through Arrhenius Equation that
states:
k=Ae-Ea/RT
Where:
A is a constant related to the geometry needed
e is a constant, approximately 2.7281
Ea is the activation energy
R is the gas law constant, 8.314 J/mol-K
T is the temperature in kelvins
If it is a simple geometry to attain, A will be large. If a large E a is needed then the
exponent becomes more negative and therefore decreases k. If the temperature
increases then the exponent becomes less negative and therefore increases k.
A pop-up calculator is available to help practice using Arrhernius' Equation to
make calculations.
The following are two (2) energy profile graphs that help demonstrate energy
changes during a reaction.

Not all reactions happen exactly as they are written. Most, in fact, go through an
intermediate step. Reaction mechanism studies look at how a reaction actually
occurs. Defined, a reaction mechanism is a series of elementary reactions that are
proposed to account for the rate law (kinetics) of a particular reaction. The diagram
below shows the two steps involved in a particular mechanism, and it shows how
we get the reaction from the mechanism.

It is helpful to remember certain terms and facts when dealing with mechanisms.
You cannot derive a mechanism from the equation and when you combine the steps
of a mechanism, you end up with the reaction. The molecularity of a step tells how
many molecules are involved (most involve two (2) molecules so they are
bimolecular). An intermediate product is a molecule formed in one step and then
used in another. One of the most important concepts to keep in mind is that the
steps are not equally important. To speed up the reaction, you must speed up the
slowest step (also called the rate-determining step).
rate law of slow step=rate law of reaction
When determining the rate of a step, simply make the exponent of the reactant's
concentration in the rate law the same as the coefficient of the reactant in the step.
Example problem: Find the slow step of the following reaction mechanism

A catalyst is a substance added to a reaction that comes out of the reaction


unchanged. As mentioned earlier, catalysts help lower the activation energy as
shown in the following graph. They do this by changing the reaction mechanism.

The following is an example of how this can be done.

Practice Kinetic Quantitative Problem:

Kinetic quantitative solution.


Practice Kinetic Qualitative Problems:

Kinetic qualitative solution.

Equilibrium
In stoichiometry calculations, we assume that reactions run to completion.
However, when a chemical reaction is carried out in a closed vessel, the system
achieves equilibrium. Equilibrium occurs when there is a constant ratio between
the concentration of the reactants and the products. Different reactions have
different equilibria. Some may appear to be completely products, however, all
reactions have some reactants present. A reaction may look "finished" when
equilibrium is reached, but actually the forward and reverse reactions continue to

happen at the same rate. A reverse reaction is when the written reaction goes from
right to left instead of the forward reaction which proceeds from left to right. This
is why equilibrium is also referred to as "steady state".
It is possible to write an equilibrium expression for a reaction. This can be
expressed by concentrations of the products divided by the concentration of the
reactants with the coefficients of each equation acting as exponents. It is important
to remember that only species in either the gas or aqueous phases are included in
this expression because the concentrations for liquids and solids cannot change.
For the reaction:
jA + kB --> lC + mD
the equilibrium expression is:

Where:
K is the equilibrium constant
[A], [B], etc. are the molar concentrations of A, B, etc.
l, m, etc. are the coefficients of the balanced reaction
For every reaction at a specific temperature, there is only one value for K. A large
value of K implies that there are more products than reactants and that the
equilibrium lies to the right. A small K value implies there are more reactants than
products and the reaction lies to the left. It is critical to remember that the only
thing that changes K is changing temperature.
For reactions in the gas phase, equilibrium positions can also be expressed in terms
of pressure. Kp, the equilibrium constant in terms of pressure, is related to K by the
equation:
Kp=K(RT)n
Where:
n is the sum of the coefficients of the gaseous products minus the sum of the
coefficients of the gaseous reactants.
R is the gas law constant (see the gas laws page)
T is the temperature in kelvins
The reaction quotient, Q, is an expression which deals with initial values instead of
the equilibrium value that K deals with. We compare Qand K to determine which
direction the reaction will proceed to obtain equilibrium. If Q is greater than K, the
system will shift to the left. IfQ is less than K, the system will shift to the right.
If Q is equal to K than the system is already at equilibrium so it will not shift in
either direction.
To find the concentrations which characterize an equilibrium, it is best to proceed
through the "start, change, equilibrium" process. This implies starting with the
initial concentrations, determining the change, and using K to find the equilibrium
concentrations.
Example "Start, change, equilibrium" problem:
C2H6(g) + Cl2(g) <---> C2H5Cl(s) + HCl(g)

If we had six (6) mols of C2H6(g) and six (6) mols of Cl2(g) originally in a three (3)
liter container at 10 C, determine the equilibrium concentration. K for this
reaction at 10 C is 0.10.
Answer:
we must first convert our values to molarity:

6 mols

=2M

3L

fill in the "start, change, equilibrium" chart:


C2H6 (g)
+ Cl2 (g)
C2H2Cl (s) +
HCl (g)
Start:
2M
2M
-0M
Change:
-x
-x
-+x
Equilibrium:
2-x
2-x
-x
now substitute what we know into the equilibrium constant
expression and solve for x:
[HCL]
(x)
x
K =
= 0.10 =
=
[C2H2][Cl2]
(2-x)(2-x)
4 - 4x + x2
.40 - .40x + .1x2 = x
.10x2 - 1.4x + .4 = 0
.02573 mol
1.4
1.96 - .16
x =
=
.07719 mol
1.25 atm
PCl2 = .4167 atm

Le Chatelier's principle allows us to predict the effects of changes in temperature,


pressure, and concentration on a system at equilibrium. It states that if a system at
equilibrium experiences a change, the system will shift its equilibrium to try to
compensate for the change.
changing the concentration (only with gases or aqueous solutions):
If you lower the concentration or remove some of a species, the system will

shift to produce more of that species. On the other hand, if you increase the
concentration or add some of a species, the system will shift to produce less
of that species. For example, in the equation:
H2+ I2 <--->2HI
If we remove some of the H2, the system will shift towards the left (the
reverse reaction will happen the most) to produce more H 2.
changing the volume/pressure (only gases):
Increasing the volume has the same effect as decreasing the pressure and
vice versa so we are only going to talk about changing the pressure. When
you increase the pressure, the system will shift so the least number of gas
molecules are formed because the more gas molecules there are, the more
collisions there are. These collisions and the presence of gas molecules are
what cause the pressure to increase. Likewise, when you decrease the
pressure, the system will shift so the highest number of gas molecules are
produced. For example, in the equation:
N2 (g) + 3H2 (g) <---> 2NH3 (g)
if the pressure is increased, the system will shift to the right because fewer
gas molecules are produced in the forward reaction than in the reverse
reaction.
changing temperature:
For every reaction which can go forwards and backwards, one direction is
endothermic and the other is exothermic. A reaction is endothermic if it
takes heat from its surroundings. On the other hand, a reaction is exothermic
if it gives heat to the surroundings. If you increase the temperature, then the
endothermic reaction will be favored because that will take in some of the
excess heat. If you decrease the temperature, the exothermic reaction will be
favored because it will produce the heat that was lost. For example, in the
equation:
PCl3(g) + Cl2(g) <----> PCl5(g) + energy
if the temperature was increased, the system would shift to the left and the
reverse reaction would happen more because that would use some of the
extra energy.
using a catalyst:
A catalyst increases the speed in which a reaction takes place, however it
never has any effect on the equilibrium.
Solubility is how much material dissolves in a solution, usually given in g/L. Ksp is
the equilibrium expression related to ion concentration in a solution. For example,
in the equation:
AgBr (s) --> Ag+ (aq) + Br- (aq)
Ksp=[Ag+][Br-]
Adding common ions, acids, or bases affects the solubility of a substance. Taking
the above reaction as an example, if you add AgNO 3, the [Ag+] would increase
causing the system to shift to the left and therefore causing the solubility to

decrease. If you add Pb(NO3)2, the Pb2+and the Br- would form a precipitate which
would decrease the [Br-] and cause the system to shift to the right and therefore
increase the solubility. Look at the following reaction:
BaCO3(s) --> Ba2+ (aq) + CO32-(aq)
If you add HNO3, the weak acid HF would form which will lower the
F- concentration and cause the system to shift to the right and therefore increase the
solubility. You should watch out for the formation of a precipitate or the formation
of a weak acid when dealing with solubility reactions.
Example Ksp Problem:
0.100 L of 0.003 M Pb(NO3)2 is added to 0.400 L of 0.005 M Na2SO4. Will
PbSO4 precipitate? Ksp=1.6x10-8

Practice Equilibrium Problem:


At a certain temperature, a 1.00L flask initially contained 0.298 mol PCl 3(g) and
0.00870 mol PCl5(g). After reaching equilibrium, 0.00200 mol Cl 2(g) was found in
the flask. PCl5 decomposes according to the equation:
PCl5(g) <---> PCl3(g) + Cl2(g)
Calculate the equilibrium concentrations of the three molecules and the value of K.
equilibrium solution.
Practice Ksp Problem:
Ksp for SrSO4=7.6x10-7. Ksp for SrF2 =7.9x10-10.
a) What is the molar solubility of SrSO4 in pure water?
b) What is the molar solubility of SrF2 in pure water?
c) Sr(NO3)2(aq) is added to 1.0 L of solution containing 0.020 mol F - and 0.10 mol
SO42- with constant volume. 1: which salt precipitates first? 2: What is [Sr 2+] in
solution when precipitate forms?
Ksp solution.

Redox Reactions
Redox reactions, or oxidation-reduction reactions, have a number of similarities to
acid-base reactions. Fundamentally, redox reactions are a family of reactions that
are concerned with the transfer of electrons between species. Like acid-base
reactions, redox reactions are a matched set -- you don't have an oxidation reaction
without a reduction reaction happening at the same time. Oxidation refers to the
loss ofelectrons, while reduction refers to the gain of electrons. Each reaction by
itself is called a "half-reaction", simply because we need two (2) half-reactions to
form a whole reaction. In notating redox reactions, chemists typically write out the
electrons explicitly:
Cu (s) ----> Cu2+ + 2 e-

This half-reaction says that we have solid copper (with no charge) being oxidized
(losing electrons) to form a copper ion with a plus 2 charge. Notice that, like
the stoichiometry notation, we have a "balance" between both sides of the reaction.
We have one (1) copper atom on both sides, and the charges balance as well. The
symbol "e-" represents a free electron with a negative charge that can now go out
and reduce some other species, such as in the half-reaction:
2 Ag+ (aq) + 2 e- ------> 2 Ag (s)
Here, two silver ions (silver with a positive charge) are being reduced through the
addition of two (2) electrons to form solid silver. The abbreviations "aq" and "s"
mean aqueous and solid, respectively. We can now combine the two (2) halfreactions to form a redox equation:

We can also discuss the individual components of these reactions as follows. If a


chemical causes another substance to be oxidized, we call it the oxidizing agent. In
the equation above, Ag+ is the oxidizing agent, because it causes Cu(s) to lose
electrons. Oxidants get reduced in the process by a reducing agent. Cu(s) is,
naturally, the reducing agent in this case, as it causes Ag + to gain electrons.
As a summary, here are the steps to follow to balance a redox equation
in acidic medium (add the starred step in a basic medium):
1. Divide the equation into an oxidation half-reaction and a reduction halfreaction
2. Balance these
o Balance the elements other than H and O
o Balance the O by adding H2O
o Balance the H by adding H+
o Balance the charge by adding e3. Multiply each half-reaction by an integer such that the number of e - lost in
one equals the number gained in the other
4. Combine the half-reactions and cancel
5. **Add OH- to each side until all H+ is gone and then cancel again**
In considering redox reactions, you must have some sense of the oxidation number
(ON) of the compound. The oxidation number is defined as the effective charge on
an atom in a compound, calculated according to a prescribed set of rules. An
increase in oxidation number corresponds to oxidation, and a decrease to reduction.
The oxidation number of a compound has some analogy to the pH and pK
measurements found in acids and bases -- the oxidation number suggests the
strength or tendency of the compound to be oxidized or reduced, to serve as an
oxidizing agent or reducing agent. The rules are shown below. Go through them in
the order given until you have an oxidation number assigned.

1. For atoms in their elemental form, the oxidation number is 0

2.
3.
4.
5.

For ions, the oxidation number is equal to their charge


For single hydrogen, the number is usually +1 but in some cases it is -1
For oxygen, the number is usually -2
The sum of the oxidation number (ONs) of all the atoms in the molecule or
ion is equal to its total charge.
As a side note, the term "oxidation", with its obvious root from the word "oxygen",
assumes that oxygen has an oxidation number of -2. Using this as a benchmark,
oxidation numbers were assigned to all other elements. For example, if we look at
H2O, and assign the value of -2 to the oxygen atom, the hydrogens must each have
an oxidation number of +1 by default, since water is a neutral molecule. As an
example, what is the oxidation number of sulfur in sulfur dioxide (SO 2)? Given
that each oxygen atom has a -2 charge, and knowing that the molecule is neutral,
the oxidation number for sulfur must be +4. What about for a sulfate ion (SO4 with
a total charge of -2)? Again, the charge of all the oxygen atoms is 4 x -2 = -8.
Sulfur must then have an oxidation number of +6, since +6 + (-8) = -2, the total
charge on the ion. Since the sulfur in sulfate has a higher oxidation number than in
sulfur dioxide, it is said to be more highly oxidized.
Working with redox reactions is fundamentally a bookkeeping issue. You need to
be able to account for all of the electrons as they transfer from one species to
another. There are a number of rules and tricks for balancing redox reactions, but
basically they all boil down to dealing with each of the two half-reactions
individually. Consider for example the reaction of aluminum metal to form alumina
(Al2O3). The unbalanced reaction is as follows:
Looking at each half reaction separately:
This reaction shows aluminum metal being oxidized to form an aluminum ion with
a +3 charge. The half-reaction below shows oxygen being reduced to form two (2)
oxygen ions, each with a charge of -2.
If we combine those two (2) half-reactions, we must make the number of electrons
equal on both sides. The number 12 is a common multiple of three (3) and four (4),
so we multiply the aluminum reaction by four (4) and the oxygen reaction by three
(3) to get 12 electrons on both sides. Now, simply combine the reactions. Notice
that we have 12 electrons on both sides, which cancel out. The final step is to
combine the aluminum and oxygen ions on the right side using a cross multiply
technique:
Taking care of the number of atoms, you should end up with:

One of the more useful calculations in redox reactions is the Nernst Equation.
This equation allows us to calculate the electric potential of a redox reaction in
"non-standard" situations. There exist tables of how much voltage, or potential, a
reaction is capable of producing or consuming. These tables, known as standard
potential tables, are created by measuring potential at "standard" conditions, with a
pressure of 1 bar (1 atm), a temperature of 298 K (or 25 C, or room
temperature) and with a concentration of 1.0 M for each of the products. This
standard potential, or E, can be corrected by a factor that includes the actual
temperature of the reaction, the number of moles of electrons being transferred,
and the concentrations of the redox reactants and products. The equation is:

Perhaps the best way of understanding this equation is through an example.


Suppose we have this reaction:
Fe(s) + Cd2+(aq) ------> Fe2+(aq) + Cd(s)

In this reaction iron (Fe) is being oxidized to iron(II) ion, while the cadmium ion
(Cd2+) in aqueous solution is being reduced to cadmium solid. The question is: how
does this reaction behave in "non-standard" conditions?
The first thing to answer is how does it behave in standard conditions? We need to
look at the standard potential for each half-reaction, then combine them to get a net
potential for the reaction. The two (2) half-reactions are:
Fe2+ (aq) + 2 e- ------> Fe (s), E = -0.44 V
Cd2+ (aq) +2 e- ------> Cd (s), E = -0.40 V
Notice that both half-reactions are shown as reductions -- the species gains
electrons, and is changed to a new form. But in the complete reaction above, Fe is
oxidized, so the half-reaction needs to be reversed. Quite simply, the potential for
the half-reaction of iron is now 0.44 V. To get the potential for the entire reaction,
we add up the two (2) half-reactions to get 0.04 V for the standard potential.
The question now is: what is the total potential (in volts) for a nonstandard
reaction? Suppose again that we have the same reaction, except now we have
0.0100 M Fe2+ instead of the standard 1.0 M. We need to use the Nernst equation to
help us calculate that value. If you go to the Redox Half-Reaction Calculator, you
should notice that the reaction is selected and the appropriate values are entered
into the boxes. Since we don't have any species "B" or "D", we have entered zero
for their concentrations. The concentration of the solid Fe is 1.0 M (actually,
concentrations of solids and solvents (liquids) don't enter into the Nernst equation,
but we set them to 1.0 so that the mathematics works out). If you click on the
"Evaluate" button, you should learn that the standard potential is -0.44 V, while the
nonstandard potential is -0.5 V. If you scroll down on the calculator, you can enter
0.5 as the first half-reaction. We again change the sign since we're actually
reversing the Fe reaction
Using the calculator again, we calculate the nonstandard potential of the Cd
reaction. Suppose we now have a concentration of Cd 2+ of 0.005 M, what is its
potential? The calculator should return a standard potential of -0.4 V and a
nonstandard potential of -0.47 V. Place this value in the box for the second halfreaction, then click on "Evaluate". You should learn that the net nonstandard
potential is 0.03 V, slightly less than the value of the net standard potential. Since
this value is less than the net standard potential of 0.04 V, there is less of a
tendency for this reaction to transfer electrons from reactants to products. In other
words, less iron will be oxidized and cadmium will be reduced than at standard
conditions.
Test your use of the redox calculator by calculating the net standard potential for
this reaction:
2 Ag+ (aq, 0.80 M) + Hg (l)------> 2 Ag (s) + Hg2+ (aq, 0.0010M)
Answer: 0.025 V. Since the value is positive, the reaction will work to form the
products indicated. Negative values of the potential indicate that the reaction tends
to stay as reactants and not form the products. The net standard potential for this
reaction is 0.01 V -- since the nonstandard potential is higher, this reaction will
form products than the standard reaction.

Free energy and the standard potential can also be related through the following
equation:
Where:
G = change in free energy
n = number of moles
If a reaction is spontaneous, it will have a positive Eo, and negative G, and a large
K value (where K is the equilibrium constant-this is discussed more in the kinetics
section).
The energy released in any spontaneous redox reaction can be used to perform
electrical work using an electrochemical cell (a device where electron transfer is
forced to take an external pathway instead of going directly between the reactants.
Think of the reaction between zinc and copper. Instead of placing a piece of zinc
directly into a solution containing copper, we can form a cell where solid pieces of
zinc and copper are placed in two different solutions such as sodium nitrate. The
two solids are called electrodes. The anode is the electrode where oxidation occurs
and mass is lost where as the cathode is the electrode where reduction occurs and
mass is gained. The two electrodes are connected by a circuit and the two (2)
solutions are connected by a "salt bridge" which allows ions to pass through.
Theanions are the negative ions and they move towards the anode. The cations are
the positive ions and they move towards the cathode.
The following is a diagram of an electrochemical cell with zinc and copper acting
as the electrodes.

An external electric current hooked up to an electrochemical cell will make the


electrons go backwards. This process is called electrolysis. This is used, for
example, to make something gold plated. You would put the copper in a solution
with gold and add a current which causes the gold ions to bond to the copper and
therefore coating the copper. The time, current, and electrons needed determine
how much "coating" occurs. The key to solving electolysis problems is learning
how to convert between the units. Useful information: 1 A=1 C/sec; 96,500

coulombs can produce one (1) mole of e-; the electrons needed is determined by the
charge of the ion involved
Example Problem: If you are trying to coat a strip with aluminum and you have a
current of 10.0 A (amperes) running for one hour, what mass of Al is formed?
The solution of this problem involves a lengthly unit conversion process:

Practice Redox Problem: balance the following redox reaction in acidic solution:
S(s) + NO3-(aq) --> SO2(g) + NO(g)
The redox solution is available.
Practice Electrolysis Problem: It takes 2.30 min using a current of 2.00 A to plate
out all of the silver from 0.250 L of a solution containing Ag +. What was the
original concentration of Ag+ in solution?
The electrolysis solution is available.
Nuclear Chemistry

Nuclear chemistry deals with the nuclei of atoms breaking


apart. Atoms are continually undergoing decay. When studying
nuclear chemistry, there is a typical format used to represent
specific isotopes.

Nuclear equations are typically written in the format shown below.


There are 5 different types of radioactive decay.
1. Alpha decay follows the form:

Where A is the parent isotope (the atom being broken apart) B is


the daughter isotope or the isotope formed. When an element is broken
down in alpha decay it looses two neutrons and two (2) protons. This means

that the name of the element will change as well, moving back two (2)
places on the periodic table. Alpha decay is not very penetrating because the
He atoms capture electrons before traveling very far. However it is very
damaging because the alpha particles can knock atoms off of molecules.
Alpha decay is the most common in elements with an atomic number greater
than 83.
2. Beta negative decay follows the form:

The beta emission increases the atomic number by one (1) by adding one (1)
proton. At the same time, one (1) neutron is lost so the mass of the daughter
isotope is the same as the parent isotope. Beta negative decay is more
penetrating than alpha decay because the particles are smaller, but less
penetrating than gamma decay. Beta electrons can penetrate through about
one (1) cm of flesh before they are brought to a halt because of electrostatic
forces. Beta decay is most common in elements with a high neutron to
proton ratio.
3. Gamma decay follows the form:

In gamma emission, neither the atomic number or the mass number is


changed. A high energy gamma ray is given off when the parent isotope falls
into a lower energy state. Gamma radiation is the most penetrating of all.
These photons can pass through the body and cause damage by ionizing all
the molecules in their way.
4. Positron emission (also called Beta positive decay) follows
the form:

In this reaction a positron is emitted. A positron is exactly like an electron in


mass and charge force except with a positive charge. It is formed when a

proton breaks into a neutron with mass and neutral charge and this positron
with no mass and the positive charge. Positron emission is most common in
lighter elements with a low neutron to proton ratio.
5. Electron capture follows the form:

In this reaction a nucleus captures one (1) of its own atom's inner shell
electrons which reduces the atomic number by one. This captured electron
joins with a proton in the nucleus to form a neutron. Electron capture is
common in larger elements with a low neutron to proton ratio.
All elements with an atomic number over 83 are considered radioactive.
Radioactivity can be measured using a geiger counter, a cylinder containing a lowpressure gas and two (2) electrodes. Radiation ionizes the atoms in the cylinder and
allows current to flow between the electrodes.
All radioactive elements disintegrate according to their specific half life. The half
life of a radioactive substance is the time required for half of the initial number of
nuclei to disintegrate. The decay rate expresses the speed at which a substance
disintegrates. The following equation represents the relationship between the
number of nuclei remaining, N, the number of nuclei initially present, N 0, the rate
of decay, k, and the amount of time, t.

The relationship between the half-life of a radioactive substance and k, the rate at
which it decays can also be found.

By using these equations, it is possible to calculate how much of a nuclear


substance will be left after a certain time and how much of a substance originally
existed. A common example is isotopic dating in which the ages of archeological
artifacts are determined by measuring the activity of the isotopes.

Practice Problems
1. The half life of a specific element was calculated to be 5200 yr.
Calculate the decay constant (k). Solution.

2. If a watch contains a radioactive substance with a decay rate of 1.40*10 -2 and


after 50 years only 25 mg remain, calculate the amount originally
present. Solution.
3. A rock contains 0.257 mg of lead-206 for every mg of uranium-238. The halflife decay for uranium to turn into lead is 4.5x109 yr. How old is the
rock? Solution.
Balancing Equations Using Matrices

NOTE: this application requires that you have a calculator


capable of doing MATRICES. Most if not all graphical calculators
have this capability. This reading uses the Texas Instrument TI-82
Graphical Calculator as an example.
Early on in your chemistry studies, you will have ample opportunity to balance
equations! This is a fundamental skill in chemistry, as you might have noticed from
the short reading in stoichiometry! Balancing equations means writing chemical
equations such that the amount of stuff you start with in the reaction equals the
amount of stuff you end up with as a product. In other words, if I start baking bread
with 10 pounds of flour, I should end up with 10 pounds of bread, unless some is
lost onto the floor or if some of it goes up in smoke!
A simple example goes a long way. We can form water by combing hydrogen gas
(H2) and oxygen (O2) in the presence of electricity. The reaction looks like this:
H2 + O2 ---> H2O
If you do some of the gram molecular weight calculations you will find this:
2 grams of hydrogen + 32 grams of oxygen = 18 grams of water
What this says is that you start with 34 grams of stuff and end up with 18 grams of
stuff. You've lost 16 grams of stuff, and in this reaction that just doesn't happen!
Where did the 16 grams go?

They're not lost, we just haven't balanced the equation! You might have also
noticed that there are two oxygens on the left and only one on the right! We need to
get things in the correct proportions for this reaction to be balanced. The balanced
reaction looks like this:
2 H2 + O2 ---> 2 H2O
This says that we need two hydrogen molecules to combine with one oxygen
molecule to form two new water molecules. If we do the math:
(2 x 2 grams of hydrogen) + 32 grams of oxygen = (2 x 18 grams of water)
we now have 36 grams of stuff on the left and 36 grams on the right. We also now
have 4 hydrogens on the left, four hydrogens on the right, two oxygens on the left,
and two oxygens on the right. We can say that this equation is mass balanced. In
your studies of chemistry, you will also need to be concerned with charge
balancing, but we'll let your profs help you with that!
Balancing equations is an art, but if you have a calculator that can handle what is
known as a "matrix", you have a foolproof way of balancing equations! A matrix is
a group of numbers, arranged in rows and columns, like this:

This is called a "2 by 2" or "2 x 2" matrix, because it has two rows (going across)
and two columns (going down). In this application, you will have to do three
matrix operations:
1. Multiply two matrices
2. Find the determinant of a matrix
3. Find the inverse of a matrix
Fortunately, graphing calculators make this particularly easy! To help you
understand a little of what you are doing, let's explain finding the determinant.
The determinant is a single number generated by cross-multiplying the terms in the
matrix. You must have a square matrix (n X n) to be able to find the determinant.
The equation for finding the determinant is:

The example below the equation shows a sample calculation for a 2 x 2 matrix.
Notice that you are cross multiplying the opposite terms, then subtracting out the
other set of opposite set of multiplied terms. Pretty easy.
Here is how this is done on the TI-82 Graphical Calculator. These instructions are
SPECIFIC to the TI-82:
1. Turn the calculator on (yep, common sense, but want to
make sure that's done!)
2. Hit the "MATRIX" button
3. Use right arrow key to scroll over to "EDIT"
4. Type "1" for Matrix A
5. Type "2" for number of rows, the ENTER
6. Type "2" for number of columns, then ENTER
7. Type each of the numbers, following each with ENTER: 8ENTER-3-ENTER-4-ENTER-2-ENTER
8. Type the blue "2nd" button then "QUIT" (above the MODE
button)
9. Type MATRIX, then scroll to MATH
10.
Hit "1" for "det"
11.
Hit MATRIX then "1". You should see "det [A]" in the
window.
12.
Hit the ENTER key, you should see the result "4"
Now we are ready to talk about balancing equations. Let's choose a simple
reaction:
a Cr + b O2 ---> c Cr2O3
We have two different elements, Cr and O, so we will need two different equations.
We are trying to calculate the values of a, b, and c, the coefficients of the reaction.
The two equations look like this:
Cr: 1a + 0b = 2c
O: 0a + 2b = 3 c

The "1a" means that there is one Cr behind the "a" coefficient, zero Cr's behind the
"b" coefficent, and 2 Cr's behind the c coefficient. We use the same technique for
oxygen. We now have two matrices (called Matrix A and Matrix B):

To obtain the values of a, b, and c, do these steps:


To calculate a and b, multiply the inverse of Matrix A times
Matrix B times the determinant of Matrix A: [A]-1 x [B] x
det[A]
To calculate c, calculate the determinant of Matrix A.
Here is how to do the first step:
1. Enter Matrix A as a 2x2 matrix, using the technique
described above
2. Enter Matrix B as a 2x1 matrix, using the same technique
3. Once this is done, you can hit "2nd" then "QUIT" to get a
blank screen.
4. Call up Matrix A by typing MATRIX 1 (you should see [A])
5. Hit "x-1" to set up the inverse
6. Hit the "x" for multiply.
7. Hit MATRIX 2 to call up Matrix B
8. Hit the "x" for multiply
9. Hit MATRIX, scroll to MATH, then 1 to do a determinant
10.
Hit MATRIX 1 to call up Matrix A. You should now have:
-1
[A] * [B] *det [A]
11.
Hit the ENTER key to get your result of [[ 4 ] [3 ] ]. The
coefficient a is equal to 4, and the coefficent b is equal to 3!
To do the second part, calculating c:
1. Hit MATRIX, scroll to MATH, select 1 for the determinant
2. Hit MATRIX 1 to call up Matrix A, hit the ENTER key to get the
result for c as 2
The balanced equation is now:
4 Cr + 3 O2 ---> 2 Cr2O3

Try It Out

1. Balance:
MgO + Fe ---> Fe2O3 + Mg
Check your work.
2. Balance:
Cu2S + O2---> Cu + SO2
Check your work.
3. Balance:
FeCl2 + Na3(PO4)---> Fe3(PO4)2 + NaCl
Check your work.

Data Fitting: Linear Least Squares


Collecting data and observing chemical processes and reactions are important
elements in chemistry. However, if you notice in your chemistry text, laws are
usually represented, mathematically, not by data. To compare data to known laws,
it is important to represent the data mathematically. For example, when dealing
with kinetics we are often concerned with the concentration of a substance.
Measuring the concentration at several different times can yield a set of data which
we need to represent with an equation rather than as separate points. To do this we
use a process called line or data fitting, and in this reading we will explain one of
these methods, a process called linear least squares fitting. This process gives a
linear fit in the slope-intercept form (y = mx + b). You can explore the behavior of
linear least squares regression by using the Linear Least Squares Regression
calculator.
For a general linear equation, y = mx + b, it is assumed that the errors in the yvalues are substantially greater than the errors in the x-values. The vertical
deviation can be calculated using this formula:
If the square of the deviations is minimized, the "best line" can be calculated:
By the use of matrix algebra (determinants), the values of the slope (m) and the yintercept (b) can be calculated.
A short review of determinants:

Now, the values for m, b, and the deviation D can be determined by these matrices:

The regression form which is available submits the entered data to a perl script,
which calculates the above matrices and graphs the data with the regression line.
Notice that this theory assumes the data are in a linear form. If data for a curve is
passed to this program, it still calculates a straight line. Deciding which type of
regression fits best is the user's responsibility. If data is a curve, there are ways to
modify the data in order to fit a linear line. Often times, taking the natural
logarithm or square root of the data will suffice.

Newton-Raphson Method
If you've ever tried to find a root of a complicated function algebraically, you may
have had some difficulty. Using some basic concepts of calculus, we have ways of
numerically evaluating roots of complicated functions. Commonly, we use the
Newton-Raphson method. This iterative process follows a set guideline to
approximate one root, considering the function, its derivative, and an initial xvalue.
You may remember from algebra that a root of a function is a zero of the function.
This means that at the "root" the function equals zero. We can find these roots of a
simple function such as: f(x) = x2-4 simply by setting the function to zero, and
solving:
f(x) = x2-4 = 0
(x+2)(x-2) = 0
x = 2 or x = -2
The Newton-Raphson method uses an iterative process to approach one root of a
function. The specific root that the process locates depends on the initial, arbitrarily
chosen x-value.

Here, xn is the current known x-value, f(xn) represents the value of the function at
xn, and f'(xn) is the derivative (slope) at xn. xn+1represents the next x-value that you
are trying to find. Essentially, f'(x), the derivative represents f(x)/dx (dx = delta-x).
Therefore, the term f(x)/f'(x) represents a value of dx.
The more iterations that are run, the closer dx will be to zero (0). To see how this
works, we will perform the Newton-Raphson method on the function that we
investigated earlier, f(x) = x2-4. Below are listed the values that we need to know in
order to complete the process.

Theoretically, we could execute an infinite number of iterations to find a perfect


representation for the root of our function. However, this is a numerical method
that we use to lessen the burden of finding the root, so we do not want to do this.
Therefore we will assume that the process has worked accurately when our delta-x
becomes less than 0.1. This value of precision should be specific to each situation.
A much more, or a much less, precise value may be appropriate when using the
Newton-Raphson method in class. The table below shows the execution of the
process.
n

xn

f(xn)

f'(xn)

xn+1

dx

x0 = 6

f(x0 = 32)

f'(x0 = 12)

x1 = 3.33

x1 = 3.33

f(x1) = 7.09

f'(x1) = 6.66

x2 = 2.27

dx = 1.06

x2 = 2.27

f(x2) = 1.15

f'(x2) = 4.54

x3 = 2.01

dx = .26

x3 = 2.01

f(x3) = 0.04

f'(x3) = 4.02

x4 = 2.00

dx = 0.01

Thus, using an initial x-value of six (6) we find one root of the equation f(x) = x 2-4
is x=2. If we were to pick a different inital x-value, we may find the same root, or
we may find the other one, x=-2.
A graphical representation can also be very helpful. Below, you see the same
function f(x) = x2-4 (shown in blue). The process here is the same as above. In the
first iteration, the red line is tangent to the curve at x 0. The slope of the tangent is
the derivative at the point of tangency, and for the first iteration is equal to 12.
Dividing the value of the function at the initial x (f(6)=32) by the slope of the
tangent (12), we find that the delta-x is equal to 2.67. Subtracting this from six (6)
we find that the new x-value is equal to 3.33. Another way of considering this is to
find the root of this tangent line. The new x-value (x n+1) will be equal to the root of
the tangent to the function at the current x-value (x n).

The Newton-Raphson method does not always work, however. It runs into
problems in several places. First, consider the above example. What would happen
if we chose an initial x-value of x=0? We would have a "division by zero" error,
and would not be able to proceed. You may also consider operating the process on
the function f(x) = x1/3, using an inital x-value of x=1. Do the x-values converge?
Does the delta-x decrease toward zero (0)?
So, how does this relate to chemistry? Consider the van der Waals equation found
in the Gas Laws section of this text. Assuming that we have a set number of moles
of a set gas, not under ideal conditions, we can use the Newton-Raphson method to
solve for one of the three variables (temperature, pressure, or volume), based on
the other two. To do this, we need to use the van der Waals equation, and the
derivative of this equation, both seen below.

As you can see, the Van der Waals equation is quite complex. It is not possible to
solve it algebraically, so a numerical method must be used. The Newton-Raphson
Method is the easiest and most dependable way to solve equations like this, even
though the equation and its derivative seem quite intimidating.
Depending on the conditions under which you are attempting to solve this
equation, several of the variables may be changing. So, it may be necessary to use
partial derivatives. For the purposes of this example, we are assuming that
pressure, temperature, and volume are the only things changing, and that these
values are all functions of time. This avoids the use of a partial derivative; we

simply differentiate all variables with respect to time, as shown above. Some
algebraic manipulation of the equation and/or its derivative may be needed
depending on the specific problem to be solved. It is assumed that all of the
variables but one are specified; that variable is used in the expression for "x n+1" that
Newton's method uses. Performing Newton's method on this equation successfully
would give a value of that variable which gives a solution when the other variables
are held constant at the values you specified.
Integration Methods in Chemistry

Integration

Integration involves finding a function based on its derivative (slope). This means
that if the slope of a function is known, the function itself can be found. Sometimes
this is done symbolically, with equations, but in chemistry it is usually done n
umerically. If we can find the amount of change going on during a little bit of time
at a lot of different times, these values can be summed, giving the total change over
that time. Then that change is added to a known starting value to give an approxim
ate ending value. "Integration" refers to the process of finding and adding up those
small changes.
Integration can be thought of as finding the area under a curve. If that curve is a
derivative, then the area under it for a given interval of x values is the same as the
change in the original function over that interval. This process can also be used to
solve differential equations, equations which represent the derivative of another
function. If a starting value is specified and the differential equation is integrated
over a given interval, that value is added or subtracted from the starting value to
find the ending value.
In chemistry, this process is most often used when we are concerned with the
course of a reaction over time. For example, it is possible to figure out how quickly
each species in a reaction is changing if the reaction mechanism (the exact way it
happe ns) and some simple data are known. This representation of how quickly the
concentrations are changing is the same as a slope, or derivative. Integration allows
us to find the actual change over time and not just how quickly the change is
happening. Fo r example, given the following reaction,

We can find how quickly each concentration is changing over time. This is
symbolized by

Now, integrating allows us to find the way the concentrations change, instead of
the rate of change.

Numerical Methods

Integration can be done with equations, but chemists are usually more interested in
real data, meaning numbers, than a symbolic integration (which can be quite tricky
for some reactions). Numerical methods are used in these cases to approximate the
ch ange in a concentration over time when the rate of change is known at several
different times. Usually the rate of change is known from a reaction mechanism
and some data.
Two major forms of numerical integration are used: Euler's method and RungeKutta methods. In this reading, we will examine Euler's method and briefly see a
Runge-Kutta example.
Euler's Method

The basic idea behind Euler's method is to approximate a curve with a series of
straight lines. The rate of change is the same as the slope of a line drawn tangent to
the curve at that time. A series of these tangent lines can be used to "follow" th e
function over time. An example is shown below.

If f'(t) is the change over time at a given time, and a is the time when the tangent is
being drawn, then the equation of a tangent line at any time is f'(t)*(t-a)+f(a).
Using the same idea, we can see that the following equations represent the change
in y and time over a given space of time. Triangle t is read "delta t", which
represents the step size being used. The subscripts represent the number of steps
that hav e been taken so far. Using this process, Euler's method "steps" along the
curve.

Integration Calculator based on Euler's


Method
Runge-Kutta Methods

The Runge-Kutta methods use multiple different approximations to the next value
of y and average them. The equations for the process with two approximations
(Runge-Kutta 2 method) is shown below.