Download - INTERMOLECULAR FORCES LIQUIDS & SOLIDS. Now it is time to consider the forces that condense matter
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INTERMOLECULAR INTERMOLECULAR FORCESFORCES
LIQUIDS & SOLIDSLIQUIDS & SOLIDS
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Now it is time to consider the Now it is time to consider the forces forces
that condense matter. that condense matter.
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These can be due to ionic or These can be due to ionic or
covalent bonding [intramolecular covalent bonding [intramolecular
forces — ionic stronger than forces — ionic stronger than
covalent] or much weaker covalent] or much weaker attractive attractive
forces we call intermolecular forces we call intermolecular forces. forces.
These are the forces These are the forces betweenbetween
(rather than within) molecules. (rather than within) molecules.
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We briefly visited the IMF’s earlier We briefly visited the IMF’s earlier
when discussing the nonideal when discussing the nonideal behavior behavior
of gases. These forces cause of gases. These forces cause
changes of state by causing changes of state by causing changes changes
among the molecules, NOT within among the molecules, NOT within
them.them.
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Dipole-DipoleDipole-DipoleStrongest IMF’sStrongest IMF’s
Molecules with Molecules with
dipoles orient dipoles orient
themselves so themselves so that that
““+” and “-” ends +” and “-” ends of of
the dipole are the dipole are
close together.close together.
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Hydrogen BondsHydrogen Bonds
Dipole-dipole attraction in which Dipole-dipole attraction in which
hydrogen on one molecule is attracted hydrogen on one molecule is attracted
to a highly electronegative atom on an to a highly electronegative atom on an
adjacent molecule. (F, O, N) adjacent molecule. (F, O, N)
bonded H
H-“bond”
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WHYWHY is there such variation among is there such variation among
the covalent hydrides of groups IV the covalent hydrides of groups IV
through VII? through VII?
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One would expect that BP would One would expect that BP would
increase with increasing molecular increase with increasing molecular
mass [since the more electrons in a mass [since the more electrons in a
molecule, the more polarizable the molecule, the more polarizable the
cloud {more about that in the next cloud {more about that in the next
section}, the stronger the IMF’s, the section}, the stronger the IMF’s, the
more E needed to overcome these more E needed to overcome these
attractions and vaporize].attractions and vaporize].
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Hydrogen bonding, Hydrogen bonding, That’s why!That’s why!
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Both reasons enhance the IMF Both reasons enhance the IMF we we
refer to as hydrogen bonding.refer to as hydrogen bonding.
TWO ReasonsTWO Reasons
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1. The lighter hydrides have the 1. The lighter hydrides have the highest En values which leads highest En values which leads to especially polar H-X bonds.to especially polar H-X bonds.
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2. The small size of each dipole 2. The small size of each dipole
allows for a closer approach allows for a closer approach of of
the dipoles, further the dipoles, further strengthening strengthening
the attractions.the attractions.
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London Dispersion ForcesLondon Dispersion ForcesWeakest IMF’sWeakest IMF’s
Relatively weak forces that Relatively weak forces that exist exist
among noble gas atoms and among noble gas atoms and
nonpolar molecules. (Ar, Cnonpolar molecules. (Ar, C88HH1818))
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Caused by instantaneous dipole Caused by instantaneous dipole
formation, in which electron formation, in which electron
distribution becomes asymmetrical. distribution becomes asymmetrical.
The newly formed dipoles now find The newly formed dipoles now find
each other FAR more attractive than each other FAR more attractive than
before! before!
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Dipole-induced dipole if an Dipole-induced dipole if an ion or ion or
polar moleculepolar molecule causes the distortion. causes the distortion.
OR OR
Induced dipole-induced dipole if a Induced dipole-induced dipole if a
nonpolar moleulenonpolar moleule sets off the chain sets off the chain
reaction of induction like in iodine.reaction of induction like in iodine.
a.k.a.a.k.a.
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The ease with The ease with which the electron which the electron ““cloud” of an cloud” of an atom can be atom can be distorted is called distorted is called polarizabilitypolarizability. . You’ll want to You’ll want to write about write about polarizability when EXPLAINING polarizability when EXPLAINING these concepts.these concepts.
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Without these forces, we could not Without these forces, we could not
liquefy covalent gases or solidify liquefy covalent gases or solidify
covalent liquids. covalent liquids.
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These forces INCREASE as we go These forces INCREASE as we go
down the family since the electron down the family since the electron
cloud becomes more polarizable with cloud becomes more polarizable with
increasing FW [more principle E levels increasing FW [more principle E levels
added, more electrons present, more added, more electrons present, more
shielding, valence farther from the shielding, valence farther from the
nucleus, etc.]. nucleus, etc.].
Consider the halogens…Consider the halogens…
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It explains WHY FIt explains WHY F22 and Cl and Cl22 are gases, are gases,
BrBr22 is a liquid [moderate dispersion is a liquid [moderate dispersion forces a.k.a. London forces, a.k.a. forces a.k.a. London forces, a.k.a. dipole-induced dipole forces] and dipole-induced dipole forces] and
ultimately Iultimately I22 is a solid! is a solid!
What does that tell us about What does that tell us about boiling points??boiling points??
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Some Properties of a Some Properties of a LiquidLiquid
All of the following are greater All of the following are greater for for
polar molecules since their polar molecules since their IMF’s IMF’s
are greater than nonpolar are greater than nonpolar
molecules.molecules.
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Surface TensionSurface Tension
The resistance to an increase in its The resistance to an increase in its
surface area (polar molecules). High surface area (polar molecules). High
ST indicates strong IMF’s. Molecules ST indicates strong IMF’s. Molecules
are attracted to each OTHER. are attracted to each OTHER.
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A molecule in the interior of a liquid A molecule in the interior of a liquid
is attracted by the molecules is attracted by the molecules
surrounding it, whereas a molecule surrounding it, whereas a molecule
at the surface of a liquid is attracted at the surface of a liquid is attracted
only by the molecules below it and only by the molecules below it and
on each side.on each side.
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Capillary ActionCapillary Action
Spontaneous rising of a liquid Spontaneous rising of a liquid
in a narrow tube.in a narrow tube.
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Adhesive forces between molecule Adhesive forces between molecule
and glass overcome cohesive forces and glass overcome cohesive forces
between molecules themselves. between molecules themselves.
The narrower the tube, the more The narrower the tube, the more
surface area of glass, the higher the surface area of glass, the higher the
column of water climbs!column of water climbs!
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The weight of the column sets the limit The weight of the column sets the limit
for the height achieved. Hg liquid for the height achieved. Hg liquid
behaves just the opposite. Water has a behaves just the opposite. Water has a
higher attraction for glass than itself so higher attraction for glass than itself so
its meniscus is inverted or concave, its meniscus is inverted or concave,
while Hg has a higher attraction for while Hg has a higher attraction for
other Hg molecules! Its meniscus is other Hg molecules! Its meniscus is
convex.convex.
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ViscosityViscosity
Resistance to flow (molecules with Resistance to flow (molecules with
large intermolecular forces). large intermolecular forces).
Increases with molecular Increases with molecular complexity complexity
[long C chains get tanagles] and [long C chains get tanagles] and
increases with increasing IMF’s. increases with increasing IMF’s.
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Glycerol [left] has Glycerol [left] has
3 OH groups 3 OH groups
which have a high which have a high
capacity for H-capacity for H-
bonding so this bonding so this
molecule is small, molecule is small,
but very viscous.but very viscous.
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Gases have VERY SMALL IMFs and Gases have VERY SMALL IMFs and lots of motion. lots of motion.
Solids have VERY HIGH IMFs and Solids have VERY HIGH IMFs and next next
to no motion. to no motion.
Liquids have both strong IMFs Liquids have both strong IMFs andand quite a bit of motion. quite a bit of motion.
Modeling a liquid is Modeling a liquid is difficult.difficult.
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Types of SolidsTypes of Solids
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Crystalline SolidsCrystalline Solids
Highly regular arrangement of Highly regular arrangement of their their
components [often ionic, table components [often ionic, table salt salt
(NaCl), pyrite (FeS(NaCl), pyrite (FeS22)].)].
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Amorphous solidsAmorphous solids
Considerable disorder in their Considerable disorder in their
structures (glass).structures (glass).
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REPRESENTATION OFREPRESENTATION OFCOMPONENTS COMPONENTS
IN A IN A CRYSTALLINE SOLIDCRYSTALLINE SOLID
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LatticeLattice
A 3-dimensional system of points A 3-dimensional system of points
designating the centers of designating the centers of
components (atoms, ions, or components (atoms, ions, or
molecules) that make up the molecules) that make up the
substance.substance.
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Network CovalentNetwork Covalent
(a) carbon in diamond (a) carbon in diamond
formform
Here, each molecule is Here, each molecule is
covalently bonded to each covalently bonded to each
neighboring C with a neighboring C with a
tetrahedral arrangement. tetrahedral arrangement.
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Graphite on the other hand, Graphite on the other hand, makes makes
sheets that slide and is MUCH sheets that slide and is MUCH softer! softer!
(pictured later)(pictured later)
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(b) ionic salt (b) ionic salt
crystal latticecrystal lattice
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(c) ice— notice the “hole” in the (c) ice— notice the “hole” in the hexagonal structure and all the hexagonal structure and all the
H-H- bonds. bonds. The “hole” The “hole” is why ice is why ice floats—it makes floats—it makes it less dense it less dense than the liquid!than the liquid!
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X-RAY ANALYSIS X-RAY ANALYSIS OF SOLIDSOF SOLIDS
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X-ray DiffractionX-ray Diffraction
A bending or scattering of light. The A bending or scattering of light. The
beams of light are scattered from a beams of light are scattered from a
regular array of points in which the regular array of points in which the
spacing between the components spacing between the components are are
comparable with the λ of the light. comparable with the λ of the light.
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It is due to constructive It is due to constructive interference interference
when the waves of parallel when the waves of parallel beams beams
are in phase and to destructive are in phase and to destructive
interference when the waves are interference when the waves are
out of phase.out of phase.
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The waves are in phase before they The waves are in phase before they
strike the crystal. strike the crystal.
IF the difference traveled after IF the difference traveled after
reflection is an reflection is an integral number of λintegral number of λ, ,
the waves will still be in phase.the waves will still be in phase.
..
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Since the distance traveled after Since the distance traveled after
reflection depends on the distance reflection depends on the distance
between the atoms, the diffraction between the atoms, the diffraction
pattern can be used to determine pattern can be used to determine the the
inter-atomic spacing.inter-atomic spacing.
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The diagram below shows two The diagram below shows two in-in-
phase waves being reflected by phase waves being reflected by
atoms in two different layers in atoms in two different layers in a a
crystal. crystal.
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The extra distance traveled by The extra distance traveled by the the
lower wave is the sum of the lower wave is the sum of the
distances xy and yz and the distances xy and yz and the waves waves
will be in phase after reflection if: will be in phase after reflection if:
xy + yz = nλxy + yz = nλ
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Trig time!Trig time!
If …If …
then, 2d sin θ = xy + yz = nλ then, 2d sin θ = xy + yz = nλ
[from above][from above]
where d is the distance between the where d is the distance between the atoms and θ is the angle of incidence atoms and θ is the angle of incidence and reflection. and reflection.
foreachd
yzxy
hypotenuse
opposite sin
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Combine all of this and you get the Combine all of this and you get the
Bragg equation named after William Bragg equation named after William
Henry Bragg and his son William Henry Bragg and his son William
Lawrence Bragg who shared the Lawrence Bragg who shared the
Nobel Prize in physics in 1915 for Nobel Prize in physics in 1915 for
their pioneering work in x-ray their pioneering work in x-ray
crystallography. crystallography.
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Do you know of any other Do you know of any other famous famous
x-ray crystallographers? x-ray crystallographers?
Why didn’t she win a Nobel Why didn’t she win a Nobel Prize?Prize?
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Bragg Equation Bragg Equation
nλ = 2d sin θnλ = 2d sin θ
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Exercise 1Exercise 1 Using the Bragg Equation Using the Bragg Equation
X-rays of wavelength 1.54 Å were X-rays of wavelength 1.54 Å were
used to analyze an aluminum crystal. used to analyze an aluminum crystal.
A reflection was produced at θ = 19.3 A reflection was produced at θ = 19.3
degrees. Assuming n = 1, calculate degrees. Assuming n = 1, calculate
the distance d between the planes of the distance d between the planes of
atoms producing this reflection.atoms producing this reflection.
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SolutionSolution
d = 2.33 Å = 233 pmd = 2.33 Å = 233 pm
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TYPES OF TYPES OF CRYSTALLINE SOLIDSCRYSTALLINE SOLIDS
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Ionic SolidIonic Solid
Contains ions at the points of the Contains ions at the points of the lattice that describe the structure lattice that describe the structure
of of the solid (NaCl). the solid (NaCl).
VERY high MP’s VERY high MP’s
Hard Hard
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Ion-Ion Coulombic forces are the Ion-Ion Coulombic forces are the
strongest of all attractive forces. strongest of all attractive forces.
““IMF” usually implies covalently IMF” usually implies covalently
bonded substances, but can bonded substances, but can apply to apply to
both types.both types.
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Molecular SolidMolecular Solid
Discrete covalently bonded Discrete covalently bonded
molecules at each of its lattice molecules at each of its lattice
points (sucrose, ice).points (sucrose, ice).
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Atomic SolidAtomic Solid
Atoms of the substance are Atoms of the substance are
located at the lattice points. located at the lattice points.
Carbon—diamond, graphite and Carbon—diamond, graphite and
the fullerenes. Boron, and the fullerenes. Boron, and silicon silicon
as well.as well.
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Know this Chart WellKnow this Chart Well
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Structure and Bonding in Structure and Bonding in MetalsMetals
Metals are characterized by high Metals are characterized by high
thermal and electrical thermal and electrical conductivity, conductivity,
malleability, and ductility. These malleability, and ductility. These
properties are explained by the properties are explained by the
nondirectional covalent bonding nondirectional covalent bonding
found in metallic crystals.found in metallic crystals.
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Closest PackingClosest Packing
A model that uses hard spheres A model that uses hard spheres to to
represent the atoms of a metal. represent the atoms of a metal.
These atoms are packed together These atoms are packed together
and bonded to each other equally and bonded to each other equally in in
all directionsall directions. .
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It will be easiest for you to It will be easiest for you to
understand if you can imagine taking understand if you can imagine taking
a cubic box and pouring in golf balls. a cubic box and pouring in golf balls.
The balls will layer, perhaps directly The balls will layer, perhaps directly
on top of one another, but perhaps on top of one another, but perhaps
one layer slides into the “dimple” one layer slides into the “dimple”
made by the first layer so that the two made by the first layer so that the two
layers are offset a bit. layers are offset a bit.
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Next, remove the golf balls and Next, remove the golf balls and
place tennis balls into the box. place tennis balls into the box.
They will fill the box differently They will fill the box differently
since they are of a different since they are of a different size.size.
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In the diagram above, in each layer, In the diagram above, in each layer,
a given sphere is surrounded by six a given sphere is surrounded by six
others.others.
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aba Packingaba Packing
The second layer is like the first, but The second layer is like the first, but it is displaced so that each sphere in it is displaced so that each sphere in the second layer occupies a dimple in the second layer occupies a dimple in the first layer. The spheres in the the first layer. The spheres in the
third third layer occupy dimples in the second layer occupy dimples in the second layer so that the spheres in the third layer so that the spheres in the third layer lie directly over those in the first layer lie directly over those in the first layer hence aba..layer hence aba..
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aba has the hexagonal unit cell shown aba has the hexagonal unit cell shown
below and the resulting structure is below and the resulting structure is
hexagonal closest packed (hcp) hexagonal closest packed (hcp)
structure. structure. ababab….ababab….
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abc Packingabc Packing
The spheres in the third layer The spheres in the third layer
occupy dimples in the second occupy dimples in the second layer layer
so that no spheres in the third so that no spheres in the third layer layer
lie above any in the first layer. The lie above any in the first layer. The
fourth layer is like the first.fourth layer is like the first.
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abc has a face-centered cubic unit abc has a face-centered cubic unit
cell and the resulting structure is cell and the resulting structure is
cubic closest packed (ccp) structure. cubic closest packed (ccp) structure.
abcabc…abcabc…
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The red sphere on The red sphere on
the right, the one in the right, the one in
the center of row ‘a’ the center of row ‘a’
that is not that is not numbered, numbered,
has 12 nearest has 12 nearest
neighbors. This one neighbors. This one
is hcp, but this is true is hcp, but this is true
for both types of for both types of
packing.packing.
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Let’s consider a face-centered Let’s consider a face-centered
cubic cell…cubic cell…
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A cubic cell is defined by the A cubic cell is defined by the centerscenters
of the spheres [atoms] on the cube’s of the spheres [atoms] on the cube’s
corners. corners.
How many corners are in a cube? How many corners are in a cube?
How many faces are in a cube? How many faces are in a cube?
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Note that face centered means an Note that face centered means an
atom is stuck smack dab in the atom is stuck smack dab in the middle middle
of the face of one cube and of the face of one cube and
consequently, the adjacent cube—1/2 consequently, the adjacent cube—1/2
in each! in each!
How many spheres [atoms] are in How many spheres [atoms] are in one one
cube that is face-centered? cube that is face-centered?
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Exercise 2 Calculating the Exercise 2 Calculating the Density of a Closest Packed Density of a Closest Packed SolidSolidSilver crystallizes in a cubic closest Silver crystallizes in a cubic closest
packed structure. The radius of a packed structure. The radius of a silver silver
atom is 144 pm. atom is 144 pm.
Calculate the Calculate the
density of solid density of solid
silver.silver.
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SolutionSolution
density = 10.6 g/cmdensity = 10.6 g/cm33
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Bonding Models for Bonding Models for MetalsMetals
Remember, metals conduct Remember, metals conduct heat heat
and electricity, are malleable and electricity, are malleable and and
ductile, and have high melting ductile, and have high melting
points. points.
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These facts indicate that the These facts indicate that the
bonding in most metals is both bonding in most metals is both
strong and nondirectional. strong and nondirectional. Difficult Difficult
to separate atoms, but easy to to separate atoms, but easy to
move them provided they stay in move them provided they stay in
contact with each other!contact with each other!
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Electron Sea ModelElectron Sea Model
A regular array of metals in a A regular array of metals in a “sea” “sea”
of electrons. of electrons.
I A & II A metals pictured belowI A & II A metals pictured below..
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Band (Molecular Orbital) Band (Molecular Orbital) ModelModel
Electrons assumed to travel Electrons assumed to travel aroundaround
metal crystal in MO’s formed metal crystal in MO’s formed from from
valence atomic orbitals of valence atomic orbitals of metal metal
atoms.atoms.
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Metal AlloyMetal Alloy
A substance A substance that that
has a mixture of has a mixture of
elements and elements and has has
metallic metallic properties. properties.
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Substitution AlloysSubstitution Alloys
In brass, 1/3 of the atoms in the In brass, 1/3 of the atoms in the
host copper metal have been host copper metal have been
replaced by zinc atoms. replaced by zinc atoms.
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Sterling silver—93% silver and 7% Sterling silver—93% silver and 7%
copper. copper.
Pewter—85% tin, 7% copper, 6% Pewter—85% tin, 7% copper, 6%
bismuth and 2% antimony. bismuth and 2% antimony.
Plumber’s solder—95% tin and 5% Plumber’s solder—95% tin and 5%
antimony.antimony.
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Interstitial AlloyInterstitial Alloy
Formed when some of the Formed when some of the
interstices [holes] in the closest interstices [holes] in the closest
packed metal structure are packed metal structure are occupied occupied
by small atoms. by small atoms.
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Steel—carbon is in the holes of an Steel—carbon is in the holes of an
iron crystal. iron crystal.
There are many different types of There are many different types of
steels. All depend on the steels. All depend on the
percentage of carbon in the iron percentage of carbon in the iron
crystal.crystal.
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NETWORK ATOMIC NETWORK ATOMIC SOLIDSSOLIDS
a.k.a. a.k.a. Network CovalentNetwork Covalent
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Composed of strong Composed of strong directional directional
covalent bonds that are best covalent bonds that are best
viewed as a “giant molecule”. viewed as a “giant molecule”.
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Both diamond and graphite are Both diamond and graphite are
network solids. The difference is network solids. The difference is
that diamond bonds with that diamond bonds with neighbors neighbors
in a tetrahedral 3-D fashion, while in a tetrahedral 3-D fashion, while
graphite only has weak bonding in graphite only has weak bonding in
the 3rd dimension. the 3rd dimension.
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Network Solids are Often Network Solids are Often BrittleBrittle
Diamond is the hardest substance Diamond is the hardest substance on on
the planet, but when a diamond is the planet, but when a diamond is
““cut” it is actually fractured to make cut” it is actually fractured to make
the facets.the facets.
Do not conduct heat or electricityDo not conduct heat or electricity
Carbon, silicon-basedCarbon, silicon-based
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Diamond is hard, Diamond is hard,
colorless and an colorless and an
insulator. insulator.
It consists of carbon atoms ALL It consists of carbon atoms ALL
bonded tetrahedrally, therefore spbonded tetrahedrally, therefore sp33
hybridization and 109.5hybridization and 109.5 bond bond angles.angles.
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Graphite is slippery, black and Graphite is slippery, black and a a
conductor. conductor.
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Graphite is bonded so that it Graphite is bonded so that it forms forms
layers of carbon atoms arranged layers of carbon atoms arranged
infused six-membered rings. infused six-membered rings.
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This indicates spThis indicates sp22 hybridization and hybridization and 120120 bond angles within the fused bond angles within the fused rings. rings.
The unhybridized p orbitals are The unhybridized p orbitals are perpendicular to the layers and form perpendicular to the layers and form bonds.bonds.
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The delocalized electrons in the The delocalized electrons in the bonds account for the electrical bonds account for the electrical
conductivity while also contributing to conductivity while also contributing to
the mechanical stability of the layers. the mechanical stability of the layers.
It is often used as a lubricant in It is often used as a lubricant in
locks—grease or oil collects dirt, locks—grease or oil collects dirt,
graphite does not.graphite does not.
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Silicon is to geology what carbon Silicon is to geology what carbon is is
to biology! to biology!
The most significant silicon The most significant silicon
compounds involve chains with compounds involve chains with
silicon-oxygen bonds.silicon-oxygen bonds.
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SilicaSilica
Empirical formula SiOEmpirical formula SiO22—not at all like —not at all like
its cousin COits cousin CO22! !
Quartz and some types of sand are Quartz and some types of sand are
silicon dioxide as opposed to a clear silicon dioxide as opposed to a clear
colorless gas such as carbon dioxide. colorless gas such as carbon dioxide.
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Why Such Drastic Why Such Drastic Differences?Differences?
Bonding.Bonding.
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Draw the Lewis Structure for Draw the Lewis Structure for COCO2.2.
What is carbon’s hybridization? What is carbon’s hybridization?
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Silicon cannot use its valence 3p Silicon cannot use its valence 3p
orbitals to form strong orbitals to form strong bonds with bonds with
oxygen, mainly due to the larger oxygen, mainly due to the larger
size of the silicon atom and its size of the silicon atom and its
orbitals—you get inefficient overlap. orbitals—you get inefficient overlap.
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INSTEAD of INSTEAD of
forming forming bonds, bonds,
the silicon atom the silicon atom
satisfies the octet satisfies the octet
rule by forming rule by forming
single σ bonds single σ bonds
with FOUR with FOUR
OXYGEN atoms. OXYGEN atoms.
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Each silicon is in the center of a Each silicon is in the center of a
tetrahedral arrangement of oxygen tetrahedral arrangement of oxygen
atoms. atoms.
This means that although the This means that although the empirical empirical
formula is SiOformula is SiO22, the structure is based , the structure is based
on a network of SiOon a network of SiO44 tetrahedra with tetrahedra with
sharedshared oxygen atoms. oxygen atoms.
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Silicates are the compounds found Silicates are the compounds found in in
most rocks, soils and clays. most rocks, soils and clays.
Silicates contain a O/Si ratio greater Silicates contain a O/Si ratio greater
than 2:1 and contain silicon-oxygen than 2:1 and contain silicon-oxygen
anionsanions. .
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That means silicates are salts That means silicates are salts
containing metallic cations that containing metallic cations that are are
needed to make neutral needed to make neutral arrangements. arrangements.
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Common Common
silicate silicate
anions are anions are
pictured on pictured on
the right.the right.
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When silica is heated above its MP of When silica is heated above its MP of
about 1600about 1600C and cooled rapidly, an C and cooled rapidly, an
amorphous [“without shape”—not a amorphous [“without shape”—not a
crystal] solid forms. crystal] solid forms.
We call it glass. It’s really a We call it glass. It’s really a
supercooled, ultra viscous liquid with supercooled, ultra viscous liquid with
a great deal of disorder. a great deal of disorder.
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At left, At left,
a) is quartz, while a) is quartz, while
b) is quartz glass. b) is quartz glass.
These pictures These pictures are are
2-D, not 3-D.2-D, not 3-D.
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Common glass results when Common glass results when NaNa22COCO33
is added to the silica melt.is added to the silica melt.
Pyrex®, a borosilicate glass [lab Pyrex®, a borosilicate glass [lab
ware] is made when Bware] is made when B22OO33 is added is added
to the silica melt. to the silica melt.
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Eyeglasses are made from glass Eyeglasses are made from glass
that is especially hard so it can that is especially hard so it can be be
ground into precise shapes. ground into precise shapes.
KK22O has been added.O has been added.
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Read the sections in your book Read the sections in your book
about ceramics and about ceramics and semiconductors! semiconductors!
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Molecular SolidsMolecular Solids
Simply where a molecule occupies Simply where a molecule occupies
the lattice position rather than an the lattice position rather than an
atom. atom.
Ice & dry ice [solid carbon dioxide] Ice & dry ice [solid carbon dioxide]
are examples. are examples.
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Allotropes of sulfur and Allotropes of sulfur and
phosphorous are included. phosphorous are included.
SS88 or P or P44 occupy the lattice positions occupy the lattice positions
in these allotropes [many forms] of in these allotropes [many forms] of
these elements. these elements.
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Characterized by strong Characterized by strong covalent covalent
bonding bonding withinwithin the molecule, the molecule, yet yet
weak forces weak forces betweenbetween the the
molecules.molecules.
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It takes 6 kJ of energy to melt one It takes 6 kJ of energy to melt one
mole of solid water since you only mole of solid water since you only
have to overcome H-bonding while have to overcome H-bonding while
it takes 470 kJ of energy to break it takes 470 kJ of energy to break
one mole of O—H bonds.one mole of O—H bonds.
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Molecules such as COMolecules such as CO22, I, I22, P, P44, and , and
SS88 have no dipole moment. have no dipole moment.
We call their IMF’s:We call their IMF’s:
London Dispersion ForcesLondon Dispersion Forces
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As the size of the molecule As the size of the molecule increases increases
[often reported in a Chem I book as [often reported in a Chem I book as
““increased MM”], the London increased MM”], the London
dispersion forces increase because dispersion forces increase because
the larger the molecule, the more the larger the molecule, the more
electrons, the more polarizable its electrons, the more polarizable its
electron cloudelectron cloud..
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If it is more polarizable, If it is more polarizable, temporary temporary
dipoles can easily form which dipoles can easily form which shifts shifts
the IMF’s from weak London the IMF’s from weak London
dispersion to a weak form of dispersion to a weak form of
induced dipole-induced dipole.induced dipole-induced dipole.
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So What?So What?
The MP and BP increase since The MP and BP increase since the the
molecules are MORE attracted molecules are MORE attracted to to
each other as a result of this each other as a result of this
polarizing of the electron cloud. polarizing of the electron cloud.
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When molecules When molecules
DO have dipole DO have dipole
moments, their moments, their
IMF’s are IMF’s are greater, greater,
especially if H-especially if H-
bonding is bonding is
present. It’s like present. It’s like
an added bonus.an added bonus.
Bonded H
H-bond, an IMF
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Ionic SolidsIonic Solids
Stable, high-melting substances Stable, high-melting substances
held together by STRONG held together by STRONG
electrostatic forces that exist electrostatic forces that exist
between oppositely charged between oppositely charged ions.ions.
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Exercise 4 Exercise 4 Types of Solids Types of SolidsUsing Table 10.7, classify each of the Using Table 10.7, classify each of the
following substances according to the following substances according to the
type of solid it forms.type of solid it forms.
a. a. GoldGold
b. b. Carbon dioxideCarbon dioxide
c. c. Lithium fluorideLithium fluoride
d. d. Krypton Krypton
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SolutionSolution
A: atomic solid w/metallic propertiesA: atomic solid w/metallic properties
B: molecular solid B: molecular solid
C: binary ionic solid C: binary ionic solid
D: atomic solid w/ properties D: atomic solid w/ properties
characteristic of molecular solid characteristic of molecular solid
w/nonpolar moleculesw/nonpolar molecules
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VAPOR PRESSURE VAPOR PRESSURE AND AND
CHANGES OF STATECHANGES OF STATE
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Vaporization or Vaporization or EvaporationEvaporation
When molecules of a liquid can escape When molecules of a liquid can escape
the liquid’s surface and form a gas. the liquid’s surface and form a gas.
ENDOTHERMIC,ENDOTHERMIC, since energy must be since energy must be
absorbed so that the liquid molecules absorbed so that the liquid molecules
gain enough energy to escape the gain enough energy to escape the
surface and thus overcome the liquid’s surface and thus overcome the liquid’s
IMFs.IMFs.
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HHvap vap -- Enthalpy of Enthalpy of VaporizationVaporization
The energy required to vaporize The energy required to vaporize ONE ONE
mole of a liquid at 1 atm pressure.mole of a liquid at 1 atm pressure.
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Water’s heat of vaporization is 40.7 Water’s heat of vaporization is 40.7
kJ/mol. kJ/mol.
This is huge! This is huge!
Water makes life on this planet Water makes life on this planet
possible since it acts as a coolant. possible since it acts as a coolant.
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The reason it’s The reason it’s HHvapvap is so large is so large
has everything to do with has everything to do with hydrogen hydrogen
bonding. bonding.
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The IMFs in water are huge, thus a The IMFs in water are huge, thus a
great deal of the sun’s energy is great deal of the sun’s energy is
needed to evaporate the rivers, needed to evaporate the rivers, lakes, lakes,
oceans, etc. of Earth. oceans, etc. of Earth.
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Perspiration is a coolant for Perspiration is a coolant for animals animals
possessing sweat glands. Energy possessing sweat glands. Energy
from your hot body is absorbed by from your hot body is absorbed by
the water solution to evaporate.the water solution to evaporate.
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CondensationCondensation
Opposite of vaporization. When the Opposite of vaporization. When the
energetic steam molecules energetic steam molecules generated generated
by your morning shower hurl by your morning shower hurl
themselves across the bathroom and themselves across the bathroom and
collide with the cold mirror, they lose collide with the cold mirror, they lose
energy and return to the liquid energy and return to the liquid
phase.phase.
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Equilibrium Vapor Equilibrium Vapor PressurePressureReached when the rate of Reached when the rate of
evaporation evaporation
equals the equals the
rate of rate of
condensation condensation
in a closed in a closed
container.container.
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Stopper a flask of a freshly poured Stopper a flask of a freshly poured liquid. liquid.
(a). Equilibrium VP (a). Equilibrium VP will be established. will be established.
(b).Moleucles leave (b).Moleucles leave and enter the liquid and enter the liquid phase @ the phase @ the SAME RATE.SAME RATE.
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(a) The VP of a (a) The VP of a
liquid can be liquid can be
measured easily measured easily
using using a using using a
simple simple barometer.barometer.
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(b) The three liquids water, ethanol, and (b) The three liquids water, ethanol, and
diethyl ether have quite different vapor diethyl ether have quite different vapor
pressures. Ether is by far the most volatile pressures. Ether is by far the most volatile
of the three [escapes easiest]. Note that of the three [escapes easiest]. Note that
in each case a little liquid remains (floating in each case a little liquid remains (floating
on the mercury).on the mercury).
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VolatileVolatile
Have high VP, thus low IMFs. These Have high VP, thus low IMFs. These liquids evaporate readily from open liquids evaporate readily from open containers since they have so little containers since they have so little attraction for each other. It takes attraction for each other. It takes
very very little energy being absorbed in order little energy being absorbed in order for them to escape the surface of the for them to escape the surface of the liquid. liquid.
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The heat energy absorbed from a The heat energy absorbed from a
warm room is usually enough to warm room is usually enough to make make
these substances evaporate these substances evaporate quickly. quickly.
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If there is an odor to the If there is an odor to the substance, substance,
these are the liquids you smell these are the liquids you smell
almost as soon as you open the almost as soon as you open the
bottle! The molecules have been bottle! The molecules have been
banging against the lid wanting banging against the lid wanting out!out!
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VP increases significantly with VP increases significantly with
temperature! temperature!
Heat ‘em up, Heat ‘em up,
Speed ‘em up, Speed ‘em up,
Move ‘em out! Move ‘em out!
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Increasing the temperature increases Increasing the temperature increases
the KE which facilitates escape AND the KE which facilitates escape AND
the speed of the escapees! They the speed of the escapees! They
bang into the sides of the container bang into the sides of the container
with more frequency [more of them with more frequency [more of them
escape] and more energy [more escape] and more energy [more
momentum].momentum].
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More molecules can attain the More molecules can attain the
energy needed to overcome the energy needed to overcome the
IMFs in a liquid at a higher T since IMFs in a liquid at a higher T since
the KE increases.the KE increases.
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In General, as MM In General, as MM VP VP
BECAUSE, as molecules increase BECAUSE, as molecules increase in in
molar mass, they also increase in molar mass, they also increase in the the
number of electrons. number of electrons.
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As the number of electrons increase, As the number of electrons increase,
the polarizability of the molecule the polarizability of the molecule
increases so more induced dipole-increases so more induced dipole-
induced dipole or dispersion forces induced dipole or dispersion forces
exist, causing stronger attractions to exist, causing stronger attractions to
form form betweenbetween molecules. This molecules. This
decreases the number of molecules decreases the number of molecules
that escape and thus lowers the VP. that escape and thus lowers the VP.
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H-bonding causes a major exception! H-bonding causes a major exception!
It’s presence greatly increases the It’s presence greatly increases the
IMFs of the liquid. IMFs of the liquid.
Water has an incredibly low VP for Water has an incredibly low VP for
such a light [MM = 18.02] molecule.such a light [MM = 18.02] molecule.
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We can put the math to this. We can put the math to this.
Plot ln VP vs. 1/T [in Kelvins] and Plot ln VP vs. 1/T [in Kelvins] and we we
get a straight line. get a straight line.
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Next, put this into y = mx + b Next, put this into y = mx + b
format:format:
CTR
HVP vap
1
ln
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R is the universal gas constant. R is the universal gas constant.
Since this is all about energy, use Since this is all about energy, use
the “energy” R, 8.31 J/K.the “energy” R, 8.31 J/K.
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C is a constant characteristic C is a constant characteristic of of
the liquid [y-intercept].the liquid [y-intercept].
slope, m = slope, m = R
H vap
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Exercise 5Exercise 5 Determining Determining Enthalpies of VaporizationEnthalpies of Vaporization
Using the plots Using the plots
shown, determine shown, determine
whether water or whether water or
diethyl ether has diethyl ether has
the larger the larger enthalpy enthalpy
of vaporization.of vaporization.
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SolutionSolution
= water= water
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If we know the values of If we know the values of Hvap Hvap
and VP at one temperature we can and VP at one temperature we can
solve the above expression for the solve the above expression for the
constant, C, and set a second constant, C, and set a second
expression for T2 equal to the first expression for T2 equal to the first
since the value of C is NOT since the value of C is NOT
dependent upon temperature.dependent upon temperature.
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which can be rearranged intowhich can be rearranged into
22
11 lnln
RT
HVPC
RT
HVP vapvap
122
1 11ln
TTR
H
VP
VP vap
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This form is called the This form is called the
Clausius-Clapeyron Clausius-Clapeyron Equation.Equation.
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Exercise 6Exercise 6 Calculating Vapor PressureCalculating Vapor Pressure
The vapor pressure of water at 25°C is The vapor pressure of water at 25°C is
23.8 torr, and the heat of vaporization 23.8 torr, and the heat of vaporization
of water at 25°C is 43.9 kJ/mol. of water at 25°C is 43.9 kJ/mol.
Calculate the vapor pressure of water Calculate the vapor pressure of water
at 50°C.at 50°C.
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SolutionSolution
= 93.7 torr= 93.7 torr
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SublimationSublimation
Solids also have vapor Solids also have vapor
pressures. Some solids pressures. Some solids
go directly to the vapor go directly to the vapor
phase at 1atm, skipping phase at 1atm, skipping
the liquid phase all the liquid phase all
together! Iodine and dry ice together! Iodine and dry ice [solid [solid
carbon dioxide] both do this. carbon dioxide] both do this.
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Melting PointMelting Point
A heating curve A heating curve is pictured here. is pictured here. Molecules break Molecules break loose from lattice loose from lattice points and solid changes to liquid. points and solid changes to liquid. (Temperature is constant as (Temperature is constant as
melting melting occurs.) PE is changing like crazy occurs.) PE is changing like crazy while KE remains constant! while KE remains constant!
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HHfusfus, Enthalpy of Fusion, Enthalpy of Fusion
The enthalpy change that occurs at the The enthalpy change that occurs at the
melting point [which is the freezing melting point [which is the freezing
point, by the way]. This energy is point, by the way]. This energy is
clearly going into increasing the PE of clearly going into increasing the PE of
the molecules since the temperature or the molecules since the temperature or
average KE of the molecules is average KE of the molecules is
plateaued, or staying the same.plateaued, or staying the same.
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vapor pressure of solid vapor pressure of solid
= =
vapor pressure of liquid vapor pressure of liquid
[equilibrium is established][equilibrium is established]
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On the plateaus, calculate the E On the plateaus, calculate the E change using change using
q = q = HH[vap or fus][vap or fus]mm
On the slants, calculate the E On the slants, calculate the E change change
usingusingq = mcq = mcTT
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The melting and boiling points of water The melting and boiling points of water
are determined by the vapor pressures are determined by the vapor pressures
of the solid and liquid states.of the solid and liquid states.
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This figure shows VP of solid and This figure shows VP of solid and
liquid water as a function of liquid water as a function of
temperatures temperatures
near zero.near zero.
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Below zero—VP of ice has a larger Below zero—VP of ice has a larger
T-Dependence.T-Dependence.
This means the VP of ice increases This means the VP of ice increases
more rapidly than the liquid’s VP more rapidly than the liquid’s VP for for
each increase in temperature. each increase in temperature.
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A point is eventually reached A point is eventually reached where where
the the
VP solid = VP liquid.VP solid = VP liquid.
We call this temperature the MP!We call this temperature the MP!
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Normal Melting PointNormal Melting Point
The temperature at which the The temperature at which the
VP solid = VP liquid VP solid = VP liquid
AND AND
P total = 1atmP total = 1atm
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Normal Boiling PointNormal Boiling Point
The temperature at which theThe temperature at which the
VP liquid = exactly 1 atmVP liquid = exactly 1 atm
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FREAKSFREAKS
Changes of Changes of
state do not state do not
always always
form at the form at the
exact MP exact MP
and BP’s. and BP’s.
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SupercooledSupercooled
Oxymoron—the substance is at a Oxymoron—the substance is at a
temperature below its FP, yet it temperature below its FP, yet it
remains a liquid. Usually happens remains a liquid. Usually happens
when the cooling has been gradual when the cooling has been gradual
and the degree of organization and the degree of organization
needed to form crystals hasn’t needed to form crystals hasn’t
happened. happened.
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At some point, organization At some point, organization
happens and the solid is readily happens and the solid is readily
formed, the temperature rises formed, the temperature rises back back
to the MP as the heat of to the MP as the heat of
crystallization is released.crystallization is released.
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SuperheatedSuperheated
Another oxymoron—the substance Another oxymoron—the substance
is at a temperature above its BP, is at a temperature above its BP,
yet it remains a liquid. Usually yet it remains a liquid. Usually
happens when heated very rapidly happens when heated very rapidly
[microwave oven] and bubbles form [microwave oven] and bubbles form
in the interior with high internal in the interior with high internal
pressures.pressures.
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They often burst before reaching They often burst before reaching
the surface making quite a mess the surface making quite a mess of of
things! things!
Really ruins an experiment. Really ruins an experiment.
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This is called bumping in the lab. This is called bumping in the lab.
Prevent it by adding boiling chips to Prevent it by adding boiling chips to the the
flask. These chips are porous and flask. These chips are porous and
have air trapped in them, upon have air trapped in them, upon heating heating
tiny air bubbles form and act as tiny air bubbles form and act as
““starters” for vapor bubble formation.starters” for vapor bubble formation.
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PHASE DIAGRAMSPHASE DIAGRAMSClosed Systems Closed Systems
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Represents phases as a function of Represents phases as a function of
temperature and pressure.temperature and pressure.
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Critical TemperatureCritical Temperature
Temperature above which the Temperature above which the vapor vapor
cannot be liquefied.cannot be liquefied.
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Critical PressureCritical Pressure
Pressure required to liquefy AT the Pressure required to liquefy AT the
critical temperature.critical temperature.
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Critical PointCritical Point
Critical temperatue and pressure Critical temperatue and pressure
(for water, Tc = 374° C and 218 (for water, Tc = 374° C and 218 atm).atm).
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The solid-liquid line tilts to the left The solid-liquid line tilts to the left [negative slope] since it’s solid is [negative slope] since it’s solid is
lessless dense than it’s liquid phase—ice dense than it’s liquid phase—ice floats. floats.
Usually the solid sinks as it is more Usually the solid sinks as it is more dense.dense.
Water is a Freak!Water is a Freak!
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Consider the Consider the cylinder pictured cylinder pictured here.here.
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Experiment 1Experiment 1
P = 1atm. P = 1atm.
Completely filled with ONLY ice Completely filled with ONLY ice at at
-20-20C. C.
Heat…Heat…
-20 -20 0 only ice present at 0, ice 0 only ice present at 0, ice melts [no vapor]melts [no vapor]
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Past 0, liquid water begins to exert Past 0, liquid water begins to exert
a VP. a VP.
When the VP of the liquid reaches When the VP of the liquid reaches
1atm, vaporization occurs and 1atm, vaporization occurs and
steam is formed.steam is formed.
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Experiment 2Experiment 2
P = 2.0 torrP = 2.0 torr
Start again with only ice at - 20Start again with only ice at - 20C. C.
Heat…Heat…
As heating proceeds, -10 is reached As heating proceeds, -10 is reached
where ice changed directly to where ice changed directly to vapor. vapor.
It sublimes. It sublimes.
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No liquid water forms No liquid water forms becausebecause the the
VP of water is always greater than VP of water is always greater than
2.0 torr. If water were placed into 2.0 torr. If water were placed into
the cylinder at these conditions, it the cylinder at these conditions, it
would freeze if less than -10 or would freeze if less than -10 or
vaporize if greater than -10. vaporize if greater than -10.
Water cannot exist at these Water cannot exist at these conditions!conditions!
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Experiment 3Experiment 3
P = 4.588 torrP = 4.588 torr
Start again with only ice at -20Start again with only ice at -20C. C.
Heat…Heat…
No new phase results until the No new phase results until the
temperature reaches 0.0098temperature reaches 0.0098C. C.
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This is the triple point of water This is the triple point of water and and
all THREE phases exist in all THREE phases exist in
equilibrium at this set of P & T equilibrium at this set of P & T
conditions.conditions.
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Experiment 4Experiment 4
P = 225 atmP = 225 atm
Start this time with only liquid Start this time with only liquid water water
in the cylinder at 300in the cylinder at 300C. C.
Heat….Heat….
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The liquid water gradually changes The liquid water gradually changes
to vapor, but it goes through a to vapor, but it goes through a fluid fluid
state that was not present at any state that was not present at any of of
the other pressures and the other pressures and
temperatures. temperatures.
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This fluid region, is neither true This fluid region, is neither true liquid liquid
nor true vapor. This occurs when nor true vapor. This occurs when the the
critical point has been exceeded. critical point has been exceeded.
For water:For water:
CT = 374CT = 374C and CP = 218 C and CP = 218 atm.atm.
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What is the effect of pressure What is the effect of pressure on on
ice? ice?
It melts it.It melts it.
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You can take a block of ice, You can take a block of ice, connect connect
a wire to two heavy weights and a wire to two heavy weights and
drape it across the block. drape it across the block.
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The wire will exert pressure on the The wire will exert pressure on the
block, melt it and begin a journey block, melt it and begin a journey
downward through the block due to downward through the block due to
the force of gravity acting on the the force of gravity acting on the
weights. weights.
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The “cool” thing [pun intended] The “cool” thing [pun intended]
is that after the wire has left is that after the wire has left the the
surface, the block refreezes!surface, the block refreezes!
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Most substances have a solid-Most substances have a solid-
liquid line that has a positive liquid line that has a positive slope slope
since their solid since their solid
phase is more phase is more
dense than the dense than the
liquid. This one liquid. This one
is for carbon is for carbon
dioxide. dioxide.
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Each phase Each phase
boundary boundary
represents an represents an
equilibrium set equilibrium set
of pressure of pressure and and
temperature temperature
conditions!!conditions!!