Chapter 1: Fundamentals

Introduction to Matter:

Anything that occupies space and has a mass.

3 physical states: solid, liquid and gas.

Made up of atoms.

Atom: basic unit of any chemical element

Element:

- Substance made up of atoms of the same kind (same atomic number)

- Represented by symbols of 1 or 2 letters (Cu, H)
- Till now 118 elements
- Allotropes: 2 or more distinct forms of an element (O, O2)

Compound: Substance made up of atoms of 2 or more elements chemically united

Substance: a form of matter (element or compound) having a fixed composition

and distinct identity

Mixture: Combination of 2 or more substances

- Homogenous mixture: Composition is uniform throughout the sample. (Tea)

- Heterogeneous mixture: Composition is not uniform throughout the sample.
(Water + Sand)

Physical and Chemical Properties of Matter:

Physical property: measured without changing the identity. (Color, MP, BP)

Chemical property: describes the way a substance may change into another.
(Flammable)
Extensive and Intensive Properties:

Extensive property: is additive. (Mass, volume)

Intensive property: not additive. (Density, concentration)

Temperature:

The Celsius scale (oC): under 1 atm

- Zero: freezing point of water

- 100: boiling point of water

The Kelvin scale (K):

- Zero is the lowest temperature that can be attained theoretically 0K=-273.15

o
C
- Tk = Tc + 273.15

Note: Celsius and Kelvin scale have the same degree size but differ in the zero
point (ΔTC = ΔTK)

The Fahrenheit scale (oF) under 1 atm:

- 32: freezing point of water

- 212: boiling point of water
- TF = (TC x 9/5) +32

Density:

D=m/V (g/cm3) or (g/L for gases)

Dalton’s Atomic Theory:

Each element is made up of tiny identical particles called atoms.

Chemical compounds are formed when atoms combine with one another.

Chemical reactions involve the reorganization of the atom. Changes in the way
they are bound together,

Atom: the smallest particle of an element that retains the properties of that element.

Early Experiments to Characterize the Atom:

The Electron:

- Cathode-ray tubes
- Negatively charged particles called electrons.
- Since atoms are electrically neutral  positively charged particles should be
present in the atom.

The Nuclear atom:

- Rutherford’s experiment on α particle

- Plum pudding model: diffuse cloud of positive charge with the negative
electrons embedded randomly in it.
- Actual atom model: dense center of positive charge (nucleus) and electrons
moving around it.

Atomic Structure:

Atoms composed of nucleus (Protons and Neutrons) surrounded by an electronic

cloud.

Particle Mass Charge

Electron 9.11 x 10-31 kg 1-
Proton 1.67 x 10-27 kg 1+
Neutron 1.67 x 10-27 kg None
The magnitude of the charge of the electron and the proton is 1.6 x 10-19C.

Representation of atoms:

Isotopes: atoms of a given element having the same Z but different A (same p + but
different n0).

Molecules and Ions:

Chemical bonds:

- Covalent bonds: sharing electrons.

- Ionic bonds: attractions between oppositely charged ions.

Molecules: collections of atoms.

They have:

- Chemical formula: water (H2O)

- Structural formula: H—O—H

Ion: an atom or group of atoms that have a net positive or negative charge

Cation: positive charge

Anion: negative charge

Anions and cations attract each other  ionic bond  result in an ionic solid or
salt (NaCl or NH4NO3)

An Introduction to the Periodic Table:

- Metals: left side of the Al-Po diagonal except hydrogen

- Nonmetals: right side of the Al-Po diagonal
- Metalloids: Al, Si, Ge, As, Sb, Te, Po, and At
Elements in the same vertical columns (groups) have similar chemical properties.

The horizontal row of elements are called periods.

Naming Simple Compounds:

Common metals that do not require a roman numeral:

Group 1A, 2A and aluminum (only forms Al3+)

Common transition metals that do not require a roman numeral:

Zinc (only forms Zn2+) and silver (only forms Ag+)

Oxyanions: Anions containing an atom of a given element and different number of

oxygen atoms.

The name of the larger # of oxygen ends in -ate. (ClO3- chlorate ion)

The name of the smaller # of oxygen ends in -ite. (ClO2- chlorite ion)

When more than 2 make up a series: hypo for the fewest and per for the
most oxygen atoms. (ClO4- perchlorate ion, ClO- hypochlorite ion)
Acid:

Atomic Masses:

Based on the mass of 12C as the standard since it is assigned a mass of exactly 12
amu

Relative atomic masses are calculated by mass spectrometry.

Average Atomic Mass:

Elements occur in nature as mixtures of isotopes.

Atomic mass is based on the abundance of isotopes.

Average atomic mass = %A * m#A + %B * m#B

The Mole:

Relates the atomic mass to a unit of gram.

One mole of something has NA units of that substance.

NA: Avogadro’s Number = 6.022137 x 1023.

1 g = 6.022 x 1023 amu

1 amu = 1.66053886 x 10-24 g

To get g grams of an element X containing n atoms and A atomic number:

g = (n x A)/NA

To get n atoms of an element X containing g grams and A atomic number:

n = (g x NA)/A

Molar Mass:

The mass in g of 1 mole of the compound.

Molar mass of XxYy = x*MMX + y*MMY.

Percent Composition:
mass of element ∈compound
Mass %= x 100
mass of compound
 Chapter 2: The Structure of Atoms

Electromagnetic Radiation:

Energy travels through space by electromagnetic radiation since it has electrical

and magnetic fields.

Waves: periodic oscillations that transmit energy through space and are
characterized by wavelength, frequency, and speed.

Wavelength λ: distance between 2 consecutive peaks or troughs in a wave (unit of

distance)

Frequency υ: number of waves per second that pass a given point in space (unit:
oscillations per second or s-1: hertz Hz)

λυ = c which c: speed of light = 2.99792458 x 108 m/s

The Nature of Matter:

h: Planck’s constant = 6.626 x 10-34 J.s

Energy is quantized and can be transferred only in units of size hυ

The photoelectric effect:

When light strikes the surface of a metal, e- are emitted:

- No e- are emitted below a specific threshold frequency υ0 regardless of the

intensity of light.
- If υ>υ0, # of e- increases with the intensity and the KE of e- emitted increases
linearly with υ.
Ephoton = hυ = hc/λ (as λ increases, E decreases)

Dual nature of light: it can either be a wave or a stream of photons.

Particles and waves are related by: λ= h

mv

The Atomic Spectrum of Hydrogen:

High energy discharge is passed through a sample of H2 gas, the H2 molecule

absorbs energy which breaks the H—H bond and causes the H atoms to be excited
and release energy in the form of light of various wavelengths which produced the
emission spectrum of the hydrogen atom.

Significance of the line spectrum of hydrogen:

- Only certain energies are allowed.

- The energy of the e- in the hydrogen atom is quantized.
- Changes in energy between discrete energy levels in hydrogen produce only
certain wavelengths of emitted light.
The Bohr Model:

e- in a hydrogen atom moves around the nucleus only in certain allowed circular
orbits.

E=-2.178 x 10-18 (1/n2). n: integer  larger its value larger the orbit radius.

Used to calculate the change in energy when the electron changes orbits.

2 important points:

1. The model correctly fits the quantized energy levels of the hydrogen atoms.
2. As the e- becomes more tightly bound, its energy becomes more negative
relative to the zero-energy transfer state, n=∞, and as the e- is brought closer
to the nucleus, energy is released from the system.

Limitation: The energies calculated only apply to the hydrogen atom.

The Quantum Mechanical Description:

Heisenberg uncertainty principle: there is a limitation to just has precisely we can

know both the position and the momentum (mxV) of a particle at a given time.

Quantum mechanics cannot pinpoint the electron in an atom but defines the region
where it might be at a given time.

Electron density: the probability of an electron being present at a specific location.

 High electron density  high probability of locating the electron.

Atomic orbital: region around the nucleus where there is a high probability of
finding an e-.
The Characteristics of Hydrogen Orbitals.

1. The principal quantum number (n):

Has integral values (1,2,3…)

It is related to the size and energy of the orbital. As n increases, the orbital
becomes larger and e- are farther from the nucleus causing it to have higher
energy (less negative energy) since e- are less tightly bound to the nucleus.

2. The angular momentum quantum number (l):

It can have integral values from 0 to n-1 for each n

It is related to the shape of the orbital.

The values of l are designated by letters s, p, d, f, …

The set of orbitals with a given value of l is called a subshell

Value of l Letter Used

0 s
1 p
2 d
3 f
4 g
3. The magnetic quantum number (ml):

Have integral values between l and -l, including 0.

It is related to the orientation in space of the angular momentum associated with

the orbital and # of orbitals.
Orbital Shapes and Energies:

Orbitals are presented by the surface that surrounds 90% of the total electron
probability:

- s orbital (l=0): spherical

- p orbitals (l=1): 2 lobes separated by a node at the nucleus.

- d orbitals (l=2): first occur in level n=3.

4. The spin quantum number (ms) and the Pauli Principle:

Only 2 values: +1/2 or -1/2

Pauli Principle: in a given atom, no 2 electrons can have the same set of
quantum numbers (n, l, ml, and ms).

An orbital can only hold 2 electrons and they should have opposite spins.

Orbital Energy Levels for the Hydrogen Atom:

For hydrogen, the energy of a particular orbital is determined by its value of n

 all orbitals of the same value n have the same energy and said to be
degenerate.

In the ground state (lowest energy state), the e- resides in the 1s orbital. If
energy is put in the atom, the e- can be transferred to a higher-energy orbital,
causing an excited state.

The Aufbau Principle and the Periodic Table:

The Aufbau principle: as protons are added one by one to the nucleus to build
up the elements, electrons are similarly added to these atomic orbitals.

As the e- are added, they assume their most stable conditions with respect to the
nucleus and the electrons already there.
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s

The electron configuration: distribution of electrons among the various atomic

orbitals.

Pauli Exclusion Principle: no 2 electrons have the same 4 quantum numbers.

Hund’s Rule: the lowest energy configuration for an atom is the one having the
maximum number of unpaired electron.

Abbreviated electron configuration: avoid writing the inner- level electrons:

Mg: [Ne] 3s2

Valence electrons: electrons of the outermost principal quantum level of an

atom.

Core electrons: the inner electrons.

Elements in the same group have the same valence electron configuration.

The number of each period corresponds to the outermost energy level that
contains electrons for the elements in that period.

Transition metals: configurations obtained by adding e- to 3d orbitals.

1. The (n+1)s orbitals always fill before the nd orbitals.

Exceptions:

Cr: [Ar] 4s1 3d5 and Cu: [Ar] 4s1 3d10

The reason of these irregularities is that half-filled (d5) and filled (d10) orbitals
have slightly greater stability.

2. After Lanthanum (La: [Xe] 6s2 5d1), a group of 14 elements, lanthanides,

occurs.

Lanthanides: filling of 4f orbitals. Sometimes one e- occupies a 5d instead of a

4f orbitals since 5d and 4f have similar energies.

3. After Actinium (Ac:[Rn] 7s2 6d1), a group of 14 elements, actinides, occurs.

Actinides: filling of 5f orbitals. Sometimes one or two e- occupies the 6d instead

of the 5f orbitals since 6d and 5f have similar energies.

4. The group labels 1A, 2A, …, 8A indicate the total number of valence
electrons.

Summary:

1. Each shell or principal level of quantum number n contains n subshells.

2. Each subshell of quantum number l contains (2l+1) orbitals.
3. No more than 2 electrons can be placed in 1 orbital, max # of electrons is
twice the number of orbitals.
4. Total number of orbitals = n2.
5. Max number of electrons an atom can have in a principal level =2n2.

Periodic Trends in Atomic Properties:

Ionization Energy:

Is the minimum energy (kJ/mol) required to remove an electron from a gaseous

atom in its ground state.

The tendency of an atom to resist the loss of an electron. The higher the
ionization energy, the stronger the attraction between the nucleus and the
electron.

Across a period: the first ionization energy increases from left to right since
electrons are bound more tightly because of the increased attraction between the
nuclear charge and the outer electrons.

Down a group: less energy needed since the number of core electrons increase
which increases shielding for the core electrons, making the attraction between
the nuclear charge and the valence e- less.

Electron Affinity:

Energy associated with the addition of an electron to the gaseous atom.

The addition is exothermic  electron affinity will have a negative sign. The
more negative the energy, the greater quantity of energy is released.

Atomic Radius:

One has the distance between 2 nuclei.

Atomic radius increases down a group since the orbital size increases.

Decreases from left to right since the attraction between electrons increases 
size decreases.

Ions: Electron Configurations and Sizes:

Atoms lose electrons so that cation has a noble gas outer electron configuration.

Atoms gain electrons so that anion has a noble gas outer electron configuration.

O2-, F-, Na+, Mg2+, and Al3+ all have the same number of electrons, the same
ground state electron configuration.

Isoelectronic: ions and atoms that have the same number of electrons.

Even though the number of electrons is the same, the number of protons still
affect the size of the ion.

As protons increase, size decreases since the attraction between the protons and
electrons increases.

Ionic radius: is the radius of a cation or an anion.

Cation is smaller than the atom from which it is formed.

Anion is larger than the atom from which it is formed.

For isoelectronic ions: cations are smaller than anions.

 Chapter 3: Lewis Structure – VSEPR Model

Electronegativity:
The ability of an atom in a molecule to attract shared electrons to itself.
Bond Polarity and Dipole Moments:
When a molecule has a center of positive charge and a center of negative charge is
said to dipolar, or to have a dipole moment.

Some molecules have polar bonds but do not have a dipole moment. This occurs
when the individual bond polarities are arranged in such a way that they cancel
each other out.9

The Localized Electron Bonding Model:

Assumes that a molecule is composed of atoms that are bound together by using
atomic orbitals to share electron pairs.
Electron pairs in the molecule are assumed to be localized on a particular atom
called lone pairs or in the space between 2 atoms called bonding pairs.
The LE model has three parts:
- Description of the valence electron arrangement in the molecule using Lewis
structures.
- Prediction of the geometry of the molecule (VSEPR).
- Description of the types of atomic orbitals used by the atoms to share
electrons or hold lone pairs.
Lewis Structures:
The Lewis structures of molecule shows how the valence electrons are arranged
among the atoms in the molecule.
The most important requirement for the formation of stable compound is that the
atoms achieve noble gas electron configuration.
Noble Gas Electron Configuration – Octet Rule:
Noble gas has 8 electrons on the valence shell except He (2 e-). They have a stable
configuration at the ground state.
The octet is reached by gaining, losing, or sharing one or many valence electrons.
 a. Elements of group I or II: losing 1 or 2 electrons to satisfy the octet rule.
b. Elements of group VI and VII: gaining 1 or 2 electrons to satisfy the octet
rule.
Lewis Structures:
Hydrogen follows the duet rule when it forms a stable molecule: 2 hydrogen atoms
each with 1 e- combine to form the H2 molecule. Now each hydrogen has a filled
valence shell.
Slide 16

 Chapter 4: Intermolecular Forces and The Liquid State

Introduction:

3 states of matter:

Gasses:

- Particles far from each other.

- Particles in random motion.
- Particles exerting relatively small forces on each other.
- Low densities, high compressibility.
- Completely fill a container.
- Kinetic molecular theory accounts for ideal behavior that real gases
approach at high temperatures and low pressures.

Solids:

- Greater densities.
- Compressible to a very small extent.
- Rigid.
- Maintain their shapes irrespective of the container.
- Solid components are close together and exert large attractive forces on each
other.

Liquids:

- Properties in between those of gases and solids, but not midway

H2O (s)  H2O (l) ΔHofus = 6.02kJ/mol
H2O (l)  H2O (g) ΔHovap = 40.7 kJ/mol
A much greater change in structure in going from the liquid state to the gas
than in going from the solid to the liquid.
In liquids: extensive attractive forces among the molecules are similar to but not
as strong as those in the solid state.

Many similarities between solids and liquids and tremendous differences from
the gaseous state.

Intermolecular Forces:

Forces that cause the aggregation of the components of a substance to form a

liquid or a solid.

Strongest to weakest: strongest means the highest Bp, Mp, Solubility in water,
but lowest vapor pressure.

- Ionic forces: between metals and nonmetals in ionic compounds

- Hydrogen bond: Molecules must have FH or OH or NH
- Dipole Dipole: in polar molecules, different electronegativity
- London Dispersion: in nonpolar molecules and noble gases.

Dipole-dipole forces:

Electrons that make up a bond are not equally shared because of the difference
in electronegativity.

Molecules with dipole moments find the best compromise between attraction
and repulsion

1% as strong as covalent or ionic bonds.

They become weaker as the distance between the dipoles increases.

At low pressures in the gas phase, these forces are unimportant.

They are strong in molecules in which hydrogen is bound to a highly

electronegative atom.:
1. Great polarity of the bond
2. Close approach of the dipoles due to the small size of the H

Hydrogen Bonding

Unusual strong dipole-dipole attraction.

London Dispersion Forces:

Molecules without dipole moments must exert forces on each other (H2, CH4,
CCl4, CO2)

The weak forces that exist among noble gas atoms and nonpolar molecules are
called London Dispersion Forces.

Temporary dipolar arrangement of charge can occur which can in turn affect the
electron distribution in a neighboring atom.

This interatomic attraction is both weak and short lived but can be significant
for large atoms.
These interactions to become strong enough to produce a solid, the motion of
the atoms must be greatly reduced (low freezing points for the noble gas).

The freezing point rises going down a group since the mass increases, the
number of electrons increases → increased chance of the occurrence of
momentary dipoles.

Large atoms with many electrons exhibit a higher polarizability than small
atoms.

 London dispersion forces greatly increases as atomic size increases.

The Liquid State:

Surface Tension:

When liquid is poured onto a solid surface, it tends to bead as droplets, a

phenomenon that depends on the intermolecular forces.

The effect of this uneven pull on the surface molecules tend to draw them into
the body of the liquid and causes the droplet to assume the shape that has the
minimum surface area  a sphere.

To increase a liquid’s surface area, molecules must move from the interior of
the liquid to the surface. This requires energy since some intermolecular forces
must be overcome.

The resistance of a liquid to an increase in its surface area is called surface

tension of the liquid.

 Liquids with high intermolecular forces have relatively high surface

tensions.

Viscosity
A measure of a liquid’s resistance to flow.

Liquids with large intermolecular forces tend to be highly viscous.

Molecular complexity also leads to higher viscosity because very large

molecules can become entangled with each other.

- Non-viscous gasoline: molecules of the type CH3-(CH2)n-CH3 (n from 3 to 8)

- Viscous grease: much larger molecules (n from 20 to 25)