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AP* Chemistry

THERMOCHEMISTRY
Lets begin with terms for you to master:

Energy (E) the ability to do work or produce heat ; the sum of all potential and kinetic energy in a system
is known as the internal energy of the system

Potential energy energy by virtue of position.


In chemistry this is usually the energy stored in
bonds (i.e., when gasoline burns there are
differences in the attractive forces between the
nuclei and the electrons in the reactants and the
products) When bonded atoms are separated, the PE
is raised because energy must be added to overcome
the coulombic attraction between each nucleus and
the shared electrons.
When atoms bond, the above mentioned coulombic
attraction results in energy being released and a
subsequently lower PE.
Kinetic energy energy of motion (translational,
rotational & vibrational motion of particles in our
case), proportional to Kelvin temperature; kinetic energy depends on the mass and the velocity of the
object: KE = mv2
Check out this simulation regarding the Boltzmann distribution:
http://phet.colorado.edu/en/simulation/atomic-interactions
And this one regarding the effect of temperature on molecular motion:
http://phet.colorado.edu/en/simulation/states-of-matter-basics

Law of Conservation of Energy You may know it as energy is never created nor destroyed which
implies that any change in energy of a system must be balanced by the transfer of energy either into or out
of the system.

AKA energy of the universe is constant & the First Law of Thermodynamics
Heat (q) Two systems with different temperatures that are in thermal contact will exchange thermal
energy, the quantity of which is call heat. This transfer of energy in a process (flows from a warmer object
to a cooler one, transfers heat because of temperature difference but, remember, temperature is not a
measure of energyit just reflects the motion of particles)
Temperature (T)is proportional to the average kinetic energy of the molecules, KEave .
Heat em up and speed em up as you saw in the states of matter animation.
Enthalpy (H) flow of energy (heat exchange) at constant pressure when two systems are in contact.
Enthalpy of reaction (Hrxn) amount of heat released (negative values) or absorbed (positive values)
by a chemical reaction at constant pressure in kJ/molrxn
Enthalpy of combustion (Hcomb)heat absorbed or released by burning (usually with O2) in
kJ/molrxn; note that combustion reactions yield oxides of that which is combusted
Enthalpy of formation (Hf) heat absorbed or released when ONE mole of compound is formed
from elements in their standard states in kJ/molrxn
Enthalpy of fusion (Hfus)heat absorbed to melt (overcome IMFs) 1 mole of solid to liquid @ MP
expressed in kJ/molrxn
Enthalpy of vaporization (Hvap)heat absorbed to vaporize or boil (overcome IMFs) 1 mole liquid to

vapor @BP in kJ/molrxn


*AP is a registered trademark of the College Board, which was not involved in the production of this product. Special thanks to the contributions of
Lisa McGaw and David Wentz. 2013 by Ren McCormick. All rights reserved.

System area of the universe we are focusing on (i.e., the experiment)


Surroundings everything outside of the system
Endothermic net absorption of energy (heat exchange) by the system; energy is a reactant; (i.e., baking
soda and vinegar when mixed get very cold to the touch) ; +H
Exothermic net release of energy (heat exchange) by the system; energy is a product; (i.e., burning
methane gas in the lab burner produces heat; light sticks give off light which is also energy); H
Entropy (s) measure of the dispersal of matter and energy; increase dispersal +S; decrease dispersal S
Gibbs Free Energy (G) criteria for determining thermodynamic favorability and calculating the
theoretical amount of energy to do work
Thermodynamics study of energy and its interconversions
Work force acting over distance in physics often expressed as work = PV where gases are involved;
expressed in Joules or kJ
Standard Conditionsyou already know about STP, but recall that the T is STP is 0C and humans are not
happy lab workers when it is that cold! So, think of standard conditions as standard lab conditions which
are 1 atm of pressure, 25C (much more comfy!) and if solutions are involved, their concentration is 1.0 M.
All of this information is communicated by adding the symbol to G, H or S. So, if you see H, then you
automatically know the pressure, temperature and conditions that apply to that value!
There has recently been a change in how enthalpy, entropy and free energy units are expressed. For
example, you may see H values expressed as kJ in older printed material. Currently, they should
be expressed in kJ/molrxn where the molrxn is moles of reaction. See Jim Spencers article on AP
Central for additional information.
ENERGY AND WORK
Energy is often defined as
the ability to do work.

E = q (heat) + w
(work)
Signs of q
+q if heat absorbed
q if heat released
Algebraic sign of w as it relates to work done by or work done
on gases
+ w if work done on the system (i.e., compression)
w if work done by the system (i.e., expansion)
When related to gases, work is a function of
pressure
Pressure is defined as force per unit of area, so
when the volume is changed work was either
done on the gas or by the gas.

work = PV

Exercise 1
Internal Energy
Calculate E for a system undergoing an endothermic process in which 15.6 kJ of heat flows and where
1.4 kJ of work is done on the system.

17.0 kJ
2
Thermochemistry

Exercise 2
PV Work
Calculate the work associated with the expansion of a gas from 46 L to 64 L at a constant external pressure of
15 atm.

270 Latm

Exercise 3
Internal Energy, Heat, and Work
A balloon is being inflated to its full extent by heating the air inside it. In the final stages of this process, the
volume of the balloon changes from 4.00 106 L to 4.50 106 L by the addition of 1.3 108 J of energy as
heat. Assuming that the balloon expands against a constant pressure of 1.0 atm, calculate E for the process.
(To convert between L atm and J, use 1 L atm = 101.3 J.)

8.0 107 J
ENTHALPY
Measure only the change in enthalpy, H ( the difference between the potential energies of the products
and the reactants)
H is a state function
H = q at constant pressure (i.e. atmospheric
pressure)
Enthalpy can be calculated from several
sources including:
Stoichiometry
Calorimetry
From tables of standard values
Hesss Law
Bond energies

3
Thermochemistry

Stoichiometrically:
Exercise 4
Upon adding solid potassium hydroxide pellets to water the following reaction takes place:
KOH(s) KOH(aq) + 43 kJ/mol
Answer the following questions regarding the addition of 14.0 g of KOH to water:
Does the beaker get warmer or colder?
Is the reaction endothermic or exothermic?
What is the enthalpy change for the dissolution of the 14.0 grams of KOH?

Answers: (a) warmer (b) exothermic (c) 10.7 kJ/molrxn


Calorimetry:
The process of measuring heat based on observing the temperature change when a body absorbs
or discharges energy as heat.
Coffee Cup calorimetry:
Coffee-cup calorimetry in the lab this is how we experiment to find energy of a
particular system. We use a Styrofoam cup, reactants that begin at the same temperature
and look for change in temperature. After all data is collected (mass or volume; initial
and final temperatures) we can use the specific formula to find the energy released or
absorbed. We refer to this process as constant pressure calorimetry. ** q = H @ these
conditions**

Terms to know:
Heat capacity energy required to raise temp. by 1 degree (Joules/ C)
Specific heat capacity (Cp) same as above but specific to 1 gram of substance and the experiment is
carried out at constant pressure. Constant pressure is achieved using open containers, so you will be doing
experiments of that kind in lab.
specific heat =

quantity of heat transferred


( g of material) (degrees of temperature change)

Molar heat capacitysame as above but specific to one mole of substance (J/mol K or J/mol C )

4
Thermochemistry

Energy (q) released or gained at constant pressure: q = mCpT


q = quantity of heat (Joules or calories)
m = mass in grams
T = Tf Ti (final initial)
Cp = specific heat capacity ( J/gC)
Specific heat of water (liquid state) = 4.184 J/gC ( or 1.00 cal/gC)
Water has one of the highest specific heats known! This property makes life on earth possible and regulates
earths temperature year round!
Heat lost by substance = heat gained by water
Units of Energy:
calorie--amount of heat needed to raise the temp. of 1.00 gram of water 1.00 C
kilocalorie1,000 calories AND the food label calorie with a capital C.
1
kgm
KE = mv 2 units are
2
s2
joule--SI unit of energy; 1 cal = 4.184 J
Exercise 5
In a coffee cup calorimeter, 100.0 mL of 1.0 M NaOH and 100.0 mL of 1.0 M HCl are mixed. Both
solutions were originally at 24.6C. After the reaction, the final temperature is 31.3C. Assuming that all
solutions have a density of 1.0 g/cm3 and a specific heat capacity of 4.184 J/gC, calculate the enthalpy
change for the neutralization of HCl by NaOH. Assume that no heat is lost to the surroundings or the
calorimeter.

5.6 kJ/molrxn

Exercise 6
Enthalpy
When 1 mole of methane (CH4) is burned at constant pressure, 890 kJ/mol of energy is released as heat.
Calculate H for a process in which a 5.8 gram sample of methane is burned at constant pressure.

H = heat flow = 320 kJ/molrxn


5
Thermochemistry

Exercise 7

Constant-Pressure Calorimetry

When 1.00 L of 1.00 M Ba(NO3)2 solution at 25.0C is mixed with 1.00 L of 1.00 M Na2SO4 solution at 25C
in a calorimeter, the white solid BaSO4 forms and the temperature of the mixture increases to 28.1C.
Assuming that the calorimeter absorbs only a negligible quantity of heat, and that the specific heat capacity of
the solution is 4.18 J/C g, and that the density of the final solution is 1.0 g/mL, calculate the enthalpy change
per mole of BaSO4 formed.

26 kJ/molrxn

Tables:

Hf = enthalpy of formation
= Production of ONE mole of compound FROM
its ELEMENTS in their standard states ()
= ZERO (0.00) for ELEMENTS in standard states
Standard States: 25C (298 K), 1 atm, 1M

The Big Mamma Equation: Hrxn = Hf (products) - Hf (reactants)


(also known as Hesss Law)

6
Thermochemistry

Exercise 8
Substance
NH4ClO4(s)
Al2O3(s)
AlCl3(s)
NO(g)
H2O(g)

Hf (kJ/mol)
295
1676
704
90.0
242

Given the information above, calculate the Hrxn for the following chemical reaction.
3 Al(s) + 3 NH4ClO4(s) Al2O3(s) + AlCl3(s) + 3 NO(g) + 6 H2O(g)

2,677 kJ/molrxn (exo)

Exercise 9

C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O() + 2800 kJ

Occasionally, not all values are found in the table of thermodynamic data. For most substances it is impossible
to go into a lab and directly synthesize a compound from its free elements. The heat of formation for the
substance must be calculated by working backwards from its heat of combustion. Calculate the Hf of
C6H12O6(s) given the combustion reaction above along with the following information.
Substance
CO2(g)
H2O()

Hf (kJ/mol)
393.5
285.8

Hf for glucose = 1276 kJ/mol


7
Thermochemistry

Exercise 10
The thermite reaction occurs when a mixture of powdered aluminum and
iron(III) oxide is ignited with a magnesium fuse. Using enthalpies of formation,
calculate the standard change in enthalpy for the thermite reaction:
2Al (s) + Fe2O3(s) A12O3(s) + 2Fe(s)

850. kJ/molrxn
Enthalpy is independent of the reaction pathway. If you can find a combination of chemical equations that add
up to give you the desired overall equation, you can also sum up the Hs for the individual reactions to get the
overall Hrxn.
First, decide how to rearrange equations such that the reactants and products are on appropriate sides of the
arrows in the chemical equation. It is often helpful to begin by working backwards from the final or
summary chemical equation.
If an equation had to be reversed, also reverse the sign of Hrxn
If an equation had to be multiplied by a given factor to obtain correct coefficients, also multiply the
H rxn by this factor since Hrxns are in kJ/MOLErxn (division applies similarly)
Double check to ensure that everything cancels out to give you the exact summary chemical equation you
desire.
Exercise 11
Calculate the H for this overall reaction 2 H3BO3(aq) B2O3(s) + 3 H2O() given the following
equations:
H3BO3(aq) HBO2(aq) + H2O()
H = 0.02 kJ/molrxn
H2B4O7(aq) + H2O() 4 HBO2(aq)

H = 11.3 kJ/molrxn

H2B4O7(aq) 2 B2O3(s) + H2O()

H = 17.5 kJ/molrxn

14.4 kJ/molrxn endothermic


Thermochemistry

Bond Energies
Energy must be added/absorbed to BREAK bonds (endothermic) in order to overcome the
coulombic attraction between each nuclei and the shared electrons. Energy is released when
bonds are FORMED (exothermic) because the resultant coulombic attraction between the
bonded atoms lowers potential energy causing a release. This is a giant misconception among
students! Once again, it takes energy to break bonds and energy is released when a bond
forms.

H = sum () of the energies required to break old bonds (positive signs since energy is added to
the system) plus the sum of the energies released in the formation of new bonds (negative signs
since energy is lost from the system).

H = Bond Energies broken Bond Energies formed


Exercise 12
Calculate the change in energy that accompanies the following reaction given the data below.
H2(g) + F2(g) 2 HF(g)
Bond Type
HH
FF
HF

Bond Energy
432 kJ/mol
154 kJ/mol
565 kJ/mol

544 kJ/molrxn

SUMMARY FOR ENTHALPY: What does it really tell you about the changes in energy regarding a
chemical reaction?
H = + reaction is endothermic and heat energy is added into the system
H = reaction is exothermic and heat energy is lost from the system
(Nature tends toward the lowest energy state!)
9
Thermochemistry

Speaking of bond energies, allow us to clear up some common misconceptions AND make
some dazzling connections.
Lets start with the vocabulary used to describe phase changes. First, you must realize that the vocabulary is
directional (hence the arrows on this diagram) as well as very specific. Youll have to mean what you say
and say what you mean when answering a free response question!
Phase transitions involving overcoming intermolecular attractions or IMFs
which should never be confused with ionic or covalent chemical bonds.
Fusion (melting), vaporization, and sublimation require an input of
energy to overcome the attractive forces between the particles of the
substance. NOTICE we did not speak of breaking bonds.
Freezing, condensation, and deposition (opposite of sublimation) release
energy as IMFs form since the particles achieve a lower energy state
mainly due to a decrease in temperature.

Is there a difference between a vapor and a gas? Yes, its primarily semantics. A gas is a gas at
room temperature, we dont speak of oxygen vapor. However, we do use the term vapor when
the substance is normally a liquid or solid at room temperature. We say water vapor, carbon
dioxide vapor, iodine vapor, etc.
Be very, very clear that changes in the phases of matter involve altering IMFs, not altering
chemical bonds.*
The strength of the intermolecular attractions between molecules, and therefore the amount of
energy required to overcome these attractive forces (as well as the amount of energy released when
the attractions are formed) depends on the molecular properties of the substance, ionic, polar,
nonpolar, etc.
Generally, the more polar a molecule is, the stronger the attractive forces between molecules
are. Hence, more polar molecules typically require more energy to overcome the intermolecular
attractions in an endothermic phase transition, and release more energy by forming intermolecular
attractions during an exothermic phase transition.
Phase transitions involve the breaking or forming of intermolecular forces (attractive interactions
between molecules). Hence, as with other chemical reactions, it is necessary to discuss the energy
that is absorbed or given off during the breaking or forming of intermolecular interactions in a
phase transition.
*UNLESS you have a network solid or covalent network solid which is a chemical compound in which the atoms are bonded by
covalent bonds in a continuous network. In a network solid there are no individual molecules and the entire crystal may be considered
a macromolecule. Examples of network solids include diamond with a continuous network of carbon atoms and silicon dioxide or
quartz with a continuous three dimensional network of SiO2 units. Graphite and the mica group of silicate minerals structurally consist
of continuous two-dimensional layers covalently bonded within the layer with other bond types holding the layers together. That
means they essentially slide in sheets the way your pencil lead (actually graphite) glides across the page leaving a trail.

10
Thermochemistry

You have probably seen a graph like this before arriving in AP Chemistry. Lets make some additional
dazzling connections!
Suppose this heating curve is for water (it isnt because the horizontal line for boiling condensing is too
short. Why? (It takes WAY more energy to boil water than what is shown here due to having to overcome all
those IMFs called hydrogen bonds).

Take a moment and ponder the differences in molecular structure and molecular motion among the different states of
water represented above, the kinetic energy changes, and the potential energy changes.
1. Does the process above represent a collection of chemical changes, physical changes or both? Physical
changes.
2. What type of force is involved in the changes you identified in question 1? Intermolecular forces as opposed
to intramolecular forces (chemical bonds). Students may also specify exact IMFs such as H-bonding.
3. Define temperature: Temperature is defined as the average kinetic energy of the molecules.
4. Which conversions involve temperature changes? warming and cooling
5. Which mathematical formula is appropriate for calculating the energy associated with the processes you
identified in question 4? q = mcT
6. Which conversions involve potential energy changes? freezing, melting, condensing, boiling, vaporizing
7. Which mathematical formula is appropriate for calculating the energy associated with the processes you
identified in question 4? q = mHvap
8. How do you calculate q for the processes identified in number 6 if you are given only the mass of the water
sample? Simply divide the mass given by the molar mass of water to determine the number of moles involved,
then multiply by the enthalpy of vaporization or fusion.
9. Which portions of this graph represent equilibrium conditions? Phase changes: ice water,

water steam, the plateaus where temperature is not changing only potential energy is changing as
system is absorbing or releasing heat. PE is added to overcome IMFs (melting or boiling) or released to
when IMFs form (condensing or freezing).

11
Thermochemistry

AP* Chemistry
ATOMIC STRUCTURE
ELECTROMAGNETIC RADIATION
James Maxwell developed an elegant mathematical theory in 1864 to describe all forms of radiation in
terms of oscillating or wave-like electric and magnetic fields in space.
electromagnetic radiationUV, visible light, IR, microwaves,
television and radio signals, and X-rays
wavelength ()(lambda) length between 2 successive crests.
frequency ()(nu in chemistry; f in physicseither is OK), number
of cycles per second that pass a certain point in space (Hz-cycles
per second)
amplitudemaximum height of a wave as measured from the axis of
propagation
nodespoints of zero amplitude (equilibrium position); always occur

axis of propagation

at /2 for sinusoidal waves


velocityspeed of the wave

velocity =

cthe speed of light; 2.99792458 [just call it 3] 108 m/s; ALL EM RADIATION TRAVELS
AT THIS SPEED! I call it easy, youll call it a trick! If light is involved, it travels at 3 108 m/s
Notice that and are inversely proportional. When one is large, the other is small.

*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this
product.
2008 by Ren McCormick. All rights reserved.

Exercise 1
Frequency of Electromagnetic Radiation
The brilliant red colors seen in fireworks are due to the emission of light with wavelengths around 650 nm when strontium
salts such as Sr(NO3)2 and SrCO3 are heated. (This can be easily demonstrated in the lab by dissolving one of these salts in
methanol that contains a little water and igniting the mixture in an evaporating dish.) Calculate the frequency of red light of
wavelength 6.50 102 nm.

= 4.61 1014 Hz

THE NATURE OF MATTER


At the end of the 19th century, physicists were feeling rather smug. All of physics had been explained
[or so they thought]. Students were being discouraged from pursuing physics as a career since all of
the major problems had been solved! Matter and Energy were distinct: Matter was a collection of
particles and Energy was a collection of waves. Enter Max Planck stage left
THE QUANTIZATION OF ENERGY
"Ultraviolet catastrophe"defined as the fact that a glowing hot object did not emit UV light as
predicted.
1900--Max Planck solved the problem. He made an incredible assumption: There is a minimum
amount of energy that can be gained or lost by an atom, and all energy gained or lost must be some
integer multiple, n, of that minimum. (As opposed to just any old value of energy being gained or
lost.)

Energy = n(h)
where h is a proportionality constant, Planck's constant, h = 6.6260755 10-34 joule seconds.
This is the lowest frequency that can be absorbed or emitted by the atom, and the minimum
energy change, h, is called a quantum of energy. Think of it as a packet of E equal to h.
No such thing as a transfer of E in fractions of quanta, only in whole numbers of quanta.
Planck was able to calculate a spectrum for a glowing body that reproduced the experimental
spectrum.
His hypothesis applies to all phenomena on the atomic and molecular scale.
Exercise 2
The Energy of a Photon
The blue color in fireworks is often achieved by heating copper(I) chloride (CuCl) to about 1200C. Then the compound
emits blue light having a wavelength of 450 nm. What is the increment of energy (the quantum) that is emitted at
4.50 102 nm by CuCl?

= 4.41 10-19 J

Atomic Structure

THE PHOTOELECTRIC EFFECT AND ALBERT EINSTEIN


In 1900 Albert Einstein was working as a clerk in the patent office in Bern, Switzerland. This left him
time to work on Physics.
He proposed that EM radiation itself was quantized; he was a great fan of Plancks work! He proposed
that EM radiation could be viewed as a stream of particles called photons.
photoelectric effect--light bombards the surface of a metal and electrons are ejected.
frequencya minimum must be met or alas, no action! Once minimum is met, intensity increases
the rate of ejection.
photon--massless particles of light.
Ephoton = h = hc

2
You know Einstein for the famous E = mc from his second work as the special theory of relativity
published in 1905. Such blasphemy, energy has mass?! That would mean:
m= E
c2
therefore,
m = E = hc/ = h
c2
c2
c
Does a photon have mass? Yep! In 1922 American physicist Arthur Compton performed experiments
involving collisions of X-rays and electrons that showed photons do exhibit the apparent mass
calculated above.
SUMMARY:
Energy is quantized.
It can occur only in discrete units called quanta [h].
EM radiation [light, etc.] exhibits wave and particle properties.
This phenomenon is known as the dual nature of light.

Since light which was thought to be wavelike now has certain characteristics of particulate matter, is
the converse also true? Enter Louis de Broglie [French physicist, 1923] stage right
IF m = h
c
substitute v [velocity] for c for any object NOT traveling at the speed of light, then rearrange and solve
for lambda

Atomic Structure

this is called the de Broglie equation:


= h
mv
Exercise 3
Calculations of Wavelength
Compare the wavelength for an electron (mass = 9.11 10-31 kg) traveling at a speed of 1.0 107 m/s with that for a ball
(mass = 0.10 kg) traveling at 35 m/s.

e = 7.27 10-11 m
b = 1.9 10-34 m

The more massive the object, the smaller its associated wavelength and vice
versa!
Davisson and Germer @ Bell labs found that a beam of electrons was
diffracted like light waves by the atoms of a thin sheet of metal foil and
that de Broglie's relation was followed quantitatively.
ANY moving particle has an associated wavelength.
Silly physicists! We now know that E is really a form of matter, and ALL
matter shows the same types of properties. That is, all matter exhibits
both particulate and wave properties.

HYDROGENS ATOMIC LINE SPECTRA AND NIELS BOHR


emission spectrumthe spectrum of bright lines, bands, or
continuous radiation that is provided by a specific emitting
substance as it loses energy and returns to its ground state OR the
collection of frequencies of light given off by an "excited"
electron
absorption spectruma graph or display relating how a
substance absorbs electromagnetic radiation as a function of
wavelength
line spectrum--isolate a thin beam by passing through a slit then a prism or a diffraction grating
which sorts into discrete frequencies or lines
Johann Balmer--worked out a mathematical relationship that accounted for the 3 lines of longest
wavelength in the visible emission spectrum of H. (red, green and blue lines)

Atomic Structure

Niels Bohr connected spectra, and the quantum ideas of Einstein and Planck: the single electron of
the hydrogen atom could occupy only certain energy states, stationary states

"The Mother of all Assumptions"


An electron in an atom would remain in its lowest E state unless otherwise disturbed.
Energy is absorbed or emitted by a change from this ground state
an electron with n = 1 has the most negative energy and is thus the most strongly
attracted to the positive nucleus. [Higher states have less negative values and are
not as strongly attracted to the positive nucleus.]
ground state--n = 1 for hydrogen

E photon = h =

hc

To move from ground to n = 2 the electron/atom must absorb no more or no less


than
0.75 Rhc. [thats a collection of constants]
So, a move of n = 2 to n = 1 emits 985 kJ of energy.
What goes up must come down. Energy absorbed must eventually be emitted.
The origin or atomic line spectra is the movement of electrons between quantized energy states.
IF an electron moves from higher to lower E states, a photon is emitted and an emission line is
observed.

Atomic Structure

Bohrs equation for calculating the energy of the E levels available to the electron in the
hydrogen atom:

Z2
E = 2.178 1018 J 2
n
where n is an integer [larger n means larger orbit radius, farther from nucleus], Z is the nuclear
charge
The NEGATIVE sign simply means that the E of the electron bound to the nucleus is lower that
it world be if the electron were at an infinite distance [n = ] from the nucleus where there is
NO interaction and the energy is zero.
E is simply the subtraction of calculating the energy of two different levels, say n=6 and n=1.
If the difference is negative, E was lost. If the difference is positive, E was gained.
TWO Major defects in Bohr's theory: 1) Only works for elements with ONE electron.
2) The one, lonely electron DOES NOT orbit the nucleus in a fixed path!!
Exercise 4
Energy Quantization in Hydrogen
Calculate the energy required to excite the hydrogen electron from level n = 1 to level n = 2. Also calculate the
wavelength of light that must be absorbed by a hydrogen atom in its ground state to reach this excited state.

E = 1.633 10-18 J
= 1.216 10-7 m

Exercise 5
Electron Energies
Calculate the energy required to remove the electron from a hydrogen atom in its ground state.

E = 2.178 10-18 J

Atomic Structure

THE WAVE PROPERTIES OF THE ELECTRON


SCHRODINGER, HEISENBERG, AND QUANTUM NUMBERS
After World War I--Niels Bohr assembled a group of physicists in Copenhagen hoping to derive
a comprehensive theory for the behavior of electrons in atoms from the viewpoint of the
electron as a particle
Erwin Schrodinger--independently tried to accomplish the same thing but focused on de
Broglie's eqn' and the electron as a wave. Schrodinger's approach was better; explained more
than Bohr's and met with more success. Quantum mechanics was born!
de Broglie opened a can of worms among physicists by suggesting the electron had wave
properties
the electron has dual properties
Werner Heisenberg and Max Born provided the uncertainty principle
- if you want to define the momentum of an electron, then you have to forego knowledge of
its exact position at the time of the measurement
Max Born on the basis of Heisenberg's work suggested: if we choose to know the energy of an electron
in an atom with only a small uncertainty, then we must accept a correspondingly large uncertainty
about its position in the space about the atom's nucleus. So What? We can only calculate the
probability of finding an electron within a given space.
THE WAVE MECHANICAL VIEW OF THE ATOM
Schrodinger equation: solutions are called wave functions--chemically
important. The electron is characterized as a matter-wave
sort of standing waves--only certain allowed wave functions (symbolized by
the Greek letter, , pronounced sigh)
Each for the electron in the H atom corresponds to an allowed energy
(Rhc/n2). For each integer, n, there is an atomic state characterized by its
own and energy En.
In English? Points 1 & 2 above say that the energy of electrons is
quantized.

Notice in the figure to the right, that only whole numbers of standing waves can fit in
the proposed orbits.
The hydrogen electron is visualized as a standing wave around the nucleus [above right]. The circumference of a
particular circular orbit would have to correspond to a whole number of wavelengths, as shown in (a) and (b) above,
OR else destructive interference occurs, as shown in (c). This is consistent with the fact that only certain electron
energies are allowed; the atom is quantized. (Although this idea encouraged scientists to use a wave theory, it does
not mean that the electron really travels in circular orbits.)

Atomic Structure

the square of gives the intensity of the electron wave or the probability of
finding the electron at the point P in space about the nucleusthe intensity
of color in (a) above represents the probability of finding the electron in that
space, the darker the colorthe more probable it is we would find the
electron in that region.
electron density map, electron density and electron probability ALL mean the
same thing! When we say orbital this image at right is what we picture in
our minds.
matter-waves for allowed energy states are also called (drum roll please)
orbitals.
To solve Schrodinger's equation in a 3-dimensional world we need the
quantum numbers n, A , and m
The amplitude of the electron wave at a point depends on the distance of
the point from the nucleus.

Imagine that the space around a H nucleus is made up of a series of thin shells like the layers of an
onion, but these shells as squishy (Very scientific word, that squishy!)
Plot the total probability of finding the electron in each shell versus the distance from the nucleus and
you get the radial probability graph you see in (b) above
The maximum in the curve occurs because of two opposing effects. 1) the probability of finding an
electron is greatest near the nucleus [electrons just cant resist the attraction of a proton!], BUT 2)
the volume of the spherical shell increases with distance from the nucleus, SO we are summing more
positions of possibility, so the TOTAL probability increases to a certain radius and then decreases as
the electron probability at EACH position becomes very small.

Try not to stress over this introduction stuff! Learn to do the


calculations in the practice exercises & do the best you can with the
theory stuff. Its my moral obligation to TRY to explain it to you.
Stress over quantum numbers and electron configurations and
periodicity if you mustthats the important stuff in this chapter!
I just feel the need to give you a complete education!

Atomic Structure

QUANTUM NUMBERS & ATOMIC ORBITALS


There are 4 quantum numbers that describe the address and spin of an electron.
The value of n limits the possible values of , which in turn limit the values of m.
nprincipal energy level--1 to infinity. Determines the total energy of the electron. It indicates the
most probable [within 90%] distance of the electron from the nucleus. A measure of the orbital size
or diameter. 2n2 electrons may be assigned to a shell. Its simply the Energy level that electron is
in. If its a 3s electron, n = 3, if its a 4d electron, n = 4, etc.
--angular momentum--0,1,2,....(n-1) electrons w/in shell may be grouped into subshells [or
sublevels, same thing!], each characterized by its certain wave shape. Each is a different orbital
shape or orbital type.
- n limits the values of to no larger than n-1. Thus, the number of possibilities for is equal to n.
(English translation: 3 sublevels for 3rd E level, 4 for 4th E level, etc.)
- s,p,d,f sublevels 0,1,2,3 -values respectively (So, what do spdf stand for? Sharp, principle,
diffuse, fundamental--early days of atomic spectroscopy)
You can keep
going from g

m--magneticassign the blanks in orbital notation with zero on the middle blank and then -
through zero to +. Ill bet this looks familiar for Sulfur from Chem. I!

1s

-1

2s

2p

+1

3s

-1

3p

+1

- that means that the range of orbitals is from + to -


- it describes the orientation of an orbital in a given subshell
- The down arrow in the 3p, -1 slot is the last electron placed [valence electron], so far its set
of quantum numbers is 3, 1, -1

DONT
try to
make this
hard!
Embrace
the elegant
patterns!

Atomic Structure

Exercise 6
Electron Subshells
For principal quantum level n = 5, determine the number of allowed subshells (different values of ), and give the designation
of each.
= 0; 5s
= 1; 5p
= 2; 5d
= 3; 5f
= 4; 5g

THE SHAPES OF ATOMIC ORBITALS


There is no sharp boundary beyond which the electrons are never found!!
s--spherical; the size increases with n. The nodes you see at left represent
ZERO probability of finding the electron in that region of space. The number
of nodes equals n-1 for s orbitals.
p--have one plane that slices through the nucleus and divides the region of
electron density into 2 halves. Nodal plane--the electron can never be found
there!!
3 orientations: px, py, and pz.

d--2 nodal planes slicing through the nucleus to create four sections; 5 orbitals.
The dz2 orbital is really strange!

Atomic Structure

10

f--3 nodal planes slicing through the nucleus; eight


sections; 7 orbitals

ELECTRON CONFIGURATIONS
Chemical properties depend on the number and arrangement of electrons in an atom. Usually only the
valence electrons play the reaction game.
ELECTRON SPIN
1920--chemists realized that since electrons interact with a magnetic field,
there must be one more concept to explain the behavior of electrons in
atoms.
ms--the 4th quantum number; accounts for the reaction of electrons in a
magnetic field
MAGNETISM
magnetite--Fe3O4, natural magnetic oxide of iron
1600--William Gilbert concluded the earth is also a large spherical magnet
with magnetic south at the geographic North Pole (Santa's habitat).
NEVER FORGET: opposites attract & likes repel whether its opposite
poles of a magnet or opposite electrical charges
PARAMAGNETISM AND UNPAIRED ELECTRONS
diamagnetic--not magnetic [magnetism dies]; in fact they are slightly repelled by a magnetic field.
Occurs when all electrons are PAIRED.
paramagnetic--attracted to a magnetic field; lose their magnetism when removed from the magnetic
field; HAS ONE OR MORE UNPAIRED ELECTRONS
ferromagnetic--retain magnetism upon introduction to, then removal from a magnetic field
All of these are explained by electron spins
o Each electron has a magnetic field with N & S poles
o electron spin is quantized such that, in an external magnetic field, only two orientations of the
electron magnet and its spin are possible
o +1/2 and 1/2
o H is paramagnetic; He is diamagnetic, WHY?
H has one unpaired electron
He has NO unpaired electrons; all spins offset and cancel each other out

Atomic Structure

11

What about ferromagnetic?


clusters of atoms have their unpaired electrons aligned within a
cluster, clusters are more or less aligned and substance acts as a
magnet. Don't drop it!!
When all of the domains, represented by these arrows are
aligned, it behaves as a magnet.
This is what happens if you drop it: The domains go in all
different directions and it no longer operates as a magnet.

THE PAULI EXCLUSION PRINCIPLE


In 1925 Wolfgang Pauli stated: no two electrons in an atom can have the same set of four quantum
numbers. This means no atomic orbital can contain more than 2 electrons & for two electrons to occupy
the same orbital, they must be of opposite spin!!
ATOMIC ORBITAL ENERGIES AND ELECTRON ASSIGNMENTS
Order of orbital energies--the value of n (E = Rhc/n2) determines the energy of an electron
many-electron atoms depend on both n &
Use the diagonal rule or Aufbau series
Orbital radius changes slightly with as well as with n
subshell orbitals contract toward the nucleus as the value of
increases
contraction is partially into the volume of space occupied by
the core electrons
the energy of the electrons in these subshells is raised due to
the repulsions between the subshell electrons and the core
electrons.
a subshell's energy rises as its quantum number increases when inner electrons
are present
Order of Orbital Assignments
each electron is lazy and occupies the lowest energy space available
based on the assumption inner electrons have no effect on which orbitals are assigned to outer or
valence electrons
not exactly true (use diagonal rule)note that the one pictured shows the lowest
energy state (1s) at the top of the diagramsome variations show 1s at the
bottom of the diagram

electron configurations (spectroscopic notation)


clump the 1's, 2's, etc. TOGETHER rather than written in the order the orbitals fill

Atomic Structure

12

HUNDS RULE
The most stable arrangement of electrons is that with the maximum number of unpaired electrons;
WHY?? it minimizes electron-electron repulsions (everyone gets their own room)
all single electrons also have parallel spins to reduce e-/e- repulsions (aligns micromagnets)
When 2 electron occupy the same orbital they must have opposite spins (Pauli exclusion
principle); this also helps to minimize e-/e- repulsions
Personally, I think this whole quantum number thing is easiest when we start with the electron
configurations THEN write the quantum numbers.
Allow me to recap: Dont try to make this hard! It just isnt.
Energy Level
1
2
3
4
5
# of sublevels
1
2
3
4
5
s
s,
p
s,p,d
s,p,d,f
s,p,d,f,g
Names of sublevels
n, principal quantum 1
2
3
4
5
number

6
6
s,p,d,f,g,h
6

7.
7.
s,p,d,f,g,h,i
7.

Name of
sublevel

, angular
momentum
quantum
number
[= n-1]
# of orbitals
[= - to +]
m for each
orbital
within a
sublevel

11

13

-1 0 +1

-2 -1 0 +1 +2

And so on, just pretend you are in second


grade and make a number line with negative
numbers on the left, ZERO in the middle,
and positive numbers on the right.

The first electron placed in an orbital is assigned the +1/2 and the second one is assigned the -1/2.

Atomic Structure

13

Lets practice: Give the electron configurations for the elements within this figure. Ill get you started!
S 1s2 2s2 2p6 3s2 3p4
Cd
La
Hf
Ra
Ac
And their Orbital Notation:
Sulfur
12

3 4

1s

2s

58

6 9 7 10

2p

11 12

3s

13 16 14 15

-1

3p

+1

Cd

La

Hf

As electrons enter these


sublevels their wave
functions interfere with each
other causing the energy of
these to change and
separate. Do not be misled
by this diagram, there ARE
INDEED energy differences
between all of these
sublevels. See below.

Ra
Ac
There is a super cool animation that illustrates this
concept. The website is from the Chief Reader of the AP Exam.
This site is http://intro.chem.okstate.edu/APnew/Default.html
Click on Electron Configuration Animation. Youll need the
shockwave plug-in. Once the animation comes up, click on the
screen to advance from Hydrogen on up by atomic number.

Atomic Structure

14

What are the quantum numbers for the outermost [valence] electron?
S--since the last electron put in is #16 and it is in the 3p sublevel, n = 3 and = 2. Its in the -1 slot, the
m = -1 and since its the second arrow placed [down arrow] its ms = -1/2. So the set of quantum
numbers for the 16th electron in sulfur is: 3,2,-1, -1/2. Youll find this really easy IF you draw the
orbital notation for the last sublevel!
Cd
La
Hf
Ra
Ac

You accepted that the sublevels had differences in energies long ago.

You even know the increasing order of energies:


s < p < d < f < g

Now you have to be able to EXPLAIN it on the AP test. Throughout this discussion keep some
fundamental scientific principles close at hand
o electrons repel each other
o electrons are negative and thus, attracted by the
positive nucleus
o forces (attractive & repulsive) dissipate with
increasing distance.
penetrates

closest to the
We need to examine the graph at the right, radial
nucleus
probabilities again.
o See the small hump near the origin? Thats the
distance from the nucleus that a 2s electron
occupies a small but significant amount of the
timewe say the 2s electron penetrates to the
nucleus more than for the 2p orbital. This causes a
2s electron to be ATTRACTED to the nucleus
mighty close to the
more than a 2p electron making the 2s orbital
nucleus.
E is ZAPPED
LOWER in E than the 2p orbital.
o Think of the nucleus as zapping the energy of the electrons that penetrate closer to it.
[Just dont write that!] Imagine a hyper childits on its best behavior, sitting still,
being quiet, etc. when its close to Mom. The closer to the Mother Nucleus the hyper
electron is, the less hyper or energetic it is. Dont EVER write this as an answer to an
essay question! Its just a model to help you get your teeth into this concept!

Atomic Structure

15

Same song second versethe last hump represents the greatest


probability for predicting the distance of an electron from the
nucleus, BUT the first humps determine the order of the energy.
o The top graph is for 3snote it has 2 humps close to the
nucleus
o The bottom graph is for 3s, 3p and note that 3d only has
one hump.
o 3s penetrates most [has least energy], then 3p [higher E
than 3s, lower E than 3d] then 3d penetrates least [so it has
the highest energy].
o MORAL: The greater the penetration, the less energy that
orbital has. Since you already knew the order with respect
to energy, s < p < d < f , the degree of penetration is ss
penetrate most and fs penetrate least.

ION ORBITAL ENERGIES AND ELECTRON CONFIGURATIONS


The dfs overlay [that thing that happens when the configurations dont fit the pattern in transition metals
and rare earth metals] does not occur in ion configurations since the valence (outermost n) electrons are
the first to go! THE SHELL ENERGY RANGES SEPARATE MORE WIDELY AS ELECTRONS
ARE REMOVED.
Atoms and ions with unpaired electrons are paramagnetic (attracted to a magnetic field)
Transition metals with +2 or higher have no ns electrons
Fe+2 is paramagnetic to the extent of 4 unpaired electrons and Fe+3 is paramagnetic to the extent
of 5 unpaired electrons
THE HISTORY OF THE PERIODIC TABLE
1800ishJohann Dobereiner, triads; 1864 John Newlands octaves;
1870--Dmitrii Mendeleev & Julius Lothar Meyer--by mass; 1913
Mosley--by number of protons.

Atomic Structure

16

o
o
o
o
o

Group IA(1A or 1)--alkali metals


Group IIA(2A or 2)--alkaline earth metals
Group VIA(6A or 16)--Chalcogens
Group VIIA(7A or 17)Halogens
Group VIIIA (8A or 18)Noble gas

SOME PROPERTIES OF COMMON


GROUPS:
Alkali metalsthe most
reactive metal family; must be stored under oil; react with water violently!
Alkaline-earth metals-- except for Be(OH)2, the metal hydroxides formed by this
group provide basic solutions in water ; pastes of these used in batteries
Chalcogen family many found combined with metal ores
Halogen family known as the salt-formers ; used in modern lighting
Noble Gas family known for their disinterest in other elements; once thought to
never react; neon used to make bright RED signs
Transition metalsfill the d orbitals.
o Anomalies occur at Chromium and Copper to minimize electron/electron
repulsions. If you learned that there is special stability associated with a halffilled sub-level, ITS A LIE!! No such stability exists! NEVER, EVER write
that! Its all about lowering energy by minimizing electron/electron
repulsions.

Atomic Structure

17

Rare Earth metalsfill the f sublevels.


Lanthanides and Actinides. These
sometimes put an electron in d [just one
or two electrons] before filling f. This is
that dsf overlay referred to earlierthe
energies of the sublevels are very similar.
PERIODIC TRENDS:
A trend is NOT an
EXPLANATION!
This is an important sectionthere is almost always an essay involving this topic on the AP exam.
There are several arguments you will evoke to EXPLAIN a periodic trend. Remember opposites attract
and likes repel. The trick is learning which argument to use when explaining a certain trend!
THE ARGUMENTS:
1. Effective nuclear charge, Zeffessentially equal to the group number. Think of the IAs having
a Zeff of one while the VII As have a Zeff of 7! The idea is that the higher the Zeff, the more
positive the nucleus, the more attractive force there is emanating from the nucleus drawing
electrons in or holding them in place. Relate this to ENERGY whenever possible.
2. Distanceattractive forces dissipate with increased distance. Distant electrons are held loosely
and thus easily removed. Relate this to ENERGY whenever possible.
3. Shieldingelectrons in the core effectively shield the nucleus attractive force for the valence
electrons. Use this ONLY when going up and down the table, NOT across. There is ineffective
shielding within a sublevel or energy level. Relate this to ENERGY whenever possible.
{I cant help but think of dodge ball, such a barbaric ritualsince youre the smart kids, you
figured out in elementary school to stay behind the bigger kids to keep from getting hit! The
electrons in the first or second energy level, shield the outer valence electrons from the Mother
Nucleus attractive force. }
4. Minimize electron/electron repulsionsthis puts the atom at a lower energy state and makes it
more stable. Relate this to ENERGY whenever possible.
Here we go!

Atomic Structure

18

1. ATOMIC RADIUS--No sharp boundary beyond which the electron never strays!!
Use diatomic molecules and determine radius then react with other atoms to
determine the radius of those atoms
ATOMIC radii decreases () moving across a period AND increases ()
moving down a row (family)
WHY across? The effective nuclear charge (Zeff) increases
(more protons for the same number of energy levels) as we
move from left to right across the periodic table, so the
nucleus has a greater positive charge, thus the entire electron
cloud is more strongly attracted and shrinks.
o This shrinks the electron cloud until
the point at which electron/electron repulsions
overcome the nuclear attraction and stop the contraction of
the electron cloud.
WHY down? The principal level, n, determines the size of
an atomadd another principal level and the atoms get
MUCH larger radii
As we move down a family, the attractive force the nucleus
exerts on the valence electrons dissipates.
Shielding is only a valid argument when comparing elements
from period to period (up and down the table) since shielding
is incomplete within a perioduse this argument with
extreme caution! It should NOT be your favorite!
2. IONIZATION ENERGY--energy required to remove
an electron from the atom IN THE GAS PHASE. Costs
Energy.
Removing each subsequent electron requires more energy:
Second IE, Third IE, etc.
Some subsequent IEs cost more E than others!! A
HUGE energy price is paid if the subsequent removal of
electrons is from another sublevel or, Heaven forbid,
another principal E level (core).
down a familyincreased distance from
the nucleus and increased shielding by full
principal E levels means it requires less E to remove an electron
across a perioddue to increasing Zeff. The higher the Zeff, the stronger the nucleus
attracts valence electrons, the more energy required to remove a valence electron.
Lets talk EXCEPTIONS!!

Atomic Structure

19

an anomaly occurs at messing up a half-filled or filled sublevel Theres nothing magical about this
and electrons are not happier as a result. The simple truth is that when electron pairing first occurs
within an orbital, there is an increase in electron/electron repulsions which makes it require less
energy [easier] to remove an electron thus the IE drops. NEVER, EVER write about the fictitious
stability of a -filled shelleven though you may see it in books!
Look at oxygen vs. nitrogenit requires less energy to remove an electron from oxygens valence
IN SPITE OF AN INCREASING Zeff because oxygens p4 electron is the first to pair within the
orbital thus experiencing increased repulsion. The increased repulsion lowers the amount of energy
required to remove the newly paired electron!
Also, look at the drop in IE from any s2 to p1. This is also IN SPITE OF AN INCREASING Zeff. This
drop in the energy required to remove a valence electron is due to the fact that you are removing a
p electron rather than an s electron. The ps are less tightly held BECAUSE they do not penetrate
the electron cloud toward the nucleus as well as an s electron. The general trend is that s is held
most tightly since it penetrates more then p, d and f
3. ELECTRON AFFINITYan affinity or liking for electronsforce feeding an element an
electronEnergy associated with the addition of an electron to a gaseous atom:
X (g) + e X (g)
If the addition of an electron is exothermic, then youll see a negative sign on the energy change and the
converse is also true. The more negative the quantity, the more E is released. This matches our sign
convention in thermodynamics.
down a family [that means becomes less negative a.k.a. more positive, giving off less energy]due
to increased distance from the nucleus with each increasing principal E level. The nucleus is farther
from the valence level and more shielded.
across a period [that means become more negative, giving off more energy]Again the increasing
Zeff more strongly attracts the electron. The interactions of electron/electron repulsions wreaks havoc
with this generalization as we shall soon see!

Atomic Structure

20

Lets talk EXCEPTIONS!! First the lines on the diagram below connect adjacent elements. The
absence of a line indicates missing elements whose atoms do not add an electron exothermically and
thus do not form stable isolated anions [remember these are all 1 ions at this point].

an anomalyNo N yet there is a C--this is due to their electron/electron repulsions compared


to their electron configurations. N is p3 while C is p2. C adds an electron WITHOUT PAIRING
which does NOT increase the e-/e- repulsions and therefore, carbon forms a stable -1 ion while
N would have to pair p electrons and the increased e-/e- repulsions overcome the increasing
attractive force due to the increase in Zeff and no -1 N ion forms! [horrid sentence structure!]
O2- doesnt exist in isolated form [gasp] for the same reason. Its p4, so adding the first electron
causes a subsequent pairing BUT it has a greater Zeff than N, so it can form O-. BUT adding the
second electron fills the ps and that increased e-/e- repulsion overpowers the Zeff of oxygen.
Never fear, oxide ions exist in plenty of compounds so we havent exactly been lying to you!
F is weird, it has really strong e-/e- repulsion since the p orbitals are really small in the second
level therefore repulsions are high. In subsequent halogen orbitals, its not as noticeable.
4. IONIC RADII
Cationsshrink big time since the nucleus is now attracting
fewer electrons
Anionsexpand since the nucleus is now attracting MORE
electrons than there are protons AND there is enhanced
electron/electron repulsion to boot.
Isoelectronicions containing the same number of electrons
- consider the # of protons to determine size. Oxide vs. Fluoride.
Fluoride has one more proton which further attracts the
electron cloud, so it is smaller.

Atomic Structure
21

5. ELECTRONEGATIVITY (En)The ability of an atom IN A MOLECULE [meaning its


participating in a BOND] to attract shared electrons to itself. Think tug of war. Now you
know why they teach you such games in elementary school!
o Linus Paulings scaleNobel Prize for Chemistry & Peace

o Fluorine is the most En and Francium is the least En


o Why is F the most? Highest Zeff and smallest so that the nucleus is closest to the valence
action.
o Why is Fr the least? Lowest Zeff and largest so that the nucleus is farthest from the
action.
o Well use this concept a great deal in our discussions about bonding since this atomic
trend is only used when atoms form molecules.
Exercise 8
Trends in Ionization Energies
The first ionization energy for phosphorus is 1060 kJ/mol, and that for sulfur is 1005 kJ/mol. Why?

Atomic Structure
22

Exercise 9
Ionization Energies
Consider atoms with the following electron configurations:
a. 1s22s22p6
b. 1s22s22p63s1
c. 1s22s22p63s2
Identify each atom. Which atom has the largest first ionization energy, and which one has the smallest
second ionization energy? Explain your choices.

A: Ne; largest IE
B: Na
C: Mg; smallest IE2

Exercise 10

Trends in Radii

Predict the trend in radius for the following ions: Be2+, Mg2+, Ca2+, and Sr2+.

Be2+ < Mg2+ < Ca2+ < Sr2+

Atomic Structure
23

AP* Chemistry
CHEMICAL BONDING &
MOLECULAR STRUCTURE
WHAT IS A CHEMICAL BOND? It will take us the next two chapters to answer this question! Bonds are
attractive forces that hold groups of atoms together and make them function as a unit. [Defined in 25 words or
less, but leaves out LOTS of details!] Bonding relates to physical properties such as melting point, hardness and
electrical and thermal conductivity as well as solubility characteristics. The system is achieving the lowest
possible energy state by bonding. If you think about it, most of the chemical substances you can name or
identify are NOT elements. They are compounds. That means being bound requires less energy than existing in
the elemental form. It also means that energy was released from the system. This is a HUGE misconception
most students haveit takes energy to break a bond, not make a bond! Energy is RELEASED when a bond is
formed, therefore, it REQUIRES energy to break a bond.
Bond energyenergy required to break the bond
TYPES OF CHEMICAL BONDS
ionic bondsan electrostatic attraction between ions; usually produced by the reaction between a metal and
nonmetal. Cause very high melting points and usually a solid state since the attraction is SO strong that
the ions are VERY close together in a crystal formation.
covalent bondselectrons are shared by nuclei [careful, sharing is hardly ever 50-50!]
Coulombs Law--used to calculate the Energy of an ionic bond.

QQ
E = 2.31 10 19 J nm 1 2
r
r is the distance between the ion centers in nanometers [size matters!]
J is the energy in Joules
Q1 and Q2 are the numerical ion charges; dont neglect their signs
There will be a negative sign on the Energy once calculatedit indicates an attractive force so that the
ion pair has lower energy than the separated ions.
You can also use Coulombs Law to calculate the repulsive forces between like charges. What sign will
that calculation have?
VALENCE ELECTRONS
valence electrons--outermost electrons; focus on ns, np and d electrons of transition elements.
Lewis dot structures--(usually main group elements) G.N. Lewis, 1916
Emphasizes rare gas configurations, s2p6, as a stable state. All rare gasses except He have 8 valence electrons
and follow the octet rule.
too
too
CHEMICAL BOND FORMATION
Level 1When 2 hydrogen atoms approach each other 2
bad E things happen: electron/electron repulsion and
proton/proton repulsion. One good E thing happens:
proton/electron attraction. When the attractive forces offset
the repulsive forces, the energy of the two atoms decreases
and a bond is formed. Remember, nature is always striving
for a LOWER ENERGY STATE.
bond lengththe distance between the 2 nuclei where the
energy is minimum between the two nuclei.
energy decrease is small--van der Waals IMFs [another chapter!]
energy decrease is larger--chemical bonds

CLOSE

FAR

getting
better
Just
right!

*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
2008 by Ren McCormick. All rights reserved.

Level 2--Orbital Theory electrons and + nucleus of one atom strongly perturb or change the spatial
distribution of the other atoms valence electrons. A new orbital (wave function) is needed to describe the
distribution of the bonding electrons bond orbital
bond orbital--describes the motion of the 2 electrons of opposite spin
lone pair orbital--the orbitals of electrons on a bonded atom that are distorted away from the bond region also
have new descriptions (wave functions)
The new bond orbital is built from the atomic orbitals of the two bonded atoms. Looks a lot like the original
BUT, the bond orbital is concentrated in the region between the bonded nuclei.
The energy of the electrons in a bond orbital, where the electrons are attracted by two nuclei, is lower than
their energy in valence electron orbitals where the electrons are attracted to only one nucleus. [ZAPPED!!]
ionic bond--the bonding orbital is strongly displaced toward one nuclei (metal from the left side of table +
nonmetal from right side of the periodic table)
covalent bond--bond orbital is more or less (polar or non-polar) evenly distributed and the electrons are
shared by two nuclei. (elements lie close to one another on the periodic table)
Most chemical bonds are in fact somewhere between purely ionic and purely covalent.
Recall the information youve already learned about electronegativity:
ELECTRONEGATIVITY (En)The ability of an atom IN A MOLECULE [meaning its
participating in a BOND] to attract shared electrons to itself. Think tug of war. Now you know why
they teach you such games in elementary school!
o Linus Paulings scaleNobel Prize for Chemistry & Peace
o Fluorine is the most En and Francium is the least En

o
o
o

Why is F the most? Highest Zeff and smallest radius so that the nucleus is closest to the
action.
Why is Fr the least? Lowest Zeff and largest radius so that the nucleus is farthest from the
action.
Well use this concept a great deal in our discussions about bonding since this atomic trend is
only used when atoms form molecules.
Use the difference in En to determine the type of
bond formed.
o ionic--Electronegativity difference
> 1.67
o covalent--Electronegativity
difference < 1.67
o NONpolar En difference < 0.4

Chemical Bonding and Molecular Structure

Exercise 1
Relative Bond Polarities
Order the following bonds according to polarity: HH, OH, ClH, SH, and FH.

bond polarity and electronegativity--En () determines polarity since it measures a


nucleus attraction or pull on the bonded electron pair. En ranges from 0--4.0.
When 2 nuclei are the same, the sharing is equal the bond is described as
NONPOLAR (a). When the 2 nuclei are different the electrons are not shared
equally, setting up slight +/ poles POLAR (b). When the electrons are shared
unequally to a greater extent IONIC (c).
The polarity of a bond can be estimated from /. Range is 0 for pure covalent bonds to 1
for completely ionic bonds.
IONIC BONDING
The final result of ionic bonding is a solid, regular array of cations and anions
called a crystal lattice. At right, you can see the energy changes involved in
forming LiF from the elements Li and F2
Enthalpy of dissociation--energy required to decompose an ion pair (from a
lattice) into ions a measure of the strength of the ionic bond
from Coulombs law:

E = H dissociation

q +q
r

where q+ is the charge on the positive ion and q is the charge on the negative ion and r is the distance between
the ion centers in the crystal lattice.
energy of attraction depends directly on the magnitude of the charges (higher the charges
the greater the attractive energy) and inversely on the distance between them (greater the
distance, the smaller the attractive energy).
the larger the ion the smaller the Hdissociation (its a distance thing)
ion-ion attractions have a profound effect on melting points and
solubilities.
Water must overcome the ion-ion attractions to dissolve an ionic substance.
Size affects this as does charge HOW??
The crystal lattice for LiF is shown at the left.
Lattice energy can be represented by a modified form of Coulombs Law: k is a
proportionality constant that depends on the structure of the solid and the
electron configurations of the ions.

QQ
Lattice Energy = k 1 2
r

Chemical Bonding and Molecular Structure

COVALENT BONDING
Most compounds are covalently bonded, especially carbon compounds.
We have 3 major bonding theories to discuss. Only one for this chapter though!
Localized Electron [LE] Bonding Modelassumes that a molecule is composed of atoms that are
bound together by sharing pairs of electrons using the atomic orbitals of the bound atoms. Electron pairs
are assumed to be localized on a particular atom [lone pairs] or in the space between two atoms
[bonding pairs].
1. Lewis Structures describe the valence electron arrangement
2. Geometry of the molecule is predicted with VSEPR
3. Description of the type of atomic orbitals blended by the atoms to share electrons or hold lone
pairs [hybridsnext chapter].

Number of Bond Pairs: The Octet Rulenoble is good


predict # of bonds by counting the number of unpaired electrons in a Lewis structure
a dash is used to represent a pair of shared electrons, : is used to represent a lone pair
SINGLE AND MULTIPLE BONDS:
single bond--one pair of electrons shared ) sigma () bond
MULTIPLE BONDS ARE MOST OFTEN FORMED by C,N,O,P and S ATOMSsay C-NOPS
double bond--two pairs of electrons shared ) one bond and one bond
triple bond--three pairs of electrons shared ) one bond and two bonds
obviously, combinations of and are stronger than alone. Pi bonds are weaker than sigma but never
exist alone
Multiple bonds increase the electron density between two nuclei and therefore decrease the nuclear
HUGE
repulsions while enhancing the nucleus to electron density attractionseither way, the nuclei move concept
closer together and the bond length is shorter for a double than a single and triple is shortest of all!
COORDINATE COVALENT BONDS:
Some atoms such as N and P, tend to share a lone pair with another atom that is short of electrons, leading to
the formation of a coordinate covalent bond: These bonds are in all coordination compounds and Lewis
Acids/Bases
ammonium ion
formation:

H
H

:+H

H
+

H+

We show that N is sharing the lone PAIR of electrons by drawing an arrow from it to the H+, remember H+ has
NO electrons to contribute to the bond. Note that all four bonds are actually identical in length and strength.
CRITICAL stuff!
EXCEPTIONS TO THE OCTET RULE:
Fewer than eight--H at most only 2 electrons (one bond)! BeH2, only 4 valence electrons around Be
(only two bonds)! Boron compounds, only 6 valence electrons (three bonds)!
ammonia + boron trifluoride is a classic Lewis A/B reaction.
Expanded Valencecan only happen if the central element has d-orbitals which means it is from the
3rd period or greater [periods 4, 5, 6] and can thus be surrounded by more than four valence pairs in
certain compounds. The number of bonds depends on the balance between the ability of the nucleus to
attract electrons and the repulsion between the pairs.
odd-electron compounds--A few stable cmpds. contain an odd number of valence electrons and thus
cannot obey the octet rule. NO, NO2 , and ClO2.

Chemical Bonding and Molecular Structure

Drawing Lewis Structures: (VERY USEFUL when predicting molecular shape)


To predict arrangement of atoms within the molecule use the following rules:
1. H is always a terminal atom. ALWAYS connected to only one other
atom!!
2. LOWEST En is central atom in molecule [not just the oddball element]
3. Find the total # of valence electrons by adding up group #s of the
elements. FOR IONS add for negative and subtract for positive charge.
Divide by two to get the number of electron PAIRS.
4. Place one pair of electrons, a bond, between each pair of bonded atoms.
5. Subtract from the total the number of bonds you just used.
6. Place lone pairs about each terminal atom (EXCEPT H) to satisfy the octet
rule. Left over pairs are assigned to the central atom. If the central atom is
from the 3rd or higher period, it can accommodate more than four electron
pairs, up to six pairs.
7. If the central atom is not yet surrounded by four electron pairs, convert one
or more terminal atom lone pairs to pi bonds pairs. NOT ALL
ELEMENTS FORM pi BONDS!! only C, N, O, P, and S!!
Exercise 6
Writing Lewis Structures
Give the Lewis structure for each of the following:
a. HF

d. CH4

b. N2

e. CF4

c. NH3

f. NO+

Exercise 7
Lewis Structures for Molecules That Violate the Octet Rule I
Write the Lewis structure for PCl5.

Exercise 8
Lewis Structures for Molecules That Violate the Octet Rule II
Write the Lewis structure for each molecule or ion.
a. ClF3

b. XeO3

Chemical Bonding and Molecular Structure

c. RnCl2

d. BeCl2

e. ICl4-

RESONANCE STRUCTURES:
Experiments show that ozone, O3 has equal bond lengths and equal bond strengths, implying that there is an
equal number of bond pairs on each side of the central O atom. When you draw the Lewis structure, that
situation is NOT what you draw! So, we draw a resonance structure:

We draw it as having a double bond and a single bond [the dashes are another way of representing lone pairs]
BUT since there are equal bond lengths and strengths, they are clearly NOT as pictured above. The bonds are
more equivalent to a bond and in terms of length and strength. We use the double edged arrows to indicate
resonance. We also bracket the structures just as we do for polyatomic ions.
In an attempt to improve the drawing, we sometimes use a single composite picture.
The drawing at right better shows the bond angle. Focus on the central atom in either
of the resonance structures above. The central atom is surrounded by three sites of
electron density: a lone pair, a single bond and a double bond (consisting of one
bond and one bond). Three electron-dense sites surrounding a central point in a
3-dimensional space will orient themselves at 120 so that electron/electron repulsions
are minimized.
Carbonate ion:
NOTE: These all 3 need brackets and the charge shown in the
upper right corner [like the composite at right] to gain full credit on
the AP Exam!!!!

..
:O

.. _
:O:
C
:O
.. :_

CO32_ ..
:O
..

_2
_

..
O:

C
:O
.. :_

_ ..
:O
..

.. _
:O :

.. _ 2/3
O:

2/3

..
:O

C
:
O
.. _

2/3

O
.. :

THREE EQUIVALENT STRUCTURES


RESONANCE HYBRID

Notice: 1) resonance structures differ only in the assignment of electron pair positions, NEVER atom positions.
2) resonance structures differ in the number of bond pairs between a given pair of atoms
Exercise 9
Resonance Structures
Describe the electron arrangement in the nitrite anion (NO2-) using the localized electron model.

Chemical Bonding and Molecular Structure

BOND PROPERTIES
bond ordersimply the number of bonding electron pairs shared by two atoms in a molecule.
1--only a sigma bond between the 2 bonded atoms
2--2 shared pairs between two atoms; one sigma and one pi (CO2 and ethylene)
3--3 shared pairs between two atoms; one sigma and two pi (acetylene and CO and cyanide)
fractional--resonance; ozone 3/2; carbonate 2/3
bond order = # of shared pairs linking X and Y
number of XY links

bond length--distance between the nuclei of two bonded


atoms CN< CC < CP
The effect of bond order is evident when you compare
bonds between the same two atoms
Bond
Bond order
Bond length (pm)

CO
1
143

C=O
2
122

CO
3
113

The bond length is reduced by adding multiple bonds since it increases the electron density between the
two nuclei. Variations in neighboring parts of a molecule can affect the length of a particular bond as
much as 10%
bond energythe greater the number of electron pairs between a pair of atoms, the shorter the bond.
This implies that atoms are held together more tightly when there are multiple bonds, so there is a
relation between bond order and the energy required to separate them.
bond dissociation energy(D)--gaseous atom; E supplied to break a chemical bond (bond energy for
short!)
o
D is + and breaking bonds is endothermic. The converse is also true.
D in table 10.4 is +
D is an average with a +/- 10%
Gaseous atoms
What is the connection between bond energy and bond order???
Calculating reaction energies from bond energies: Bonds in reactants are broken while bonds in
products are formed. Energy released is greater than energy absorbed in EXOthermic reactions. The
converse is also true.
o
reaction

= mD (bonds broken) nD(bonds made)

Chemical Bonding and Molecular Structure

Horeaction = reactants(E cost)

products(E payoff)

NOTE THIS IS BACKWARDS FROM THE THERMODYNAMICS BIG MAMMA EQUATION.


Were back to that misconception if you are confused by this. It takes energy to break bonds NOT make
bonds! First we must break the bonds of the reactants [costs energy] then subtract the energy gained by
forming new bonds in the products.

Exercise 5
H from Bond Energies
Using the bond energies listed in Table 8.4, calculate H for the reaction of methane with chlorine and fluorine to give
Freon-12 (CF2Cl2).
CH4(g) + 2Cl2(g) + 2F2(g) CF2Cl2(g) + 2HF(g) + 2HCl(g)

H = -1194 kJ/mol

FORMAL CHARGE
Often, many nonequivalent Lewis structures may be obtained which all follow the rules. Use the idea of formal
charge to determine the most favored structure. Physicists tell us that oxidation states of more than +/ two are
pure fantasy and that formal charges are much more realistic.
formal charge--The difference between the number of valence electrons on the free element and the number of
electrons assigned to the atom in the molecule.
Atoms formal charge = group number [# of lone electrons 2 (# of bonding electrons)]
THE SUM OF THE FORMAL CHARGES MUST EQUAL AN IONS CHARGE!!
Use formal charges along with the following to determine resonance structure
- Atoms in molecules (or ions) should have formal charges as small as possibleas close to zero as
possible [principle of electroneutrality]
- A molecule (or ion) is most stable when any negative formal charge resides on the most
electronegative atom.
Chemical Bonding and Molecular Structure

Example: Draw all possible structures for the sulfate ion. Decide which is the most plausible using formal
charges.

** Caution** Although formal charges are considered closer to the atomic charges than the oxidation states,
they are still only estimates and should not be taken as the actual atomic charges. Second, using formal charges
can often lead to erroneous structures, so tests based on experiments must be used to make the final decisions on
the correct description of bonding.
Exercise 10
Formal Charges
Give possible Lewis structures for XeO3, an explosive compound of xenon. Which Lewis structure or structures are most
appropriate according to the formal charges?
Structures with the lower values of
formal charge would be most appropriate

MOLECULAR SHAPEMINIMIZE ELECTRON PAIR REPULSIONS!!!


VSEPR--valence shell electron pair repulsion theory

Molecular shape changes with the numbers of bonds plus lone pairs about the central atom
bonds + lone pairs
on central atom

STRUCTURAL PAIR or ELECTRONIC GOMETRY


(NOT to be confused with molecular geometry!)

Linear

Trigonal planar

Tetrahedral (or pyramidal)

Trigonal bipyramidal

Octahedral

THE VSPER MODEL AND MOLECULAR SHAPE

molecular geometry--the arrangement in space of the atoms bonded to a central atom


not necessarily the same as the structural pair geometry ) lone pairs have a different
repulsion since they are experiencing an attraction or pull from only one nucleus as
opposed to two nuclei. They also take up more space around an atom as you can see on
the left.

Each lone pair or bond pair repels all other lone pairs and bond pairs--they try to avoid
each other making as wide an angle as possible.
works well for elements of the s and p-blocks
VSEPR does not apply to transition element compounds (exceptions)

Chemical Bonding and Molecular Structure

MOLECULAR SHAPES FOR CENTRAL ATOMS WITH NORMAL


VALENCE: no more than 4 structural pairs if the atom obeys the octet rule. Since
no lone pairs are present, the molecular and structural pair [or electronic] geometry
is the same. 109.5 bond angle.
- Ignore lone pairs AFTER youve determined the angles only the
relative positions of the atoms are important in molecular geometry
- Below is ammonia3 sigma bonds and one lone pairwhen lone pairs
are present, the structural pair or electronic geometry are different!!
- electronic geometrytetrahedral while molecular geometrytrigonal pyramidal, 107.5
bond angle
ANY time lone pairs
are present, the
electronic and molecular
geometries will be
different.

"

Water has 2 lone pairs and still obeys the octet rule. Again, the electronic and molecular
geometries will be different. The electronic is still tetrahedral since the octet rule is obeyed
BUT the molecular geometry is described as bent or V-shaped, 104.5 bond angle.

Now, lets discuss the warping of the 109.5 bond angle. The lone pairs have more repulsive

force than shared pairs and are space hogs. They force the shared pairs to squeeze together.
-

To determine the geometry:


1. Sketch the Lewis dot structure [DO NOT SKIP THIS STEP.]
2. Describe the structural pair or electronic geometry
3. Focus on the bond locations (ignore lone pairs) and assign a molecular geometry based on their
locations

Chemical Bonding and Molecular Structure

10

MOLECULAR SHAPES FOR CENTRAL ATOMS WITH


EXPANDED VALENCEonly elements with a principal energy
level of 3 or higher can expand their valence and violate the octet
rule on the high side. Why?
d orbitals are needed for the expansion to a 5th or 6th bonding
locationthe combination of 1 s and 3 ps provides the four
bonding sites that make up the octet rule.
- seems to be a limit of 3 lone pairs about the central atom
- XeF4; There are 2 lone pairs and 4 shared pairs. Two possible
arrangements exist for this situation.
- equatorialshared pairs surround Xe. In both molecular
arrangements the electronic geometry is octahedral with 90 angles. (a) has a molecular geometry known
as see saw. This puts the lone pairs only 90 apart.
- axiallone pairs are located top and bottom This is preferred for this molecule since the lone pairs are
180 apart which minimizes their repulsion. Lone pairs prefer maximum separationuse this in your
determinations! (b at upper right) has a molecular geometry that is more stablesquare planar
Which of these arrangements do you predict to be the most stable for I3 ?
Remember to look at the lone pair-lone pair angles to make your determination.

Exercise 11
Prediction of Molecular Structure I
Describe the molecular structure of the water molecule.
Two bonding and two non-bonding pairs of electrons
Forming a V shape molecule

Exercise 12
Prediction of Molecular Structure II
When phosphorus reacts with excess chlorine gas, the compound phosphorus pentachloride (PCl5) is formed. In the gaseous and
liquid states, this substance consists of PCl5 molecules, but in the solid state it consists of a 1:1 mixture of PCl4+ and PCl6- ions.
Predict the geometric structures of PCl5, PCl4+, and PCl6-.

Chemical Bonding and Molecular Structure

11

RECAP including bond angles for all


structural pairs-- bond ( bond pairs occupy the same space) pairs about an atom
linear [and of course, planar]
2 @ 180o

3 @ 120o

"

"

4 @ 109.5o

"

"

"

3 @ 120 & 2 @ 90o with each other through central atom trigonal bipyramidal

6 @ 90o

trigonal planar

tetrahedral

NOT SQUARE PLANAR!

octahedral

The presence of lone pairs alters the six basic MOLECULAR geometries, but the electronic or structural pair geometry remains
one of these six basic types.

Chemical Bonding and Molecular Structure

12

MOLECULAR POLARITY
polar--bonds can be polar while the entire molecule isnt and vice versa.
dipole moment--separation of the charge in a molecule; product of the size of the
charge and the distance of separation
align themselves with an electric field (figure b at right)
align with each other as well in the absence of an electric field
water2 lone pairs establish a strong negative pole
ammoniahas a lone pair which establishes a neg. pole
note that the direction of the arrow indicating the dipole moment always points to the negative pole with the cross
hatch on the arrow (looks sort of like were trying to make a + sign) is at the positive pole. Logical?

IF octet rule is obeyed [which it is in both water and ammonia] AND all the surrounding bonds are the same [even if
very polar] then the molecule is NONpolar since all the dipole moments cancel each other out.

carbon dioxide, above is nonpolar since the dipole moments cancel. For those of you in physics, the dipole moments
are vector quantities.
Methane is a great example. Replace one H with a halogen and it becomes polar. Replace all and its
nonpolar again!
Draw CH4 , CH3Cl, CH2Cl2, CHCl3, CCl4 Indicate dipole moment(s) where necessary.

Chemical Bonding and Molecular Structure

13

Exercise 2
Bond Polarity and Dipole Moment
For each of the following molecules, show the direction of the bond polarities and indicate which ones have a dipole moment:
HCL, Cl2, SO3 (a planar molecule with the oxygen atoms spaced evenly around the central sulfur atom), CH4 [tetrahedral (see
Table 8.2) with the carbon atom at the center], and H2S (V-shaped with the sulfur atom at the point).

Exercise 13
Prediction of Molecular Structure III
Because the noble gases have filled s and p valence orbitals, they were not expected to be chemically reactive. In fact, for many
years these elements were called inert gases because of this supposed inability to form any compounds. However, in the early
1960s several compounds of krypton, xenon, and radon were synthesized. For example, a team at the Argonne National
Laboratory produced the stable colorless compound xenon tetrafluoride (XeF4). Predict its structure and whether it has a dipole
moment.

Exercise 14
Structures of Molecules with Multiple Bonds
Predict the molecular structure of the sulfur dioxide molecule. Is this molecule expected to have a dipole moment?

Chemical Bonding and Molecular Structure

14

ONCE MORE WITH FEELING


CHEMICAL BONDSForces of attraction that hold groups of atoms together within a molecule or crystal
lattice and make them function as a unit.

IONIC
Characteristics of ionic substances usually include:
electrons that are transferred between atoms having high differences in electronegativity (greater than
1.67)
compounds containing a metal and a nonmetal (Remember that metals are located on the left side of the
periodic table and nonmetals are to the right of the stairs.)
strong electrostatic attractions between positive and negative ions
formulas given in the simplest ratio of elements (empirical formula; NaCl, MgCl2)
crystalline structures that are solids at room temperature
ions that form a crystal lattice structure as pictured in Figure 1
compounds that melt at high temperatures
substances that are good conductors of electricity in the molten or dissolved state

Fig. 1

COVALENT
Characteristics of covalent substances usually include:
the sharing of electrons between atoms having small differences in electronegativities (less than 1.67)
nonmetals attracted to other nonmetals
formulas that are given in the true ratios of atoms (molecular formulas; C6H12O6)
substances that may exist in any state of matter at room temperature (solid, liquid, or gas)
compounds that melt at low temperatures
substances that are nonconductors of electricity

METALLIC
Characteristics of metallic substances usually include:
substances that are metals
a sea of mobile or delocalized electrons surrounding a positively charged metal center
an attraction between metal ions and surrounding electrons
formulas written as a neutral atom (Mg, Pb)
solids with a crystalline structure at room temperature
a range of melting pointsusually depending on the number of valence electrons
substances that are excellent conductors of electricity since the electrons in the sea are free to move
Chemical Bonding and Molecular Structure

15

Most chemical bonds are in fact somewhere between purely ionic and purely covalent.

DRAW THE DANG LEWIS STRUCTURE


when answering bonding multiple choice or free-response questions.

Chemical Bonding and Molecular Structure

16

AP* Chemistry
COVALENT BONDING: ORBITALS
The localized electron model views a molecule as a collection of atoms bound together by sharing electrons
between their atomic orbitals. The arrangement of valence electrons is represented by the Lewis structure
and the molecular geometry can be predicted from the VSEPR model. There are 2 problems with this.
1) Using the 2p and the 2s orbitals from carbon in methane would result in 2 different types of bonds
when they overlap with the 1s from Hydrogen. [three 2p/1s bonds and one 2s/2p bond] However,
experiments show that methane has FOUR IDENTICAL bonds. Uh, oh.we need to modify the
model!
2) Since the 3p orbitals occupy the x, y and z-axes, you would expect those overlaps of atomic orbitals
to be at bond angles of 90. Darn those experiments! All 4 angles are 109.5.
Its not that the localized electron model is wrong; its just that carbon adopts a set of orbitals rather than its
native 2s & 2p. THIS IS WHY THESE ARE MODELS/THEORIES rather than LAWS!!
VALENCE BOND THEORYan extension of the LE modelits all about hybridization!
Two atoms form a bond when both of the following conditions occur:
1. There is orbital overlap between two atoms.
2. A maximum of two electrons, of opposite spin, can be present in the overlapping orbitals.
Because of orbital overlap, the pair of electrons is found within a region influenced by both nuclei. Both
electrons are attracted to both atomic nuclei and this leads to bonding.
As the extent of overlap increases, the strength of the bond increases. The electronic energy drops as the
atoms approach each other but, increases when they become too close. This means there is an optimum
distance, the observed bond distance, at which the total energy is at a minimum.
sigma () bond--overlap of two s orbitals or an s and a p orbital or head-to-head p orbitals. Electron
density of a sigma bond is greatest along the axis of the bond.
maximum overlap: forms the strongest possible bond, two atoms are arranged to give the greatest
possible orbital overlap. Tricky with p orbitals since they are directional.
hybrid orbitals-- a blending of atomic orbitals to create orbitals of intermediate energy. Methane: all of
the CH bonds are 109.5 apart while p orbitals are only 90 apart. Pauling explained:
The orbitals on the left are for a carbon atom [no
bonding]
Once the carbon atom begins to bond with say, H to
keep it simple, the atomic orbitals HYBRIDIZE
which changes their shape considerably! Theres an
energy payoff, else they wouldnt behave this way!

leads to

*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
2008 by Ren McCormick. All rights reserved.

Ammonia also has sp3 hybridization even though it has a lone pair.
I find it helpful to think of electron pairs as sites of electron density that can be
occupied by either a lone pair or a shared pair. If there are 4 sites then 4 orbitals
need to hybridize so use one s and three ps to make FOUR equivalent orbitals
named sppp or sp3 orbitals . [1 s + 3 p = 4 sp3 orbitals]
MULTIPLE BONDINGlowers the number of hybridizing orbitals since Unhybridized orbitals are
necessary to form the pi bonds
Pi () bonds--come from the sideways overlap of p atomic orbitals; the region above and below the
internuclear axis. NEVER occur without a sigma bond first!
may form only if unhybridized p orbitals remain on the bonded atoms
occur when sp or sp2 hybridization is present on central atom NOT sp3 hybridization.
Carbon often does this with N, O, P, and S since they have p orbitals (remember CNOPS?)

This is the formation of an sp2 set of orbitals [3 orbitals formed, 3 sites, 3 letters!]. This molecule would
contain a double bond like ethene. The molecule reserves a set of ps to form the bond.

leads to

The set of ps that


are UNhybridized
are not pictured here
at left, they are hovering above and below this very page.

A different view, without the hydrogens, centering on the C atoms shows the
unhybridized p orbitals that are making the sideways overlap necessary to create the
double () bond.
Heres the whole mess altogether:

Carbon #1

Carbon #2

OVERLAPPING UNhybridized p-orbitals


that form pi bond.
Covalent Bonding: Orbitals

This is the formation of an sp set of orbitals [2 orbitals formed, 2 sites, 2 letters!]. This molecule
would contain a triple bond like ethyne or the double-double arrangement in carbon dioxide.
leads to

The molecule reserves TWO sets of UNhybridized ps to form the 2 -bonds.


At right, is a picture of the 2 unhybridized ps on the C atom that is about to make a
triple bond. The one labeled at the top is in the plane of this page, the other plain p
is in a plane perpendicular to this page. (No typojust appropriate use of
homonyms; plain vs. plane!)
Look at the CO2 Lewis diagram. The carbon has 2 sites of electron density, each occupied by a double bond,
and is therefore sp [2 sites, 2 letters] hybridized while the oxygens have 3 sites [2 lone pairs and a double
bond]. The oxygens have sp2 hybridization [3 sites, 3 letters].

This should help:


HYBRIDIZATION

# OF HYBRID
ORBITALS

sp

Linear

sp2

Trigonal planar

sp3

Tetrahedral

dsp3

Trigonal bipyramidal

d2sp3

Octahedral

Covalent Bonding: Orbitals

GEOMETRY

EXAMPLE

Check out Benzene


The sigma bond formations

The pi bond formations

Draw the Lewis structure for benzene:

Covalent Bonding: Orbitals

Exercise 1
The Localized Electron Model I
Describe the bonding in the ammonia molecule using the localized electron model.

tetrahedral, sp3 hybrid

Exercise 2
The Localized Electron Model II
Describe the bonding in the N2 molecule.

linear, sp hybrid

Exercise 3
The Localized Electron Model III
Describe the bonding in the triiodide ion (I3-).

trigonal bipyramidal arrangement,


e- pair geometry, linear molecular geometry
central iodine is dsp3 hybridized

Exercise 9
The Localized Electron Model IV
How is the xenon atom in XeF4 hybridized?

d2sp3 hybridized

Covalent Bonding: Orbitals

Exercise 5
The Localized Electron Model V
For each of the following molecules or ions, predict the hybridization of each atom, and describe the molecular structure.
a. CO

b. BF4-

c. XeF2

A: linear, sp hybridized
B: tetrahedral, sp3 hybridizied
C: trigonal bipyramidal e- pair,
Xe dsp3, linear

THE MOLECULAR ORBITAL MODEL


Though the molecular orbital model will not be covered on the AP exam, I feel that students should
be exposed to a little of this theory for several reasons.
1.
Electrons are not always localized as in the VSEPR theory; therefore resonance must
be added and explained as best possible.
2.
Molecules containing unpaired electrons are not easily dealt with using the localized
model.
3.
Magnetism is easily described for molecules using the MO theory.
(Oxygen is paramagnetic which is unexplained by the localized electron model.)
4.
Bond energies are not easily related using the localized model.

TERMS TO KNOW:
Bonding molecular orbital - an orbital lower in energy than the atomic orbitals from which it is
composed.(favors formation of molecule)
Antibonding molecular orbital - an orbital higher in energy than the atomic orbitals from which it is
composed. (favors separated atoms) represented by a * [The diagram at the top of the next page uses A for
antibonding and B for bondingI prefer the *, it has more personality!]
Bond order - the difference between the number of bonding electrons and the number of antibonding
electrons divided by two. Indicates bond strength.
Homonuclear diatomic molecules - those composed of two identical atoms.
Heteronuclear diatomic molecules - those composed of two different atoms
Paramagnetism - causes the substance to be drawn into a magnetic field; associated with unpaired electrons.
Diamagnetic - causes the substance to be repelled by the magnetic field; associated with paired electrons.

General Energy Level Sequence for Filling Orbitals


Using the MO Theory
2
2
2
2
1s 1s * 2s 2s * ( 2px2 2py2)2p2(2px2* 2py2*) 2p2*

Covalent Bonding: Orbitals

If we assume that the molecular orbitals can be constructed from the


atomic orbitals, the quantum mechanical equations result in two
molecular orbitals
MO1 = 1sA + 1sB
MO2 = 1sA 1sB

and

Lets start simple. 2 Hydrogen atoms.

Where 1sA and 1sB represent the 1s orbitals from the two separated hydrogen atoms.
This is actually a simple model to follow.
Look at the diagram on the right, each H entered
with its lone 1s electron. As they approach each
other, their atomic orbitals [two of them] blend to
form molecular orbitals [two of themno magic
here]. One MO is of high energy and one MO is
of low energy. Which will the electrons choose?
The LOW, of course! The electrons occupy the
lower energy level and thus a bond is formed.
The diagram at left uses the symbols we want to
use.

Try this again with He:

Since 4 electrons are involved, the first 2 get to be lazy and go to the low E state, the other 2
must occupy the higher energy state and thus cancel out the bond, therefore He2 DOES NOT
EXIST!!
Now bond order can be redefined in this theory:
Bond order = number of bonding electrons number of antibonding electrons
2
If the bond order is zero no bond!

Covalent Bonding: Orbitals

Shall we predict if Li2 is possible? Li has its valence electrons in the 2s sublevel.

Yes! It may also exist. What is its bond order?


Can Be2 exist?

Things get slightly more complicated when we leave Be and move to 2p

General Energy Level Sequence for Filling Orbitals


Using the MO Theory
2
2
2
2
1s 1s * 2s 2s * ( 2px2 2py2)2p2(2px2* 2py2*) 2p2*
The filling order for ps is pi, pi, sigma all bonding, followed by pi, pi, sigma all antibonding.
HUNDS RULE AND PAULI EXCULSION
PRINCIPLES APPLY!!

Try to predict the configuration of B2

Covalent Bonding: Orbitals

One of the most useful parts of this model is its ability to accurately
predict para- and diamagnetism as well as bond order.
This device is used to test the paramagnetism of homonuclear samples.
When the electromagnet is on, a paramagnetic substance is drawn down
into it and appears heavier on the balance.
B2 is paramagnetic! That means that the pi orbitals are of LOWER
energy than the sigmas and Hunds rule demands that the 2 electrons
fill the 2 bonding pi orbitals singly first before paring.

Will C2 exist? Will it be para- or diamagnetic?

Exercise: Write the appropriate energy diagram using the MO theory for the nitrogen molecule. Find the
bond order for the molecule and indicate whether this substance is paramagnetic or diamagnetic.

Covalent Bonding: Orbitals

If you use the usual models to examine the paramagnetism of


oxygen, youd say it was diamagnetic. The truth is that it is
paramagnetic. If you pour liquid oxygen into the space between
the poles of a strong horseshoe magnet, it says there until it boils
away in the warm room!

Covalent Bonding: Orbitals

10

Exercise 6
For the species O2, O2+, O2-, give the electron configuration and the bond order for each. Which has the
strongest bond?

Exercise 7
Use the molecular orbital model to predict the bond order and magnetism of each of the following molecules.
a) Ne2
b) P2

This model also works in heteronuclear molecules.


Exercise 8
Use the MO Model to predict the magnetism and bond order of the NO+ and CN- ions.

Covalent Bonding: Orbitals

11

AP* States of Matter & Intermolecular Forces Free Response Questions

page 1

1991
Experimental data provide the basis for interpreting differences in properties of substances.
TABLE 1
Melting
Electrical
Compound Point (C)
Conductivity of
Molten State (ohm-1)
BeCl2
405
0.086
MgCl2
714
> 20
SiCl4
70
0
MgF2
1261
> 20
TABLE 2
Substance Bond Length
(angstroms)

F2
1.42
Br2
2.28
N2
1.09
Account for the differences in properties given in Tables 1 and 2 above in terms of the differences in structure and
bonding in each of the following pairs.
(a) MgCl2 and SiCl4
(b) MgCl2 and MgF2
(c) F2 and Br2
(d) F2 and N2

1992
Explain each of the following in terms of atomic and molecular structures and/or intermolecular forces.
(a) Solid K conducts an electric current, whereas solid KNO3 does not.
(b) SbCl3 has measurable dipole moment, whereas SbCl5 does not.
(c) The normal boiling point of CCl4 is 77C, whereas that of CBr4 is 190C.
(d) Iodine has a greater boiling point than bromine even though the bond energy in bromine is greater than the
bond energy in iodine.

(1) AP is a registered trademark of the College Board. The College Board was not involved in the production of and does not endorse this product. (2) Test Questions
are Copyright 1984-2008 by College Entrance Examination Board, Princeton, NJ. All rights reserved. For face-to-face teaching purposes, classroom teachers are
permitted to reproduce the questions. Web or Mass distribution prohibited.

AP* States of Matter & Intermolecular Forces Free Response Questions

page 2

1995

The phase diagram for a pure substance is shown above. Use this diagram and your knowledge about changes
of phase to answer the following questions.
(a) What does point V represent? What characteristics are specific to the system only at point V?
(b) What does each point on the curve between V and W represent?
(c) Describe the changes that the system undergoes as the temperature slowly increases from X to Y to Z
at 1.0 atmosphere.
(d) In a solid-liquid mixture of this substance, will the solid float or sink? Explain.

2003
For each of the following, use appropriate chemical principles to explain the observation. Include chemical
equations as appropriate.
(a) In areas affected by acid rain, statues and structures made of limestone (calcium carbonate) often show signs
of considerable deterioration.
(b) When table salt (NaCl) and sugar (C12H22O11) are dissolved in water, it is observed that
(i)
both solutions have higher boiling points than pure water, and
(ii)
the boiling point of 0.10 M NaCl(aq) is higher than that of 0.10 M C12H22O11(aq).
(c) Methane gas does not behave as an ideal gas at low temperatures and high pressures.
(d) Water droplets form on the outside of a beaker containing an ice bath.

AP* States of Matter & Intermolecular Forces Free Response Questions

page 3

2004
Use appropriate chemical principles to account for each of the following observations. In each part, your
response must include specific information about both substances.
(a)
(b)
(c)
(d)

At 25C and 1 atm, F2 is a gas, whereas I2 is a solid.


The melting point of NaF is 993C, whereas the melting point of CsCl is 645C.
The shape of the ICl4 ion is square planar, whereas the shape of the BF4 ion is tetrahedral
Ammonia, NH3 , is very soluble in water, whereas phosphine, PH3 , is only moderately soluble in water.

AP* Chemistry
INTERMOLECULAR FORCES
LIQUIDS & SOLIDS
Now it is time to consider the forces that condense matter. The forces that hold one molecule to another
molecule are referred to as intermolecular forces (IMFs). These forces arise from unequal distribution
of the electrons in the molecule and the electrostatic attraction between oppositely charged portions of
molecules. We briefly visited the IMFs earlier when discussing the nonideal behavior of gases. These
forces cause changes of state by causing changes among the molecules NOT within them.
Physical properties such as melting points, boiling points, vapor pressures, etc. can be attributed to the

strength of the intermolecular attractions present between molecules. It works like this: the lower the
boiling point (or vapor pressure or melting point), the weaker the intermolecular attractions; the higher
the boiling point, the stronger the intermolecular attractions. For example, gasoline evaporates much
more quickly than water. Therefore, the intermolecular attractive forces that hold one gasoline molecule
to another are much weaker than the forces of attraction that hold one water molecule to another water
molecule. In fact, water molecules are held together by the strongest of the intermolecular attractive
forces, hydrogen bonds. Hydrogen bonds are not true bondsthey are just forces of attraction that exist
between a hydrogen atom on one molecule and the unshared electron pair on fluorine, oxygen or
nitrogen atoms of a neighboring molecule. The strands of DNA that make up our genetic code are held
together by this type of intermolecular attraction.
THE TYPES OF INTERMOLECULAR FORCES IN ORDER OF DECREASING STRENGTH:

Dipole-dipolethe force of attraction that enables two polar molecules to


attract one another. Polar molecules are those which have an uneven charge
distribution since their dipole moments do not cancel. Compounds exhibiting
this type of IMF have higher melting and boiling points than those exhibiting
weaker IMFs.
o Hydrochloric acid molecules are held to each other by this type of
force. HClthe chlorine pulls the electrons in the bond with greater
force than hydrogen so the molecule is polar in terms of electron
distribution. Two neighboring HCl molecules will align their
oppositely charged ends and attract one another.

*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
2008 by Ren McCormick. All rights reserved.

o Hydrogen bondingthe force of attraction between the


hydrogen atom of one molecule and an unshared electron
pair on F, O, or N of a neighboring molecule (a special
case of dipole-dipole). This is the strongest IMF. Never
confuse hydrogen bonding with a bonded hydrogen. The
unique physical properties of water are due to the fact
that it exhibits hydrogen bonding. As a result of these
attractions, water has a high boiling point, high specific
heat, and many other unusual properties.

bonded H

H bond

o WHY is there such variation in the boiling point among the covalent hydrides of groups
IV through VII? One would expect that BP would increase with increasing molecular
mass [since the more electrons in a molecule, the more polarizable the cloud {more about
that in the next section}, the stronger the IMFs, therefore the more E needed to overcome
those increased attractions and vaporize, thus the higher the boiling point. Thats how it
is supposed to work!]. Hydrogen bonding, thats why!
o TWO reasons: both enhance the IMF we refer to as hydrogen bonding.
1. The lighter hydrides have the highest En values which lead to especially polar HX
bonds. Increased polarity means increased attraction which makes for a stronger
attraction.
2. The small size of each dipole allows for a closer approach of the dipoles, further
strengthening the attractions. Remember, attractive forces dissipate with increased
distance.

Ion-induced dipolethe force of attraction between a charged ion and a


nonpolar molecule. The ion greatly perturbs the electron cloud of the
nonpolar molecule and polarizes it transforming it into a temporary dipole
which enhances the ions attraction for it.

Intermolecular Forces, Liquids & Solids

Dipole-induced dipolethe force of attraction between a polar molecule and a


nonpolar molecule. The polar molecule induces a temporary dipole in the nonpolar
molecule. Larger molecules are more polarizable than smaller molecules since
they contain more electrons. Larger molecules are more likely to form
induced dipoles.

Induced dipole-induced dipole or London dispersion forcethe force


of attraction between two non polar molecules due to the fact that they
can form temporary dipoles. Nonpolar molecules have no natural
attraction for each other. This IMF is known by both names! Without
these forces, we could not liquefy covalent gases or solidify covalent
liquids.

o These forces are a function of the number of electrons in a given molecule and how
tightly those electrons are held.
o Let us assume that the molecule involved is nonpolar.
A good example would be H2. Pretend that the
molecule is all alone in the universe. If that were the
case, the electrons in the molecule would be perfectly
symmetrical. However, the molecule is not really
alone. It is surrounded by other molecules that are
constantly colliding with it. When these collisions
occur, the electron cloud around the molecule is
distorted. This produces a momentary induced dipole
within the molecule. The amount of distortion of the
electron cloud is referred to as polarizability. Since
the molecule now has a positive side and a negative
side, it can be attracted to other molecules. Youll
want to write about polarizability when explaining
these concepts.
o Since all molecules have electrons, all molecules have these forces. These forces range
from 540 kJ/mol. The strength of this force increases as the number of electrons
increases due to increasing polarizability.
o To better understand the induced dipole-induced dipole IMF, examine the halogens.
Halogens exist as diatomic molecules at room temperature and atmospheric conditions.
F2 and Cl2 are gases, Br2 is a liquid and I2 is a solid. Why?
All of these molecules are completely nonpolar and according to theory, not
attracted to each other, so one might predict they would all be gases at room
temperature.

Intermolecular Forces, Liquids & Solids

Bromine exists as a liquid at room temperature simply because there is a greater


attractive force between its molecules than between those of fluorine or chlorine.
Why?
Bromine is larger than fluorine or chlorine; it has more electrons and is thus more
polarizable. Electrons are in constant motion so it is reasonable that they may
occasionally pile up on one side of the molecule making a temporary negative
pole on that end, leaving a temporary positive pole on the other end.
This sets off a chain-reaction of sorts and this temporary dipole induces a dipole
in its neighbors which induces a dipole in its neighbors and so on.
Iodine is a solid since it is larger still, has even more electrons, is thus even more
polarizable and the attractive forces are thus even greater. Note the two spheres
representing I2 the diagram at right. Each iodine atom experiences a nonpolar
covalent bond within the molecule. Be very clear that the IMF is between
molecules of iodine, NOT atoms of iodine!

Clear as mud? This flow chart is worth studying. NOTE that dipole-dipole (and its special case of
Hydrogen bonding), dipole-induced dipole, induced dipole-induced dipole (a.k.a. London dispersion
forces) are collectively called van der Waals forces. Its a simple conspiracy designed to keep you
confusedmuch like the scoring scheme in tennis!

Intermolecular Forces, Liquids & Solids

The Liquid State


All of the following are greater for liquids composed of polar molecules since their IMFs are greater
than nonpolar molecules.
o Surface Tension: The resistance to an increase in its surface area
(polar molecules). High ST indicates strong IMFs. Molecules are
attracted to each OTHER. A molecule in the interior of a liquid is
attracted by the molecules surrounding it, whereas a molecule at the
surface of a liquid is attracted only by the molecules below it and on
each side.
o Capillary Action: Spontaneous rising of a liquid in a narrow tube.
Adhesive forces between molecule and glass overcome cohesive
forces between molecules themselves. The narrower the tube, the
more surface area of glass, the higher the column of water climbs!
The weight of the column sets the limit for the height achieved. Hg
liquid behaves opposite to water. Water has a higher attraction for
glass than itself so its meniscus is inverted or concave, while Hg
has a higher attraction for other Hg molecules! Its meniscus is
convex.
o Viscosity: Resistance to flow (molecules with strong intermolecular
forces). Increases with molecular complexity [long C chains get
tangled and larger electron clouds are more polarizable due to the
presence of additional electrons] and increased with increasing IMFs.
Glycerol [left] has 3 OH groups which have a high capacity for Hbonding so this molecule is small, but very viscous.
o Modeling a liquid is difficult. Gases have VERY WEAK IMFs and
lots of motion. Solids have VERY STRONG IMFs and next to no motion. Liquids have both
strong IMFs and quite a bit of motion.

Types of Solids

Crystalline Solids: highly regular arrangement


of their components [often ionic, table salt
(NaCl), pyrite (FeS2)].
Amorphous solids: considerable disorder in their
structures (glass).

Intermolecular Forces, Liquids & Solids

Representation of Components in a Crystalline Solid


Lattice: A 3-dimensional system of points designating the centers of components (atoms, ions, or
molecules) that makes up the substance.

(a) network covalentcarbon in diamond formhere each molecule is covalently bonded to each
neighboring C with a tetrahedral arrangement. Graphite on the other hand, exists as sheets that slide and
is MUCH softer! (pictured later)
(b) ionic salt crystal lattice; Coulombs Law dictates the strength of the lattice
(c) icenotice the hole in the hexagonal structure and all the H-bonds. The hole is why ice
floatsit is less dense in the solid state than in the liquid state!

X-RAY Analysis of Solids

X-ray diffractionA bending or scattering of light. The beams of light are scattered from a
regular array of points in which the spacing between the components are comparable with the
of the light. It is due to constructive interference when the waves of parallel beams are in phase
and to destructive interference when the waves are out of phase.
The waves are in phase before they strike the crystal. IF the difference traveled after
reflection is an integral number of , the waves will still be in phase.
Since the distance traveled after reflection depends on the distance between the atoms, the
diffraction pattern can be used to determine the interatomic spacing.

Intermolecular Forces, Liquids & Solids

The diagram below shows two in-phase waves being reflected by atoms in two different layers in
a crystal. The extra distance traveled y the lower wave is the sum of the distances xy and yz and
the waves will be in phase after reflection if xy + yz = n.

Trig time! If sin =

opposite
xy = yz
=
hypotenuse d for each

then, 2d sin = xy + yz = n [from above]


where d is the distance between the atoms and is the angle of incidence and reflection.
Combine all of this and you get the Bragg equation named after William Henry Bragg and his son
William Lawrence Bragg who shared the Nobel Prize in physics in 1915 for their pioneering work in xray crystallography. Do you know of any other famous x-ray crystallographers? Why didnt she win a
Nobel Prize?

Bragg Equation n = 2d sin


Exercise 1
Using the Bragg Equation
X rays of wavelength 1.54 were used to analyze an aluminum crystal. A reflection was produced at
= 19.3 degrees. Assuming n = 1, calculate the distance d between the planes of atoms producing this
reflection.
d = 2.33 = 233 pm

Types of Crystalline Solids

Ionic Solid: contains ions at the points of the lattice that describe the structure of the solid
(NaCl). VERY high MPs. Hard. Ion-Ion Coulombic forces are the strongest of all attractive
forces. IMF usually implies covalently bonded substances, but can apply to both types.

Molecular Solid: discrete covalently bonded molecules at each of its lattice points (sucrose, ice).

Atomic Solid: atoms of the substance are located at the lattice points. Carbondiamond,
graphite and the fullerenes. Boron, and silicon as well.

Intermolecular Forces, Liquids & Solids

Know this chart well:

Structure and Bonding in Metals


Metals are characterized by high thermal and electrical conductivity, malleability, and ductility. These
properties are explained by the nondirectional covalent bonding found in metallic crystals.

closest packinga model that uses hard spheres to


represent the atoms of a metal. These atoms are packed
together and bonded to each other equally in all
directions. It will be easiest for you to understand if
you can imagine taking a cubic box and pouring in golf
balls. The balls will layer, perhaps directly on top of
one another, but perhaps one layer slides into the
dimple [pun intended] made by the first layer so that
the two layers are offset a bit. Next, remove the golf
balls and place tennis balls into the box. They will fill
the box differently since they are of a different size.

In the diagram above, in each layer, a given sphere is surrounded by six others.
o a) above exhibits aba packingthe second layer is like the first, but it is displaced so that
each sphere in the second layer occupies a dimple in the first layer. The spheres in the
third layer occupy dimples in the second layer so that the spheres in the third layer lie
directly over those in the first layer hence aba.
o b) above exhibits abc packingthe spheres in the third layer occupy dimples in the
second layer so that no spheres in the third layer lie above any in the first layer. The
fourth layer is like the first.

Intermolecular Forces, Liquids & Solids

aba has the hexagonal unit cell shown below and


the resulting structure is hexagonal closest packed
(hcp) structure. ababab.
abc has a face-centered cubic unit
cell and the resulting structure is
cubic closest packed (ccp)
structure. abcabc
The red sphere on the right, the
one in the center of row a that is
not numbered, has 12 nearest
neighbors. This one is hcp, but
this is true for both types of
packing.

Lets consider a face-centered cubic cell:

A cubic cell is defined by the centers of the spheres [atoms] on the cubes corners. How many corners
are in a cube? How many faces are in a cube? Note that face centered means an atom is stuck smack
dab in the middle of the face of one cube and consequently, the adjacent cube1/2 in each! How many
1 1
spheres [atoms] are in one cube that is face-centered? 8 + 6 = 4
8 2
Exercise 2
Calculating the Density of a Closest Packed Solid
Silver crystallizes in a cubic closest packed structure. The radius of a silver atom is 144 pm. Calculate
the density of solid silver.

density = 10.6 g/cm3

Bonding Models for Metals


Remember, metals conduct heat and electricity, are malleable and ductile, and have high melting points.
These facts indicate that the bonding in most metals is both strong and nondirectional. Difficult to
separate atoms, but easy to move them provided they stay in contact with each other!
Electron Sea Model: A regular array of
metals in a sea of electrons. I A & II
A metals pictured at left.
Band (Molecular Orbital) Model:
Electrons assumed to travel around
metal crystal in MOs formed from
valence atomic orbitals of metal atoms.

Intermolecular Forces, Liquids & Solids

Metal alloys: a substance that has a mixture of elements and has metallic
properties

substitution alloysin brass 1/3 of the atoms in the host copper metal
have been replaced by zinc atoms. Sterling silver93% silver and 7%
copper. Pewter85% tin, 7% copper, 6% bismuth and 2% antimony.
Plumbers solder95% tin and 5% antimony.

interstitial alloyformed when some of the interstices [fancy word for


holes] in the closest packed metal structure are occupied by small
atoms. Steelcarbon is in the holes of an iron crystal. There are many
different types of steels, all depend on the percentage of carbon in the
iron crystal.

Network Atomic Solidsa.k.a. Network Covalent


Composed of strong directional covalent bonds that are best viewed as a giant
molecule. Both diamond and graphite are network solids. The difference is that
diamond bonds with neighbors in a tetrahedral 3-D fashion, while graphite only has
weak bonding in the 3rd dimension. Network solids are often:
o brittlediamond is the hardest substance on the planet, but when a
diamond is cut it is actually fractured to make the facets
o do not conduct heat or electricity
o carbon or silicon-based
o Diamond is hard, colorless and an insulator. It consists of carbon
atoms ALL bonded tetrahedrally, therefore sp3 hybridization and
109.5 bond angles.
o Graphite is slippery, black and a conductor. Graphite is bonded so

that it forms layers of carbon atoms arranged in fused six-member rings. This indicates
sp2 hybridization and 120 bond angles within the fused rings. The unhybridized p
orbitals are perpendicular to the layers and form bonds. The delocalized electrons in
the bonds account for the electrical conductivity while also contributing to the
mechanical stability of the layers. It is often used as a lubricant in locksgrease or oil
collects dirt, graphite does not.

Silicon is to geology what carbon is to biology! The most significant silicon compounds
involve chains with silicon-oxygen bonds.
silicaempirical formula SiO2not at all like its cousin CO2! Quartz and some types of
sand are silicon dioxide as opposed to a clear colorless gas such as carbon dioxide. Why
such drastic differences? Bonding.

Intermolecular Forces, Liquids & Solids

10

Draw the Lewis Structure for CO2:

What is carbons hybridization?

Silicon cannot use its valence 3p orbitals to form


strong bonds with oxygen, mainly due to the larger
size of the silicon atom and its orbitalsyou get
inefficient overlap.
INSTEAD of forming bonds, the silicon atom
satisfies the octet rule by forming single bonds with
FOUR OXYGEN atoms.
Each silicon is in the center of a tetrahedral
arrangement of oxygen atoms. This means that
although the empirical formula is SiO2, the structure is
based on a network of SiO4 tetrahedra with shared
oxygen atoms.
Silicates are the compounds found in most rocks, soils and clays.
Silicates contain a O/Si ratio greater than 2:1 and contain siliconoxygen anions. That means silicates are salts containing
metallic cations that are needed to make neutral arrangements.
Common silicate anions are pictured on the right.

Intermolecular Forces, Liquids & Solids

When silica is heated above its MP


of about 1600C and cooled
rapidly, an amorphous [without
shapenot a crystal] solid forms.
We call it glassits really a supercooled, ultra viscous
liquid with a great deal of disorder.

At left, a) is quartz while b) is quartz glass. These pictures


are 2-D, not 3-D.

Common glass results when Na2CO3 is added to the silica


melt.

Pyrex, a borosilicate glass [lab ware] is made when B2O3


is added to the silica melt.

Eyeglasses are made from glass that is especially hard so it


can be ground into precise shapes. K2O has been added.

11

Read the sections in your book about ceramics and semiconductors!

Molecular Solids
These solids differ in that a molecule occupies the lattice position rather than an atom. Ice & dry ice,
[solid carbon dioxide] are examples. Allotropes of sulfur and phosphorous are included. S8 or P4
occupy the lattice positions in these allotropes [many forms] of these elements.
Characterized by strong covalent bonding within the molecule yet weak forces between the
molecules.
It takes 6 kJ of energy to melt one mole of solid water since you only have to overcome Hbonding while it takes 470 kJ of energy to break one mole of OH bonds.
Molecules such as CO2, I2, P4, and S8 have no dipole moment.
We call their IMFs induced dipoleinduced dipole or London dispersion forces.
As the size of the molecule increases [often reported in a Chem I book as increased MM],
the London dispersion forces increase because the larger the molecule the more electrons,
the more polarizable its electron cloud. If it is more polarizable, temporary dipoles can
easily form.
So what? The MP and BP increase since the
molecules are MORE attracted to each other
as a result of this polarizing of the electron
cloud.

Ionic Solids
Stable, high-melting substances held together by STRONG electrostatic forces that exist between
oppositely charged ions. Coulombs Law dictates the strength of the electrostatic force.

Intermolecular Forces, Liquids & Solids

12

Exercise 4
Types of Solids
Using Table 10.7, classify each of the following substances according to the type of solid it forms.
a.
b.
c.
d.

Gold
Carbon dioxide
Lithium fluoride
Krypton
A: atomic solid w/metallic properties
B: molecular solid
C: binary ionic solid
D: atomic solid w/ properties characteristic of molecular solid w/nonpolar molecules

Vapor Pressure and Changes of State

vaporization or evaporationwhen molecules of a liquid can escape the liquids surface and
form a gas. ENDOTHERMIC since energy must be absorbed so that the liquid molecules gain
enough energy to escape the surface and thus overcome the liquids IMFs.
Hvapenthalpy of vaporizationthe energy required to vaporize ONE mole of a liquid at 1
atm pressure
Waters heat of vaporization is 40.7 kJ/mol. This is huge! Water makes life on this planet
possible since it acts as a coolant. The reason its )Hvap is so large has everything to do with
hydrogen bonding. The IMFs in water are huge, thus a great deal of the suns energy is needed to
evaporate the rivers, lakes, oceans, etc. of Earth. Perspiration is a coolant for animals possessing
sweat glands. Energy from your hot body is absorbed by the water soln to evaporate.
condensationopposite of vaporization. When the energetic steam molecules generated by
your morning shower hurl themselves across the bathroom and collide with the cold mirror, they
lose energy and return to the liquid phase.
equilibrium vapor pressurereached when the rate of evaporation
equals the rate of condensation in a closed container

Stopper a flask of a freshly poured liquid (a).


Equilibrium VP will be established (b).
Moleucles leave and enter
the liquid phase @ the
SAME RATE.
(a) The VP of a liquid can be measured easily using a
simple barometer. (b) The three liquids water,
ethanol, and diethyl ether have quite different vapor
pressures. Ether is by far the most volatile of the three
[weakest IMFs thus escapes easiest]. Note that in each
case a little liquid remains (floating on the mercury).

Intermolecular Forces, Liquids & Solids

13

volatilehave high VP, thus weak IMFs. These liquids evaporate readily from open containers
since they have so little attraction for each other. It takes very little energy being absorbed in
order for them to escape the surface of the liquid. The heat energy absorbed from a warm room
is usually enough to make these substances evaporate quickly. If there is an odor to the
substance, these are the liquids you smell almost as soon as you open the bottle! The molecules
have been banging against the lid wanting out!

VP increases significantly with temperature! Heat em up, speed em up, move em out!
Increasing the temperature increases the KE which facilitates escape AND the speed of the
escapees! They bang into the sides of the container with more frequency [more of them escaped]
and more energy [more momentum].

More molecules can attain the energy needed to overcome the


IMFs in a liquid at a higher T since the KE increases

In general, as MM VP

BECAUSE as molecules increase in molar mass, they also increase in the number of electrons.
As the number of electrons increase, the polarizability of the molecule increases so more induced
dipole-induced dipole or dispersion forces exist, causing stronger attractions to form between
molecules. This decreases the number of molecules that escape and thus lowers the VP.
H-bonding causes a major exception! Its presence greatly increases the IMFs of the liquid.
Water has an incredibly low VP for such a light [MM = 18.02] molecule.
We can put the math to this. Plot lnVP vs. 1/T [in Kelvins] and we get a straight line. Next, put
this into y = mx + b format:
ln VP =

H vap 1
+C
R T

R is the universal gas constant


since this is all about energy, use
the energy R, 8.31 J/molK.

C is a constant characteristic of
the liquid [y-intercept].
H vap
slope, m =
R

Intermolecular Forces, Liquids & Solids

14

Exercise 5
Determining Enthalpies of Vaporization
Using the plots in (b) above, determine whether water or diethyl ether has the larger enthalpy of
vaporization.
water

If we know the values of Hvap and VP at one temperature we can solve the above expression for the
constant, C and set a second expression for T2 equal to the first since the value of C is NOT dependent
upon temperature:
H vap
H vap
VP H vap 1 1

ln VP1 +
= C = ln VP2 +
which can be rearranged into ln 1 =
VP
R
RT1
RT2
T2 T1
2
This form is called the Clausius- Clapeyron equation.
Exercise 6

Calculating Vapor Pressure

The vapor pressure of water at 25C is 23.8 torr, and the heat of vaporization of water at 25C is
43.9 kJ/mol. Calculate the vapor pressure of water at 50C.

93.7 torr
sublimationsolids also have vapor pressures. Some solids go directly to the
vapor phase at 1atm, skipping the liquid phase all together! Iodine and dry ice
[solid carbon dioxide] both do this.

Melting Point

A heating curve is pictured below:


Molecules break loose from lattice points and solid changes to liquid.
Temperature remains constant during ANY phase change. PE is
changing like crazy while KE remains constant!
Hfus, enthalpy of fusionthe enthalpy
change that occurs at the melting point [which
is the freezing point, by the way]. This energy
is clearly going into increasing the PE of the
molecules since the temperature or ave KE of
the molecules is plateaued or staying the same.
vapor pressure of solid = vapor pressure of
liquid [equil. is established]
On the plateaus, calculate the E change using
q = H[vap or fus]m
On the slants, calculate the E change using
q = mc[solid, liquid or gas]T

Intermolecular Forces, Liquids & Solids

15

The melting and boiling points of water are determined by the vapor
pressures of the solid and liquid states. This figure shows VP of solid
and liquid water as a function of temperatures near zero.

Below zeroVP of ice has a larger T-dependence


This means the VP of ice increases more rapidly than the liquids
VP for each increase in temperature.
A point is eventually reached where the VP solid = VP liquid.
We call this temperature the MP!

normal melting pointthe temperature at which the VP solid = VP liquid AND P total = 1atm
normal boiling pointthe temperature at which the VP liquid = exactly 1 atm
FREAKSchanges of state do not always form at the exact MP and BPs.
supercooledoxymoronthe substance is at a
temperature below its FP, yet it remains a liquid.
Usually happens when the cooling has been gradual
and the degree of organization needed to form
crystals hasnt happened. At some point, organization
happens and the solid is readily formed, the
temperature rises back to the MP as the heat of
crystallization is released.
superheatedanother oxymoronthe substance is
at a temperature above its BP, yet it remains a liquid.
Usually happens when heated very rapidly
[microwave oven] and bubbles form in the interior
with high internal pressures. They often burst before reaching the surface making quite a mess
of things! Really ruins an experiment. This is called bumping in the lab. Prevent it by adding
boiling chips to the flask. These chips are porous and have air trapped in them, upon heating tiny
air bubbles form and act as starters for vapor bubble formation.

Intermolecular Forces, Liquids & Solids

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Phase Diagramsclosed
systems

Represent phases of matter as a function of


temperature and pressure.
critical temperature: temperature above which the
vapor cannot be liquefied.
critical pressure: pressure required to liquefy AT
the critical temperature.
critical point: critical temperature and pressure
coordinates (for water, Tc = 374C and 218 atm).

Water is a freak! The solid-liquid line tilts to the left


[negative slope] since its solid is less dense than its liquid
phaseice floats. Usually the solid sinks as it is more dense.
Consider the cylinder pictured right.
Experiment 1: P = 1atm.
Completely filled with
ONLY ice at 20C. Heat
20 0 only ice present
at 0, ice melts [no vapor]
past 0 liquid water begins to exert a VP. When the
VP of the liquid reaches 1atm, vaporization occurs
and steam is formed.
Experiment 2: P = 2.0 torr
Start again with only ice at 20C. Heat
As heating proceeds, 10 is reached where ice
changed directly to vapor. It sublimes. No liquid
water forms because the VP of water is always
greater than 2.0 torr. If water were placed into the
cylinder at these conditions, it would freeze if less
than 10 or vaporize if greater than 10. Water
cannot exist at these conditions!
Experiment 3: P = 4.588 torr
Start again with only ice at 20C. Heat
No new phase results until the temperature reaches 0.0098C. This is the triple point of water and all
THREE phases exist in equilibrium at this set of P & T conditions.
Experiment 4: P = 225 atm
Start this time with only liquid water in the cylinder at 300C. Heat.
The liquid water gradually changes to vapor, but it goes through a fluid state that was not present at any
of the other pressures and temperatures. This fluid region, is neither true liquid nor true vapor.
This occurs when the critical point has been exceeded. For water CT = 374C and CP = 218 atm.

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What is the effect of pressure on ice? It melts it.


You can take a block of ice, connect a wire to two heavy weights and drape it
across the block. The wire will exert pressure on the block, melt it and begin a
journey downward through the block due to the force of gravity acting on the
weights. The cool thing [pun intended] is that after the wire has left the
surface, the block refreezes!
Most substances have a solid-liquid line
that has a positive slope since their solid
phase is more dense than the liquid. This one is for carbon
dioxide.
EACH PHASE BOUNDARY REPRESENTS AN
EQUILIBRIUM SET OF PRESSURE AND
TEMPERATURE CONDITIONS!! Be sure and use the word
equilibrium in your writing as you explain phase diagrams.

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