Chemistry 14 Notes

Gabriel Christian V. Alava

2014
ii
Alava, G. C. V. (2014).
Chemistry 14 Notes.
Manila: Author.
For any corrections or revisions,
you may contact the author at alavayou@icloud.com.
Syllabus in Chem 14
Course title Fundamentals of General Chemistry 1
Credit 3 hours (3 lecture hours)
Prerequisite Math 11 / Math 17
General objectives At the end of the course, the student should be able to:
1. Know chemical concepts and principles about matter.
2. Understand chemical concepts and principles about matter.
3. Apply chemical concepts and principles about matter.
Content
I. Atomic structure
A. Development of the dierent atomic models
B. The subatomic particles
C. Quantum mechanical model and quantum numbers
D. The periodic table
1. Periodicity of properties
II. The chemical bond
A. Ionic or electrovalent bond
B. The covalent bond
i. Theories on covalent bonds
a. Valence Bond Theory
b. Molecular Orbital Theory
First departmental exam
III. Changes in matter
iii
iv SYLLABUS IN CHEM 14
A. Nuclear changes
1. Nuclear versus chemical reactions
2. Types of radiation
3. Types of nuclear change
4. Radioactive disintegration
B. Chemical changes
1. Quantitative relations involving formulas and equations
a. Mole concept
b. Empirical and molecular formula
c. Stoichiometry and balanced equations % yield, % purity, lim-
iting reactant
IV. Phases of matter
A. Intermolecular forces
B. Comparative descriptions of the states of matter
C. Phase changes and phase diagrams
D. The gaseous state
1. The Kinetic Molecular Theory
2. Ideal gas laws
3. Real versus ideal gases Van der Waals equation of state
4. Gas mixtures Daltons Law, Amagats Law
E. The liquid state properties of liquids
F. The solid state
1. Types of solids
2. Properties of solids
Second departmental exam
V. Solutions
A. The dissolution process
B. Factors aecting solubility
C. Types of solutions
D. Ideal versus non-ideal solutions: vapour pressure of solutions of com-
pletely miscible liquids
v
E. Concentration
1. Methods of expressing concentration
2. Dilution
F. Electrolytes and nonelectrolytes
1. Colligative properties
2. Acids, bases and salts
Third departmental exam
VI. Chemical thermodynamics
A. Basic concepts
B. First law of thermodynamics
1. Heats of reaction: heats of formation, Hess law
C. Second and third laws of thermodynamics
1. Entropy
2. Gibbs free energy
VII. Chemical kinetics
A. Theories on reaction rates
B. Factors aecting rates of reactions
VIII. Chemical equilibrium
A. Molecular equilibrium
1. Kinetic approach to equilibrium
2. Thermodynamic approach to equilibrium
3. Factors aecting equilibrium
B. Ionic equilibrium
1. Ionisation of strong and weak electrolytes
2. pH and pOH
3. Hydrolysis Concept
4. Neutralisation and titration
Fourth departmental exam
Course requirements Refer to Table 1.
vi SYLLABUS IN CHEM 14
Table 1: Course requirements
Class standing 2/3
Departmental examinations 80%
Non-departmental 20%
Quizzes
Recitation
Assignments / Problem sets
Final exam 1/3
Table 2: Grading scale
90 1.00
85 1.25 89
80 1.50 84
75 1.75 79
70 2.00 74
65 2.25 69
60 2.50 64
55 2.75 59
50 3.00 54
40 4.00 45
5.00 39
Exemption policies A student may be exempted from taking the nal exam
provided all of the following conditions are met:
1. All major exams are taken
2. No grade lower than 50% in any of the major exams
3. A class standing of 60% or better
4. Additional requirements by the professor or instructor
Absences Any student who failed to take a major exam due to illness may
be excused upon presentation of a medical certicate issued by the U.P. Health
Service. The nal exam may then be substituted for the missed exam. This can
be done for only one exam.
Scholastic integrity All forms of cheating merits a grade of 5.00 for the
course. A student who is found guilty of cheating will not be allowed to drop
the course in order to avoid getting a grade of 5.00.
Grading scale Refer to Table 2
Contents
Syllabus in Chem 14 iii
I Coverage of the rst departmental exam 1
1 The atom 3
1.1 Development of the atomic model . . . . . . . . . . . . . . . . . . 3
1.2 The subatomic particles . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Quantum numbers . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2 The periodic table 7
2.1 Groups and periods . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Periodicity of trends . . . . . . . . . . . . . . . . . . . . . . . . . 8
3 Chemical combination 11
3.1 Electron sharing . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2 Writing Lewis structures . . . . . . . . . . . . . . . . . . . . . . . 13
3.3 Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4 The covalent bond 15
4.1 Valence Shell Electron Pair Repulsion Theory . . . . . . . . . . . 15
4.2 Hybridisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.3 Molecular Orbital Theory . . . . . . . . . . . . . . . . . . . . . . 16
II Coverage of the second departmental exam 19
5 Phases of matter 21
5.1 Intermolecular forces . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.2 The gaseous state . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.3 The solid state . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
6 Nuclear chemistry 27
6.1 Radioactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
vii
viii CONTENTS
6.2 Nuclear equations . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Part I
Coverage of the rst
departmental exam
1
Chapter 1
The atom
Democritus (460-370 BC) suggested that matter was made up of tiny indivisible
particles called atoms. His theory was rejected in favour of Aristotelean philos-
ophy. John Dalton (1766-1844) however resurfaced Democritus suggestion and
drew up the following postulates
1
in his own atomic theory:
1. Each element is composed of extremely small particles called atoms.
2. All atoms of a given element are identical, but the atoms of one element
are dierent from the atoms of all other elements.
3. Atoms of one element cannot be changed into atoms of a dierent element
by chemical reactions; atoms are neither created nor destroyed in chemical
reactions.
4. Compounds are formed when atoms of more than one element combine; a
given compound always has the same relative number and kind of atoms.
1.1 Development of the atomic model
Rutherfords nuclear model You will later on see that an electrons mass
is 0.05% of a protons mass. This disparity led J. J. Thomson to suggest that
the electron similarly occupies a small volume in the atom. He proposed the
plum pudding model wherein the atom was a sphere of positive charges wherein
electrons are embedded.
However, in Ernest Rutherfords -scattering experiment, in contrast to Thom-
sons model, while most particles were not deected by the gold foil that
stands in its way, some were by a degree or so and an even smaller percentage
of those particles were deected by larger angles.
1
The following postulates are copied verbatim from [2].
3
4 CHAPTER 1. THE ATOM
This led him to draw up the nuclear model of the atom, where the all posi-
tive charges are concentrated in a nucleus and the electrons inhabit the empty
periphery of the nucleus.
Bohrs planetary model Having agreed upon the nuclear model, the next
question is where in the empty space around the nucleus the electron resides.
Niels Bohr suggested that an electron move around the nucleus in orbits. Each
orbit has a corresponding principal quantum number n and energy E, given
by
E =
R
H
n
2
where the Rydberg constant R
H
= 2.18 10
18
m
1
.
Electrons may move from one orbit to another by absorbing or emitting energy
E, but only in packets or quanta. E is given by
E = R
H
_
1
n
2
i

1
n
2
f
_
=
hc

where Plancks constant h = 6.63 10

34
J s, the speed of light c = 3.00
10
8 m
s
, and is the wavelength of the photon emitted by the electron.
Quantum mechanical model The quantum mechanical model refuted Bohrs
proposition that the electrons orbit the nucleus in two-dimensional circular
paths. Instead, it suggested the existence of three-dimensional orbitals wherein
there is most probable to nd an electron. It does not tackle the motion of an
electron around the nucleus since the Heisenberg uncertainty principle states
that that cannot be precisely determined.
1.2 The subatomic particles
Table 1.1 summarises the properties of each of the three principal subatomic
particles. Note that
1 amu = 1.66054 10
24
g
1 g = 6.02214 10
23
amu
J. J. Thomson is credited with the discovery of the electron by his discovery
of the cathode rays negative charge. James Cavendish is credited with the
discovery of the neutron and its location in the nucleus along with the protons,
thus the name nucleon.
1.3. QUANTUM NUMBERS 5
Table 1.1: Subatomic Particles
Particle Mass (g) Mass (amu) Charge (C)
Electron 9.1095 10
28
0.000549 1.6022 10
19
Proton 1.67252 10
24
1.007260 +1.6022 10
19
Neutron 1.67495 10
24
1.008670 0
Atomic number, mass number, charge, and atomic weight The afore-
mentioned terms are dened below.
Atomic number Z number of protons in an atom of an element. Atoms of
the same element have the same atomic numbers while those of dierent
elements do not.
Charge number of protons minus number of electrons, represented as C in this
paragraph.
Mass number A number of protons and neutrons in an atom. This may vary
even among atoms of the same element.
Isobars atoms with the same mass number.
Isotones atoms with the same number of neutrons.
Isotopes atoms of the same element which have dierent numbers of electrons.
Atomic weight =

(isotope mass fractional isotope abundance)

An atom of an element with symbol X may be written as
A
Z
X
C
.
1.3 Quantum numbers
To determine the location of an electron, we use quantum numbers, dened be-
low, to describe the region where we will most probably nd that electron.
The principal quantum number n {1, 2, 3, . . . } corresponds to the main
energy level or electron shell and determines the distance of the electron
from the nucleus, the size of the orbital it is in, and its energy, as discussed
in Niels Bohrs model of the hydrogen atom.
The angular momentum quantum number l {0, 1, 2, . . . , n 1} corre-
sponds to the sublevel or subshell and determines the shape of the orbital.
While l may have numerical values, it may also take literal designations
as listed in Table 1.2
The magnetic quantum number m
l
{l, l + 1, l + 2, . . . , l 2, l 1, l}
determines the orientation of the orbital.
6 CHAPTER 1. THE ATOM
Table 1.2: l values
Number Letter Shape
0 s
1 p
2 d
3 f
The spin magnetic quantum number m
s
determines the spin of the elec-
tron magnetic moment in a magnetic eld. If the moment is against the
eld, m =
1
2
and m =
1
2
if otherwise.
?The Pauli exclusion principle states that no two electrons in an atom can have
the same four quantum numbers.
The electron conguration of an atom describes how its electrons are ar-
ranged. The following principles are applied when distributing electrons:
n +l rule As n +l increases, so too does E.
Aufbau principle The buildup of electrons in atoms results from continually
increasing the quantum number, starting with the lowest n, l, and m
l
values.
Hund?s rule of maximum multiplicity Electrons introduced into a subshell
will rst occupy an empty orbital before sharing one with another electron.
Chapter 2
The periodic table
2.1 Groups and periods
First, let us dene period and group. A horizontal row of elements is called a
period and a vertical column is a group or family. We dene s-block to be the
7
8 CHAPTER 2. THE PERIODIC TABLE
set of elements whose last electron is in s sublevel and we dene the p, d, and
f-blocks in the same way. Note that the number of families in each block is the
same as the maximum number of electrons in each sublevel.
While the period number is simply the highest n-value of the elements electron
congurations in that period, there are two systems followed in determining
group numbers.
The U.S. convention splits the periodic table into two: A families, which
comprise the s and p-blocks, and the B families, which comprise the d and f-
blocks. The group number to which the letter A or B is axed is correlated to
the number of valence electrons of that groups constituent elements as described
below, where n is the period number of the element.
A family group number = number of electrons in the ns subshell
+ number of electrons in the np subshell
B family group number = number of electrons in the ns subshell
+ number of electrons in the (n 1)d subshell
The IUPAC notation however simply numbers the families 1 to 18, but
there is still a correlation between the groups number and the valence electrons
of its constituent elements. In fact the IUPAC notation applies the relation
above for the s and d-blocks. However, for the p-block, the group number is
given below:
p-block group number = 10 + number of electrons in the ns subshell
+ number of electrons in the np subshell
The f-block Neither convention designates group numbers for the f-block.
The number of valence electrons of an f-block element can be calculated as
A family group number = number of electrons in the ns subshell
+ number of electrons in the (n 1)d subshell
+ number of electrons in the (n 2)f subshell
Since these elements vary only in the number of electrons in their inner main
energy levels, their chemical properties are very similar, which is why neither
convention bothers to give them group numbers.
2.2 Periodicity of trends
Atomic radius decreases through each period and increases down each group.
The rest of the properties, dened below, increases through each period and
2.2. PERIODICITY OF TRENDS 9
decreases down each group. All of these trends are due to the increase in the
eective nuclear charge across a period and the increase in n down a group,
which increases the distance between the most distant electron and the nucleus.
Exceptions are also explained below.
Atomic radius is dened as half the distance between the two nuclei of either
two adjacent atoms as in the case of metals or two bonded atoms as in the case of
diatomic molecules. Atomic radius decreases through each period and increases
down each group. Cations are smaller than their parent atoms and anions are
larger. The larger the net charge, the smaller the atom.
Ionisation energy U is the minimum energy required to remove an electron
from an atom or ion in its ground state, i.e.
X
n
+ U x
n + 1
+ e

The rst, second, third, and succeeding ionisation energies are related as de-
scribed below:
A + U
1
A
1+
+ e

A
1+
+ U
2
A
2+
+ e

A
2+
+ U
3
A
3+
+ e

and so on. When an electron is removed, the repulsion between electrons de-
creases. Since the eective nuclear charge is constant, each ionisation energy is
always less than the succeeding ionisation energy, i.e. U
n
< U
n+1
.
A possible break in the trend between the s and p-blocks is due to the higher
energy associated with the p-sublevel. Likewise, a possible break in the trend
in the middle of the p-block may arise due to the repulsion of the electron to
be added when moving from Group 15 to 16. Also note that the ionisation
energy of a Group 12 is higher than that of a Group 13 element from the same
period.
Electron anity is the energy released or absorbed when an electron is added
to an atom, i.e.
A + e

Note that this is not simply the opposite of ionisation energy. Our sign conven-
tion here will be that, if the system released energy, the electron anity must
be positive.
Electron anity generally increases through the period but a break in Groups
2 and 18 may be explained by the fact that these elements are already stable
and would rather give electrons away rather than receiving them, which takes
more energy because they will have to place it in the next sublevel.
10 CHAPTER 2. THE PERIODIC TABLE
Electronegativity is the tendency of an atom to attract electrons when
bonded.
Metals and nonmetals Using the information above, we can classify ele-
ments as either metals or nonmetals. Metals, occupying the left side of the pe-
riodic table, have larger atoms, lower ionisation energies, and lower electronega-
tivities than their nonmetallic counterparts. In between are the metalloids. We
will also observe that metallic properties decrease across the period.
Chapter 3
Chemical combination
We have learned from the previous lessons that an atom whose orbitals are com-
pletely lled probably will not react and we can see this in Group 18 elements.
Those that have partially lled orbitals will tend to combine with another atom
to either ll them up or give away the electrons in them. This is the basis of
the octet rule.
Atoms also have two modes of combination: electron sharing and electron trans-
fer. The mode by which they will combine is determined by the dierence in
their electronegativities, which we will represent here as |
A

B
|.
Electron transfer If the dierence |
A

B
| > 1.7 or if one of the two atoms
tend to gains electrons and the other tends to lose, the two atoms combine
through electron transfer. An electrostatic or ionic bond is established between
them. Take for example NaCl.
Na + Cl Na
+
_
Cl

_
The less electronegative atom becomes a cation and gives up its electron(s) to
the more electronegative ion, which will take it and become an anion. Note that
the electron given up is farthest one from the nucleus, not the last electron we
assign.
3.1 Electron sharing
When neither atom is willing to give or if |
A

B
| < 1.7, the two atoms form a
molecule held together by covalent bonds, each one formed by a pair of electrons
shared by the two atoms.
11
12 CHAPTER 3. CHEMICAL COMBINATION
Polarity These covalent bonds are further divided into two: nonpolar and
polar covalent bonds. For non polar bonds, |
A

B
| 0.4. For polar
bonds, 0.5 |
A

B
| 1.7. Beyond that, the chemical bond is classied
as ionic.
In polar bonds, the shared electron pair is shared unequally. The more elec-
tronegative atom naturally gets the larger electron density than the less elec-
tronegative atom. The molecule possesses a dipole moment.
If the dipole moments within the molecule balance out or if the molecule is
symmetrical, the molecule is nonpolar. However, this is dierent from the polar
bonds within the molecule.
Bond dissociation energy or bond energy, the energy required to break a bond
in one mole of a gaseous molecule, increases with polarity, along with the bond
order or number of bonds between two atoms in the molecule.
and bonds bonds are formed by the overlap of atomic orbitals between
the nuclei of the two bonding atoms. Sigma bonds are formed by an s, p, and
hybrid orbitals and another one of those orbitals.
Additional bonds may be formed by the sideways overlap of additional p or-
bitals alongside a bond to form a double or triple bond.
Covalency number The number of covalent bonds that a nonmetal or a
metalloid can form is called its covalency number. If the central atom follows
the octet rule, its covalency number is eight minus the number of its valence
electrons. If not, its covalency number is simply the number of its valence
electrons.
Coordinate covalent bonds While a covalent bond is formed by a pair of
electrons shared by the two atoms, there are cases in which only one atom con-
tributes both of the electrons that form the bond. Take for example NOCl
3
.
Cl
N
Cl
Cl
+ O Cl N
O
Cl
Cl
In this case, N shared its electrons to to form Os octet even though N already
had a complete octet and did not need to do so.
Formal charge is the apparent charge an atom would have if it were to share
electrons equally with the other atom it is covalently bonded to. Formal charge
3.2. WRITING LEWIS STRUCTURES 13
may be computed using the formula
Formal charge = number of valence electrons in a neutral atom
lone electrons
lone pairs 2
number of bonds
Charge of molecule =

[Formal charges]
This preference for minimal formal charges often overrides the octet rule and
gives rise to expanded octets, which may only occur for elements where n 3.
Note that in these cases, the maximum possible number of valence electrons of
the central atom in the compound is twice the number of valence electrons in
the free atom.
3.2 Writing Lewis structures
The procedure below enumerates the steps to draw a Lewis structure.
1. Count the available valence electrons.
2. Write down the atoms as they are connected. The central atom usually
has the highest covalency number, the largest size, or the lowest elec-
tronegativity. The following tips may also help:
(a) If one atom is unique, its probably the central atom. Hydrogen and
oxygen are not probable candidates.
(b) If there are two unique atoms, the one with the larger atomic number
is probably the central atom.
(c) Carbon family elements usually form four bonds. Nitrogen family
elements form three. Oxygen family elements form two. Halogens
usually form one.
(d) When oxygen and hydrogen are in the same molecule, they usually
form the combination HOX where X is the other atom in the
molecule.
(e) Three-membered rings are unlikely for most molecules. Larger rings
are possible but nevertheless uncommon.
3. Fill the octets of the peripheral atoms and, if there are still electrons,
assign them to the central atom.
4. If there arent enough electrons to ll the central atoms octet, try multiple
bonds.
14 CHAPTER 3. CHEMICAL COMBINATION
3.3 Resonance
In molecules with double bonds, the location of the double bonds is arbitrary,
allowing for more than one Lewis structure. However, when all of the bonds are
examined, all of them are identical, hybrids of single and double bonds. This
phenomenon is called resonance.
When choosing a resonance structure, we try to minimise formal charges and
assign the negative formal charges to the more electronegative atoms. It is also
advisable that should there be formal charges with opposite signs, they are to
alternate signs across the adjacent atoms.
Chapter 4
The covalent bond
4.1 Valence Shell Electron Pair Repulsion The-
ory
Each single bond, multiple bond and lone pair aliated with an atom comprises
an electron domain. The VSEPR Theory posits that the molecule arranges itself
by maximising the distance between the electron domains of the central atom to
minimise the repulsion between them. Table 4.1 summarises the possible shapes
of a molecule.
Bond angles Repulsion between lone pairs is greater than repulsion between
bonding pairs, and repulsion between a lone pair and a bonding pair is some-
where in between. Additionally, repulsion by multiple bonds is stronger than
that of a single bond but still smaller than that of a lone pair. This results in
smaller bond angles and larger angles between lone pairs and bonding pairs in
molecules which have lone pairs.
This is because a bond pair, being attracted by two positive nuclei, is stretched
along the line connecting the two nuclei, reducing its volume. Lone pairs, on the
other hand, are attracted by only one nucleus, to which it becomes closer.
Likewise, the sizes of a molecules constituent atoms aects its bond angles.
As the central atoms size increases, the overall electron-electron repulsion de-
creases. However, as the size of a surrounding atom increases, so too does the
bond angle.
Bond angle decreases with the increase in the central atoms size because that
increase in size increases the distance between the nucleus and the surrounding
electron pairs and between the electron pairs themselves.
15
16 CHAPTER 4. THE COVALENT BOND
Table 4.1: Molecular geometries
e

domains Hybridisation Bonding

domains
Lone
pairs
Molecular geometry
2 sp 2 0 Linear
3 sp
2
3 0 Trigonal planar
2 1 Bent
4 sp
3
4 0 Tetrahedral
3 1 Trigonal pyramidal
2 1 Bent
5 sp
3
d
5 0 Trigonal bipyramidal
4 1 Seesaw
3 2 T-shaped
2 3 Linear
6 sp
3
d
2
6 0 Octahedral
5 1 Square pyramidal
4 2 Square planar
4.2 Hybridisation
More often than not, the electron conguration of an atom will not allow another
atoms electrons to interact with its own because of energy dierences. For this
reason, two or more atomic orbitals may undergo hybridisation to form the
same number of degenerate hybrid orbitals, i.e. hybrid orbitals of the same
energy.
Table 4.1 likewise details the hybridisation necessary to make each molecular
geometry possible. Likewise, you may calculate the number of hybrid orbitals
produced by adding the number of the central atoms lone pairs and its bonds,
counting double or triple bonds as only one.
4.3 Molecular Orbital Theory
Where the Valence Bond Theory falls short, the Molecular Orbital Theory com-
pensates. Rather than associating orbitals with atoms, it associates orbitals
with the molecule as a whole.
A pair of atomic orbitals combine to form a more stable bonding pair with
lower energy and a less stable antibonding molecular orbital with higher en-
ergy. As their names state, the bonding molecular orbital keeps the molecule
together while the antibonding molecular orbital destabilises it. There are also
nonbonding electrons which do not signicantly aect the bonding.
4.3. MOLECULAR ORBITAL THEORY 17
With this, we can also compute for the bond order using the equation
Bond order =
1
2
[(bonding electrons) (antibonding electrons)]
Two factors are considered in forming molecular orbitals: the symmetry of
atomic orbitals and the dierence in the energies of the two atomic orbitals.
The following equations will detail which molecular orbitals are formed from
atomic orbitals:
+ * = s +s
= p
z
+p
z
+ * = p
x
+p
x
= p
y
+p
y
Note that these equations are not real and are just representations.
The energy level diagram of a diatomic molecule of an element whose Z 8 is
drawn below.
1s
2s
2p 2p 2p
1s
2s
2p 2p 2p
1s

1s
2s

2s
2pz

2pz
2px

2px
2py

2py
For a diatomic molecule of an element whose Z 7, where there is signi-
cant 2s-2p interaction, the
2px
and
2py
orbitals switch energy levels with
2pz
orbital.
18 CHAPTER 4. THE COVALENT BOND
Part II
Coverage of the second
departmental exam
19
Chapter 5
Phases of matter
Table 5.1 summarises the properties of the three phases of matter.
A phase diagram like Figure 5.1 contains the vapour pressure, sublimation,
and melting curves. Each curve bounds two phases and is the set of conditions
where the two phases coexist in equilibrium and where the transition between
the two phases occurs.
The triple point, the intersection of the three curves, details the conditions
where the three phases coexist in equilibrium. The critical point, the endpoint
of the vapour pressure curve, details the conditions where the liquid and gas
phases are identical.
5.1 Intermolecular forces
The following properties of substances are indicators of strength of intermolec-
ular forces:
Heat or enthalpy of fusion, vaporisation, or sublimation heat required
to undergo the phase change, increases with the strength of intermolecular
forces
Melting or boiling point temperature required to undergo the phase change,
increases with the strength of intermolecular forces
Normal melting or boiling point melting or boiling point at 1 atm.
Viscosity measure of a uids resistance to ow, increases with the strength of
intermolecular forces
21
22 CHAPTER 5. PHASES OF MATTER
Table 5.1: Properties of matter
Property Gas Liquid Solid
Volume Assumes the vol-
ume of the con-
tainer
Has denite volume
Shape Assumes the shape of the container Has denite
shape
Density Low High
Compressibility Very compress-
ible
Slightly com-
pressible
Virtually incom-
pressible
Diusion Rapid Slow Very slowly
Flow Flows readily Does not ow
Particles move freely move freely rela-
tive to each other
virtually dont
move
Figure 5.1: A generic phase diagram
5.1. INTERMOLECULAR FORCES 23
Vapour pressure pressure exerted by gas molecules on the surface of the liq-
uid with which it is in equilibrium, decreases with the strength of inter-
molecular forces
Surface tension amount of energy required to increase the surface of a liquid
by a unit area, increases with the strength of intermolecular forces
Solubility maximum amount of solute that will dissolve in a given solvent or
solution at a given temperature, increases with the strength of intermolec-
ular forces between solute and solvent.
Intermolecular forces are classied into the following categories, arranged in in-
creasing strength. Note that intermolecular forces are simply a result of charges
and their attraction or repulsion in accordance with Coulombs law.
London dispersion forces are forces that exist between nonpolar substances.
Instantaneous dipoles arise when electrons are concentrated at a certain location
at an innitesimal duration, and these in turn repel the electrons of a neigh-
bouring molecule, making an induced dipole. The strength of London dispersion
forces increases with atomic size because a larger electron cloud allows electrons
to move within a larger space.
When a polar molecule and a nonpolar molecule are present, the polar molecule
may induce polarity in the nonpolar molecule, thus the dipole-induced dipole
force. The presence of an ion also has the same eect on a nearby nonpolar
molecule, thus the ion-induced dipole force.
Dipole-dipole forces are forces that exist between polar substances as a
result of permanent dipoles. Since the dipoles are permanent, the attractions
and repulsions of these dipoles are more constant, making this type of force
stronger than London dispersion forces. The strength of dipole-dipole forces
increases with polarity.
Hydrogen bonding is a type of dipole-dipole force that exists between a hydrogen
atom bonded to an atom of nitrogen, oxygen, or uorine to another atom of
nitrogen, oxygen, or uorine. Hydrogen bonding is much stronger than other
dipole-dipole forces.
Ion-dipole forces are forces that exist between ions and polar substances
where an ion attracts an oppositely-charged pole of a polar molecule. This
interparticle force is stronger than dipole-dipole forces because of the permanent
charge of the ion.
Ionic bonds are forces that exist between ionic species. Since both species
have permanent charges, their attractions are much stronger than ion-dipole
forces.
24 CHAPTER 5. PHASES OF MATTER
5.2 The gaseous state
The Kinetic Molecular Theory explains the macroscopic properties of
matter as a result of the behaviour of its constituent molecules. The theory
comprises the following postulates
1
:
1. A gas is composed of a very large number of extremely small particles
(molecules or, in some cases, atoms) in constant, random, straight-line
motion.
2. Molecules of a gas are separated by great distances. The gas is mostly
empty space. (The molecules are treated as so-called point masses, as
though they have mass but no volume.)
3. Molecules collide only eetingly with one another and with the walls of
their container, and most of the time molecules are not colliding.
4. There are assumed to be no forces between molecules except very briey
during collisions. That is, each molecule acts independently of all the
others and is unaected by their presence, except during collisions.
5. Individual molecules may gain or lose energy as a result of collisions. In a
collection of molecules at constant temperature, however , the total energy
remains constant.
The gas laws We will use the following variables to refer to each property of
a gas or its container:
P = pressure
V = volume
n = number of moles
T = temperature
M = molar mass
= density =
PM
RT
Z = compressibility factor =
PV
RT
R = 0.08205
L atm
mol K
= 8.3145
J
mol K
u
rms
= root-mean-square speed =
_
u
2
=
_
3RT
M
The equation below details how the dierent units of pressure are related.
1 atm = 760 mmHg = 760 torr = 101, 325 Pa = 1.01325 bar
1
The following postulates are copied verbatim from [1].
5.3. THE SOLID STATE 25
STP or standard temperature and pressure is dened as T = 273.15 K and,
according to IUPAC, P = 1 bar, although this used to be P = 1 atm.
The following laws predict the properties of an ideal gas:
P
1
V
(Boyles law)
V T (Charles law)
PV = nRT (Ideal gas law)
P
i
V
i
n
i
T
i
=
P
f
V
f
n
f
T
f
(General gas equation)
rate of eusion = u
rms

1
M
(Grahams law)
V n (Avogadros law)
Avogadros law also states that, at STP where P = 1 atm, a mole of gas occupies
22.414 L. If P = 1 bar, V = 22.711 L.
The van der Waals equation of state takes into account the intermolecular forces
between gas molecules and the volume of the gas, which the Kinetic Molecular
Theory treats as negligible. The van der Waals equation of state predicts the
nonideal behaviour of gases. Given the correction a for intermolecular forces
and the excluded volume per mole b,
_
P +
an
2
V
2
_
(V nb) = nRT
Gas mixtures For a mixture of gases in a single container, the total pressure
in the container is equal to the sum of partial pressure of each gas according to
Daltons law of partial pressures. Likewise, the total volume in the container is
equal to the sum of the partial volume of each gas according to Amagats law
of partial volumes.
The mole fraction is the ratio of the number of moles of a gas to the total
number of moles of gas in a container. The mole fraction is also the ratio of the
partial pressure of a gas to the total pressure or its partial volume to the total
volume, i.e.

A
=
n
A
n
tot
=
P
A
P
tot
=
V
A
V
tot
Note that 1 =
A
+
B
+. . . .
5.3 The solid state
Solids may be classied according to the arrangement of its constituents:
26 CHAPTER 5. PHASES OF MATTER
Crystalline solids have a regular pattern all throughout the solid.
Amorphous solids have almost no orderly arrangement at all.
Polycrystalline solids are aggregates of crystalline structures.
Likewise, solids may be classied according to the bonds that hold it together:
Ionic and covalent solids are held together by their respective chemical
bonds. These chemical bonds give these solids their hardness and high melting
points. However, their structures are fragile and will break all throughout once
the structure is distorted, making it brittle.
Covalent solids lack the ions to carry charges through it and therefore cannot
conduct electricity. Ionic solids cannot conduct electricity either because the
ions are held in place by ionic bonds. However, in liquid form, ions are free to
move and can therefore conduct electricity.
Molecular solids comprise molecules bound together by intermolecular forces,
which are much weaker than the chemical bonds, making them softer and giv-
ing them much lower melting temperatures. They also lack the ions to conduct
electricity.
Metallic solids comprise positive metal ions in a sea of electrons coming from
the ionised metals. The electrons of the metal atoms are insucient to ll each
others orbitals and, as a result, they are delocalised and shared by many atoms,
enabling the solid to conduct electricity.
The sea of electrons attracts the positive metal ions, giving the solid a high
melting point. The smaller distance between the metal ions gives the solid
higher density. Unlike the brittle ionic and covalent solids, metallic solids are
malleable and ductile because distortion will not break the metallic bonds that
hold the solid together.
Chapter 6
Nuclear chemistry
The concept of chemical reactions is more familiar to us since it abounds in
nature. Only valence shell electrons are involved in chemical reactions, unlike in
nuclear reactions where particles in the nucleus are involved. Chemical reactions
simply makes and breaks bonds between the reacting atoms. Nuclear reactions
can create new elements or isotopes. The energy involved in nuclear reactions
dwarf those involved in chemical reactions.
6.1 Radioactivity
Radioactivity is the spontaneous emission of particles or ionising radiation by
unstable nuclei of heavier elements. Radioactive nuclei are called radionuclides
and atoms which have these nuclei are called radioisotopes. These nuclei un-
dergo radioactivity to lose energy and make themselves stable.
The stable nuclei, when plotted with the number of protons on the y-axis and
the atomic number on the x-axis, form a belt of stability, printed in Figure 6.1
in blue.
Below is a summary of the three kinds of radiation, , , and , in addition
to two more nuclear changes a nucleus can undergo,
+
emission and electron
capture.
A
Z
X
A 4
Z 2
Y +
4
2
( radiation)
A
Z
X
A
Z + 1
Y +
0
1
( radiation)
A
Z
X
A
Z
X + ( radiation)
A
Z
X
A
Z 1
Y +
0
+1
(
+
emission)
0
1
e +
A
Z
X
A
Z 1
Y (e

capture)
27
28 CHAPTER 6. NUCLEAR CHEMISTRY
Figure 6.1: The belt of stability
The mass and atomic numbers on a reaction are not simply balanced to follow
the rules. The equations below explain how
0
-1
and
0
1
e emission and
0
-1
e capture
occur:
1
1
n
1
1
p +
0
1
e ( radiation)
1
1
p
1
0
n +
0
1
e (
0
1
e emission)
1
1
p +
0
1
e
1
0
n (
0
-1
e capture)
The rate of decay A of a substance is directly proportional to the number
of atoms present N, i.e.
A = N
where is the decay constant of the substance. The decay constant is also used
in the formula for the half-life t 1
2
of a substance
t 1
2
=
ln 2

6.2 Nuclear equations

Nuclear reactions are not limited to the generic equations above. Nuclei can
even undergo ssion or fusion, although ssion usually happens to an atom
whose mass number is greater than 200. Nuclear equations follow a rule similar
6.2. NUCLEAR EQUATIONS 29
to the law of conservation of mass: the sums of the mass and atomic numbers
on each side must be equal to each other.
Mass-energy conversions may also occur in a reaction. Given the mass
change m and the speed of light c, the energy change is given by
E = mc
2
While the equation usually gives the energy change in joules, the energy change
may also be expressed in mega-electron volts (MeV) using the equation
1 MeV = 1.6022 10
13
J
Nuclear transmutation is the process by which a nucleus is bombarded with
a neutron or another nucleus to experience change. The shorthand notation for
nuclear transmutation is as follows:
Original nucleus (Bombarding particle, Resulting particle) Resulting nucleus
A nuclear chain reaction is a self-sustaining sequence of nuclear ssion
reactions. This reaction occurs only when the amount of ssionable material
is equal to or greater than the critical mass, the minimum amount of material
required to generate a self-sustaining nuclear chain reaction.
1
Radioactive series As mentioned earlier, there are nuclei which are unstable
and undergo nuclear reactions to become more stable. There are elements which
undergo a succession of these nuclear reactions to go from unstable to stable,
and this is called a radioactive series. There are three radioactive series in
nature, the
238
92
U series which ends with
206
82
Pb, the
236
92
U series which ends with
207
82
Pb, and the
232
90
Th series which ends with
208
82
Pb.
1
This denition is copied verbatim from [3].
30 CHAPTER 6. NUCLEAR CHEMISTRY
Bibliography
[1] Bissonnete, C, Herring, F. G., Madura, J. D., & Petrucci, R. H. (2010).
General Chemistry: Principles and Modern Applications. Toronto: Pearson
Canada Inc.
[2] Brown, T. L., Bursten, B. E., LeMay, H. E., Murphy, C. J., & Woodward, P.
M. (2012). Chemistry: The Central Science. Upper Saddle River: Pearson
Education, Inc.
[3] Engle, H. L. & Ilao, L. V. (2008). Learning Modules in General Chemistry
1. Manila: University of the Philippines Manila.
[4] Logronio, A. J. (2011). Chemistry 14: The Fundamentals of General Chem-
istry I. Manila: Author.
31