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Figure 10.9
Chapter 10 | Slide 1 Copyright Houghton Mifflin Company. All rights reserved.
Body-Centered Cubic
2r
Face-Centered Cubic
4r 3
Concept Check
Determine the number of metal atoms in a unit cell if the packing is: a) Simple cubic b) Body centered cubic
2r 2
Chapter 10 | Slide 8
Concept Check
A metal crystallizes in a face-centered cubic structure. Determine the relationship between the radius of the metal atom and the length of an edge of the unit cell.
Problem
Polonium crystallizes in a simple cubic arrangement, with the edge of a unit cell having a length d=334pm. What is the radius (pm) of a polonium atom?
Chapter 10 | Slide 9
Calculate the density of Al if it crystallizes in a fcc and has a radius of 143 pm Given: Find: Concept Plan: Relationships: Solution:
face-centered cubic, r = 1.43 143 pm x 10-8 cm, m = 1.792 x 10-22 g 3 density, g/cm density, g/cm3
Problem
Silver metal crystallizes in face centered cubic arrangement with the edge of a unit cell having a length of d=407pm. What is the radius (pm) of a silver atom? What is the density of silver?
fcc
mass
l = 2r2
V = l3
m, V
102 m,
d = m/V 1 cm = 1 pm = 10-12 m V = l3, l = 2r 2 , d = m/V fcc = 4 atoms/uc, Al = 26.982 g/mol, 1 mol = 6.022 x 1023 atoms
-8 1 mol 26.982 g= 4.045 ! 10 l atoms = 2r Al 2" = 2(1.43 !10 "8 cm)(1.414) 4 " = 1.792 "10 ! 22 cm g 6.022 "10 23 atoms 1 mol m 1.792 !10 "22 g 3 !8 m 1 cmd = V = 6.618 V = l 3 = 4.045 "10-12 cm !10 " 23 cm 3 143 pm " " -2 = 1.43 "10 !8 cm ! 23 3 g = 6.618 "10 cm1 pm 10 m = 2.71 cm3
Check:
the accepted density of Al at 20C is 2.71 g/cm3, so the answer makes sense
Chapter 10 | Slide 12
Crystal Structures
Closest-Packed Structures First Layer with spheres, it is more efficient to offset each row in the gaps of the previous row than to line-up rows and columns
Closest-Packed Structures Second Layer the second layer atoms can sit directly over the atoms in the first called an AA pattern
Hexagonal Closest-Packed
Figure 10.14
Chapter 10 | Slide 17 Copyright Houghton Mifflin Company. All rights reserved.
Figure 10.15
Figure 10.16
Chapter 10 | Slide 19 Copyright Houghton Mifflin Company. All rights reserved.
Molecular Solids
the lattice site are occupied by molecules the molecules are held together by intermolecular attractive forces
dispersion forces, dipole-dipole attractions, and H-bonds (if it is able to)
Ionic Solids held together by attractions between opposite charges nondirectional therefore every cation attracts all anions around it, and vice versa the coordination number represents the number of close cation-anion interactions in the crystal the higher the coordination number, the more stable the solid lowers the potential energy of the solid
because the attractive forces are weak, they tend to have low melting point
generally < 300C
Ionic Solids
Lattice Holes
Tetrahedral Hole Octahedral Hole Simple Cubic Hole
Lattice Holes
in hexagonal closest packed or cubic closest packed lattices there are 8 tetrahedral holes and 4 octahedral holes per unit cell in simple cubic there is 1 hole per unit cell number and type of holes occupied determines formula (empirical) of salt
= Octahedral = Tetrahedral
Fluorite Structures
coordination number = 4 Ca2+ ions in a face-centered cubic arrangement of each corner Ca2+ inside the unit cell of each face Ca2+ inside the unit cell each F in holes between Ca2+ tetrahedral holes 1 whole in all the holes Ca:F = ( x 8) + ( x 6): (8 x 1) = 4:8 = 1:2, therefore the formula is CaF2
Atomic Solids
atomic solids are solids that contain atoms at the lattice points nonbonding atomic solids (Group 8A) are held together by London dispersion forces metallic atomic solids are held together by metallic bonds network covalent atomic solids are held together by covalent bonds
melting point varies mostly closest packed arrangements of the lattice points
cations
Metallic Bonding
metal atoms release their valence electrons metal cation islands fixed in a sea of mobile electrons
+ + + ee+ + + ee+ + + ee+ + + ee+ + + ee+ + + ee+ + + ee+ + + ee+ + +
Properties of Diamond
very high melting, ~3800C
need to overcome some covalent bonds
very rigid
due to the directionality of the covalent bonds
very hard
due to the strong covalent bonds holding the atoms in position used as abrasives
this effectively makes each crystal one giant molecule held together by covalent bonds
you can follow a path of covalent bonds from any atom to every other atom
Figure 10.12
Properties of Graphite
hexagonal crystals high melting, ~3800C need to overcome some covalent bonding slippery feel because there are only dispersion forces holding the sheets together, they can slide past each other glide planes lubricants electrical conductor parallel to sheets thermal insulator chemically very nonreactive
sp2
each C has 3 sigma and 1 pi bond
the sheets are then stacked and held together by dispersion forces
sheets are 341 pm apart
Silicates
Most common network covalent atomic solid ~90% of earths crust extended arrays of SiO
sometimes with Al substituted for Si aluminosilicates
tetrahedral
Quartz -SiO2
3-dimensional array of Si covalently bonded to 4 O melts at ~1600C very hard
10
Table 10.3
Chapter 10 | Slide 41
Chapter 10 | Slide 42
Band Theory
the structures of metals and covalent network solids result in every atoms orbitals being shared by the entire structure for large numbers of atoms, this results in a large number of molecular orbitals that have approximately the same energy, we call this an energy band
Figure 10.18
Chapter 10 | Slide 43
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Band Theory
when 2 atomic orbitals combine they produce both a bonding and an antibonding molecular orbital when many atomic orbitals combine they produce a band of bonding molecular orbitals and a band of antibonding molecular orbitals the band of bonding molecular orbitals is called the valence band the band of antibonding molecular orbitals is called the conduction band
Figure 10.20
Chapter 10 | Slide 46 Copyright Houghton Mifflin Company. All rights reserved.
Band Gap
at absolute zero, all the electrons will occupy the valence band as the temperature rises, some of the electrons may acquire enough energy to jump to the conduction band the difference in energy between the valence band and conduction band is called the band gap
the larger the band gap, the fewer electrons there are with enough energy to make the jump
if the band gap is small, then a significant number of the electrons will be in the conduction band at normal temperatures and the material will be a semiconductor
graphite the conductivity of a semiconductor increases with temperature
if the band gap is large, then effectively no electrons will be in the conduction band at normal temperatures and the material will be an insulator
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Doping Semiconductors
doping is adding impurities to the semiconductors crystal to increase its conductivity goal is to increase the number of electrons in the conduction band n-type semiconductors do not have enough electrons themselves to add to the conduction band, so they are doped by adding electron rich impurities p-type semiconductors are doped with an electron deficient impurity, resulting in electron holes in the valence band. Electrons can jump between these holes in the valence band, allowing conduction of electricity
Diodes
when a p-type semiconductor adjoins an ntype semiconductor, the result is an p-n junction electricity can flow across the p-n junction in only one direction this is called a diode this also allows the accumulation of electrical energy called an amplifier
Metal Alloys
Substitutional Alloy some of the host metal atoms are replaced by other metal atoms of similar size Interstitial Alloy some of the holes in the closest packed metal structure are occupied by small atoms
Figure 10.21
Chapter 10 | Slide 51 Copyright Houghton Mifflin Company. All rights reserved. Chapter 10 | Slide 52 Copyright Houghton Mifflin Company. All rights reserved.
13
Vaporization
molecules in the liquid are constantly in motion the average kinetic energy is proportional to the temperature however, some molecules have more kinetic energy than the average if these molecules are at the surface, they may have enough energy to overcome the attractive forces the larger the surface area, the faster the rate of evaporation this will allow them to escape the liquid and become a vapor
53
Figure 10.41
54
Condensation
some molecules of the vapor will lose energy through molecular collisions the result will be that some of the molecules will get captured back into the liquid when they collide with it also some may stick and gather together to form droplets of liquid
particularly on surrounding surfaces
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Energetics of Vaporization
when the high energy molecules are lost from the liquid, it lowers the average kinetic energy if energy is not drawn back into the liquid, its temperature will decrease therefore, vaporization is an endothermic process
and condensation is an exothermic process
57
58
Heat of Vaporization
the amount of heat energy required to vaporize one mole of the liquid is called the Heat of Vaporization, Hvap
sometimes called the enthalpy of vaporization
Calculate the mass of water that can be vaporized with 155 kJ of heat at 100C
Given: Find: Concept Plan: kJ Relationships: 1 mol H2O = 40.7 kJ 1 mol = 18.02 g 155 kJ g H2O
1 mol 40.7 kJ
18.02 g 1 mol
mol H2O
g H2O
Examples; Hvap of water = 44.0kJ/mol Hvap of isopropanol = 45.4kJ/mol Hvap of acetone = 29.1kJ/mol
Solution:
155 kJ !
Check:
since the given amount of heat is almost 4x the Hvap, the amount of water makes sense
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Dynamic Equilibrium
once the rates of vaporization and condensation are equal, the total amount of vapor and liquid will not change evaporation and condensation are still occurring, but because they are opposite processes, there is no net gain or loss or either vapor or liquid when two opposite processes reach the same rate we call it a dynamic equilibrium
this does not mean there are equal amounts of vapor and liquid it means that they are changing by equal amounts
Figure 10.39
61 Chapter 10 | Slide 62 Copyright Houghton Mifflin Company. All rights reserved.
Dynamic Equilibrium
Vapor Pressure
the pressure exerted by the vapor at equilibrium is called the vapor pressure the weaker the attractive forces between the molecules, the more molecules will be in the vapor therefore, the weaker the attractive forces, the higher the vapor pressure the higher the vapor pressure, the more volatile the liquid
Figure 10.38
63
64
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Vapor Pressure
Dynamic Equilibrium
a system can respond to changes in the conditions while at equilibrium the system shifts its position to relieve or reduce the effects of the change
Figure 10.40
Chapter 10 | Slide 65
66
Figure 10.42
67 Chapter 10 | Slide 68 Copyright Houghton Mifflin Company. All rights reserved.
17
Boiling Point
when the temperature of a liquid reaches a point where its vapor pressure is the same as the external pressure then bubbles form (not just at the surface) called boiling and the temperature required to have the vapor pressure = external pressure is the boiling point
Boiling Point
the normal boiling point is the temperature at which the vapor pressure of the liquid = 1 atm the lower the external pressure, the lower the boiling point of the liquid
69
70
Concept Check
What is the vapor pressure of water at 100C? How do you know?
Superheating
Liquid can be heated to a temperature higher than its boiling point without actually boiling Surface tension suppresses the formation of bubbles
Chapter 10 | Slide 71
Chapter 10 | Slide 72
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Clausius-Clapeyron Equation
the graph of vapor pressure vs. temperature is an exponential growth curve
Clausius-Clapeyron Equation
the logarithm of the vapor pressure vs. inverse absolute temperature is a linear function
) (H ' $ ln(Pvap ) = ln% ! e RT " % " & # ) (H ' $ ln(Pvap ) = ln ( ! ) + ln% e RT " % " & # ' ) (H vap $ % " ln(Pvap ) = ln ( ! ) + % " & RT # ' ) (H vap $ 1 ln(Pvap ) = % % R " " T + ln ( ! ) & #
vap vap
" !H vap
Pvap = # e
RT
Figure 10.42
73 74
Figure 10.42
Clausius-Clapeyron Equation
if you know the heat of vaporization and the vapor pressure at one temp, then we can calculate the vapor pressure at another temp
remember: the vapor pressure at the normal boiling point is 760 torr
ln) = constant C (H vap (H vap ln(P1 ) + = C = ln(P2 ) + RT1 RT2 ln(P1 ) ' ln(P2 ) = (H vap 1 1 ( ' ) R1 T2 T1
P2
Relationships:
!
torr K %1 %% +( "J=760 % 2.31 1 % " T1"= 64.6 273.15 H vap mol " P P 1 "337.8 35,200 1 1= e = 10.090 1P 1 ln$ = 2.31 $ '= ln 2 ln = $ P) ' $ ' $ '( 337.8 K ' J T2 = 12.0 273.15 = 285.2 K P22 & & P 285.2 K R mol#K T T1 P# torr # P#2 & & +8.314 & 22= 75.3
Check:
! ! !
the units are correct, the size makes sense since the vapor pressure is lower at lower temperatures
19
Melting = Fusion
as a solid is heated, its temperature rises and the molecules vibrate more vigorously once the temperature reaches the melting point, the molecules have sufficient energy to overcome some of the attractions that hold them in position and the solid melts (or fuses) melting is an endothermic process the opposite of melting is freezing
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78
Heat of Fusion
the amount of heat energy required to melt one mole of the solid is called the Heat of Fusion, Hfus
sometimes called the enthalpy of fusion
Concept Check
Which would you predict should be larger for a given substance: Hvap or Hfus? Explain why.
always endothermic, therefore Hfus is + generally much less than Hvap Hsublimation = Hfusion + Hvaporization
79
Chapter 10 | Slide 80
20
Pressure
A convenient way of representing the phases of a substance as a function of temperature and pressure: Triple point (temperature/pressure condition where all
three states exist simultaneously curve)
freezing
Solid
normal melting pt.
Sublimation Curve
Liquid
normal boiling pt.
Critical point (furthest point on the vapor pressure for most substances, freezing point increases as pressure increases
Gas Temperature
Chapter 10 | Slide 81
82
Ice
Pressure
Water
Ice
Water
normal melting pt. 0C normal boiling pt. 100C
1 atm
Steam
Steam
83
Temperature
84
Temperature
21
Pressure
Solid
Liquid
triple point
Gas
1 atm
85
Temperature
Supercritical Fluid
as a liquid is heated in a sealed container, more vapor collects causing the pressure inside the container to rise and the density of the vapor to increase and the density of the liquid to decrease at some temperature, the meniscus between the liquid and vapor disappears and the states commingle to form a supercritical fluid supercritical fluid have properties of both gas and liquid states
Considering the following phase diagram for UF6, which of the following conditions is true?
A. B. C. D. At 1 atm, UF6 boils. UF6 melts at 1 atm. At 1 atm, UF6 sublimes. UF6 does not boil until it reaches the critical temperature. P (atm) Solid Liquid
Temp (F)
87
22
Considering the following phase diagram for UF6, which of the following conditions is true?
A. B. C. D. At 1 atm, UF6 boils. UF6 melts at 1 atm. At 1 atm, UF6 sublimes. UF6 does not boil until it reaches the critical temperature. P (atm) Solid
Concept Check
As intermolecular forces increase, what happens to each of the following? Why? Boiling point Viscosity Surface tension Enthalpy of fusion Freezing point Vapor pressure Heat of vaporization
Temp (F)
Chapter 10 | Slide 90 Copyright Houghton Mifflin Company. All rights reserved.
Practice Problem
Oxygen has a Tt = 54.3K, Pt = 1.14mm Hg, T c = 154.6K and Pc = 49.77atm. The density of the liquid is 1.14/cm3, and the density of the solid is 1.33g/cm3 . (small t stands for triple point and c for critical point) A) Sketch a phase diagram (pressure (atm) versus temp (C )) for oxygen, and label all the points of interest. B) Using the phase diagram that you drew, tell what the physical state is under the following conditions: i) ii) T = - 210C, P = 1.5atm T = -100C, P = 66atm
C) On your phase diagram above, trace a path starting from 0.0011atm and -225C. First, increase P to 35atm while keeping the T constant. Next, increase T to -150 C while keeping P constant. Then, decrease P to 1.0atm while keeping T constant. Finally, decrease T to -215 C while keeping P constant. What is your starting phase and what is your final phase?
Chapter 10 | Slide 91 Copyright Houghton Mifflin Company. All rights reserved.
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