chapter 10 liquids and solids
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Chapter 10 Chapter 10 Liquids and SolidsLiquids and Solids
TopicsTopics Intermolecular forcesIntermolecular forces
– Dipole-dipole forcesDipole-dipole forces Hydrogen bondingHydrogen bonding
– London ForcesLondon Forces The liquid stateThe liquid state
– Surface tensionSurface tension– Capillary actionCapillary action– ViscosityViscosity
An introduction to structures and types of solidsAn introduction to structures and types of solids– X-ray analysis of solidsX-ray analysis of solids– Types of crystalline solidsTypes of crystalline solids
Structure and bonding in metalsStructure and bonding in metals– Bonding metals for metals Bonding metals for metals – Meta alloysMeta alloys
Molecular solidsMolecular solids Ionic solidsIonic solids Vapor pressure and changes of stateVapor pressure and changes of state Phase diagramsPhase diagrams
10.510.5 Section is self studySection is self study
Intra- vs. Inter-molecular forcesIntra- vs. Inter-molecular forces
intramolecular forcesintramolecular forces– inside molecules (bonding)inside molecules (bonding)– hold atoms together into moleculehold atoms together into molecule
intermolecular forcesintermolecular forces– These are what hold the molecules together in the
condensed states.– Forces between moleculesForces between molecules– They get weaker as phase changes from S – L – GThey get weaker as phase changes from S – L – G
When a substance changes state, molecule stays together When a substance changes state, molecule stays together but intermolecular forces are but intermolecular forces are weakenedweakened
10.1 Intermolecular Forces10.1 Intermolecular Forces
Intermolecular ForcesIntermolecular Forces
GasesGases – fill container, random rapid motion, never coming to rest or clumping together• Motion is mainly translational
LiquidsLiquids – fixed volume, flow and assume shape of container, only slightly compressible, stronger forces hold molecules together• Motion is mainly translationalMotion is mainly translational
Solids – fixed volume, definite shape, generally less compressible than liquids, forces hold particles in a fixed shape
• Motion is mainly vibrational
Intermolecular Forces
Intermolecular forces are attractive forces between molecules
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)
Generally, intermolecular forces are much weaker than intramolecular forces.
“Measure” of intermolecular force
boiling point
melting point
Hvap
Hfus
Hsub
Dipole – Dipole Foces
Molecules that line up in the presence of a electric field are dipoles.
The opposite ends of the dipole can attract each other so the molecules stay close together.
1% as strong as covalent bonds Weaker the covalent bonds with greater distance. Small role in gases. Molecules with these forces possess higher
melting points and boiling points than nonpolar molecules of comparable molar mass
The strengths of intermolecular forcesintermolecular forces are generally weaker than either ionic or covalent bonds.
16 kJ/mol (to separate molecules)
431 kJ/mol (to break bond)
++-
-
Polar molecules have dipole-dipole attractions for one another.
Types of intermolecular forces (between neutral moleculesthat posses dipole moment):
Dipole-dipole forces: (polar molecules)
SO O.. ::
....
:
+
--
..:
..
--
SO O:
..:
+
dipole-dipole attraction
What effect does this attraction have on the boiling point?
Nonpolar PolarMolecule MM BP Molecule MM BP
N2 28 -196 CO 28 -192
SiH4 32 -112 PH3 34 -88
GeH4 77 -90 AsH3 78 -62
Br2 160 69 ICl 162 97
Effect of polarity on boiling points
• Effect of polarity is usually small enough to be obscured by differences in molar mass
HCl -85BP (oC)
HBr -60
HI -30
BP increase although polarity decreases
Hydrogen BondsHydrogen Bonds
• A hydrogen bond is an intermolecular force in which a hydrogen atom covalently bonded to a nonmetal atom in one molecule is simultaneously attracted to a nonmetalnonmetal atom of a neighboring molecule
• The strongest hydrogen bonds are formed if the nonmetal
atoms are smallsmall and highly electronegativehighly electronegative – e.g., N, O, F
very strong type of dipole-dipole attractionvery strong type of dipole-dipole attraction–because bond is so polarbecause bond is so polar–because atoms are so smallbecause atoms are so small
Hydrogen bondHydrogen bond
Cl(HCl)Cl(HCl) and and S(HS(H22S)S) do not form hydrogen do not form hydrogen
bonding although they have bonding although they have electronegativity similar to N, why? electronegativity similar to N, why? – They are of bigger size to approach the They are of bigger size to approach the
hydrogen atomhydrogen atom
Hydrogen bond is 5-10% as strong as the Hydrogen bond is 5-10% as strong as the covalent bondcovalent bond
Hydrogen bonding is a weak to moderate attractive force that exists between a hydrogen atom covalently bonded to a very small and highly electronegative atom
and a lone pair of electrons on another small, electronegative atom (F, O, or N).
Hydrogen bonding: It is very strong dipole-dipole interaction (bonds involving H-F, H-O, and H-N are most important cases).
+H-F- --- +H-F-
Hydrogen bonding
Hydrogen bonding between water molecules
WaterWater
+
-
+
Hydrogen BondingHydrogen Bonding
• Bonding between hydrogen and more electronegative neighboring atoms such as oxygen and nitrogen
Hydrogen bonding between ammonia and water
Examples of hydrogen bond
The hydrogen bond is a special dipole-dipole interaction between the hydrogen atom in a polar N-H, O-H, or F-H bond and an electronegative O, N, or F atom. IT IS NOT A BOND.
A H…B A H…Aor
A & B are N, O, or F
Hydrogen Bonding EffectsHydrogen Bonding Effects
• Solid water is less dense than liquid water due to hydrogen bonding
• Hydrogen bonding is also the reason for the unusually high boiling point of water
The larger the molecule the larger the Van der Waals attraction due to more electrons in the molecule.
The stronger the attraction, the higher the boiling point.
Boiling Points for Some Non Polar MoleculesBoiling Points for Some Non Polar Molecules
CH4
SiH4
GeH4SnH4
PH3
NH3 SbH3
AsH3
H2O
H2SH2Se
H2Te
HF
HI
HBrHCl
Boilin
g Poin
ts
0ºC
100
-100
200Molar massMolar mass
Hydrogen Bonding in other moleculesHydrogen Bonding in other molecules
Many organic acids can form dimers due to hydrogen bonding
Certain organic molecules can also form an intramolecular hydrogen bond
Ethanol shows hydrogen bonding
O
H
CH3 C O H
H
H CH2 CH3
Do these compounds show hydrogen bonding?
A. NH
H
N
H
H (Hydrazine)
B. CH3 C CH3
O
(Acetone)
C. CH3 O CH3 (dimethyl ether)
Do these compounds show hydrogen bonding?
Hydrogen bonding and solubilityHydrogen bonding and solubility
Some compounds containing O, N & F show Some compounds containing O, N & F show
high solubilities in certain hydrogen high solubilities in certain hydrogen containing solvents.containing solvents.
NHNH33 & CH & CH33OH dissolves in HOH dissolves in H22O through the O through the
formation of H-bondsformation of H-bonds
N
H
H
H
OH
H
CH
H
H
O
H
OH
H
London Dispersion ForcesLondon Dispersion Forces
Non - polar molecules also exert forces on Non - polar molecules also exert forces on each other.each other.
Otherwise, no solids or liquids.Otherwise, no solids or liquids. Electrons are not evenly distributed at Electrons are not evenly distributed at
every instant in time.every instant in time. Have an instantaneous dipole.Have an instantaneous dipole. Induces a dipole in the atom next to it.Induces a dipole in the atom next to it. Induced dipole- induced dipole interaction.Induced dipole- induced dipole interaction.
London Dispersion ForcesLondon Dispersion Forces
The temporary separations of The temporary separations of charge that lead to the London charge that lead to the London force attractions are what attract force attractions are what attract one one nonpolar nonpolar molecule to its molecule to its neighbors.neighbors.
Fritz London Fritz London 1900-19541900-1954
London forces increase with London forces increase with the size of the molecules.the size of the molecules.
London Dispersion ForcesLondon Dispersion Forces
They exist in every molecular They exist in every molecular compoundcompound
They are significant only for nonpolar They are significant only for nonpolar molecules and noble gas atomsmolecules and noble gas atoms
They are weak, short-livedThey are weak, short-lived Caused by formation of temporary Caused by formation of temporary
dipole moments dipole moments
Instantaneous polarization causes instantaneous dipole
“Electrons are shifted to overload one side of an atom or molecule”.
+ +- -
attraction
London Dispersion ForcesLondon Dispersion Forces
- Relatively weakRelatively weak forces that exist among forces that exist among noble gas atoms and nonpolar moleculesnoble gas atoms and nonpolar molecules. . ((Ar, CAr, C88HH1818))
- Caused by Caused by instantaneous dipoleinstantaneous dipole, in which , in which electron distribution becomes asymmetricalelectron distribution becomes asymmetrical..
- The ease with which electron “cloud” of an The ease with which electron “cloud” of an atom can be distorted is called atom can be distorted is called polarizabilitypolarizability..
Polarizability: the ease with which an atom or molecule can be distorted to have an instantaneous dipole. “squashiness”
In general big moleculesare more easily polarized
than little ones.
Intermolecular Forces
Polarizability
Polarizability is the ease with which the electron distribution in the atom or molecule can be distorted.
Polarizability increases with:
• greater number of electrons
• more diffuse electron cloud
Dispersion forces usually increase with molar mass.
London Dispersion ForcesLondon Dispersion Forces
Weak, short lived.Weak, short lived. Lasts longer at low temperature.Lasts longer at low temperature. Eventually long enough to make liquids.Eventually long enough to make liquids. More electrons, more polarizable.More electrons, more polarizable. Bigger molecules, higher melting and Bigger molecules, higher melting and
boiling points.boiling points. Much, much weaker than other forces.Much, much weaker than other forces. Also called Also called Van der Waal’s forces..
RelativeRelative Magnitudes of ForcesMagnitudes of Forces
The types of bonding forces vary in their The types of bonding forces vary in their strength as measured by average bond strength as measured by average bond energy. energy.
Covalent bonds (400 kcal/mol)
Hydrogen bonding (12-16 kcal/mol )
Dipole-dipole interactions (2-0.5 kcal/mol)
London forces (less than 1 kcal/mol)
Strongest Weakest
Halogen Boiling Pt (K)
Noble Gas Boiling Pt (K)
F2 85.1 He 4.6
Cl2 238.6 Ne 27.3
Br2 332.0 Ar 87.5
I2 457.6 Kr 120.9
Which one(s) of the above are most polarizable?Hint: look at the relative sizes.
London Forces in HydrocarbonsLondon Forces in Hydrocarbons
PracticePractice
which has highest boiling pt?which has highest boiling pt?– HF, HCl, or HBr?HF, HCl, or HBr?
Identify the most important Identify the most important intermolecular forces :intermolecular forces :– BaSOBaSO44
– HH22SS
– XeXe
– CC22HH66
– PP44
– HH22OO
– CsICsI
ionic
dipole-dipole
H-bonding
London Dispersion
Which has stronger intermolecuar forcesWhich has stronger intermolecuar forces??
COCO22 or OCS or OCS
– COCO22: nonpolar so : nonpolar so
only LDonly LD– OCS: polar so OCS: polar so
dipole-dipoledipole-dipole
PFPF33 or PF or PF55
– PFPF33: polar so : polar so
dipole-dipoledipole-dipole
– PFPF55: nonpolar so : nonpolar so
only LDonly LD
SFSF22 or SF or SF66
– SFSF22: polar so : polar so
dipole-dipoledipole-dipole
– SFSF66: nonpolar so : nonpolar so
only LDonly LD
SOSO33 or SO or SO22
– SOSO33: nonpolar so : nonpolar so
LD onlyLD only
– SOSO22: polar so : polar so
dipol-dipoledipol-dipole
SO
O
What type(s) of intermolecular forces exist between each of the following molecules?
HBrHBr is a polar molecule: dipole-dipole forces. There are also dispersion forces between HBr molecules.
CH4
CH4 is nonpolar: dispersion forces.
SO2
SO2 is a polar molecule: dipole-dipole forces. There are also dispersion forces between SO2 molecules.
11.2
10.210.2 The Liquid stateThe Liquid state
Properties of LiquidsProperties of LiquidsLow compressibilityLow compressibilityLack of rigidityLack of rigidityHigh density compared to gasesHigh density compared to gasesBeading (beads up as droplets) Beading (beads up as droplets) Surface tensionSurface tensionCapillary actionCapillary actionViscosityViscosity
Stronger intermolecular forces cause Stronger intermolecular forces cause each of these to increase.each of these to increase.
Surface tensionSurface tension
The resistance to an The resistance to an increase in its surface increase in its surface areaarea
Polar molecules and Polar molecules and liquid metalsliquid metals
show high surfaceshow high surface
tensiontension
Surface tensionSurface tension
Molecules in Molecules in the middle are the middle are attracted in all attracted in all directions.directions.
Molecules at the the top are only pulled inside.
Minimizes surface area.
Surface TensionSurface Tension
One water molecule One water molecule can hydrogen bond can hydrogen bond to another because to another because of this electrostatic of this electrostatic attraction.attraction.
Also, hydrogen Also, hydrogen bonding occurs with bonding occurs with other molecules other molecules surrounding them on surrounding them on all sides.all sides.
H HO
+
+
-
H HO
+
-
+
Surface TensionSurface Tension
A water A water molecule in molecule in the the middlemiddle of a of a solution is solution is pulled in all pulled in all directions.directions.
Surface TensionSurface Tension This is This is NotNot true for true for
molecules at the molecules at the surfacesurface.. Molecules at the surface Molecules at the surface
are only pulled down and are only pulled down and to each side.to each side.
This holds the molecules This holds the molecules at the surface together at the surface together tightly.tightly.
This causes surface This causes surface tensiontension..
Surface tensionSurface tension
AllAll liquids have surface tension liquids have surface tension– water is just higher than most otherswater is just higher than most others
How can we decrease surface How can we decrease surface tension?tension?– Use a Use a surfactantsurfactant - - sursurface face actactive ive aagegentnt– Also called a wetting agent, like Also called a wetting agent, like
detergent or soapdetergent or soap– Interferes with hydrogen bondingInterferes with hydrogen bonding
BeadingBeading Water drops are Water drops are
roundedrounded, , because all because all molecules on the molecules on the edge are pulled edge are pulled to the middle- to the middle- not outward to not outward to the air!the air!
Adhesive forcesAdhesive forces are intermolecular forces between unlike molecules
Cohesive forcesCohesive forces are intermolecular forces between like molecules
BeadingBeading
If a polar substance is If a polar substance is placed on a non-polar placed on a non-polar surface. surface. – There are cohesive,There are cohesive,– But no adhesive forces.But no adhesive forces.
And Visa VersaAnd Visa Versa
Meniscus is the interface between a liquid and the air above it
Adhesion
attracted to glass
Cohesionattracted to each other
Capillary ActionCapillary Action
Capillary action results from
intermolecular interactions Liquids spontaneously rise in a narrow Liquids spontaneously rise in a narrow
tube.tube. Glass is polar.Glass is polar. It attracts water molecules (adhesive It attracts water molecules (adhesive
forces)forces)
Glass has polar Glass has polar molecules.molecules.
Glass can also Glass can also hydrogen bond.hydrogen bond.
This attracts the This attracts the water molecules.water molecules.
Some of the pull is Some of the pull is up a cylinderup a cylinder..
Water curves up along Water curves up along the side of glass.the side of glass.
This makes the This makes the meniscusmeniscus, as in a , as in a graduated cylindergraduated cylinder
Plastics are non-Plastics are non-wetting; no attractionwetting; no attraction
MeniscusMeniscus
In Glass In Plastic
ViscosityViscosity
Viscosity is a measure of a liquid’s resistance to flow
–strong inter molecular strong inter molecular forces forces highly viscous highly viscous–large, complex molecules large, complex molecules highly viscous highly viscous–Cyclohexane has a lower Cyclohexane has a lower viscosity than hexane.viscosity than hexane.–Because it is a circle- Because it is a circle- more compact.more compact.
ModelModel
Can’t see molecules so picture them as-Can’t see molecules so picture them as- In motion but attracted to each otherIn motion but attracted to each other With regions arranged like solids butWith regions arranged like solids but
– with higher disorder.with higher disorder.– with fewer holes than a gas.with fewer holes than a gas.– Highly dynamic, regions changing between Highly dynamic, regions changing between
types.types.
10.3 An introduction to structures 10.3 An introduction to structures and types of solidsand types of solids
Types of SolidsTypes of Solids
Crystalline SolidsCrystalline Solids: : highly regular three dimensional highly regular three dimensional arrangement of their components arrangement of their components [[table salt table salt ((NaClNaCl))]]
Amorphous solidsAmorphous solids: : considerable disorder in their considerable disorder in their structures structures ((glass: components are frozen in place glass: components are frozen in place before solidifying and achieving an ordered before solidifying and achieving an ordered arrangementarrangement))
The positions of components in a crystalline solid are The positions of components in a crystalline solid are usually represented by a lattice usually represented by a lattice
Crystalline solidsAmorphous solids
An amorphous solid does not possess a well-defined arrangement and long-range molecular order.
A glass is an optically transparent fusion product of inorganic materials that has cooled to a rigid state without crystallizing
Crystallinequartz (SiO2)
Non-crystallinequartz glass
Representation of Components Representation of Components in a Crystalline Solidin a Crystalline Solid
LatticeLattice: : A 3-dimensional system that describes the locations of components A 3-dimensional system that describes the locations of components ((atoms, ions, or moleculesatoms, ions, or molecules) ) that make up the unit cells of a substancethat make up the unit cells of a substance..Unit CellUnit Cell: The smallest repeating unit in the lattice: The smallest repeating unit in the lattice..There are ThreeThree common types of unit cells:
– simple cubicsimple cubic– bodybody--centered cubiccentered cubic– faceface--centered cubiccentered cubic
Crystal Structures - Crystal Structures - CubicCubic
a
aa
SimpleSimple Face-CenteredFace-Centered Body-CenteredBody-Centered
Unit CellsUnit Cells
The simple cubic cell is the simplest unit cell and has structural particles centered only at its corners
The body-centered cubic (bcc) structure has an additional structural particle at the center of the cube
TheThe face-centered face-centered cubic (fcc)cubic (fcc) structure structure has an additional has an additional structural particle at structural particle at the center of each the center of each faceface
Cubic
Unit cells in 3 dimensions
At lattice points:
•Atoms
•Molecules
•Ions
lattice points
The simple cubic cell is the simplest unit cell and has structural particles centered only at its corners
Body-Centered Cubic
Unit cells in 3 dimensions
The body-centered cubic
(bcc) structure has an additional structural particle at the center of the cube
Face-Centered CubicThe face-centered cubic (fcc) structure has an additional structural particle at the center of each face
• Sample is powdered• X-rays of single wavelength is used• Distance between planes of atoms in the crystal are calculated from the angles at which the rays are diffracted using Bragg equation
X-Ray analysis of solids
Spots from diffracted X-rays
Spot from incident beam
X-Ray analysis of solids
X-Ray diffraction
Extra distance traveled by lower ray = BC + CD = n = 2d sin
Reflection of X-rays from two layers of atoms
1st layer of atoms
2nd layer of atoms
n = 2d sin
Bragg Equation
n 2 = d sin
d = distance between atoms n = an integer = wavelength of the x-rays
X rays of wavelength 0.154 nm are diffracted from a crystal at an angle of 14.170. Assuming that n = 1, what is the distance (in pm) between layers in the crystal?
n = 2d sin n = 1 = 14.170
= 0.154 nm = 154 pm
d =n
2sin=
1 x 154 pm
2 x sin14.17= ____________
When silver crystallizes, it forms face-centered cubic cells. The unit cell edge length is 408.7 pm. Calculate the density of silver.
d = mV
V = a3 = (408.7 pm)3 = 6.78X107 pm3
___ atoms/unit cell in a face-centered cubic cell
m = 4 Ag atoms107.9 gmole Ag
x1 mole Ag
6.022 x 1023 atomsx = 1.79X10-22 g
d = mV
7.17 x 10-22 g6.83 x 10-23 cm3
= = 1.79X10-22 g / 6.78X107 pm3
= 2.6X10-30 g/pm3
Types of crystalline Solids Ionic solids (ionic compounds)
• Ions (held by electrostatic attraction) at point in lattice
• They conduct electric current when dissolved in water
Molecular solids (molecular compounds)• Molecules (held by: dispersion and/or dipole-dipole forces)
at each point in lattice. Ice is a molecular solid H2O atomic solids (metals, nonmetals, noble gases)
• Elements (C, B, Si) that are composed of atoms at lattice points. Three types:
• Metallic– metallic bond• Network – strong covalent bonding• Group 8A –London Dispersion Forces
atomic- network ionic molecular
Name type of solid Force(s) Melting Pt.(oC)
Boiling Pt.(oC)
Ne molecular -249 -246
H2S molecular -86 -61
H2O molecular 0 100
Mercury metallic -39 357
W metallic 3410 5660
CsCl ionic 645 1290
MgO ionic 2800 3600
Quartz (SiO2) covalent network 1610 2230
Diamond (C) covalent network 3550 4827
Types of Crystals
Ionic Crystals – Ion-Ion interactions are the strongest Lattice points occupied by cations and anions
• Held together by electrostatic attraction• Hard, brittle, high melting point• Poor conductor of heat and electricity
CsCl ZnS CaF2
Types of Crystals
Molecular Crystals• Lattice points occupied by molecules• Held together by intermolecular forces (dipole-dipole, and/or London dispersion forces• Soft, low melting point• Poor conductor of heat and electricity
Types of Crystals
Atomic solids/Network – Stronger than IM forces but generally weaker than ion-ion
• Lattice points occupied by atoms• Held together by covalent bonds• Hard, high melting point• Poor conductor of heat and electricity
diamond graphite
carbonatoms
Types of Crystals
Metallic Crystals – Typically weaker than covalent, but can be in the low end of covalent
• Lattice points occupied by metal atoms• Held together by metallic bonds• Soft to hard, low to high melting point• Good conductors of heat and electricity
11.6
Cross Section of a Metallic Crystal
nucleus &inner shell e-
mobile “sea”of e-
Types of Crystals
11.6
10.410.4 Structure and Bonding of MetalsStructure and Bonding of Metals Physical properties of metals Ionization energy E is small (outer electrons
move relatively free); this results in• High electrical conductivity• High thermal conductivity• They are
– Ductile: can be drawn oust into wires– Malleable: can be hammered into thin sheets
Electrons act like a glue holding atomic nuclei Crystals of nonmetals break into small pieces if it
is hammered (brittle) They have luster (reflect light) They form alloys
Metallic Crystals
Can be viewed as containing atoms (spheres) packed together in the closest arrangement possible
The spheres are packed in layers
Closest packing- when each sphere has 12 neighbors
• 6 on the same plane
• 3 in the plane above
• 3 in the plane below
Packing in Crystals
“Open” packing has larger voids in between particles compared to close-packed crystals
Closest packing in MetalsClosest packing in Metals
Closest packed structures
It has (aba) arrangements that occur when the spheres of the third layer occupy positions so that each sphere in the third layer lies directly over a sphere in the first layer
Hexagonal closest-packed (hcp) structure
Closest packed structures
It has (abc) arrangement that occurs when the spheres of the third layer occupy positions that NO sphere lies over one in the first layer
Cubic closest-packed (ccp) structure
An atom in every fourth layerlies over an atom in the First layer
Net number of spheres (atoms) in a unit cell, length of the edge of the cell, density of the closest packed solid
Face centered cubic cell Atoms occupy corners and centers of the faces Atoms at the corners do not touch each other Atoms contact is made at the face diagonal 74% of the space is occupied Ca, Sr, transition metals An atom at the center of the face of cube is
shared by another cube that touches that face. Only atom is assigned to a given cell An atom at the center of the cube is a part of 8-different cubes touching that point. Only cornenr atom belongs to the cell
2
1
8
1
Density of closest packed solid
# of spheres (atoms) per unit cell =
Density of closes packed solid
4)2
16(
8
18 XX
itcellvolumeofun
atomsmassofDensity
unitcellfatomsNetnumbero
deunitcellVolumeofth
rd
dr
)4(
4/
8
24
3
Body centered cubic cell Atoms contact along a body diagonal Atoms occupy the corners and one
at the center In a unit cell, 8 atoms occupy the
corners plus one in the center 68% of the space is occupied Available in Group I elements + Ba
Number of atoms assigned to each type of cell Simple cube
Body centered cube
Face centered cube
eatompercubsXcorneratom 18
18
atomsatomcenteratomsXcorner 2 18
1 8
atomscorner 42
1atomsX face6
8
1atomsX 8
1 atom/unit cell
(8 x 1/8 = 1)
2 atoms/unit cell
(8 x 1/8 + 1 = 2)
4 atoms/unit cell
(8 x 1/8 + 6 x 1/2 = 4)
Relationship between the atomic the radius and the edge length in different unit cells
When silver crystallizes, it forms face-centered cubic cells. The unit cell edge length is 408.7 pm. Calculate the density of silver.
d = mV
V = a3 = (408.7 pm)3 = __________________
___ atoms/unit cell in a face-centered cubic cell
m = 4 Ag atoms107.9 gmole Ag
x1 mole Ag
6.022 x 1023 atomsx = ___________
d = mV
7.17 x 10-22 g6.83 x 10-23 cm3
= = ___________________
12.4Compare Ex 12.3, p.384
Bonding models for Metals
Shape of pure metals con be changed but most metals have high melting points
Thus, bonding in most metals is strong and non-directional (although difficult to separate metal atoms, it is easy to move them provided they stay in contact of each other
The highest energy level for most metal atoms does not contain many electronsThese vacant overlapping orbitals allow outer electrons to move freely around the entire metalMetallic crystal is an array of positive ions (cations) in a sea of roaming valence electrons
Electron Sea Model
Metallic Bonding: “sea of e-’s”
Bonding models for Metals These roaming electrons
form a sea of electrons
around the metal atoms Malleability and ductility
• bonding is the same in
every direction• one layer of atoms can slide past
another without friction Conductivity of heat and electricity
• from the freedom of electrons (mobile electrons) to move around the atoms
Metallic bonding: Molecular orbital model for metals (Band model)
Electrons are assumed to travel around the metal crystal in molecular orbitals formed from the valence atomic orbitals of metal atoms
When many metal atoms interact in a crystal a large number of resulting molecular orbitals become more closely spaced and form a continuum of levels called bands
Metallic bonding: Molecular orbital model for metals (Band model)
1s
2s2p
3s
3pFilled Molecular Orbitals
Empty Molecular Orbitals
Magnesium Atoms
Filled Molecular OrbitalsEmpty Molecular Orbitals
The 1s, 2s, and 2p electrons are close to nucleus, so they are not able to move around (localized).
1s
2s2p
3s
3p
Magnesium Atoms
Filled Molecular OrbitalsEmpty Molecular Orbitals
1s
2s2p
3s
3p
Magnesium Atoms
The 3s and 3p orbitals overlap and form molecular orbitals.
Filled Molecular OrbitalsEmpty Molecular Orbitals
1s
2s2p
3s
3p
Magnesium Atoms
Electrons in these energy level can travel freely throughout the crystal.
Filled Molecular OrbitalsEmpty Molecular Orbitals
1s
2s2p
3s
3p
Magnesium Atoms
This makes metals conductors
Malleable because the bonds are flexible.
Metal Alloys An alloy is a mixture of elements and has metallic
properties substitutional alloy
• host metal atoms are replaced by other metal atoms
• happens when they have similar sizes interstitial alloy
• metal atoms occupy spaces created between host metal atoms
• happens when metal atoms have large difference in size
Examples
Brass
• substitutional
• 1/3 of Cu atoms replaced by Zn
Steel
• interstitial
• Fe with C atoms in between
• makes harder and less malleable
Metal AlloysMetal Alloys Substitutional AlloySubstitutional Alloy: :
some metal atoms some metal atoms replaced by others of replaced by others of similar size. similar size.
• brass = Cu/Zn brass = Cu/Zn •
Metal AlloysMetal Alloys(continued)(continued)
Interstitial AlloyInterstitial Alloy: : Interstices (holes) in Interstices (holes) in closest packed metal closest packed metal structure are occupied structure are occupied by small atoms. by small atoms.
• steel = iron + carbon steel = iron + carbon
10.6 Molecular solids. Molecules occupy the corners of the
lattices. Common examples: ice, dry CO2, S8, P4, I2
Different molecules have different forces between them (H-bonds, or dipole-dipole or London forces, or a combination of all these forces)
These forces depend on the size of the molecule.
They also depend on the strength and nature of dipole moments.
Molecular solids with nonpolar molecules (without dipoles): H2, CCl4
Most are gases at 25ºC. The only forces are London Dispersion
Forces. These depend on size of atom. Large molecules (such as I2 ) can be
solids even without dipoles.
Molecular solids with polar molecules (with dipoles): HCl, NH3
Dipole-dipole forces are generally stronger than L.D.F.
Hydrogen bonding is stronger than Dipole-dipole forces.
No matter how strong the intermolecular force, it is always much, much weaker than the forces in bonds.
Stronger forces lead to higher melting and freezing points.
Water is special Each molecule has two polar
O-H bonds. Each molecule has two lone
pair on its oxygen. Each oxygen can interact with
4 hydrogen atoms.
HO
H
Water is special
HO
H
HO
H
HO
H
This gives water an especially high melting and boiling point.
Examples of molecular solids
10.7 Ionic Solids They comprise the extremes in dipole dipole forces-
(ionic forces) Atoms are actually held together by electrostatic
attractions of opposite charges. They possess huge melting and boiling points. Atoms are locked in lattice so they are hard and
brittle. Every electron is accounted for so they are poor
conductors-good insulators.
In most of binary ionic compounds, larger ions are arranged in closest packing arrangement, hexagonal (hcp) or cubic (ccp) closest packing smaller ions fit in the holes created by the larger ions
Closest Closest Packing Packing
HolesHoles
The hole is formedby 3 spheres in the Same layer
The hole formed when a sphere occupies a dimple formed by three spheres in an adjacent layer
The holes formedbetween two sets of three spheres in adjoining layers of closest packed structure
Closest packing holesTetrahedral holes: are located above a sphere in the bottom layer
Octahedral holes: are located above a void in the bottom layer
Examples Trigonal holes are so small that they are never
occupied in binary ionic compounds The type of the hole whether tetrahedral or
octahedral depends mainly on• Relative sizes of cations and anions
In ZnS S2-, ions are arranged in ccp with the smaller Zn2+ ions in the tetrahedral holes
In NaCl, ions are arranged in ccp with Na+ ions in the octahedral holes.
Two Examples
Ionic Crystal Structures
Smaller cations can fill the voids between the larger anions
Tetrahedral hole filling occurs when the radii ratio is:
0.225 < rc/ra < 0.414Octahedral hole filling occurs when the radii ratio is:
0.414 < rc/ra < 0.732
The arrangement is cubic if rc/ra > 0.732
10 .7 Vapor Pressure and changes of state
vapor- gas phase above a substance gas phase above a substance that exists as solid or liquid at 25°C that exists as solid or liquid at 25°C and 1 atm.and 1 atm.
Vaporization or Evaporation - change from liquid to gas at or below change from liquid to gas at or below the boiling point . (Endothermic the boiling point . (Endothermic process)process)
Condensation is the change of a gas to a liquid (Exothermic process)
Heat or enthalpy of vaporization, ∆HHeat or enthalpy of vaporization, ∆Hvap vap ::
Energy required to vaporize 1 mole of a liquid at 1 atm
water has a large ∆Hvap (40.7 kJ/mol), (because of hydrogen bonding)
Molar Heats of Vaporization for Selected Liquids
Vapor pressure Initially, liquid in a closed container decreases as
molecules enter gaseous phase When equilibrium is reached, no more net change
occurs Rate of condensation and rate of vaporization
become equal Molecules still are changing phase but no
net change (Dynamic equilibrium)
• Gas liquid
Vapor pressure is independent of volumeindependent of volume of container as long as some liquid is present (liquid-vapor equilibrium)
Evaporation and condensation
H2O (l) H2O (g)
Rate ofcondensation
Rate ofevaporation=
Dynamic Equilibrium
Equilibrium vapor pressure or vapor pressure
It is the pressure exerted by the vapor when it is in dynamic equilibrium with a liquid at a constant temperature.
Vapor Pressure’s measurement
Liquid can be injected under inverted tube
part of the liquid evaporates to the top of tube
Pvap can be determined
by height of Hg
Patm = Pvap + PHg
The pressure of the vapor phase at equilibrium: Pvap
can be measured when using a simple barometer
Dish of Hg
Vacuum
Patm=
760 torr
A barometer will hold a column of
mercury 760 mm high at one atm
Dish of Hg
Vacuum
Patm= 760 torr
A barometer will hold a column ofmercury 760 mm high at one atm.
If we inject a volatile liquid in thebarometer it will rise to the top ofthe mercury.
Dish of Hg Patm= 760 torr
A barometer will hold a column of
mercury 760 mm high at one atm.
If we inject a volatile liquid in the
barometer it will rise to the top of
the mercury.
There it will vaporize and push the
column of mercury down.
Water
Dish of Hg
736 mm Hg
Water Vapor
The mercury is pushed down by the vapor pressure.
Patm = PHg + Pvap
Patm - PHg = Pvap
760 - 736 = 24 torr
Vapor pressure and nature of liquidsnature of liquids
Vapor pressure depends upon the nature nature of the liquidof the liquid
Liquids with high vapor P (volatile liquids)• liquids with a high vapor pressure• evaporate quickly• weak intermolecular forces
Liquids with low vapor P• Strong IMFs, London dispersion forces (large molar masses) or dipole-dipole
forces
Vapor pressure and temperature Vapor pressure increases with T More molecules have enough KE to
overcome IMFs
VAPOR PRESSURE CURVES
A liquid boils when its vapor pressure =‘s the external pressure.
Temperature Effect
Kinetic energy
# of
mol
ecu
les T1
Energy needed to overcome intermolecular forces in iquid
Kinetic energy
# of
mol
ecu
les T1T1
T2
At higher temperature more molecules have enough energy - higher vapor pressure.
Energy needed to overcome intermolecular forces in liquid
Molar heat of vaporization (Hvap) is the energy required to vaporize 1 mole of a liquid.
ln P = -Hvap
RT+ C
Clausius-Clapeyron Equation P = (equilibrium) vapor pressure
T = temperature (K)
R = gas constant (8.314 J/K•mol)
Vapor pressure and Temperature
Mathematical relationship
ln is the natural logarithm• ln = Log base e• e = Euler’s number an irrational number like
Hvap is the heat of vaporization in J/mol
12
vap
2T vap,
1Tvap,
T
1-
T
1
R
H =
P
Pln
R = 8.3145 J/K mol.
Mathematical relationship
12
vap
Tvap,
1Tvap,
T
1-
T
1
R
H =
P
Pln
2
Vapor Pressure for solids
Solids also have vapor pressure
Sublimination• solid gas directly
• Example: dry ice: CO2
heat of fusion (∆Hfus)
• enthalpy of fusion• enthalpy change at
melting point
Heating Curve
as energy is added, it is used to increase the T
when it reaches melting point, the energy added is used to change molecules from (s) to (l)
plot of T vs. time where plot of T vs. time where energy is added at constant energy is added at constant raterate
Changes of state
What happens when a solid is heated? The graph of temperature versus heat
applied is called a heating curve. The temperature a solid turns to a liquid is
the melting point. The energy required to accomplish this
change is called the Heat (or Enthalpy) of Fusion Hfus
-40
-20
0
20
40
60
80
100
120
140
0 40 120 220 760 800
Heating Curve for Water
IceWater and Ice
Water
Water and Steam Steam
mp
bp
Tem
p
Time (Heat added)
-40
-20
0
20
40
60
80
100
120
140
0 40 120 220 760 800
Heating Curve for Water
Heat of fusion
Heat of vaporization
Slope is Heat Capacity
Time (Heat added)
Tem
p
Hvap=2260 J/g
Hfus=334 J/g
Heating curve for 1 gram of water
Heating curve for 1 gram of water
Hfus=334 J/g
Specific Heat of ice = 2.09 J/g•K
Specific Heat of water = 4.184 J/g•K
Hvap=2260 J/g
Specific Ht. Steam = 1.84 J/g•K
Calculate the enthalpy change upon converting 1 mole of water from ice at -12oC to steam at 115oC.
solid-12oC
solid0oC
liquid0oC
liquid100oC
gas100oC
gas115oC
H1 + H2 + H3 + H4 + H5 = Htotal
Sp. Ht. + Hfusion + Sp. Ht. + HVaporization + Sp. Ht. = Htotal
Specific Heat of ice = 2.09 J/g•K
Hfus=334 J/g
Specific Heat of water = 4.184 J/g•K
Specific Ht. Steam = 1.84 J/g•K
Hvap=2260 J/g
Calculate the enthalpy change upon converting 1 mole of water from ice at -12oC to steam at 115oC.
solid-12oC
solid0oC
liquid0oC
liquid100oC
gas100oc
gas115oc
H1 + H2 + H3 + H4 + H5 = Htotal
Sp. Ht. + Hfusion + Sp. Ht. + HVaporization + Sp. Ht. = Htotal
Specific Heat of ice = 2.09 J/g•K
Hfus=334 J/g
Specific Heat of water = 4.184 J/g•K
Specific Ht. Steam = 1.84 J/g•K
Normal melting Point
Melting point is determined by the vapor pressure of the solid and the liquid.
Melting point is the temp at which
the vapor pressure of the solid = vapor pressure of the
liquid
where the total pressure is 1 atm.
Solid Water
Liquid Water
Water Vapor Vapor
Apparatus that allows solid and liquid water to interact only through the vapor state
Solid Water
Liquid Water
Water Vapor Vapor
A temp at which the vapor pressure of the solid is higher than that of the liquid the solid will release
molecules to achieve equilibrium.
Solid Water
Liquid Water
Water Vapor Vapor
While the molecules of water condense to a liquid to achieve equilibrium.
This can only happen if the temperature is above the melting point since solid is turning to liquid.
Solid Water
Liquid Water
Water Vapor Vapor
A temperature at which the vapor pressure of the solid is less than that of the liquid, the liquid will release
molecules to achieve equilibrium.
Solid Water
Liquid Water
Water Vapor Vapor
Solid Water
Liquid Water
Water Vapor Vapor
While the molecules of water condense to a solid.
The temperature must be below the melting point since the liquid is turning to a solid.
Solid Water
Liquid Water
Water Vapor Vapor
Temperature at which the vapor pressure of the solid and liquid are equal, the solid and liquid are vaporizing and condensing at the same rate. This is the Melting (freezing) point (Temp at which solid and vapor can coexist)
Solid Water
Liquid Water
Water Vapor Vapor
Normal Boiling Point Temp when vapor
pressure inside the bubbles equals 1 atm
If Pvap < 1 atm, no bubbles can form, there is too much pressure on surface
Normal Boiling Point Boiling occurs when the vapor pressure of
liquid becomes equal to the external pressure.
Normal boiling point is the temperature at which the vapor pressure of a liquid is exactly 1 atm pressure.
Super heating - Heating above the boiling point.
Supercooling - Cooling below the freezing point.
Exceptions
supercooling• Material can stay liquid
below melting point because doesn’t achieve level of organization needed to make solid
superheating• when heated too quickly,
liquid can be raised above boiling point
• causes “bumping”
• Changes of state do not always occur exactly at bp or bp
10.9 Phase Diagrams
A plot Representing phases of a substance in a closed system (no material escapes into the surroundings and no air is present) as a function of temperature and pressure.
Phase changesPhase changes
Gas and liquid areindistinguishable.
Critical temperatureand critical pressure
(all 3 phases exists here)
Phase Diagrams
fusion curve
triple point
critical point
vapor pressure curve
sublimation curve
Critical PointCritical Point
where if the T is increased, vapor where if the T is increased, vapor can’t be can’t be liquefied no matter what P is liquefied no matter what P is appliedapplied
at the end of liquid/gas lineat the end of liquid/gas line after this point, only after this point, only one fluid phaseone fluid phase
exists that is neither gas nor liquidexists that is neither gas nor liquid called called supercritical fluidsupercritical fluid
Critical temperatureCritical temperature
Temperature above which the vapor can Temperature above which the vapor can
not be liquefied. not be liquefied. Critical pressure Critical pressure
pressure required to liquefy gas pressure required to liquefy gas ATAT the the
critical temperature. critical temperature. Critical point Critical point
critical temperature and pressure (for critical temperature and pressure (for
water, water, TTcc = 374°C and 218 atm). = 374°C and 218 atm).
Phase diagram Phase diagram for Waterfor Water
Normal mp
No
rmal b
p
Critical tem
pWaterExpands uponfreezing
-ve slope of S/L boundaryline means that mp of icedecreases as the externalP increases
Phase Diagram for H2O
Most Most substances substances have a positive have a positive slope of slope of solid/liquid line solid/liquid line
because because solid is usually solid is usually more dense more dense than liquidthan liquidwater has a water has a negative slopenegative slope
Temperature
SolidLiquid
Gas
1 Atm
AA
BB
CCD
D D
Pre
ssur
e
D
SolidLiquid
Gas
Triple Point
Critical Point
Temperature
Pre
ssur
e
SolidLiquid
Gas
This is the phase diagram for water. The density of liquid water is higer than solid
water.
Temperature
Pre
ssur
e
Solid Liquid
Gas
1 Atm
This is the phase diagram for CO2
The solid is more dense than the liquid The solid sublimes at 1 atm.
Temperature
Pre
ssur
e
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