Chemical Nomenclature
+
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+
aluminum (Al3+)
oxide (O2)
chromium(III) (Cr3+)
peroxide (O22)
iron(III) (Fe3+)
sulfate (SO42)
sulfide (S2)
sulfite (SO32)
3nitride (N3)
phosphate (PO43)
phosphide (P3)
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
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
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
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
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
Atomic Structure
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
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 threedimensional 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 m1
c = speed of light, 3.00 X 108 m/s
h = Planck's constant, 6.63 X 10 34 Js
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
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 (Js)
is frequency (s1)
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 (s1)
= 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
2.18E18
6.63E34
3
2
2.42222E19
5.45E19
3.02778E19
4.56678E+14
656.92
4
2
1.363E19
5.45E19
4.09E19
6.165E+14
486.61
5
2
8.72E20
5.45E19
4.58E19
6.905E+14
434.47
Subshell designation
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
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.
Number of Orbitals
Maximum Number
of Electrons
10
14
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 hydrogenlike 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 hydrogenlike
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
electronelectron 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 (dblock) elements and the inner transition (fblock) elements. We will not concern
ourselves with these in this review.
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.
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
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:
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.
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.
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)
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. Doubleheaded 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 doubleheaded arrow will be placed between
these structures. (Do not forget your brackets and to put your charge on the outside
of the brackets)
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.
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!
4.
5.
6.
7.
Ammonia (NH3)
Hydrogen fluoride (HF)
Ozone (O3)
Xenon difluoride (XeF2)
Chemical Reactions
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 shorthand 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 AcidBase Chemistry contain additional
background reading, example problems, and information on the topics covered in this unit.
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.
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 oxygencontaining 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 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.
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
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
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
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
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:
4(16.00)
oxygen:
64.00
=
98.09
1 mol
x
1
56.3 grams O
= 1.41 moles
30.97 grams
1 mol
x
1
= 3.52 moles
16.00 grams
= 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.
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
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
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
1 mL
x
1L
1L
x
3.25 g
1000 g
x
1000 mL
= 0.09 mols / kg
1 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
AcidBase Chemistry
Water
pH
Definitions of Acids and Bases
Salts
AcidBase Character
AcidBase Titrations
Water
We typically talk about acidbase reactions in aqueousphase
environments  that is, in the presence of water. The most
fundamental acidbase 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] = 1.00x1014
Base
Salt pH
strong
strong
pH = 7
weak
strong
pH > 7
strong
weak
pH < 7
weak
weak
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.
AcidBase Character
For a molecule with a HX 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
XOH bond (also called an oxoacid) to be an acid, the hydrogen
must again ionize to form H+. To be a base, the OH 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:
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 1.8x105.
Answer:
Write an equilibrium equation for the acid:
HC2H3O2
H+ + C2H3O2 Write the equilibrium expression and the Ka value:
[H+][C2H3O2]
Ka =
= 1.8x105
[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
NH4+ + OH
Ka x Kb = Kw = 1.00x1014
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]
= 1.8x105
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 = 1.8x105 =
=
(.15  x)
.15
x = [OH] = 1.6x103 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 1.8x108 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 = 1.8x108 =
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(9.0x109) = 8.05
AcidBase Titrations
An acidbase 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 acidbase 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 theHendersonHasselbalch 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
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=1.8x105) 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
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*m2 = 1 kg*m1*s2
1 atmosphere (atm)
1.01325*105 Pa
1 atmosphere (atm)
760 torr
1 bar
105 Pa
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 mol1 K1.
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
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
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
Ptotal
.02573 mol
=
.07719 mol
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
b (dm3 mol1)
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
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
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/gC
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/gC.
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)
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:
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.
(The bond dissociation energy for NN is 163 kJ/mol; HH is 436
kJ/mol; NH 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 NH bonds so in 2 NH3
there are 6 NH bonds. In N2 there is 1 NN bond and in 3H2 there are 3 HH
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
gas
highest S
aqueous
high S
liquid
medium S
solid
lowest S
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 nonspontaneous in the reverse direction.
Enthalpy Change
Entropy Change
Spontaneous Reaction?
Exothermic (H < 0)
Exothermic (H < 0)
Enthalpy Practice Problem: Given the following bond dissociation energies (HC
is 413 kJ/mol; HH is 436 kJ/mol; C=C is 614 kJ/mol; CC is 348 kJ/mol),
determine H for the reaction:
H2C=CH2(g) + H2(g) > H3CCH3(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 temperaturethis 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 catalysthelps 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. Zeroorder 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=M1s1
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=AeEa/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/molK
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 popup 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 ratedetermining 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
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
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=1.6x108
Redox Reactions
Redox reactions, or oxidationreduction reactions, have a number of similarities to
acidbase reactions. Fundamentally, redox reactions are a family of reactions that
are concerned with the transfer of electrons between species. Like acidbase
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 "halfreaction", simply because we need two (2) halfreactions to
form a whole reaction. In notating redox reactions, chemists typically write out the
electrons explicitly:
Cu (s) > Cu2+ + 2 e
This halfreaction 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 halfreaction:
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:
2.
3.
4.
5.
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
"nonstandard" 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:
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 "nonstandard" conditions?
The first thing to answer is how does it behave in standard conditions? We need to
look at the standard potential for each halfreaction, then combine them to get a net
potential for the reaction. The two (2) halfreactions are:
Fe2+ (aq) + 2 e > Fe (s), E = 0.44 V
Cd2+ (aq) +2 e > Cd (s), E = 0.40 V
Notice that both halfreactions 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 halfreaction needs to be reversed. Quite simply, the potential for
the halfreaction of iron is now 0.44 V. To get the potential for the entire reaction,
we add up the two (2) halfreactions 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 HalfReaction 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 halfreaction. 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 constantthis 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.
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
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:
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 halflife of a radioactive substance and k, the rate at
which it decays can also be found.
Practice Problems
1. The half life of a specific element was calculated to be 5200 yr.
Calculate the decay constant (k). Solution.
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 crossmultiplying 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 TI82 Graphical Calculator. These instructions are
SPECIFIC to the TI82:
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: 8ENTER3ENTER4ENTER2ENTER
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):
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.
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.
NewtonRaphson 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
NewtonRaphson 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) = x24 simply by setting the function to zero, and
solving:
f(x) = x24 = 0
(x+2)(x2) = 0
x = 2 or x = 2
The NewtonRaphson 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 xvalue.
Here, xn is the current known xvalue, f(xn) represents the value of the function at
xn, and f'(xn) is the derivative (slope) at xn. xn+1represents the next xvalue that you
are trying to find. Essentially, f'(x), the derivative represents f(x)/dx (dx = deltax).
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 NewtonRaphson method on the function that we
investigated earlier, f(x) = x24. Below are listed the values that we need to know in
order to complete the process.
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 xvalue of six (6) we find one root of the equation f(x) = x 24
is x=2. If we were to pick a different inital xvalue, 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) = x24 (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 deltax is equal to 2.67. Subtracting this from six (6)
we find that the new xvalue is equal to 3.33. Another way of considering this is to
find the root of this tangent line. The new xvalue (x n+1) will be equal to the root of
the tangent to the function at the current xvalue (x n).
The NewtonRaphson 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 xvalue 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 xvalue of x=1. Do the xvalues converge?
Does the deltax 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 NewtonRaphson 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 NewtonRaphson
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
RungeKutta 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)*(ta)+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.
The RungeKutta methods use multiple different approximations to the next value
of y and average them. The equations for the process with two approximations
(RungeKutta 2 method) is shown below.