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1
Uncertainties in Scientific Measurements Robert Millikan (1906-1914) determined
Systematic Errors measuring instruments the electron charge e (e = -1.6022x10 -19 C)
have built-in or inherent errors through a series of oil drop experiments
Random Errors limitation in an
experimenters skill or ability to read a X-Rays and Radioactivity
scientific instrument that leads to errors and Wilhelm Roentgen (1895) fluorescence
give results that maybe either too low or too was caused by radiation emitted by the
high cathode ray tubes; he coined the term X-ray
2
For nonmetals, they tend to gain
Chemical Elements electrons equal to: 8 group number
Chemical Symbol representation of an
element Group B (Transition Metals) like the
main-group metals, transition metals form
Elements beyond uranium (Z = 92) do not positive ions, but the number of electrons lost
occur naturally and must be synthesized in is not generally related to the group number.
particle accelerators Most transition metals are able to form 2 or
more ions of differing charge
Isotopes two or more atoms having the
same atomic number but different atomic
mass Chapter 3: Chemical Compounds
A X
ZE
Z: atomic number or the proton number Chemical Compounds composed of 2 or
A: mass number more different elements; represent by
A Z: neutron number chemical formulas
X: number of proton number of electron
Chemical Formula indicates the elements
Atoms with the same number of protons are present and the relative number of atoms of
atoms of the same element each element in the compound
3
The Mole Concept and Chemical (5) In its compound, hydrogen has an
Compound O.S. of +1
(6) In its compound, oxygen has an
Formula Mass mass of a formula unit O.S. of 2
relative to a mass of exactly 12 u for carbon- (7) In their binary compounds with
12 (for ionic compound) metals, the Group 7A elements
have an O.S. of 1; the Group 6A
Molecular Mass mass of a molecule elements, 2; and the Group 5A
relative to a mass of exactly 12 u for carbon- elements, 3
12 (for molecular compound)
4
Polyatomic Ions Stoichiometric Coefficients the
Two or more ions are joined together by coefficients required to balance a
covalent bonds chemical equation
Na2SO4 sodium sulfate
CaC2O4 calcium oxalate Balancing by inspection adjust
CaHPO4 calcium hydrogen phosphate stoichiometric coefficients by trial and error
(see pp. 86-87) until a balanced condition is found
5
Chapter 5: Introduction to (3) chlorides, bromides, and iodides
Reactions in Aqueous (Those of Pb2+, Ag+, and Hg22+ are
insoluble)
Solution
(4) sulfates (Those of Sr2+, Ba2+, Pb2+,
and Hg22+ are insoluble)
The Nature of Aqueous Solutions
The ability to conduct electricity requires that
Compounds that are mostly insoluble
ions be present in the solution and these ions
(1) hydroxides and sulfides (Those of
must come from the solute
the Group 1A and ammonium are
soluble, Sulfides of Group 2A metals
Nonelectrolyte a substance that is not
are soluble, the hydroxides of Ca2+,
ionized and does not conduct
Ba2+ and Sr2+ are slightly soluble)
electric current
(2) carbonates and phosphates
(Those of Group 1A metals are
Strong Electrolyte a substance that is
soluble)
completely ionized in aqueous solutions, and
the solution is a good electrical conductor
Acid-Base Reactions
Svante Arrhenius (1884) the acid-base
Weak Electrolyte partially ionized in
concept
aqueous solution, and the solution is only a
fair conductor of electricity
Acid derived from the Latin acidus (sour);
a substance that provides hydrogen ions (H+)
All soluble ionic compounds and only a
in aqueous solution
relatively few molecular compounds are
strong electrolytes
Base/Alkali comes from the Arabic al-qali,
referring to the ashes of certain plants form
Most molecular compounds are either
which alkaline substances can be extracted;
nonelectrolytes or weak electrolytes
a substance capable of producing hydroxide
ions (OH-) in aqueous solution
Precipitation Reactions
Precipitation reactions occur when certain
Neutralization an acid and a base react to
cations and anions combine to produce an
form water and an aqueous solution of an
insoluble ionic solid called precipitate
ionic compound called a salt
Net Ionic Equation an equation that
(See p. 139 for some common gas-forming
includes only the actual participants in a
reactions)
reaction
Oxidation-Reduction Reactions
Spectator Ions these ions are not
Oxidation a reaction in which a substance
reactants; they go through the reaction
gains O atoms
unchanged
Oxidation a process in which the O.S. of
Solubility Rules
some element increases, and in which
Compounds that are mostly soluble
electrons appear on the right side of a half
(1) the Alkali metals (Group 1A) and
equation
the ammonium ion
(2) nitrates and acetates Z n ( s) Z n 2 (aq) 2 e
6
Reduction a reaction in which a substance Chapter 6: Gases
loses O atoms
Pressure
Reduction -- a process in which the O.S. of The molecules of a gas are in constant
some element decreases, and in which motion, frequently colliding with one another
electrons appear on the left side of a half and with the walls of their container. In their
equation collision the gas molecules exert a force on
C u 2 (aq) 2 e C u ( s) the container walls:
3
Hg
oxidizing agent
reducing agent
2 hH2O hHg
H2O
1
0 The column height is inversely
1 proportional to the liquid density. For a
2 given liquid pressure, the lower the density
the greater the height of the liquid column.
7
Simple Gas Laws Ideal Gas Equation
(1) Boyles Law nT
V
Robert Boyle (1662) discovered the 1 st of P
the simple gas law P V nR T
For a fixed amount of gas at a constant R: ideal gas constant
temperature, gas volume is inversely m
proportional to gas pressure n
1 M
P
V m
Plot: rectangular hyperbola PV RT
M
(2) Charless Law Gas Densities
Jacques Charles (1787) m
The volume of a fixed amount of gas at
V
constant pressure is directly proportional to
the Kelvin (absolute) temperature PM R T
VT
Plot: straight line
Gas densities differs from solid and liquid
Standard Conditions of Temperature and densities in two different ways:
Pressure (1) Gas densities depend strongly on P
Standard T for gas: 273.15 K and T, increasing as the gas
Standard P for gas: 1 atm = 760 mmHg pressure increases and decreasing
as the temperature increases.
(3) Avogadros Law Densities of liquids and solids also
Amedeo Avogadro (1811) equal volume depend somewhat on T, but they
equal numbers means that equal volume depend far less on P
of different gases at the same temperature (2) The density of a gas is directly
and pressure contain equal number of proportional to its molar mass. No
molecules simple relationship exist between
At a fixed temperature and pressure, the density and molar mass for liquids
volume of a gas is directly proportional to the and solids
amount of gas
Vn Mixture of Gases
1 mol gas = 22.4 L (at STP) The simple gas laws and the ideal gas
At STP the number of molecules equation apply to a mixture of nonreactive
contained in 22.4 L of a gas is 6.02 x 10 23 gases as well as to individual gases
8
Kinetic-Molecular Theory of Gases Diffusion the migration or intermingling of
(1) A gas is composed of a very large molecules of different substances as a result
number of extremely small particles of random molecular motion
in constant, random, straight-line
motion Effusion -- the escape of gas molecules
(2) Molecules of a gas are separated by from their container through a tiny orifice or
great distances. The gas is mostly pinhole
empty space
(3) Molecules collide with one another Grahams Law
and with the walls of their container. The rates of effusion (or diffusion) of two
These collisions occur very rapidly, different gases are inversely proportional to
however, and most of the time the square roots of their molar masses
molecules are not colliding r A vA 3RT / M A
(4) There are assumed to be no forces
r B vB 3RT / M B
between molecules except very
briefly during collisions. That is, each
molecule acts independently of all rA v MB
A
the others and is unaffected by their rB vB MA
presence
(5) Individual molecules may gain or
lose energy as a result of collisions. Grahams Law can be used to determine
In a collection of molecules at (1) molecular speeds
constant temperature, however, the (2) rates of effusion
total energy remains constant (3) effusion times (t)
(4) distance traveled by molecules
Root-Mean-Square Speed the square root (5) amount of gas effused (n)
of the average of the squares of the speeds
of all the molecules in the sample
3RT Nonideal (Real) Gases
vr ms Compressibility Factor measure how
M
much a gas deviates from ideal gas behavior
where
PV
R 8.3145 kg m 2 /( s 2 mol K ) z
nR T
M must be in kg/mol
z = 1 for ideal gas
z > 1 at very high pressure
The Kelvin Temperature of a gas is directly
proportional to the average translational
Gases tend to behave ideally at high T
kinetic energy of its molecules
and low P
3 R
Kt r T
2 NA
Gases tend to behave nonideally at low
T and high P
Absolute Zero it is the temperature at
which translational molecular motion should
cease (p. 189)
9
Chapter 7: Thermochemistry Specific heat of water
cal J
1 4.184
Thermochemistry the branch of chemistry gC gC
concerned with heat effect accompanying
chemical reactions Heats of Reaction the quantity of heat
exchange between a system and its
System -- the part of the universe we choose surroundings when a chemical reaction
to study occurs within the system, at constant T
Exothermic Reaction produces a
Surroundings the part of the universe with temperature increase in an isolated system
which the system interacts or, in nonisolated system, gives off heat to
the surroundings: q rxn 0
Interactions refer to the transfer of energy or
Endothermic Reaction -- produces a
matter
temperature decrease in an isolated system,
or a gain of heat from the surroundings:
Internal Energy the total amount of energy
q rxn 0
contained within a system
Thermal Energy energy associated
with random molecular motion
Chemical Energy energy associated The First Law of Thermodynamics
with chemical bonds and intermolecular E q w
forces
Internal Energy, E the total energy (kinetic
Heat and potential) associated with chemical
Heat energy transferred between a system bonds, intermolecular attractions, kinetic
and its surroundings as a result of a energy of molecules, and so on
temperature difference
SI: J Convention
q (heat)
calorie the quantity of heat required to
change the temperature of one gram of water + Absorbed by the system
by one degree Celcius Given off by the system
1 cal = 4.184 J
w (work)
Heat Capacity the quantity of heat
required to change the temperature of a + Work done on the system
system by one degree Work done by the system
SI: J/C
10
For constant P: The enthalpy of formation of a pure element
Work done by the system as it expands: in its most stable form is zero:
w p dV At 298K,
Na ( s) H 2 ( g)
Another important quantity N 2 ( g) O 2 ( g)
H EPV C graphite ( s) Br2 (l)
H E P V
H (q p w ) P V Standard Enthalpy of Reaction, H o -- the
H q p P V P V enthalpy change of a reaction in which all the
E q p reactants and their products are in their
standard states
Ho v p H0f (products) v r H0f (reac tan ts)
Hesss Law by Germain H. Hess
If a process occurs in stages or steps, the
enthalpy change for the overall (net) process
is the sum of the enthalpy changes for the Chapter 8: The Atmospheric Gases
individual steps and Hydrogen
11
atmosphere consists of positive and negative N 2 ( g) 3H 2 ( g) 2NH 3 ( g)
ions, free electrons, neutral atoms, and see p. 246
molecules. The dissociation of molecules into
atoms and the ionization of atoms into NH3 Uses
positive ions and free electrons require the (1) nitrogen fertilizer
absorption of energy. The source of that (2) household cleaning products
energy is electromagnetic radiation from the (3) its OH- reacts with grease and oil
sun. An interesting natural phenomenon molecules to convert them into
associated with the ionosphere is the aurora compounds that are more soluble in
borealis or northern lights water and that do not hold dirt well
Water Vapor in the Atmosphere NH3 Derivatives
Vapor Pressure the maximum possible NH4Cl (NH3 + HCl) manufacture of dry cell
partial pressure of water vapor at a given batteries
temperature
NH4NO3 (NH3 + HNO3) fertilizer and as an
vapor pressure increases with temperature explosive
If p water p vapor pressure water , the water will Urea, CO(NH2)2 excellent fertilizer; also
condense used as a feed supplement for cattle and in
the production of polymers and pesticides
2 NH 3 CO 2 CO (NH 2 ) 2 H 2 O
Relative Humidity the ratio of partial
pressure of water vapor to the vapor HNO3 used in the preparation of various
pressure of water at the same temperature dyes; drugs; fertilizers and explosives such
(expressed on a % basis) as nitroglycerin, nitrocellulose, and
trinitrotoluene (TNT)
partial pressure of water vapor
R.H. x 100%
vapor pressure of water Nitrogen Oxides
N2O (laughing gas) anesthetic properties
and dentistry
Nitrogen
Sources NO2 manufacture of nitric acid
Minerals KNO3 (niter or salt peter) and
NaNO3 (soda niter or Chile saltpeter) N2O4 oxidizer in rocket fuels
Natural plant and animal proteins and
fossilized remains of ancient plant life NO ostwald process; unwanted combustion
products (high T)
Ammonia
One of the most useful chemicals. It can be Catalytic Converter to control smog: CO
converted into a variety of other nitrogen- and hydrocarbons are oxidized to CO 2 and
containing chemicals H2O in the presence of catalyst Pt or Pd
metal. The catalyst is dual purpose, it can
also reduce NO to N2
The Haber-Bosch Process
Fritz Haber (1908) and Carl Bosch
12
Oxygen Noble Gases
Allotropy used to describe the existence HeO2: a breathing mixture for deep sea
of 2 or more forms of an element that differ in diving
their bonding and molecular structure
O 2 dioxygen ArN2: electric light bulbs
O 3 trioxygen excellent oxidizing
Kr and Xe: used in lasers and in flash lamps
agent, a substitute for chlorine in purifying
in photography
drinking water
13
Other Greenhouse gases: Chapter 9: Electrons in Atoms
CH 4 N2O
O3 CFC Electromagnetic Radiation
Electromagnetic Radiation a form of
Hydrogen energy transmission through a vacuum
Henry Cavendish (1785) discovered (empty space) or a medium in which electric
hydrogen and magnetic fields are propagated as
waves
Humphry Davy (1810) proposed that
hydrogen is the key element in acids Wave a disturbance that transmits energy
through a medium
In the universe as a whole, hydrogen
accounts for about 90% if the atoms and James Clerk Maxwell (1865) proposed
75% of the mass, and even on Earth it that electromagnetic radiation (a propagation
occurs in more compounds than any other of electric and magnetic fields) is produced
element by accelerating charged particle
Preparation where
Water Gas Reactions c 2.997925 x 10 8 m / s
C ( s) H2O ( g) CO ( g) H 2 ( g)
CO ( g) H 2O ( g) CO 2 ( g) H 2 ( g) Electromagnetic radiation has constant
velocity (c) in a vacuum
Reforming of Methane
CH 4 ( g) H 2O ( g) CO ( g) 3 H 2 ( g)
Atomic Spectra
Continuous Spectra lines blend together
Compounds of Hydrogen
into an unbroken band of color form red to
Hydrides binary compounds of hydrogen
violet
Covalent Hydride formed between H
and nonmetals
Discontinuous Spectra/ Atomic Spectra/
H 2 Cl 2 2 HCl
Line Spectra the spectra produced by
Ionic Hydride formed between H and certain gaseous substances which is consist
the most active metals (Grp IA and 2A); ionic of only a limited number of colored lines
hydrides react vigorously with water to
produce H2 (g) Robert Bunsen and Gustav Kirchhoff
CaH 2 H 2O Ca (OH ) 2 2 H 2 ( g) developed the 1st spectroscope and used it to
identify elements (cesium, rubidium, and
Uses: manufacture of NH3 and in the helium)
production of light octane gasoline
14
Quantum Theory Niels Bohr blend classical and quantum
Max Planck (1900) proposed that energy, theory
like matter is discontinuous; he postulated
that the energy of a quantum of Bohrs Postulates (inability to deal with
electromagnetic radiation is proportional to multielectron atoms)
the frequency of the radiation: higher (1) The electron moves in circular orbits
frequency greater energy about the nucleus
(2) The electron has only a fixed set of
Plancks Equation allowed orbits called stationary
E h states. As long as an electron
where Plancks constant remains in a given orbit its energy is
Js constant and no energy is emitted
h 6.626 x 10 34
photon (3) An electron can pass only from one
allowed orbit to another. In such
The Photoelectric Effect transitions, fixed discrete of energy
H. Hertz discovered photoelectric effect (quanta) are involved, in accordance
with Plancks equation E h
Photoelectric Effect a beam of electrons
(electric) is produced by shining light (photo) For Hydrogen
on a certain metal surface R H 2.179 x 10 18 J
En 2
n n2
The electron energy depend on the
where n is a quantum number and must be
frequency (color) of the light. The freed
an integral number
electron have greater energies when a
photoelectric material is struck by blue light
Ground State lowest allowed energy
(low intensity, high frequency) than a bright
Excited State high energy level
red one (high intensity, low frequency)
15
2
: the intensity of the wave (intensity
Louis de Broglie (1924) small particles of relates to the number of photons present in a
matter may at times display wave-like region the photon density); it relates to the
properties electron charge density
l 0 1 2 3
Wave Mechanics designation s p d f
Wave Mechanics is a form of quantum
theory based on the concepts of wave-
particle duality, the Heisenberg uncertainty, n l Subshell
and the treatment of electrons as matter 1 0 1s
waves. Mathematical solutions of the 2 0, 1 2s, 2p
equation of wave mechanics area known as 3 0, 1, 2 3s, 3p, 3d
wave function ( ) 4 0, 1, 2, 3 4s, 4p, 4d, 4f
16
The number of orbitals in a subshell: (more negative) with increasing atomic
2l 1 number. Also orbital energies in multielectron
atoms depend on the type of orbital; the
ml l , ( l 1) , ...0 orbitals are not degenerate.
The first three quantum numbers (m, l, and The energy level of a principal shell is
m l ) arise from solutions to the Schrodinger split into separate level for its subshells.
wave equation spdf
17
Rules for Assigning Electrons to Orbitals Except for configuration in which a 3d
(1) Electrons occupy orbital in a way subshell is half-filled with electrons or
that minimizes the energy of the completely filled
atom Sc : Ar 3 d1 4 s 2 (2 valence e)
The order in which orbital fills is: Ti : Ar 3 d 2 4 s 2 (2 valence e)
1s V : Ar 3 d 3 4 s 2 (2 valence e)
2s 2p Cr : Ar 3 d 5 4 s1 (half-filled)
3s 3p 3d Mn : Ar 3 d 5 4 s 2 (2 valence e)
4s 4p 4d 4f
Fe : Ar 3 d 6 4 s 2 (2 valence e)
5s 5p 5d 5f Co : Ar 3 d7 4 s2 (2 valence e)
6s 6p 6d Ni : Ar 3 d8 4 s2 (2 valence e)
7s 7p Cu : Ar 3 d10 4 s1 (completely
filled)
Zn : Ar 3 d10 4 s 2 (2 valence e)
(2) Paulis Exclusion Principle
Wolfgang Pauili (1926)
Electronic Configuration and the Periodic
No two electrons in an atom may
Table
have all four quantum numbers
s block: n Groups 1A and 2A
alike only 2 electrons may occupy
the same orbital and these electrons
p block: n Groups 3A, 4A, 5A, 6A, 7A, 8A
must have opposing spins (+, -)
d block: n 1 Groups 3B, 4B, 5B, 6B, 7B,
(3) Hunds Rule: when orbitals of
8B, 1B, 2B
identical energy, electrons initially
occupy these orbitals singly an
f block: n 2 lanthanides and actinides
atom tends to have as many
unpaired electrons as possible
For the transition elements (B Groups), the
1s 2s 2p
group numerals do not correspond to the
number of valence electrons except for
Groups 1B and 2B
Aufbau Process: building up principle
Most transition metals have 2 electrons in the
A method of writing the probable electron
s subshell of the valence shell but some only
configuration of the element. Each
have one
element is described as differing from the
Cu : Ar 3 d10 4 s1 (1 valence e)
preceding one in terms of orbital to which
the one additional electron is assigned V : Ar 3 d 3 4 s 2 (2 valence e)
Z 1, H : 1s1 Ag : Kr 4 d10 5 s1 (1 valence e)
Z 2, He : 1s 2
Z 3, Li : 1s 2 2 s1
18
Chapter 10: The Periodic Table and Transuranium Elements elements with
Some Atomic Properties atomic number greater than 92
The Periodic Law and Periodic Table Metals and Nonmetals and Their Ions
Johann W. Dobereiner (1817 and 1829) Within a transition series, differences in
published articles in which he examined the electron configurations are mostly in
properties the properties of sets of elements inner shells, and so a transition element
that he called triads has some similarities to neighboring
transition elements in the same period
John A. R. Newlands (1863-66) proposed
and developed his law of octaves Noble Gases
Atoms of the noble gases have the
Dmitri Mendeleev and Lothar Meyer (1869) maximum number of electrons the valence
proposed the periodic law: shell of an atom:
When the elements are arranged in order He : 1 s 2 ( 2 valence electrons )
of increasing atomic mass, certain sets of Others: n s 2 n p 6 ( 8 valence electrons )
properties recur periodically
These electron configuration are very difficult
to alter and seem to conger a high degree of
Henry G. J. Moseley assigned the correct
chemical inertness
atomic number to any element on the basis
of its X-ray spectrum. With his work, the
Main Group Metal Ions
periodic law was redefined:
Groups 1A and 2A the most active metals
The chemical and physical properties of
differ from those of the noble gas of the
the elements are periodic functions of
preceding period by only one or two
atomic number
electrons
19
The Sizes of Atoms and Ions The atomic radius decreases from left to
Atomic Radius right through a period of elements
Covalent Radius one-half the distance
between the nuclei of two identical atoms (3) Variation of atomic radii within a
joined by a single covalent bond transition series: The transition elements
Ionic Radius the distance between the and inner-transition elements show some
nuclei of ions joined by an ionic bond variation from the general pattern. For the
Metallic Radius one-half the distance transition elements, the differentiating
between the nuclei of two atoms in contact in electrons fill inner d orbitals. The effect of
the crystalline solid metal nuclear charge on outer, size-determining,
electrons is reduced by the effect of inner
io n ic r a d iu s m e ta llic r a d iu s electrons. For a transition series, therefore,
the gradual buildup of electrons in inner d
r orbitals at first retards the rate of decrease
of atomic radius and then, toward the end
of the series when the inner d subshell
c o v a le n t r a d iu s nears completion, causes the radius to
r increase.
Sc : 3 d1 4 s 2 Z eff 21 19 2
Ti : 3 d2 4 s 2 Z eff 22 20 2
(1) Variation of atomic radii within a group
3 2
of the periodic table: The more electronic V : 3d 4 s Z eff 23 21 2
shells in an atom, the larger the atom. 5
Cr : 3 d 4 s 1
Z eff 24 23 1
Atomic radius increases from top to (larger)
bottom through a group of elements Mn : 3 d5 4 s 2 Z eff 25 23 2
20
For isoelectronic cations, the more the As ionization energy increases, the
positive the charge, the smaller the ionic element becomes less metallic
radius
1s 2 2 s 2 2 p 6 : Mg 2 and Na More energy is required for I2, I3 because as
the atom loses electron it becomes smaller.
Atomic size: Mg 2 Na Hence, more ionization energy is required
Because of the nuclear charge: I3 I2 I 1
Mg : 12
Na : 11
Electron Affinity
Anions are larger than the atoms from Electron Affinity, EA a measure of energy
which they are formed. For isoelectronic change that occurs when a gaseous atom
anions, the more the negative charge, the gains an electron
larger the ionic radius F ( g) e F ( g) EA 328 kJ / mol
Z eff is reduced because more electrons
than protons present EA is a negative quantity
Energy is added to remove an electron, by
Nonmetals tend to gain electrons to form thermochemical convention, its opposite
negative ions. The electrons are not held as which is the addition of electron must release
tightly. Repulsion among the electrons energy
increases. The electron spread out more,
and the size of the atom increases Atom with the greatest tendency toward
electron gain (largest negative value) is the
group 7A
Ionization Energy
Ionization Energy, I the quantity of energy Generally: a small atom should have greater
a gaseous atom must absorb so that an tendency toward electron gain than a large
electron is stripped from the atom atom
Mg ( g) Mg ( g) e I 1 738 kJ / mol
Mg ( g) Mg 2
( g) e
I 2 1451 kJ / mol From top to bottom: decreasing EA
21
Magnetic Properties (3) Amphoteric (Greek amphos meaning
Properties of atoms and ions, their behavior both) can either an acidic or basic oxides
in a magnetic field, is also helpful in Ex. Al2O3 can react with both acidic and basic
establishing electron configuration solutions
22
Lewis Symbols and Lewis Structures Bond Length the distance between the
Use only dots to represent electrons centers of 2 atoms joined by covalent bond
Bond length:
For Ionic Compounds C C C CC C
(1) The Lewis symbol of the metal ion
has no dots if all the valence Polar Covalent Bonds
electrons are lost Ionic Bond involves a complete transfer
(2) The ionic charges of both ions are of electrons
shown
Nonpolar Covalent Bond involves equal
Examples sharing of electron pair: Ex. H2, Cl2
2
Ba 2
O
Polar Covalent Bond a covalent bond in
2 which electrons are not equally shared
2 A l 3 3 O
between two atoms; electrons are displace
toward the more nonmetallic: Ex. HCl
Covalent Bonding
H is considered to be a nonmetal because Electronegativity, EN a measure of the
hydrogen atom does not give up electron to attracting power of a bonded atom; metals
another nonmetal atom instead it shares have low electronegativies, and nonmetals
electron have high electronegativities
Lower EN more metallic
Covalent Bond formed when electrons are Higher EN more nonmetallic
shared between atoms. In valence bond Trend
theory, the covalent bond is described as the From top to bottom: EN decreases
sharing of a pair of electrons in the region From left to right: EN increases
which atomic orbitals overlap
Linus Pauling constructed the relative
Bond Pair pair of electrons in a covalent electronegativity scale based on bond
bond energies
Lone Pair electron pairs that are not The concept of electronegativity is inexact.
involved in bonding Since, this property depends not only upon
the structure of the atom under consideration
Multiple Bonds but also upon the number and nature of the
atoms to which it is bonded. The
O O electronegativity of an atom is not constant.
N N
EN Property
Bond Order describes whether a covalent 1.7 or more ionic
bond is single (bond order = 1), double 1.1 1.6 high polarity
(bond order = 2), or triple (bond order = 3) 0.6 1.0 moderate polarity
0.1 0.5 low polarity
0 nonpolar
(Ref. Mortimer p. 196)
23
Writing Lewis Structure
Skeleton Structure an arrangement of Coordinate Covalent Bond when lone
atoms in order in which they are bonded pair of the central atom is used in the
together formation of covalent bond: Ex ammonium
ion
Central Atom bonded to 2 or more other
atoms H
1
H N H
Terminal Atom bonded to just one other
atom H
H atoms are always terminal atom, and C The formation of coordinate covalent bonds
atoms are almost always central leads to the formal charges in the Lewis
atom (except CO) structure
24
Exceptions to the Octet Rule The Shape of Molecules
(1) Odd-Electron species and Free Radical Lewis theory does not tell us anything about
Has odd number of valence electrons. Ex: the shape of molecules
NO has 11 valence electrons
OH ion has 7 valence electrons Bond Angles the angle between adjacent
lines representing bond
(2) Incomplete Octets
The number of species with incomplete A diatomic molecule has only one bond and
octets is limited to some beryllium, boron, no bond angle. All diatomic molecules are
and aluminum compounds linear.
F
F
Valence-Shell Electron-Pair Repulsion
1
1 (VSEPR pronounced vesper) electrons
F B F
F B F
pairs repel each other, whether they are in
chemical (bond pairs) or unshared (lone
pairs). Electron pairs assume orientation
1
about an atom to minimize repulsions
F F
1 1 1
F
B F
F B F
(1) Electron Group Geometry (EGG)
refers to the geometrical distribution
about a central atom of the electron
(3) Expanded Octets pairs in its valence shell
Molecules with expanded octets typically
involve nonmetal atoms of the third period (2) Molecular Geometry refers to the
and beyond that are bonded to highly geometrical shape of the molecule
electronegative atoms or polyatomic ion. In a species in
Ex. PCl5 (10 electrons), SF6 (12 electrons) which all electron pairs are bond
pairs, the molecular geometry is the
This expansion has been rationalized by same as electron group geometry. In
assuming that after the 3s and 3p subshells other cases the two properties are
fill to capacity in the central atom (octet), related but not the same]
extra electrons go into the empty 3d
subshell. The thought is that the energy
difference between 3p and 3d levels is not
very large, and so the octet expansion
seems reasonable.
25
VSEPR Notation
A: central atom
X: terminal atom S central atom
S
E: loner pair of electrons
VSEPR: A X 2 E
O O
Molecular
The close together two groups of electrons Geometry: angular
are forced, the stronger the repulsion
between them
Repulsion for bond angles: C central atom
9 0 12 0 18 0 O
VSEPR: A X 3
C Molecular
Lone pair electrons spread out more than do H H Geometry: trigonal
bond pair electrons planar
Repulsion strength:
lone pair lone pair lone pair bond pair bond pair bond pair
26
Molecular Shapes and Dipole Moments strong bonds weak bonds H0
Dipole Moment (rxtnts) (products)
d
where
in Coulomb
d in m Chapter 12: Chemical Bonding II:
C m 1 de b y e 1 D Additional Aspects
Carbon Dioxide Lewis Theory
O C O Strength
nonpolar: 0 (1) the ease with which we can apply it
(2) we can write a Lewis structure
Water quickly
H
O O Weakness
polar (1) has problem with odd-electron
species
Methane (2) it is not possible to represent a
H molecule through a single electronic
structure (resonance)
H C H
VSEPR
H Can propose molecular shapes that are
nonpolar: 0 generally in good agreement with experiment
Bond Energies
Energy is released when isolated atoms join Introduction to Valence-Bond Method
to form covalent bond and energy must be Valence Bond Method a description of
absorbed to break apart convalently bonded covalent bond formation in terms of atomic
atom overlap
27
VSEPR prediction to accommodate lone pair sp 2 trigonal B F3
and bond pair repulsions: the bond angle planar
must be less than 109.5 s p3 tetrahedral CH 4
s p 3d trigonal PC l 5
bipyramidal
Hybridization of Atomic Orbitals s p 3d2 octahedral S F6
Hybridization mathematical process of
replacing pure atomic orbitals by
reformulated atomic orbitals; refers to the
combining of pure atomic orbitals to generate Examples:
hybrid orbitals in the valence bond approach Xe F4 : A X 4E 2 s p 3d 2
to covalent bonding N H 3 : A X 3E 1 s p 3
C C
To describe hybridization schemes to
correspond to the 5 and 6 electron groups 1 bond, 1 bond
geometries of VSEPR theory, we need to go
beyond the s and p subshells of the valence C C
shell, and traditionally this has meant 1 bond, 2 bonds
including d orbital contribution hybrid orbitals
Examples:
Hybridization schemes are well established sp 2 sp 2
and very well commonly encountered,
H H
particularly among the second period C C
H H
element (C, O, N)
C 2H 4 trigonal planar
28
: C (sp2 ) O (2p)
H
C O
H Malleable the ease of deformation of
metals can be explained this way: if one
: C ( sp 2 ) O (2p) layer of metal ions is forced across another,
perhaps by hammering, no bonds are
CH 2 O trigonal planar broken, the internal structure of the metal
remains essentially unchanged, the sea of
electrons adjust to the new situation
Molecular Orbital Theory
Molecular orbital theory describes the
covalent bonds in a molecule by (2) Band Theory
considering that the atomic orbitals Band Theory a form of molecular orbital
of the component atoms are theory to describe bonding in metals and
replaced by electron orbitals semiconductors
belonging to the molecule as a whole
molecular orbitals. A set of rules is The band theory describes the bonding in
used to assign electrons to these metals in terms of molecular orbitals that
molecular orbitals, thereby yielding extend over the entire metallic structure. This
the electronic structrure of the band theory can be used to explain
molecule electrical conductivities of conductor,
insulator, and semiconductors
Like atomic orbitals, molecular orbitals are
mathematical functions. Also like atomic Pure substances (such as Si and Ge) that
orbital, molecular orbital can accommodate functions as semiconductors are called
two electrons, the electrons must have intrinsic semiconductors
opposing spins
The addition of small traces of certain
impurities to either Si or Ge enhances its
Bonding in Metals conductivity and produces what is called an
(1) Electron Sea Model extrinsic semiconductor
Electron Sea Model pictures a solid metal
as a network of positive ions immersed in a The use of acceptor impurity (such as B,
sea of electrons; a simple qualitative Al, Ga, or In) produces p-type
description of metallic state semiconductor
Electrons in the sea are free and they are The use of donor impurity (such as P, As,
mobile Sb, or Bi) produces n-type semiconductor
29
Valence Band a band in which a metallic
crystal that contains the valence electrons of Cohesive Forces the intermolecular forces
the metal between like molecules
When white light interacts with the Effects of adding detergent to water
semiconductor, electrons are excited (1) the detergent solution dissolves
(promoted) to the conduction band grease to expose a clean surface
(2) detergent lowers the surface tension
of water. Substances that reduce the
surface tension of water to allow it to
spread more easily are known as
Chapter 13: Liquids, Solids, and wetting angents
Intermolecular Forces
30
The stronger the intermolecular forces of standard atmospheric pressure
attraction, the greater the viscosity. Cohesive (1atm = 760mmHg)
forces within the liquid create an internal
friction which reduces the rate of flow
Volatile liquids with high vapor pressure at An Equation For Expressing Vapor
room temperature; weak intermolecular Pressure Data
forces H vap 1
Ex. Acetone ln p
R T
Nonvolatile liquids with very low vapor where T in Kelvin
pressures; strong intermolecular forces
Ex. Hg Clausius-Clayperon Equation
p H vap 1 1
ln 2
p1 R T1 T2
Boiling and Boiling Point
Boiling a process in which vaporization
occurs throughout a liquid. Pockets of vapor Some Properties of Solids
rise through the liquid and escape. Boiling Melting (fusion) transition of a solid to a
occurs when the vapor pressure of a liquid and occurs at the melting point. The
liquid is equal to barometric pressure melting point and freezing point of a
substance are identical
Normal Boiling Point the T at which the
vapor pressure of a liquid is equal to
31
Freezing (solidification) the conversion of How it extinguishes fire?
a liquid to a solid that occurs at fixed point (1) displacing air around the fire with
known as the freezing point blanket of CO2 (gas)
32
normally nonpolar species to become boiling point, and enthalpy of
momentarily polar (an instantaneous dipole/ vaporization
induced dipole) Ex. Boiling Point: HCl F2
(3) When comparing substance of
Polarizability the ease with which a dipole widely different molecular mass
can be induced in an atom or molecules dispersion forces are more
significant
Ex. BP: HI H B r H C l
33
In most covalent substances, intermolecular
forces are quite weak, this is why covalent
substances of low molecular mass are
generally gaseous at room temperature
Molecular mass:
C l2 ( gas) B r2 ( liquid) I 2 ( solid)
Mole Fraction
moles of component i
xi
total moles of all components
x i x j x k ... 1
Mole Percent
Mole fractions multiplied by 100%
Molarity
34
moles of solute where
M
L of solution C is the solubility of a gas in a particular
solvent
Molality k is the proportionality constant
moles of solute
m Applications of Henrys Law
kg of solvent (1) when a soda bottle is opened, the
pressure quickly drops and some of the CO 2
Independent of T difference unlike molarity is released as bubbles
volume increases as T is increased, hence, (2) to avoid the painful and dangerous
molarity decreases slightly condition of bends divers must avoid not
surface to quickly from great depths
35
Osmotic pressures of dilute solutions of Assumptions
nonelectrolytes (1) Solute in nonvolatile
V nR T
(2) The solid that freezes from a solution is a
Blood Cells (0.92% NaCl) pure solvent
Isotonic a solution with the same osmotic
pressure as body fluids T f k f m
T b k b m
Hypertonic cells is placed into a solution
with concentration greater than 0.92% NaCl;
water flows out the cells and shrink
Colligative Properties
(1) vapor pressure lowering
(2) freezing point depression
(3) boiling point elevation
(4) osmotic pressure
36
First-Order Reactions
A products
d[A]
r k [A]
dt
d[ A ]
[ A]
kdt
[A] t
ln k t
[A] 0
ln[ A ] t k t ln[ A ] 0
Chapter 15: Chemical Kinetics
t Second-Order Reactions
A products
37
1 1
kt
[A] t [A] t
1
t 1/ 2
k [A] 0
38
Arrhenius Equation to form adsorbed product, and desorption of
the product
k2 E a 1 1
ln
k1 R Enzymes high molar mass proteins
T1 T2
Substrate reacting substance
Reaction Mechanism
Reaction Mechanism a detailed Chapter 16: Principles of Chemical
description of a chemical reaction as a series Equilibrium
of one-step changes called elementary
processes Equilibrium two opposing processes take
place at equal rates
Characteristic of Elementary Processes
(1) The exponent of the concentration
terms in the rate equation for an a A bB c C dD
elementary processes are the same
as thestoichiometric coefficient in the Equilibrium Constant Expression
balanced equation [ C ]c [ D ]d
(2) Elementary process are either K c
unimolecular (a process which a [ A ]a [ B ]b
single molecule dissociates) or The concentrations must be expressed as
bimolecular (a process involving the molarities
collision of 2 molecules)
(3) In a proposed mechanism, Equlibrium Constant: K c
intermediates must not appear either The numerical value of K c depends on
in the net chemical equation or the particular reaction and on the temperature
overall rate equation
(4) One elementary process may occur
more slowly than other, and in some Relationship of Equilibrium Constant to
cases may determine the rate of the Balanced Chemical Equation
overall reaction. Such a process is (1) When we reverse an equation, we invert
called the rate-determining step
the value of K c
a A bB c C dD
See p. 530 Petrucci Ex. 15-10
[ C ]c [ D ]d
K c
[ A ]a [ B ]b
Catalysis
Catalyst provides an alternative pathway c C dD a A bB
of lower activation energy
[ A ]a [ B ]b 1
K 'c c d
Heterogenous Catalysis involves [C ] [D] Kc
adsorption of reactants, diffusion of reactants
along the surface, reaction at an active site
39
(2) When we multiply the coefficients in a
balanced equation by a common factor, we c d
PC PD
raise the equilibrium constant to the KP
P aA P Bb
corresponding power
na A nb B n c C n dD
[ C ] n c[ D ] n d
K 'c na nb
(K c )n
[A] [B]
( c d) ( a b )
1
K c KP
RT
(3) When we divide the coefficients in a n g a s
1
balance equation by a common factor, we K c KP
RT
take the corresponding root of the
equilibrium constant n gas n gaseous products n gaseous reac tan ts
na A nb B nc C n dD
c d n
n n
1 KP K c ( RT ) ga s
[C] [D] n
K 'c a b
(K c ) n K c
[A] n [B] n
concentration must be expressed as
molarities and pressure in atm, and
R =0.0821 Latm / Kmol
Combining Equilibrium Constant
Expression
Equilibria Involving Pure Liquids and
1
N 2 O( g) N 2 ( g) O 2 ( g) K c1 Solids
2 For Heterogenous Reactions
N 2 ( g) O 2 ( g) 2 N O( g) K c2 Equilibrium constant expression does not
1 contain terms for solid or liquid phases of a
N 2 O( g) O 2 ( g) 2 N O( g) Kc ? single component
2
K c K c1 K c 2 H 2O ( l ) H 2O ( g )
K C [ H 2 O ( g ) ] and K P P H 2 O ( g )
n 1 : K P K C R T
Equilibria Involving Gases
na A nb B nc C n dD
C aC O 3 ( s) C a O( s) CO 2 ( g)
nA P K C [ CO 2 ( g) ] and K P P C O 2( g)
Let [ A ] A
V RT n 1 : K P K C R T
c d
PC PD
RT RT
K c
a
b Significance of Magnitude of an
PA PB
Equilibrium Constant
RT R T
c ( c d) ( a b ) [ products ]
PC P Dd 1 KC
Kc
P aA P Bb RT [ reac tan ts ]
40
If the reaction goes to completion
[ reac tan t ] 0
K C or K P
ABC H 197 k J
(3) If Q C K C : a net reaction proceeds
Is equivalent to A B C H
from right to left (the reverse direction)
41
Ex.
add heat: favors reverse direction NH3 is a base but it does contain hydroxide
remove heat: favors forward direction NH 3 H 2 O NH 4 OH
42
K W [ H 3O ] [ OH ] 1.0 x 10 14
pH and pOH
Soren Sorensen (1909) proposed the term
Arrhenius Theory vs Bronsted-Lowry pH to refer to the potential of hydrogen ion
Theory
(1) Any species that is an acid by the p H log [ H 3 O ]
Arrhenius theory an acid in the
p O H log [ OH ]
Bronsted-Lowry theory; the same is
true of bases pK W p H p O H 14.00
43
x Hydrolysis
deg ree of ionization
M Hydrolysis the reaction between ion
(which acts as acid or base) and water
Percent Ionization
x As a result of hydrolysis, for many salt
percent ionization 100% solutions, pH 7
M
(1) Salts of strong base and strong acids
(Ex. NaCl) do not hydrolyze:
M A (or M B ) pH = 7
M x M if 100
K a (or K b )
(2) Salts of strong base and weak acids
(Ex. NaC2H3O2) hydrolyze:
pH > 7 the anion acts as a base
Polyprotic Acids
Polyprotic Acids acids with more than one (3) Salts of weak bases and strong acid
ionizable H atom per molecule (Ex. NH4Cl) hydrolyze:
pH < 7 the cation acts as an acid
K a1 K a 2 K a 3
(4) Salts of weak bases and weak acids
(Ex. NH4C2H3O2) hydrolyze:
pH depends on the relative values of Ka and
Ions as Acids and Bases Kb for ions: If
Ion can act as acid or base Ka > Kb: pH < 7
Ka < Kb: pH > 7
Important consequence of the Bronsted-
Lowry Theory:
Molecular Structure and Acid-Base
K a (acid) x K b (its conjugate base) K W Behavior
Acid behavior requires the loss of proton, we
K b (base) x K a ( its conjugate acid) K W
expect acid strength to be related to bond
length
C 2H 3O 2 H 2O H C 2H 3O 2 OH
Within a Group
KW [ HC 2H 3O 2 ] [ OHAcidity
] increases with increasing bond length
K b
K a (HC 2H 3O 2 ) [ C 2H 3O 2 ] (atomic radius) and when dissociation energy
decreases
Acidity: H I H B r H C l H F
NH 4 H 2 O N H 3 H 3O
Within a Period
KW [ NH 3 ][ H 3 O ] The greater the electronegativity difference
K a
K b (N H 3) [ NH (EN) is the bond HX, the more polar the
4 ]
bond. The lose of H+ to a molecule occur
more readily from a polar bond than from a
nonpolar bond
44
Acidity: C H 4 N H 3 H 2 O H F Sulfuric acid vs Sulfurous acid
O O
EN: 0.4 < 0.9 < 1.4 < 1.9
H O S O
H H O S O
H
O
Acidic, Basis, and Amphoteric
E XO Y H 2 O E O H
Acetic acid vs Ethanol
Acid Anhydride, ExOY
H O
When E is a nonmetal such as Cl, S, N, or P H H
(highly electronegative), it attracts H C C O
H H C C O
H
electrons away from the OH bond in the E H H H
O H (an oxoacid)
The Cl atom withdraws electrons more
E O H O H EO H2O strongly when it is directly adjacent to the
carboxyl group
H C l O H H O
45
In general, to identify Lewis acids we should
look for species with vacant orbitals that can Common buffer solutions are described
accommodate electron pairs, and for Lewis either as a mixture of
bases, species having lone pair electrons (1) a weak acid and its conjugate base
(2) a weak base and its conjugate acid
OH , a Bronsted-Lowry base, is also a Lewis
base
Henderson-Hasselbalch Equation:
Not all Bronsted-Lowry acids are Lewis acids Equations for Buffer Solution
Ex HCl it is not a Lewis acid because it (1) H A H 2 O H 3 O A
does not have vacant orbitals
[ A ] [ H 3 O ]
K a
[HA ]
[HA ]
[ H 3 O ] K a
Chapter 18: Additional Aspects of [A ]
Acid-Base Equilibria
[A ]
pH p K a log
[HA ]
Common Ion Effect the suppression of the
ionization of a weak electrolyte
caused by the addition of an ion that
is also a product (2) B H 2 O B H O H
[ B H ] [ O H ]
K b
0.1 M NH3 and 0.1 M NaOH [B]
N H 3 H 2 O NH 4 OH [ OH ]
K W
[ H 3O ]
O.1 M NH3 and 0.1 M NH4Cl [ BH ] K W
K b
NH3 H2O NH 4 OH [ B ] [ H 3O ]
K W [ BH ]
[ H 3O ]
O.1 M HC2H3O2 and 0.1 M NaC2H3O2 Kb [B]
Let Ka be the acid ionization constant of the
H C 2H 3O 2 H 2O C 2H 3O 2 H 3O
conjugate acid of the base B
K a KW/K b
O.1 M HC2H3O2 and 0.1 M HCl [ BH ]
[ H 3O ] K
H C 2H 3O 2 H 2O C 2H 3O 2 H 3O a
[B]
[B]
pH p K a log
[ BH ]
Buffer Solutions solution whose pH
values change only very slightly on the
addition of small amounts of either an acid or
a base
In general:
46
pH p K a log
[ conjugate base ] buffer capacity exists when the
[ acid ] concentrations of a weak acid and its
conjugate base are kept large and
or approximately equal to each other
n conjugate base / V Buffer Range the pH range in which a
pH p K a log
n acid / V buffer effectively neutralizes added acids and
bases and maintain a fairly constant pH
(2) the molarity of each buffer Ex. What is the pH of 0.1M NaOH and 0.2M
component exceeds the value of K a NH4Cl?
by a factor of at least 100 NH
4 OH NH 3 H 2 O
All the NaOH will react to produce 0.1M NH 3.
see p. 629 Ex. 18-5 Hence, the solution becomes a buffer
0.1M NH3 0.1M NH4+
47
Ca F2 ( s) Ca 2 (aq) 2 F (aq) Nonspontaneous Process a process that
will not occur unless some external action is
K c K sp [ Ca 2 ] [ F ] 2 continuously applied
H sys
Chapter 20: Spontaneous Change: S univ S sys
T
Entropy and Free Energy Multiply by T
T S univ H sys T S sys
Spontaneous Process a process that
occurs in a system left to itself Gibbs Free Energy, G
48
G = H TS The entropy of a pure perfect crystal at OK is
Let G T S univ zero
H S G Result
+ spontaneous at all T
Criterion for Spontaneous Change
spontaneous at low T The direction of spontaneous change in both
+ nonsponstaneous at high T the forward and reverse reaction is that in
+ + + nonspontaneous at low T which free energy decreases: G < 0. As a
spontaneous at high T consequence, free energy reaches a
+ + nonspontaneous at all T minimum at some point. This is the
equilibrium point
See p. 698 Ex. 20-3 p. 706 Fig 20-10
Phase Transition
G 0 H tran T S tran
H t ran Thermodynamic Equilibrium Constant
S tran K eq is an equilibrium constant base on
Ttran
activities
Troutons Rule for many liquids at their
normal boiling points K eq is sometimes identical to K c and K p
H vap J ; and in other instances this is not the case
S vap 87
Tvap K mol
49
Examples: Half-Cell a combination of an electrode
Ca F2 ( s) Ca 2 (aq) 2 F (aq) and a solution
K eq [ Ca 2 ] [ F ] 2 K s p Electrochemical Cell a combination of 2
half cells
Cell Diagrams
Relation between the K eq of a reaction and
T
Zn ( s) Zn 2 (aq) 2e
K 2 H 1 1 Cu 2 (aq) 2e Cu ( s)
ln
K1 R T1 T2
Zn ( s) Cu 2 (aq) Zn 2 (aq) Cu ( s)
50
C
96,485
(3) / represents the boundary between mol e
different phases
51
Ca(OH) 2 ( s) CO 2 ( g) CaCO 3 ( s) H 2 O(l)
52
on the use of superheated water to melt the Ionizing Radiation interacts with matter to
sulfur produce ions; it has sufficient energy to break
chemical bonds
Contact Process a process for
manufacturing sulfuric acid that has as its Alpha Particles, 42 He 2
key reaction the oxidation of SO 2 (g) to
Penetrating power is low they can be
SO3(g) in contact with a catalyst
stopped by a sheet of paper
Eutrophication the deterioration of a 238 234 4
92 U Th 2 He
freshwater body caused by nutrients such as 90
53
238 234 4 (2) Slight Exposure to Ionizing Radiation
92 U 90 Th 2 He changes in cell chromosomes
234 234
90 Th 90 Th (3) Low Dosage of Ionizing Radiation
birth defects, leukemia, bone cancer,
Neutrons, 01 n and other forms of cancer
rate of decay N
A k N
No A
o
N A
N
ln kt
No
0.693
t1 / 2
k
Ionizing Power :
54