2012 General Chemistry I

CHEMISTRY
The science of matter and the changes it can undergo.
A science that deals with the
composition, structure, and
properties of substances and
with the transformations that
they undergo.
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2012 General Chemistry I
Chemistry: A Science at Three Levels
Macroscopic level
The level dealing with the properties
of large, visible objects
Microscopic level
An underworld of change
The level of atoms and molecules
Symbolic level
The expression of chemical phenomena in terms
of chemical symbols and mathematical equations
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How Science Is Done
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The Branches of Chemistry
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Traditionally,
Organic chemistry (carbon compounds)
Inorganic chemistry (all other elements and their compounds)
Physical chemistry (principles of chemistry)
Biochemistry (chemistry in living systems)
Analytical chemistry (techniques for identifying substances)
Theoretical (computational) chemistry (mathematical and computational)
Medicinal chemistry (application to the development of pharmaceuticals)
Specialized area
Interdisciplinary branches
Molecular biology (chemical basis of genes and proteins)
Materials science (structure and composition of materials)
Nanotechnology (matter at the nanometer level)
2012 General Chemistry I
Chapter 1.
ATOMS: THE QUANTUM WORLD
2012 General Chemistry I
INVESTIGATING ATOMS
QUANTUM THEORY
1.1 The Nuclear Model of the Atom
1.2 The Characteristics of Electromagnetic Radiation
1.3 Atomic Spectra
1.4 Radiation, Quanta, and Photons
1.5 The Wave-Particle Duality of Matter
1.6 The Uncertainty Principle
1.7 Wavefunctions and Energy Levels
2012 General Chemistry I
INVESTIGATING ATOMS (Sections 1.1-1.3)
1.1 The Nuclear Model of the Atom
Electron:
J.J. Thomson (English physicist,
1856-1940) in 1897 discovers
the electron and determines
the charge to mass ratio (e/m
e
)
By cathode rays. In 1906 he
wins the Nobel Prize.
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Robert Millikan designed an ingenious
Apparatus in which he could observe
tiny electrically charged oil droplet.
Fundamental charge,
the smallest increment of charge
e = 1.60210
-19
C
From the value of e/m
e
measured
by Thomson,
m
e
= 9.10910
-31
kg
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Ernest Rutherford (Cambridge University, England, 1871-1937) studied
emission from newly-discovered radioactive elements.
Nucleus:
Experiment by Geiger and Marsden
Nucleus occupy a small volume at the center of the atom
Nucleus contains particles called proton (+e) and neutron (uncharged).
2012 General Chemistry I
Nuclear Model of the Atom
In the nuclear model of the atom, all the positive charge and
almost all the mass is concentrated in the tiny nucleus, and the
negatively charged electrons surround the nucleus. The atomic
number of proton in the nucleus.
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1.2 The Characteristics of Electromagnetic Radiation
Spectroscopy the analysis of the light emitted or absorbed by
substances
- Light is a form of electromagnetic radiation, which is the periodic
variation of an electric field (and a perpendicular magnetic field).
amplitude: the height of the wave
above the center line
intensity: the square of the amplitude
wavelength, : peak-to-peak distance
wavelength frequency = speed of light
v =
c
4
c = 2.9979 x 10
8
ms
-1
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visible light = 700 nm (red light)
to 400 nm (violet light)
infrared > 800 nm
the radiation of heat
ultraviolet < 400 nm
responsible for sunburn
The color of light depends on its frequency and wavelength;
long-wavelength radiation has a lower frequency than
short-wavelength radiation.
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1.3 Atomic Spectra
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white light
discharge lamp of
hydrogen
spectral lines
discrete energy
levels
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Johann Rydbergs general equation
R (Rydberg constant) = 3.2910
15
Hz
an empirical constant
n
1
= 1 (Lyman series), ultraviolet region
n
1
= 2 (Balmer series), visible region
n
1
= 3 (Paschen series), infrared region
For instance, n
1
= 2 and n
2
= 3,
= 6.5710
-7
m
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QUANTUM THEORY (Sections 1.4-1.7)
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1.4 Radiation, Quanta, and Photos
Black body radiation the radiation emitted at different wavelength
by a heated black body, for a series of temperatures.
Stefan-Boltzmann law:
Total intensity = constant T
4
Wiens law:
T
max
= constant
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Ultraviolet catastrophe:
Classical physics predicted that any hot
body should emit intense ultraviolet
radiation and even X-rays and -rays!
Quantization of electromagnetic radiation
by Max Planck
E = hv
Radiation of frequency v can be generated only if an oscillator of
that frequency has acquired the minimum energy required to
start oscillating.
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Photoelectric effect
the ejection of electrons from a metal when
its surface is exposed to ultraviolet radiation
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1. No electrons are ejected
< a certain threshold value of metal
2. Electrons are ejected immediately
at a certain value.
3. The kinetic energy of e- increases
linearly with the frequency of the
radiation.
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Albert Einstein proposed that electromagnetic radiation consists
of particles, called photons.
- The energy of a single photon is proportional to the radiation
frequency by E = hv.
work function
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Bohr frequency condition:
relates photon energy to energy difference
between two energy levels in an atom
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1.5 The Wave-Particle Duality of Matter
- Wave behavior of light:
Diffraction and interference effects of
superimposed waves
(constructive and destructive)
- Louis de Broglie proposed that all particles
have wavelike properties.
De Broglie wavelength with the linear
Momentum p = mv
electron diffraction reflected from a crystal
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1.6 The Uncertainty Principle
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Complementarity of location (x) and momentum (p)
- uncertainty in x is Ax; uncertainty in p is Ap
Heisenberg uncertainty principle
where = h / 2t = 1.054610
-34
Js
- x and p cannot be determined simultaneously.
For instance, an object of 1.0 g mass with v = 2.0 mms
-1
,
Ax = 2.610
-29
m, very small
an electron confined to the diameter of a typical atom (200 pm),
Av = 2.8910
5
ms
-1
, very large
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1.7 Wavefunctions and Energy Levels
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Erwin Schrdinger introduced a central concept
of quantum theory.
particle trajectory wavefunction
- wavefunction (, psi): a mathematical function
with values that vary with position
- Born interpretation: probability of finding the
particle in a region is proportional to the value
of
2
- probability density (
2
): the probability that the
particle will be found in a small region divided by
the volume of the region
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Schrdinger equation: for a particle of mass m moving in one dimension
in a region where the potential energy is V(x)
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H = hamiltonian of the system
- H represents the sum of potential energy and kinetic energy in a system
Particle in a box
- Mass m confined between two rigid walls a distance L apart
- = 0 outside the box at the walls (boundary condition)
n = quantum number
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The Solutions of Particle in a Box
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- For the kinetic energy of a particle of mass m,
- Whole-number multiples of half-wavelengths
can follow the boundary condition,
- When this expression for is inserted into
the energy formula,
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More General Approach
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- From the Schrdinger equation with V(x) = 0 inside the box,
Solution:
- k
2
= 2mE/, and it follows
- From the boundary conditions of (0) = 0 and (L) = 0,
0
L
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Energies of a particle of mass m in a one dimensional box of length L,
Energy of the particle is quantized, and restricted to energy levels.
- Energy quantization stems from the boundary
conditions on the wavefunction.
- Energy separation between two neighboring levels
with quantum numbers n and n+1:
n = quantum number
- L (the length of the box) or m (the mass of the
particle) increases, the separation between
neighboring energy levels decreases.
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Zero-point energy:
The lowest value of n is 1, and the lowest energy is E
1
= h
2
/8mL
2
,
not zero.
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According to quantum mechanics, a
particle can never be perfectly still
when it is confined between two walls:
it must always possess an energy.
consistent with the uncertainty
principle
- The shapes of the wavefunctions of
a particle in a box
E
1
= h
2
/8mL
2
,
E
2
= h
2
/2mL
2
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Chapter 1.
ATOMS: THE QUANTUM WORLD
2012 General Chemistry I
THE HYDROGEN ATOM
1.8 The Principal Quantum Number
1.9 Atomic Orbitals
1.10 Electron Spin
1.11 The Electronic Structure of Hydrogen
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THE HYDROGEN ATOM (Sections 1.8-1.11)
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1.8 The Principal Quantum Number
A particle in a box
An electron within the atom by
the pull of the nucleus
For a hydrogen atom, V(r) = coulomb potential energy
Solutions of the Schrdinger equation
R (Rydberg constant) = 3.2910
15
Hz
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For other one-electron ions, such as He
+
, Li
2+
, and even C
5+
,
- Z = atomic number, equal to 1 for hydrogen
- n = principal quantum number
- As n increases, energy increases, the atom
becomes less stable, and energy states
become more closely spaced (more dense).
- ground state of the atom:
the lowest energy state, E = hR when n = 1.
- ionization: the bound electron reaches at E = 0
and freedom, and has left the atom.
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ionization energy: the minimum energy needed
to achieve ioniztion
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1.9 Atomic Orbitals
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Atomic orbitals: the wavefunctions of electrons in atoms
- The square of a wavefunction is the probability density of an
electron at each point.
- Expressing wavefunctions in terms of spherical
polar coordinates, , u, |
radial
wavefunction
angular
wavefunction
- For the ground state of hydrogen atom (n = 1),
= 52.9 pm
Bohr radius
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For hydrogen-like wavefunctions (atomic orbitals), = R()Y(u,|)
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Three quantum numbers (n, l, m
l
) specify an atomic orbital.
n, principal quantum number
- related to the size and energy of the orbital
- shell: AOs with the same n value
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l, orbital angular momentum quantum number
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- the values of l = 0, 1, 2, , n-1
- subshell: AOs with the same n and l values
n subshells with a principal quantum number n
Value of l 0 1 2 3
Orbital type s p d f orbitals
- related to the orbital angular momentum of the electron
orbital angular momentum =
m
l
, magnetic quantum number
- the values of m
l
= l, l-1, l-2, , -l
- 2l+1 different values of m
l
for a given value of l
when l = 1, m
l
= +1, 0, -1
- related to the orientation of the orbital motion of the electron
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A summary of the
three quantum numbers
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Shape of the s-orbitals
Radial distribution function: the probability
that the electron will be found anywhere in a
thin shell of radius r and thickness or is given
by P(r)or, with
For s orbitals, = RY = R/2t
1/2
,
Visualizing AO as a cloud of points,
proportional to probability of
finding the electron in that volume
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Visualizing AO as a boundary surface, that encloses most of the cloud
The 95% boundary surface
the probability of finding an electron
of 95%
radial wavefunction versus radius,
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Shape of the p-orbitals
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boundary surface radial function
- two lobes with + and - signs
- nodal plane ( = 0) separating
the two lobes
- l = 1 and m
l
= +1, 0, -1
triply degenerate in energy
- three p-orbitals of p
x
, p
y
, p
z
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Shape of the d- and f-orbitals
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d-orbitals
l = 2 and
m
l
= +2, +1, 0, -1, -2
- five d-orbitals with
d
z2
, d
x2-y2
, d
xy
, d
zx
, d
yz
f-orbitals
l = 3 and
seven m
l
values
- seven f-orbitals
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1.10 Electron Spin
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- An electron has two spin states,
as (up) and (down), or o and |.
m
s
, spin magnetic quantum number
- the values of m
s
, only +1/2 and -1/2
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1.11 The Electronic Structure of Hydrogen
In the ground state, n = 1, and 1s orbital.
The 1s electron with the following quantum numbers,
n = 1, l = 0, m
l
= 0, m
s
= +1/2 or -1/2
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In the excited state by absorbing a photon of radiation,
- The first excited state with n = 2, four orbitals,
2s, 2p
x
, 2p
y
, or 2p
z
The average distance of an electron from the nucleus increases.
- The next excited state with n = 3, nine orbitals,
one 3s, three 3p, and five 3d orbitals with larger distances
- Eventually, the electron can escape the atom by absorbing
enough energy, and thus ionization of hydrogen occurs.
2012 General Chemistry I
Chapter 1.
ATOMS: THE QUANTUM WORLD
2012 General Chemistry I
MANY-ELECTRON ATOMS
THE PERIODICITY OF ATOMIC PROPERTIES
1.12 Orbital Energies
1.13 The Building-Up Principle
1.14 Electronic Structure and the Periodic Table
1.15 Atomic Radius
1.16 Ionic Radius
1.17 Ionization Energy
1.18 Electron Affinity
1.19 The Inert-Pair Effect
1.20 Diagonal Relationships
1.21 The General Properties of the Elements
2012 General Chemistry I
MANY-ELECTRON ATOMS (Sections 1.12-1.14)
1.12 Orbital Energies
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- In many-electron atoms, Coulomb potential energy equals the sum of
nucleus-electron attractions and electron-electron repulsions.
- No exact solutions of Schrdinger equation
- In a helium atom,
r
1
= the distance of
electron 1 from
the nucleus
r
2
= the distance of
electron 2 from
the nucleus
r
12
= the distance
between the
two electrons
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the hydrogen atom: no electron-electron repulsion
All the orbitals of a given shell are degenerate.
many-electron atoms: electron-electron repulsions
The energy of a 2p-orbital > that of a 2s-orbital
Shielding:
Each electron attracted by the nucleus,
and repelled by the other electrons.
shielded from the full nuclear attraction
by the other electrons.
- effective nuclear charge, Z
eff
e < Ze
the energy of electron,
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Penetration:
s-electron very close to the nucleus
highly penetrates through the inner shell.
p-electron penetrates less than an s-orbital
effectively shielded from the nucleus
In a many-electron atom, because of the effects of
penetration and shielding, the order of energies
of orbitals in a given shell is s < p < d < f.
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1.13 The Building-Up Principle
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Electronic configuration of the atom
a list of all its occupied orbitals, with the numbers of electrons
that each one contains.
i.e. Li: 1s
2
2s
2
Pauli exclusion principle
No more than two electrons may occupy any given orbital.
When two electrons do occupy one orbital, their spins must be paired.
or
No two electrons in an atom can have the same set of
four quantum numbers (n, l, m
l
, and m
s
).
H, 1s
1
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He, 1s
2
- closed shell: a shell containing the maximum number of electrons
allowed by the exclusion principle
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Li, 1s
2
2s
1
or [He]2s
1
- core electrons: electrons in filled orbitals
valence electrons: electrons in the outermost shell
Be, 1s
2
2s
2
or [He]2s
2
- stable ionic form: Be
2+
- stable ionic form losing valence electrons: Li
+
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B, 1s
2
2s
2
2p
1
or [He]2s
2
2p
1
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C, 1s
2
2s
2
2p
2
or [He]2s
2
2p
2
Hunds rule
If more than one orbital in a subshell is available, add electrons with
parallel spins to different orbitals of that subshell rather than pairing
two electrons in one of the orbitals.
parallel spins
1s
2
2s
2
2p
x
1
2p
y
1
- excited state: An atom with electrons in energy states higher than
predicted by the building-up principle
In carbon, ground state, [He]2s
2
2p
2
excited state, [He]2s
1
2p
3
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- Elements in Period 2 (from Li to Ne), the valence shell with n = 2.
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All atoms in a given period have the same type of core with the same n.
All atoms in a given group have analogous valance electron configurations
that differ only in the value of n.
Period 2
Period 3
Period 4
Group 1
Group 18/VIII
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Period 5
Period 6
Period 7
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n = 3: Na, [He]2s
2
2p
6
3s
1
or [Ne]3s
1
to Ar, [Ne]3s
2
3p
6
n = 4: from Sc (scandium, Z = 21) to Zn (zinc, Z = 30)
the next 10 electrons enter the 3d-orbitals.
The (n+l rule)
Order of filling subshells in neutral atoms is determined by filling those
with the lowest values of (n+l) first. Subshells in a group with the same
value of (n+l) are filled in the order of increasing n.
order: 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d <
- two exceptions: Cr, [Ar]3d
5
4s
1
instead of [Ar]3d
4
4s
2
Cu, [Ar]3d
10
4s
1
instead of [Ar]3d
9
4s
2
due to the complete subshell of d
10
with a low energy
n = 6: 5s-electrons followed by the 4d-electrons
Ce (cerium, [Xe]4f
1
5d
1
6s
2
)
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1.14 Electronic Structure and the Periodic Table
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- H and He, unique properties
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38
- main group: s- and p-blocks
- The group number tells us how many valence-shell electrons are present.
Group 1
Group 18/VIII
- Group I-VIII or Group 1-18
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Period 2
Period 3
Period 4
Period 5
Period 6
Period 7
- Period 1: H, He ; 1s orbital
- Period 2: Li through Ne ; 8 elements, one 2s and three 2p orbitals
- Period 3: Na thorugh Ar ; 8 elements, 3s and 3p
- Period 4: K thorugh Kr ; 18 elements, 4s, 4p and 3d
- Period 5: Rb thorugh Xe ; 18 elements, 5s, 5p and 4d
- Period 6: Cs thorugh Rn ; 32 elements, 6s, 6p, 5d and 4f
2012 General Chemistry I
THE PERIODICITY OF ATOMIC PROPERTIES
(Sections 1.15-1.21)
1.15 Atomic Radius
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Atomic radius: defined as half the distance between the centers of
neighboring atoms
- For metal, r in a solid sample
- For nonmetal, r for diatomic molecules (covalent radius)
- For a noble gas, r in the solidified gas (Van der Waals radius)
- r decreases from left to right across
a period
(effective nuclear charge increases)
- r increases from top to bottom down
a group
(change in n and size of valence shell)
General trends
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1.16 Ionic Radius
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Ionic radius: its share of the distance between
neighboring ions in an ionic solid
- Cations are smaller than parent atoms.
i.e. Zn (133 pm) and Zn
2+
(83 pm)
- Anions are larger than parent atoms.
i.e. O (66 pm) and O
2-
(140 pm).
Isoelectronic atoms and ions
Atoms and ions with the same
number of electrons
i.e. Na
+
, F
-
, and Mg
2+
radius: Na
+
< Mg
2+
< F
-
due to different nuclear charges
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1.17 Ionization Energy
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Ionization Energy, I
The minimum energy need to remove an electron from an atom
in the gas phase
the first ionization energy, I
1
the second ionization energy, I
2
- I
1
typically decreases down a group.
(change in n of valence electron)
- I
1
generally increases across a period.
(Z
eff
increases)
- metallic: lower left of the periodic table, low ionization energies
- nonmetallic: upper right of the periodic table, high ionization energies
I
1
(746 kJmol
-1
)
I
2
(1958 kJmol
-1
)
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1.18 Electron Affinity
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Electron Affinity, E
ea
The energy released when an electron is added to a gas-phase atom.
i.e.
- E
ea
decreases down a group.
(change in n of valence electron)
- E
ea
increases across a period.
(Z
eff
increases)
- Group 17/VII, the highest 1
st
E
ea
(F
-
)
strongly negative 2
nd
E
ea
(F
2-
)
- Group 16/VI, positive 1
st
E
ea
(O
-
)
negative 2
nd
E
ea
(O
2-
)
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1.19 The Inert-Pair Effect
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- Tendency to form ions two units lower in charge
than expected from the group number
- Due in part to the different energies of the
valence p- and s-electrons
1.20 Diagonal Relationships
- A similarity in properties between diagonal
neighbors in the main groups of the periodic
table
- Similarity in atomic radius, ionization energy,
and chemical property
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1.21 The General Properties of the Elements
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s-block elements: low ionization energy, easy to lose electrons
likely to be a reactive metal
Left of p-block with heavier elements:
relatively low ionization energy
metallic, but less reactive than those in s-block
Right of p-block: high electron affinities, tend to gain electrons
mostly nonmetals, forming molecular compounds
s-block
right
p-block
left
p-block
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d-block: metals, transitional between the s- and p-block elements
transition metals, similar properties
form ions with different oxidation states (Fe
2+
and Fe
3+
)
catalytic properties, facilitating subtle changes in organisms
form alloys
Lanthanoids (f-block): incorporated in superconducting materials
actinide radioactive, not naturally exist on earth
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lanthanoids
d-block