Chemistry 7 Reviewer

Chapter 1

Chemistry
 We study matter, its properties and its behavior

Matter
 Anything that has mass and takes up space
 Atoms: building blocks of matter
 Element: made of the same kind of atom
 Compound: matter of two or more stoms
 Molecule: made of two or more atoms
 States: solid, liquid and gas
o Change of state is a PHYSICAL change
o Solid: definite shape and volume, liquid: def. volume
only, gas: indefnite volume and shape
 Classification
o Heterogeneous
o Homogeneous
 Pure substance (no variable composition)
 Element (cannot be simplified), compound
(can be simplified)
 Homogenous mixture (solution) (variable
composition)
 Properties
o Physical (boiling point, density, mass, volume, etc.)
 Can be observed w/o changing a substance
o Chemical (flammability, corrosiveness, reactivity with
acid, etc.)
 Can only be observed when a substance is
changed
o Types
 Intensive (density, boiling point, color, etc.)
 independent of the amount of the substance
 Extensive (mass, volume, energy, etc.)
 dependent of the amount of the substance
 Changes
 o Physical (changes of state, temperature, volume, etc.)
 does not change substance into new one
o Chemical (combustion, oxidation, decomposition, etc.)
 changes substance into new one
 Separation
o Filtration
 solid substances are separated from liquid
o Distillation
 boiling points are used to separate a homogenous
mixture
o Chromotography
 solubility levels are used to separate liquids
o Evaporation
 separates solids and liquids

Units of Measurement
 SI units
o mass (kg), length (m), time (sec.), temperature (K),
amount of substance (mol), electric current (ampere),
luminous intensity (cd)
 Metric system
o Prefixes amount base units into units that are
appropriate
 Volume
o L, mL
o L is a cube 1 dm long on each side
o mL is a cube 1 cm long on each side
 Tempeature
o Measure of average kinetic energy of particles
o C = (F – 32) 5/9
o F = 9/5C + 32
o K = C + 273.15
o C based on property of water (O° C is freezing, 100° C
is boiling)
 Derived Units
o Density (physical, d=m/v, uses g/mL as unit)
 Uncertainty
 o Diff measuring devices have different degrees of
accuracy
o Significant Figures
 Digits that were measured
 Used to make figures certain
 Non-zero digits, zeroes between sig figs, zeroes at
end of number if after decimal point
 NOT zeroes of beginning of number
 Addition/subtraction – least significant decimal
place
 Multiplication/division – least number of sig figs

 Accuracy and precision

o Accuracy – proximity of value to true value
o Precision – proximity of value to other values
 Dimensional analysis
o Converting units

Chapter 2

Atomic Theory of Matter

 Democritus
o Atomos
o “tiny indivisible particles”
 Dalton
o Atomic Theory (w/ 4 postulates)
1. Each element is composed of atoms
2. All atoms of a given element are identical in
mass/other properties, atoms of one element is
different than atoms of another element
3. Atoms of an element are not changed into atoms
of another element; atoms are neither created nor
destroyed in chemical reactions (taking *Law of
Conservation of Mass into mind)
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
(w/ **Law of Definite Proportion and ***Law of
Multiple Proportion in mind
 *The total mass of substances present at the end of a
chemical process is the same as the mass of
substances present before the process took place
**Every chemical compound contains fixed and
constant proportions (by weight)
***When two elements combine with each other to
form two or more compounds, the ratios of the
masses of one element that combines with the fixed
mass of the other are simple whole number
Atomic Structure
 The Electron
o Streams of negatively charged particles were found to
emanate tables, coursing flourescence
o J. J. Thomson is credited w/ their discovery (1897)
o Thomson measured the charge/mass ratio of the
electron to be 1.76 x 10^8 coulombs/gram (C/g)
o Millikan Oil-Drop Experiment: Once the charge/mass
ratio of the electron was known, determinations of
either the charge or the mass of the elcctron would
yield the other
 Radioactivity
o Radioactivity is the spontaneos emission of radiation by
an atom
o It was first observed by Henri Bequerel
o Marie and Pierre Curie also studied it
o Three types
 α particles
 β particles
 γ particles
 The Atom, circa 1900
o The prevailing theory was that of the “plum pudding”
model, put forward by Thomson
o It featured a positive sphere of matter w/ negative
electrons embedded in it
 Discovery of the Nucleus
o Ernest Rutherford shot α particles at a thin sheet of gold
foil and observed the pattern of scatter of the particles
 The Nuclear Atom
 o Since some particles were delfected at large angles,
Thomson’s model could not be correct
o Rutherford postulated a small, dense nucleus w/ the
electrons around the atom
o Most of the atom is empty space
 Other Subatomic Particles
o Protons: discovered by Rutherford (1919)
o Neutrons: discovered by James Chadwick (1932)
 Subatomic Particles
o Protons/electrons are charged
o Protons/neutrons have same mass
o Mass of electron is too small to be taken into account

 Symbols of Elements

 Isotopes
o Isotopes: atoms of the same element w/ different
masses
o Have different numbers of neutrons
 Average Mass
o We have average mass for atoms/molecules
o Calculated from isotopes of an element weighted by
abundances
Periodic Table
  Systematic catalog of elements
 Arranged in order of atomic number
 Rows are called periods
 Columns are groups
 Elements in group have similar chemical properties
 Nonmetals are on right side of the periodic table
 Metalloids border the stair-step line (B, Si, Ge, As, Sb, Te)
 Metals are on the left side of the chart
 Periodicity
o When one looks at the chemical properties of elements,
one notices a repeating pattern of reactivities
 Groups
o Alkali metals, alkaline earth metals, chalcogen metals,
halogen metals, noble gases, nonmetals

Chapter 6: Electronic Structure of Atoms

Waves
 To understand the elctronic structure, one must understand
the nature of electromagnetic radiation
 The distance between corresponding points on adjacent
waves is the wavelength
 3 x 10^8 m/s – speed of light
 Number of waves passing a given point per unit of time –
frequency
 Longer the wavelength, the smaller the frequency
Electromagnetic Radiation
 All electromagnetic radiation travel at the same velocity: the
speed of light (c), 3.00 x 10^8 m/s
 Therefore: c = λν
The Nature of Energy
 The wave nature of light does not explain how an object can
glow when its temperature increases
  Max Planck explained it by assuming that energy comes in
packets called quanta (E = hν)
 Einstein used this assumption to explain the photoelectric
effect
o He concluded that energy is proportional to frequency:
E = hν where h is Planch’s constant, 6.626 x 10^-34 Js
 Therefore, if one knows the wavelength of light, one can
calculate the energy
 Emission spectra observed from energy emitted by atms and
molecules became another mystery
 For atoms and molecules, one does not observe a continuous
spectrum as one gets form a white light source
 Only a line spectrum of discrete wavelengths is observed
 Neils Bohr adopted Planck’s assumption and explained these
phenomena in this way:
1. Electrons in an atom can only occupy certain orbits
(corresponding to certain objects)
2. Electrons in permitted objects have specific, “allowed”
energies; these energies will not be radiated from the
atom
3. Energy is only absorbed or emitted in such a way is to
move an electron from one “allowed” energy state to
another, destined by E = hv
4. The energy absorbed or emitted from the process of
electron promotion or demotion can be calculated by
the equation
ΔE = -hcR (1/nf^2 – 1/ni^2)
where R is the Rydberg constant 1.097 x 10^7 m^-1,
and ni and nf are the initial and final energy levels of
the electron (-hcR is -2.18x 10-18)
The Wave Nature of Matter
 Louis de Broglie posited that if light can have material
properties, matter should exhibit wave properties
 He demonstrated that the relationship between mass and
wavelength was λ = h/mν
The Uncertainty Principle
 Heisenberg showed that the more precisely the momentum
of a particle is known, the less precisely is its position is
known:
 (Δx)(Δmν) ≥ h/4π
Quantum Mechanics
 Erwin Schrodinger developed a mathematical treatment into
which both the wave and partice nature of matter could be
incorporated
 This is known as quantum mechanics
 The wave equation is designated with a lowercase Greek psi
(ψ)
 The square of the wave equation, ψ^2 gives a probability
Quantum Numbers
 Solving the wave equation gives a set of wave functions, or
orbitals, and their corresponding energies
 Each orbital describes a spatial of distribution of elctron
density
 An orbital is described by a set of three quantity numbers
Principal Quantum Number (n)
 The principal quantum number, n, describes the energy level
on which the orbital resides
 The values of n are integers ≥ 1.
Angular Momentum Quantum Number (l)
 This quantum number defines the shape of the orbital
 Allowed values of l are integers ranging from 0 to n-1
 We use letter designations to communicate the different
values of l and therefore, the shapes and types of orbitals (s-
0, p-1, d-2, f-3)
Magnetic Quantum Number (m1)
 The magnetic quantum number describes the 3D orientation
of the orbital
 Allowed values of m1 are integers ranging from -1 to 1: -1 ≤
m1 ≤1
 Therefore, on any given energy level, there can be up to 1 s
orbital, 3 p orbitals, 5 d orbitals, 7 f orbitals and so forth
Energies of Orbitals
 For one electron H atom, orbitals on the same energy level
have the same energy
 As the number of electrons increase, repulsion between
them increases
Spin Quantum Number (ms)
  Either +1/2 or -1/2 depending on the spin
Pauli Exclusion Principle
 No two electrons in the same atom can have exactly the
same energy
 Therefore, no two electrons in the same atom can have
identical sets of quantum numbers
Electron Configuration
 Term shows the distribution of all electrons in an atom
Orbital Diagrams
 Half-arrows represent electrons
 Direction of atom represent spin
Hund’s Rule
 For degenerate orbitals, the lowest energy is attained when
the number of electrons with the same spin is maximized
Some Anomalies
 For instance, the electron configuration for copper is [Ar]
4s^1 3d^5 rather than the expected [Ar] 4s^2 3d^4

Chapter 7 Periodic Properties of the Elements

Development of Periodic Table
 Dimitri Mendeleev and Lothar Meyer independently came to
the same conclusion about how elements should be grouped
 Mendeleev for instance, predicted the discovery of
germanium
Periodic Trends
 Sizes of atoms and ions
 Ionization energy
 Electron affinity
Effective Nuclear Charge
 In a many charge atom, electrons are both attracted to the
nucleus and repelled by other electrons
 The nuclear charge that an electron experiences depends on
both factors
charge x charge
 Eσ distance Coulomb’s Law
  Zeff (effective nuclear charge) is found by: Zeff = Z – S
where Z is the atomic number and S is a screening constant,
usually close to the number of inner electrons
What is the size of an atom?
 The bonding atomic radius is defined as one-half of the
distance between covalently boarded nuclei
 Left  Right (decreases because of increasing Zeff)
 Top  Bottom (increases because of increasing shells or
value of n)
 Depends on nuclear charge, number of electrons, orbitals in
which electrons reside
 Cations are smaller than their parent atoms
 Anions are larger than parent atoms
 Ions increase in size as you go down (due to increasing value
in n)
 In an isoelectric series, ions have the same number of
electrons
 Ionic size decreases with an increasing nuclear charge
Ionization energy
 Amount of energy required to emove an electron from the
ground state of a gaseous atom or ion
o The first ionization energy is that energy required to
remove the first electron
o The second ionization energy is that energy required to
remove the second electron, etc.
 Left  Right (increases)
 Top  Bottom (decreases)
 It requires more energy to remove each successive electron
 When all valence electrons have been removed, the
ionization energy takes a quantum leap
 There are two apparent discontinuities in this trend
o Between IIA and IIIA
o Between VA and VIA
Electron Affinity
 Energy charge accompanying the addition of an electron to a
gaseous atom
o Cl + e-  Cl-
 Becomes more exothermic as you go from left to right
Metals and Nonmetals
 Tend to revolve around physical properties in differences
 Metals tend to form cations
 Nonmetals tend to form anions

Chapter 8 – Chemical Bonding

Types
 Ionic
o Electrostatic attraction between ions
 Covalent
o Sharing of electrons
 Metallic
o Metals atoms bonded to several other atoms
Octet Rule
 Atoms tend to add or subtract electrons until they are
surrounded by eight valence electrons
Ionic Bonding
 Results from the interaction between a metal and a non-
metal
Characteristics of Ionic Compounds
 Usually brittle with high melting point
 Usually crystalline
 Can be broken apart along, smooth, flat surfaces
Energetics of Ionic Bond Formation
 To lose/give up an electron, energy must be supplied. The
reaction is ENDORTHERMIC
 To gain an electron, energy must be released. The reaction is
EXOTHERMIC
 But these numbers don’t explain why the reaction of sodium
metal and chlorine gas to form sodium chloride is exothermic
 The electrostatic attraction between the sodium cation and
chlorine anion causes release of energy
 Lattice energy – the energy required to completely separate
one mole of solid compound into its ions
 The magnitude of lattice energy depends on the charges of
the ions and their arrangement in the solid
kQ1 Q 2
o Elattice = d k=8.99x10^9
  Where energy increases with the charge on the ions
 It also increases with decreasing size of ions
Covalent Bonds
 In covalent bonds, atoms share electrons
 There are several electrostatic interaction in these bonds:
o Attractions between electrons and nuclei
o Repulsions between electrons
o Repulsions between nuclei
 Polar: Electrons not shared equally
Electronegativity
 Is the ability of atoms in a molecule to sttract electrons to
themselves
Polar Covalent Bonds
 When two atoms share electrons unequally, a bond dipole
results
 The dipole moment, μ produced by two equal but opposite
charges separated by a distance is calculated by μ = Qr
 Measured in deloyes (D), 1D = 3.34 x 10^-30 C-m 1A 10^-
10 m
 The greater the difference in electronegativity, the more
power in the bond
Ionic vs Covalent Bonds
Ionic Covalent
Usually solid Liquid or gas state
Brittle
High melting point Low melting and boiling point
Strong electrolyte Weak electrolyte
High electronegativity No or small difference in
difference electronegativity

Lewis structures
 Representations of molecules showing all electrons, bonding
and nonbonding
1. Find sum of valence electrons of all atoms in the polyatomic
ion or molecule.
o If it is an anion, add one electron for each negative charge
o If it is a cation, subtract one electron for each positive
charge
 2. The central atoms is the least electronegative element that
isn’t hydrogen – connect the outer atoms to it by single
bonds.
3. Fill the octets of the outer atoms.
4. Fill the octet of the central atom.
5. If you run out of electrons before the central atom has an
octet, form multiple bonds until it does.
 Then assign formal charges
o For each atom, count the elctrons in lone pairs and half
the electrons, it shares with other atoms
o Subtract that form the number of valence electrons for
that atom: is its formal charge
o FC = valence electrons – non-bonding – ½ bonding
 The best Lewis structure…
o …is the one with the fewest charges
o …puts a negative charge on the most electromagnetic
atom
Resonance
 One Lewis structure cannot accurately depict a molecule-like
ozone
 We use multiple structures, resonance structures, to describe
the molecule
 In truth, the electrons that form the second C-O bond in the
double bonds below do not always do not always sit between
that C and that O, but rather can.
Exceptions
 Three types of ions or molecules that do not follow the octet
rule
o Ions or molecules with an odd number of electrons
o Ions or molecules with less than an octet
o Ions or molecules with more than eight valence
electrons
Odd Number of Electrons
 Though relativly rare and usually quite unstable and
reactive, there are ions or molecules with an odd number of
electrons
Fewer than 8 electrons
  If filling the octet of the central atom results in a negative
charge on the central atom and a positive charge on the
more electronegative outer atom, don’t fill the octet of the
central atom.
More than 8 electrons
 When the central atom is on the third row or below and
expanding its octet eliminates some formal charges, do so.
Enthalpies of Reaction
 Yet another way to estimate DH for a reaction is to compare
the bond enthalpies of bonds broken to the bond enthalpies
of the new bonds formed.
o In other words,
DHrxn = S(bond enthalpies of bonds broken) −
S(bond enthalpies of bonds formed)

Ionic Compounds
1) Binary
MgCl2 – Magnesium chlrodie
NaBr – Sodium bromide
SrI2 – strontium iodide
2) Transition Metals
Cu, Fe, Co, Pb, Sn, Hg, Zn, Ag, Mn
3) Polyatomic Ions
4) Acids
HCl, HBr, HI, HF
5) Bases
OH, NaOH, Mg(OH)2, Al(OH)3
6) Hydrates
CuSO4 – 5H2O
7) Ternary
KAl(SO4)2

Covalent Compounds  NM +NM

 PCl3 – phosphorus trichloride
 IF6 – iodine hexaflouride
 P2Cl5 – diphosphorus pentachloride
Chapter 9: Molecular Geometry
Molecular Shape
 The shape of a molecule plays an important role in its
reactivity
 By noting the number of bonding and nonbonding electron
pairs, we can easily predict the shape of the molecule

What Determines the Shape of a Molecule

 Simply put, electron pairs, whether they be bonding or
nonbonding, repel each other
 By assuming the electron pairs are placed as far as possible
from each other, we can predict the shape of the molecule

Electron Domains
 We can refer to the electron pairs as electron domains
  In a double or triple bond, all electrons shared between
these two atoms are on the same side of the central atom,
therefore, they count as one electron domain

Valence-Shell Electron-Pair Repulsion Theory (VSEPR)

 “The best arrangement of a given number of electron
domains is the one that minimizes the repulsions among
them.”

Electron-Domain Geometries
 All one must do is count the number of electron domains in
the Lewis structure
 The geometry will be that whichh corresponds to the number
of electron domains

Molecular Geometries
 The elctron-domain geometry is often not the shape of the
molecule
 The molecular geometry is that defined by the positions of
only the atoms in the molecules, not the nonbonding pairs
 Within each electron domain, then, there might be more
than one molecular geometry

Linear Electron Domain

 In the linear domain, there is only one molecular geometry:
linear

Trigonal Planar Electron Domain

 There are two molecular geometries:
o Trigonal planar, if all the electron domains are bonding,
o Bent, if one of the domains is a nonbonding pair.
Nonbonding Pairs and Bond Angles
 Nonbonding pairs are physically bigger than bonding pairs
 Therefore, their repulsions are greater, this tends to
decrease bond angles in a molecule

Multiple Bonds and Bond Angles

  Double and triple bonds place greater electron density on
one side of the central atom than do single bonds
 Therefore, they also attract bond angles

Tetrahedral Electron Domain

 There are three molecular geomtries
o Tetrahedral, if all are bonding pairs
o Trigonal pyramidal, if one is a nonbonding pair
o Bent, if there are two nonbonding pairs

Trigonal Bipyramidal Electron Domain

 There are two distinct positions in the geometry:
o Axial
o Equatorial
 Lower-energy conformations result from having nonbonding
electron pairs
 There are four distinct molecular geometries in this domain
o Trigonal bipyramidal
o Seesaw
o T-shaped
o Linear
Octahedral Electron Domain
 All positions are equivalent in the octahedral domain
 There are three molecular geometries
o Octahedral
o Square pyramidal
o Square planar

Larger Molecules
 It makes more sense to talk about the geomtry about a
particular atom other than the geometry of the molecula as
a whole

Polarity
 Just because a molecule possesses polar bonds does not
mean the molecule as a whole will be polar
  By adding the individual bond of poles, one can determine
the overall dipole mount for the molecule

Overlap and Bonding

 We think of covalent bonds forming through the sharing of
electrons by adjacent atoms
 In such an approach this can only occur when orbitals on the
two atoms overlap
 Increased overlap brings the electrons and nuclei close
together while simultaneously decreasing electron-electron
repulsion
 However, if atoms get too close, the internuclear repulsion
greatly raises the energy

Hybrid Orbitals
 Consider beryllium
o In its ground electronic statem beryllium would not be
able to form bonds, because it has not singly occupied
orbitals
 But if it absorbs the small amount needed to promote an
electron from the 2s to the 2p orbital, it can form two bonds.
 Mixing the s and p orbitals yields two degenerate orbitals
that are hybrids of the two orbitals.
o These sp hybrid orbitals have two lobes like a p orbital.
o One of the lobes is larger and more rounded, as is the s
orbital.
 These two degenerate orbitals would align themselves 180°
from each other.
 This is consistent with the observed geometry of beryllium
compounds: linear.
 The sp orbitals are higher in energy than the 1s orbital, but
lower than the 2p.
 Using a similar model for boron leads to three degenerate
sp2 orbitals.
 With carbon, we get four degenerate sp3 orbitals

Valence Bond Theory

  Hybridization is a major player in this approach to bonding.
 There are two ways orbitals can overlap to form bonds
between atoms.

Sigma (s) Bonds

 Sigma bonds are characterized by
o Head-to-head overlap.
o Cylindrical symmetry of electron density about the
internuclear axis.

Pi (p) Bonds
• Pi bonds are characterized by
o Side-to-side overlap.
o Electron density above and below the internuclear axis.

Single Bonds
 Single bonds are always s bonds, because s overlap is
greater, resulting in a stronger bond and more energy
lowering.

Multiple Bonds
 In a multiple bond, one of the bonds is a s bond and the rest
are p bonds.
 In a molecule like formaldehyde (shown at left), an sp2
orbital on carbon overlaps in s fashion with the
corresponding orbital on the oxygen.
 The unhybridized p orbitals overlap in p fashion.
 In triple bonds, as in acetylene, two sp orbitals form a s bond
between the carbons, and two pairs of p orbitals overlap in p
fashion to form the two p bonds.

Chapter 4: Reactions in Aqueous Solutions

Solutions
 Solutions are defined as homogeneous mixtures of two or
more pure substances.
 The solvent is present in greatest abundance.
 All other substances are solutes.
  An electrolyte is a substance that dissociates into ions
when dissolved in water.
 A nonelectrolyte may dissolve in water, but it does not
dissociate into ions when it does so.

Dissociation
 When an ionic substance dissolves in water, the solvent pulls
the individual ions from the crystal and solvates them.
 This process is called dissociation.
 An electrolyte is a substances that dissociates into ions
when dissolved in water.

Electrolytes and Nonelectrolytes

 Soluble ionic compounds tend to be electrolytes.
 Molecular compounds tend to be nonelectrolytes, except for
acids and bases.
 A strong electrolyte dissociates completely when
dissolved in water.
 A weak electrolyte only dissociates partially when
dissolved in water.
 Strong acids
 Strong bases
 Soluble ionic salts

Precipitation Reactions
 When one mixes ions that form compounds that are
insoluble (as could be predicted by the solubility guidelines),
a precipitate is formed.

Metathesis (Exchange) Reactions

 Metathesis comes from a Greek word that means “to
transpose.”
 It appears as though the ions in the reactant compounds
exchange, or transpose, ions:
o AgNO3(aq) + KCl(aq) ¾® AgCl(s) + KNO3(aq)

Solution Chemistry
  It is helpful to pay attention to exactly what species are
present in a reaction mixture (i.e., solid, liquid, gas, aqueous
solution).
 If we are to understand reactivity, we must be aware of just
what is changing during the course of a reaction.

Molecular Equation
 The molecular equation lists the reactants and products in
their molecular form:
o AgNO3(aq) + KCl(aq) ¾® AgCl(s) + KNO3(aq)

Ionic Equation
 In the ionic equation all strong electrolytes (strong acids,
strong bases, and soluble ionic salts) are dissociated into
their ions.
 This more accurately reflects the species that are found in
the reaction mixture:
o Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq) ¾® AgCl(s) +
K+(aq) + NO3−(aq)

Net Ionic Equation

 To form the net ionic equation, cross out anything that does
not change from the left side of the equation to the right:
o Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq) ¾® AgCl(s) + K+
(aq) + NO3−(aq)
 The only things left in the equation are those things that
change (i.e., react) during the course of the reaction:
o Ag+(aq) + Cl−(aq) ¾® AgCl(s)

Solubility Rule
 SOLUBLE IONIC COMPOUNDS
o All group 1 cations
o Nitrates (NO3-)
o Acetates (CH3COO-)
o Halides (except halides of silver, mercury and lead)
o Sulfates (SO4-2) except sulfates of strontium, barium,
mercury and lead
 INSOLUBLE IONIC COMPOUNDS
 o Sulfides (S-2) except ammonium, alkali metal cations,
calcium, strontium and barium
o Carbonates (CO3-2) except ammonium and alkali metal
cations
o Phosphates (PO4-3) except ammonium and alkali metal
cations
o Hydroxides (OH-) except ammonium, alkali metal
cations, calcium, strontium and barium

Writing Net Ionic Equations

1. Write a balanced molecular equation.
2. Dissociate all strong electrolytes.
3. Cross out anything that remains unchanged from the left
side to the right side of the equation.
4. Write the net ionic equation with the species that remain.

Acids
 The Swedish physicist and chemist S. A. Arrhenius defined
acids as substances that increase the concentration of H +
when dissolved in water.
 Both the Danish chemist J. N. Brønsted and the British
chemist T. M. Lowry defined them as proton donors.
 There are only seven strong acids:
o Hydrochloric (HCl)
o Hydrobromic (HBr)
o Hydroiodic (HI)
o Nitric (HNO3)
o Sulfuric (H2SO4)
o Chloric (HClO3)
o Perchloric (HClO4)

Bases
 Arrhenius defined bases as substances that increase the
concentration of OH− when dissolved in water.
 Brønsted and Lowry defined them as proton acceptors.
 The strong bases are the soluble metal salts of hydroxide
ion:
o Alkali metals
 o Calcium
o Strontium
o Barium

Acid-Base Reactions
 In an acid–base reaction, the acid donates a proton (H +) to
the base.

Neutralization Reactions
 Generally, when solutions of an acid and a base are
combined, the products are a salt and water:
o CH3COOH(aq) + NaOH(aq) ¾®CH3COONa(aq) + H2O(l)
 When a strong acid reacts with a strong base, the net ionic
equation is
o HCl(aq) + NaOH(aq) ¾® NaCl(aq) + H2O(l)
o H+(aq) + Cl−(aq) + Na+(aq) + OH−(aq) ¾® Na+(aq) +
Cl−(aq) + H2O(l)
o H+(aq) + OH−(aq) ¾® H2O(l)

Gas-Forming Reactions
 Some metathesis reactions do not give the product
expected.
 In this reaction, the expected product (H2CO3) decomposes
to give a gaseous product (CO2):
o CaCO3(s) + HCl(aq) ¾®CaCl2(aq) + CO2(g) + H2O(l)
 When a carbonate or bicarbonate reacts with an acid, the
products are a salt, carbon dioxide, and water:
o CaCO3(s) + HCl(aq) ¾®CaCl2(aq) + CO2(g) + H2O(l)
o NaHCO3(aq) + HBr(aq) ¾®NaBr(aq) + CO2(g) + H2O(l)
 Similarly, when a sulfite reacts with an acid, the products are
a salt, sulfur dioxide, and water:
o SrSO3(s) + 2HI(aq) ¾®SrI2(aq) + SO2(g) + H2O(l)
 This reaction gives the predicted product, but you had better
carry it out in the hood, or you will be very unpopular!
 But just as in the previous examples, a gas is formed as a
product of this reaction:
o Na2S(aq) + H2SO4(aq) ¾® Na2SO4(aq) + H2S(g)
Oxidation-Reduction Reactions
 An oxidation occurs when an atom or ion loses electrons.
 A reduction occurs when an atom or ion gains electrons.
 One cannot occur without the other.

Oxidation Numbers
 To determine if an oxidation–reduction reaction has occurred,
we assign an oxidation number to each element in a
neutral compound or charged entity.
 Elements in their elemental form have an oxidation number
of 0.
 The oxidation number of a monatomic ion is the same as its
charge.
 Nonmetals tend to have negative oxidation numbers,
although some are positive in certain compounds or ions.
o Oxygen has an oxidation number of −2, except in the
peroxide ion, in which it has an oxidation number of −1.
o Hydrogen is −1 when bonded to a metal, +1 when
bonded to a nonmetal.
o Fluorine always has an oxidation number of −1.
o The other halogens have an oxidation number of −1
when they are negative; they can have positive
oxidation numbers, however, most notably in
oxyanions.
 The sum of the oxidation numbers in a neutral compound is
0.
 The sum of the oxidation numbers in a polyatomic ion is the
charge on the ion.

Displacement Reactions
 In displacement reactions, ions oxidize an element.
 The ions, then, are reduced.
 In this reaction, silver ions oxidize copper metal:
o Cu(s) + 2Ag+(aq) ¾® Cu2+(aq) + 2Ag(s)
 The reverse reaction, however, does not occur:
 o Cu2+(aq) + 2Ag(s) ¾® Cu(s) + 2Ag+(aq) X

Molarity
 Two solutions can contain the same compounds but be quite
different because the proportions of those compounds are
different.
 Molarity is one way to measure the concentration of a
solution:
o Molarity (M) = moles of solute/volume of solution in
liters

Mixing a Solution
 To create a solution of a known molarity, one weighs out a
known mass (and, therefore, number of moles) of the solute.
 The solute is added to a volumetric flask, and solvent is
added to the line on the neck of the flask.

Dilution
 One can also dilute a more concentrated solution by
o Using a pipet to deliver a volume of the solution to a
new volumetric flask, and
o Adding solvent to the line on the neck of the new flask.
 The molarity of the new solution can be determined from the
equation Mc ´ Vc = Md ´ Vd, where Mc and Md are the
molarity of the concentrated and dilute solutions,
respectively, and Vc and Vd are the volumes of the two
solutions.

Titration
 Titration is an analytical technique in which one can
calculate the concentration of a solute in a solution.

Chapter 5: Thermochemistry

Energy
 Energy is the ability to do work or transfer heat.
o Energy used to cause an object that has mass to move
is called work.
 o Energy used to cause the temperature of an object to
rise is called heat.
 Kinetic Energy
o Kinetic energy is energy an object possesses by virtue
1 2
of its motion: Ek= 2 m v
 Potential Energy
o Potential energy is energy an object possesses by
virtue of its position or chemical composition.
o The most important form of potential energy in
molecules is electrostatic potential energy, Eel:
kQ 1Q 2
Eel=
d
 Units
o The SI unit of energy is the joule (J):
2
kg m
 1 J =1
s2
o An older, non-SI unit is still in widespread use: the
calorie (cal):
 1 cal = 4.184 J
 Definitions: System and Surroundings
o The system includes the molecules we want to study
(here, the hydrogen and oxygen molecules).
o The surroundings are everything else (here, the
cylinder and piston).
 Definitions: Work
o Energy used to move an object over some distance is
work:
o w = F ´ d where w is work, F is the force, and d is the
distance over which the force is exerted.
 Heat
o Energy can also be transferred as heat.
o Heat flows from warmer objects to cooler objects.
 Conversion of Energy
o Energy can be converted from one type to another.
 o
o For example, the cyclist in Figure 5.2 has potential
energy as she sits on top of the hill.
o As she coasts down the hill, her potential energy is
converted to kinetic energy.
o At the bottom, all the potential energy she had at the
top of the hill is now kinetic energy.
First Law of Thermodynamics
 Energy is neither created nor destroyed.
 In other words, the total energy of the universe is a constant;
if the system loses energy, it must be gained by the
surroundings, and vice versa.

Internal Energy
 The internal energy of a system is the sum of all kinetic
and potential energies of all components of the system; we
call it E.
 By definition, the change in internal energy, DE, is the final
energy of the system minus the initial energy of the system:
o DE = Efinal − Einitial
 Changes
o If DE > 0, Efinal > Einitial
 Therefore, the system absorbed energy from the
surroundings.
 This energy change is called endergonic.
o If DE < 0, Efinal < Einitial
 Therefore, the system released energy to the
surroundings.
 This energy change is called exergonic.
 o When energy is exchanged between the system and
the surroundings, it is exchanged as either heat (q) or
work (w).
o That is, DE = q + w.
 DE, q, w, and Their Signs
o For q: + means system gains heat, - means system
loses heat
o For w: + means work done on system, - means work
done by system
o For DE: + means net gain of energy by system, - means
net loss of energy by system

Exchange of Hear between System and Surroundings

 When heat is absorbed by the system from the surroundings,
the process is endothermic.
 When heat is released by the system into the surroundings,
the process is exothermic.

State Functions
 Usually we have no way of knowing the internal energy of a
system; finding that value is simply too complex a problem.
 However, we do know that the internal energy of a system is
independent of the path by which the system achieved that
state.
o In the system depicted in Figure 5.9, the water could
have reached room temperature from either direction.
 Therefore, internal energy is a state function.
 It depends only on the present state of the system, not on
the path by which the system arrived at that state.
 And so, DE depends only on Einitial and Efinal.
 However, q and w are not state functions.
 Whether the battery is shorted out or is discharged by
running the fan, its DE is the same.
o But q and w are different in the two cases.

Work
  Usually in an open container the only work done is by a gas
pushing on the surroundings (or by the surroundings pushing
on the gas).
 We can measure the work done by the gas if the reaction is
done in a vessel that has been fitted with a piston: w = −PDV

Enthalpy
 If a process takes place at constant pressure (as the majority
of processes we study do) and the only work done is this
pressure–volume work, we can account for heat flow during
the process by measuring the enthalpy of the system.
 Enthalpy is the internal energy plus the product of pressure
and volume:
o H = E + PV
 When the system changes at constant pressure, the change
in enthalpy, DH, is DH = D(E + PV)
 This can be written: DH = DE + PDV
 Since DE = q + w and w = −PDV, we can substitute these
into the enthalpy expression:
DH = DE + PDV
DH = (q + w) − w
DH = q
 So, at constant pressure, the change in enthalpy is the heat
gained or lost.

Endothermicity and Exothermicity

 A process is endothermic when DH is positive.
 A process is exothermic when DH is negative.

Enthalpy of Reaction
 The change in enthalpy, DH, is the enthalpy of the products
minus the enthalpy of the reactants: DH = Hproducts − Hreactants
 This quantity, DH, is called the enthalpy of reaction, or the
heat of reaction.
1. Enthalpy is an extensive property.
2. DH for a reaction in the forward direction is equal in size, but
opposite in sign, to DH for the reverse reaction.
 3. DH for a reaction depends on the state of the products and
the state of the reactants.

Calorimetry
 Since we cannot know the exact enthalpy of the reactants
and products, we measure DH through calorimetry, the
measurement of heat flow.

Heat Capacity and Specific Heat

 The amount of energy required to raise the temperature of a
substance by 1 K (1°C) is its heat capacity.
 We define specific heat capacity (or simply specific heat)
as the amount of energy required to raise the temperature of
1 g of a substance by 1 K (or 1 °C).
heat transferred
 Specific heat, then, is: Specific heat= mass x temperature change or
q
s=
m x ΔT
Constant Pressure Calorimetry
 By carrying out a reaction in aqueous solution in a simple
calorimeter such as this one, one can indirectly measure the
heat change for the system by measuring the heat change
for the water in the calorimeter.
 Because the specific heat for water is well known (4.184 J/g-
K), we can measure DH for the reaction with this equation: q
= m ´ s ´ DT

Bomb Calorimetry
 Reactions can be carried out in a sealed “bomb” such as this
one.
 The heat absorbed (or released) by the water is a very good
approximation of the enthalpy change for the reaction.
 Because the volume in the bomb calorimeter is constant,
what is measured is really the change in internal energy, DE,
not DH.
 For most reactions, the difference is very small.

Hess’ Law
  DH is well known for many reactions, and it is inconvenient
to measure DH for every reaction in which we are interested.
 However, we can estimate DH using published DH values and
the properties of enthalpy.
 Hess’s law states that “[i]f a reaction is carried out in a
series of steps, DH for the overall reaction will be equal to
the sum of the enthalpy changes for the individual steps.”
 Because DH is a state function, the total enthalpy change
depends only on the initial state of the reactants and the
final state of the products.

Enthalpies of Formation
 An enthalpy of formation, DHf, is defined as the enthalpy
change for the reaction in which a compound is made from
its constituent elements in their elemental forms.
 Standard enthalpies of formation, DHf°, are measured under
standard conditions (25 °C and 1.00 atm pressure)
 We can use Hess’s law in this way:
DH = SnDHf,products – SmDHf°,reactants
where n and m are the stoichiometric coefficients.

Energy in Foods
 Most of the fuel in the food we eat comes from
carbohydrates and fats.
 The vast majority of the energy consumed in this country
comes from fossil fuels.

Chapter 10: Gases

Characteristics of Gases
 Unlike liquids and solids, gases
o Expand to fill their containers.
o Are highly compressible.
o Have extremely low densities.
o Has widely separated particles
o Are readily mixable
o Has very free movement
Pressure
F
 Pressure is the amount of force applied to an area: P=
A
 Atmospheric pressure is the weight of air per unit of area.
 Units:
o Pascals: 1 Pa = 1 N/m2
o Bar: 1 bar = 105 Pa = 100 kPa
o mmHg or torr: These units are literally the difference in
the heights measured in mm (h) of two connected
columns of mercury.
o Atmosphere: 1.00 atm = 760 torr
 Manometer:
o The manometer is used to measure the difference in
pressure between atmospheric pressure and that of a
gas in a vessel.
 Standard Pressure:
o Normal atmospheric pressure at sea level is referred to
as standard pressure.
o It is equal to
 1.00 atm
 760 torr (760 mmHg)
 101.325 kPa

Boyle’s Law
 The volume of a fixed quantity of gas at constant
temperature is inversely proportional to the pressure.
 PV = k  V = k (1/P)

Charles’ Law
 The volume of a fixed amount of gas at constant pressure is
directly proportional to its absolute temperature.
 V/T=k

Gay-Lussac’s Law
 P/T = k

Avogadro’s Law
  The volume of a gas at constant temperature and pressure is
directly proportional to the number of moles of the gas.
 Mathematically, this means V=kn

Ideal-Gas Equation
 So far we’ve seen that
o V µ 1/P (Boyle’s law)
o V µ T (Charles’s law)
o V µ n (Avogadro’s law)
 Combining these, we get
nT
 V µ P  PV = nRT
 The constant of proportionality is known as R, the gas
constant.

Densities of Gases
 If we divide both sides of the ideal-gas equation by V and by
RT, we get
n P
o =
V RT
 We know that Moles ´ molecular mass = mass (n ´ M = m)
 So multiplying both sides by the molecular mass ( M) gives
m PM
o =
V RT
m PM
 Mass ¸ volume = density so d= V = RT
 Note: One needs to know only the molecular mass, the
pressure, and the temperature to calculate the density of a
gas.

Molecular Mass
 We can manipulate the density equation to enable us to find
the molecular mass of a gas:
PM dRT
o d= RT becomes M = P
 Dalton’s Law of Partial Pressures
o The total pressure of a mixture of gases equals the sum
of the pressures that each would exert if it were present
alone.
 o In other words, Ptotal = P1 + P2 + P3 + …
o Partial Pressures
 When one collects a gas over water, there is water
vapor mixed in with the gas.
 To find only the pressure of the desired gas, one
must subtract the vapor pressure of water from
the total pressure.

Kinetic-Molecular Theory
 This is a model that aids in our understanding of what
happens to gas particles as environmental conditions
change.
 Main Tenents:
o Gases consist of large numbers of molecules that are in
continuous, random motion.
o The combined volume of all the molecules of the gas is
negligible relative to the total volume in which the gas
is contained.
o Attractive and repulsive forces between gas molecules
are negligible.
o Energy can be transferred between molecules during
collisions, but the average kinetic energy of the
molecules does not change with time, as long as the
temperature of the gas remains constant.
o The average kinetic energy of the molecules is
proportional to the absolute temperature.

Effusion
 Effusion is the escape of gas molecules through a tiny hole
into an evacuated space.
 The difference in the rates of effusion for helium and
nitrogen, for example, explains why a helium balloon would
deflate faster.

Diffusion
 Diffusion is the spread of one substance throughout a space
or throughout a second substance.
 KE1 = KE2
Real Gases
 In the real world, the behavior of gases only conforms to the
ideal-gas equation at relatively high temperature and low
pressure.
 Even the same gas will show wildly different behavior under
high pressure at different temperatures.

Deviations from Ideal Behavior

 The assumptions made in the kinetic-molecular model
(negligible volume of gas molecules themselves, no
attractive forces between gas molecules, etc.) break down at
high pressure and/or low temperature.

Corrections for Nonideal Behavior

 The ideal-gas equation can be adjusted to take these
deviations from ideal behavior into account.
 The corrected ideal-gas equation is known as the van der
Waals equation.

The van der Waals Equation

n2 a (
 ( P+ 2 ¿ v −nb ) =nRT
V

Chapter 11: Liquids and Intermolecular Forces

States of Matter
 The fundamental difference between states of matter is the
distance between particles.
 Because in the solid and liquid states particles are closer
together, we refer to them as condensed phases.
 The state a substance is in at a particular temperature and
pressure depends on two antagonistic entities:
o The kinetic energy of the particles.
o The strength of the attractions between the particles.

Intermolecular Forces
  The attractions between molecules are not nearly as strong
as the intramolecular attractions that hold compounds
together.
 These intermolecular attractions are, however, strong
enough to control physical properties, such as boiling and
melting points, vapor pressures, and viscosities.
 These intermolecular forces as a group are referred to as
van der Waals forces.
 van der Waals forces
o Dipole–dipole interactions
o Hydrogen bonding
o London dispersion forces

London Dispersion Forces

 While the electrons in the 1s orbital of helium would repel
each other (and, therefore, tend to stay far away from each
other), it does happen that they occasionally wind up on the
same side of the atom.
 At that instant, then, the helium atom is polar, with an
excess of electrons on the left side and a shortage on the
right side.
 Another helium atom nearby, then, would have a dipole
induced in it, as the electrons on the left side of helium atom
2 repel the electrons in the cloud on helium atom 1.
 London dispersion forces, or dispersion forces, are
attractions between an instantaneous dipole and an induced
dipole.
 These forces are present in all molecules, whether they are
polar or nonpolar.
 The tendency of an electron cloud to distort in this way is
called polarizability.
 Factors:
o The shape of the molecule affects the strength of
dispersion forces: long, skinny molecules (like n-
pentane) tend to have stronger dispersion forces than
short, fat ones (like neopentane).
o This is due to the increased surface area in n-pentane.
 o The strength of dispersion forces tends to increase with
increased molecular weight.
o Larger atoms have larger electron clouds that are
easier to polarize.

Dipole-Dipole Interactions
 Molecules that have permanent dipoles are attracted to each
other.
o The positive end of one is attracted to the negative end
of the other, and vice versa.
o These forces are only important when the molecules
are close to each other.
 The more polar the molecule, the higher its boiling point.

Which Have a Greater Effect?: Dipole-Dipole Interactions or

Dispersion Forces
 If two molecules are of comparable size and shape, dipole–
dipole interactions will likely be the dominating force.
 If one molecule is much larger than another, dispersion
forces will likely determine its physical properties.
 How Do We Explain This?
o The nonpolar series (SnH4 to CH4) follow the expected
trend.
o The polar series follow the trend until you get to the
smallest molecules in each group.

Hydrogen Bonding
 The dipole–dipole interactions experienced when H is bonded
to N, O, or F are unusually strong.
 We call these interactions hydrogen bonds.
 Hydrogen bonding arises in part from the high
electronegativity of nitrogen, oxygen, and fluorine.
 Also, when hydrogen is bonded to one of those very
electronegative elements, the hydrogen nucleus is exposed.

Ion-Dipole Interactions
 Ion–dipole interactions (a fourth type of force) are important
in solutions of ions.
  The strength of these forces is what makes it possible for
ionic substances to dissolve in polar solvents.

Intermolecular Forces Affect Many Physical Properties

 The strength of the attractions between particles can greatly
affect the properties of a substance or solution.
 Viscosity
o Resistance of a liquid to flow is called viscosity.
o It is related to the ease with which molecules can move
past each other.
o Viscosity increases with stronger intermolecular forces
and decreases with higher temperature.
 Surface Tension
o Surface tension results from the net inward force
experienced by the molecules on the surface of a liquid.

Phase Changes
 

Energy Changes Associated with Changes of State

 The heat of fusion is the energy required to change a solid
at its melting point to a liquid
 The heat of vaporization is defined as the energy required
to change a liquid at its boiling point to a gas.
 The heat of sublimation is defined as the energy required
to change a solid directly to a gas.
 The heat added to the system at the melting and boiling
points goes into pulling the molecules farther apart from
each other.
 The temperature of the substance does not rise during a
phase change.
Vapor Pressure
 At any temperature some molecules in a liquid have enough
energy to break free.
 As the temperature rises, the fraction of molecules that have
enough energy to break free increases.
 As more molecules escape the liquid, the pressure they exert
increases.
 The liquid and vapor reach a state of dynamic equilibrium:
liquid molecules evaporate and vapor molecules condense
at the same rate.
  The boiling point of a liquid is the temperature at which its
vapor pressure equals atmospheric pressure.
 The normal boiling point is the temperature at which its
vapor pressure is 760 torr.
 The natural log of the vapor pressure of a liquid is inversely
proportional to its temperature.
 This relationship is quantified in the Clausius–Clapeyron
equation:
o ln P = −DHvap/RT + C,
where C is a constant.

Phase Diagrams

 Phase diagrams display the state of a substance at various

pressures and temperatures, and the places where equilibria
exist between phases.
 The liquid–vapor interface starts at the triple point (T), at
which all three states are in equilibrium, and ends at the
critical point (C), above which the liquid and vapor are
indistinguishable from each other.
 Each point along this line is the boiling point of the
substance at that pressure.
 The interface between liquid and solid marks the melting
point of a substance at each pressure.
 Below the triple point the substance cannot exist in the liquid
state.
 Along the solid–gas line those two phases are in equilibrium;
the sublimation point at each pressure is along this line.
Phase Diagram of Water

 Note the high critical temperature and critical pressure.

o These are due to the strong van der Waals forces
between water molecules.
 The slope of the solid–liquid line is negative.
o This means that as the pressure is increased at a
temperature just below the melting point, water goes
from a solid to a liquid.

Phase Diagram of Carbon Dioxide

 Carbon dioxide cannot exist in the liquid state at pressures

below 5.11 atm; CO2 sublimes at normal pressures.
