Phase Diagrams and structures
of Solids
Chapter Goals.
• Learn to use and answer questions using phase diagrams.
• Defining, determining and using unit cells and basic structures of crystalline solids.
• Relating these structures to ionic solids.
• Learning about network covalent atomic solids.
• Note: We will not cover x-ray crystallography, if you want to go into any sort of biological graduate field
please read this over and ask me questions as needed!
Phase Diagrams
Learning Outcomes
• Identify and create a phase diagram given the appropriate information.
• For a given region in a phase diagram, identify the state of matter present
• Identify which states are in equilibrium for a given line on a phase diagram.
• Define and identify the triple point.
Phase Diagram
• a map of the state or phase of a substance.
• any region between lines: a specific state is stable.
• any line: an equilibrium of two states is stable.
• triple point: all three states are in equilibrium.
• Critical point: above this a super critical fluid is present.
Example
Carbon Dioxide: • If a sample at -78.5 oC and 5.5 atm is heated, what transition(s)
occurs?
Critical Melting and then boiling
solid liquid Point
72.9
Pressure atm(not to scale)
• If a sample at -78.5 oC and 4.5 atm is heated, what transition(s)
occurs?
5.1 Triple
sublimation
Triple Point
Point
gas
0.9
-78.5 oC -56.7 oC 31oC
Temperature (not to scale)
Example
Carbon Dioxide:
• If a sample at -78.5 oC and 0.9 atm is placed under greater
Critical pressure, what transition(s) occurs?
solid liquid Point
72.9 deposition
Pressure atm(not to scale)
5.1 Triple
Triple Point
Point
gas
0.9
-78.5 oC -56.7 oC 31oC
Temperature (not to scale)
Example: Compare the phase diagrams of water and carbon dioxide. Ice floats, would you
expect dry ice to float in liquid carbon dioxide? Why?
Carbon Dioxide: Water:
Critical
solid liquid Point Critical
72.9 Point
Pressure atm(not to scale)
Pressure atm(not to scale)
218
liquid
5.1 Triple
Triple Point solid
Point
Triple
Point
gas
gas
0.006 Triple Point
0.9
-78.5 oC -56.7 oC 31oC 0o C 374oC
Temperature (not to scale) Temperature (not to scale)
Critical
solid liquid Point
72.
9
Review
Pressure atm(not to scale)
5. Triple Point
• A phase diagram is a map of the states of a 1 Triple
Point
substance at various pressures and gas
temperatures.
0.
• Each region represents a particular phase 9
-56.7 oC 31oC
that is stable at that region. Temperature (not to scale)
• Each line represents an equilibrium
condition where two states exist
simultaneously.
• The triple points represents the place
where all three states can coexist.
Types Solids
Learning Outcomes: Classifying Matter
• Identify the basic crystal solids as molecular, ionic and atomic.
• Identify atomic solids into nonbonding, metallic and covalent
Crystalline Solids
Molecular Ionic Atomic (Composite units are
(Composite units (Composite atoms)
are molecules) units are ions)
Non-bonding Network Covalent
Metallic
Low Melting High Melting Low Melting Variable melting High Melting points
Points points Points points
Ice, butter, dry Table Salt, Dispersion Network covalent
ice (CO2) Epsom salts, forces Metallic bonding bonds
Solid xenon Gold, iron, copper Quartz (SiO2),
diamond,
Classifying Matter
• Identify the type of crystalline solid based on its composite units.
• Use this to rank melting temps
Crystalline Solids
Molecular
(Composite
units are
molecules)
Low Melting
Points
Ice, butter, dry
ice (CO2)
Classifying Matter
• Identify the type of crystalline solid based on its composite units.
• Use this to rank melting temps
Crystalline Solids
Ionic
(Composite
units are ions)
High Melting
points
Table Salt,
Epsom salts,
Classifying Matter
• Identify the type of crystalline solid based on its composite units.
• Use this to rank melting temps
Crystalline Solids
Atomic (Composite units are
atoms)
Non-bonding
Metallic
Low Melting Variable melting
Points points
Dispersion
forces Metallic bonding
Solid xenon Gold, iron, copper
Classifying Matter
• Identify the type of crystalline solid based on its composite units.
• Use this to rank melting temps
Crystalline Solids
Atomic (Composite units are
atoms)
Non-bonding Network Covalent
Metallic
Low Melting Variable melting High Melting
Points points points
Dispersion Network covalent
forces Metallic bonding bonds
Solid xenon Gold, iron, copper Quartz (SiO2),
diamond,
Classifying Matter
• Identify the type of crystalline solid based on its composite units.
• Use this to rank melting temps
Crystalline Solids
Molecular Ionic Atomic (Composite units are
(Composite (Composite atoms)
units are units are ions)
molecules) Non-bonding Network Covalent
Metallic
Low Melting High Melting
Points points Low Melting Variable melting High Melting
Points points points
Ice, butter, dry Table Salt, Dispersion Network covalent
ice (CO2) Epsom salts, forces Metallic bonding bonds
Solid xenon Gold, iron, copper Quartz (SiO2),
diamond,
Which type of solid will have the
Crystalline Solids
highest melting point?
• H2O (s)
Molecular Ionic Atomic (Composite units are • MgS (s)
(Composite (Composite atoms)
units are units are ions) Non-bonding Network Covalent
• Xe (s)
molecules)
Metallic
Low Melting High Melting
• Au (s)
Low Melting Variable melting High Melting
Points points Points points points
Ice, butter, dry Table Salt, Dispersion Network covalent
ice (CO2) Epsom salts, forces Metallic bonding bonds
Solid xenon Gold, iron, copper Quartz (SiO2),
diamond,
Crystalline Solids
Molecular Ionic Atomic (Composite units are
(Composite (Composite atoms)
units are units are ions) Non-bonding Network Covalent
molecules)
Metallic
Low Melting High Melting Low Melting Variable melting High Melting
Points points Points points points
Ice, butter, dry Table Salt, Dispersion Network covalent
ice (CO2) Epsom salts, forces Metallic bonding bonds
Solid xenon Gold, iron, copper Quartz (SiO2),
diamond,
Crystalline structures
Learning Outcomes
• Define a crystal lattice.
• Identify the basic cubic unit cells (simple cubic, body-centered cubic,
and face centered cubic)
• Identify coordination number for unit cells.
Unit cell
• Crystal lattices: repeating regular arrangements of atoms.
• Unit cell: the minimum unit needed to repeat the pattern
• Aggregates in a manner to minimize energy.
• Many types of packing. We will focus on:
• Simple cubic, body-centered cubic, face-centered cubic.
• Lightly cover cubic close packed.
Simple Cubic Unit Cell
•
Coordination number: Simple Cubic Unit Cell
• Number of atoms with which each atom is in direct
contact.
• Focus on center atom in figure to the right.
• Each atom is in direct contact with six others.
Simple Cubic: Geometry
• Edge Length
2 * radius
l=2r
Body Centered Cubic Unit Cell
•
Coordination number: Body Cubic Unit Cell
• Focus on center atom in figure to the right.
• Each atom is in direct contact with eight
others.
Body-centered cubic: Geometry
c
b
l
Face Centered Cubic Unit Cell
•
Coordination number: Face Centered Cubic Unit Cell
• Number of atoms with which each
atom is in direct contact.
• Each atom is in direct contact with
twelve others.
Face-centered cubic: Geometry
b l
r l
Review and Summary
Cell name Atoms/ structure Coord. # Edge length
cell
Simple cubic 1 6
Body centered 2 8
cubic
Face centered 4 12
cubic
Closest Packed Structures
Learning Goals.
• Visualize closed packed structures.
• Hexagonal Closest Packing
• Cubic closest packed: Face centered cubic.
Introduction:
http://www.london-institute.org/people/farr/packing.shtml
• More efficient way of packing than simple
cubic cell (packing efficiency 52%).
• Two types of packing (74% efficiency)
that this leads to:
• Hexagonal
• Cubic (Same as face centered cubic)
Hexagonal Closest Packed:
• Layering A-B-A
• Every other layer aligns.
• Forms hexagonal shape.
Cubic Closest Packed.
• Layering A-B-C
• Forms a face centered cubic unit
cell.
Review
• Closest packed structures form a more efficient packing structure.
• Hexagonal closest packed forms from an A-B-A packing order and is in the shape of a
hexagon.
• Cubic closest packed forms from an A-B-C packing order and is another way of looking
at a face centered cubic unit cell.
The Structures of Ionic Solids
Learning Outcomes
• Match Cesium Chloride, Sodium chloride, Zinc sulfide and calcium fluoride to
their unit cells.
• Given some common trends, identify, for a given ionic compounds are most
likely to crystallize into a structure like CsCl, like NaCl, a zinc blende, a fluorite,
or an antifluorite structure.
1:1 Ratio
Similar sized
Cl-
Cs+
1:1 Ratio
Similar sized Medium difference
in size
Cl-
Cs+
Cl-
Na+
1:1 Ratio
Similar sized Medium difference Very different
in size Sized
“Zinc Blende”
Cl-
Cs+
Cl- Zn+
Cl-
Na+
2:1 or 1:2 ratio
S2-
Li
+
F-
Ca2+
Example
• Which compound is most likely to crystallize in the zinc blende structure?
The 1:1 ratio with the largest difference in size:
RbCl ( Rb+ radius= 148 pm; Cl- radius= 181pm)
• 1.22x as large
MgCl2 (Mg2+ radius= 65pm; Cl- radius- 181pm)
CuI (Cu+ radius= 96m; I-= 216 pm.)
• 2.25x as large
Review
• We can now match Cesium Chloride, Sodium chloride, Zinc sulfide and calcium
fluoride to their unit cells.
• Based on the ratios of anions to cations and comparative sizes of ions you can
tell which structure it is most likely to form.
Examples using crystal
structures.
Learning Outcomes:
• We won’t do all of these, as they are different version of the same problem. However you
need to know how to:
• Calculate the density of a metal based on information given about the unit cell.
• Calculate the unit cell based on information given.
• Calculate cell length based on given information.
• Calculate molar mass based on given information.
Example 1:
• An unknown metal is found to have a density of 7.8748 g/mL and to crystallize in a body centered
cubic lattice. The edge of the unit cell is 0.28664 nm. Calculate the atomic mass of the metal.
An unknown metal is found to have a density of 7.8748 g/mL and to crystallize in a body centered cubic
lattice. The edge of the unit cell is 0.28664 nm. Calculate the atomic mass of the metal.
L= 0.28664 nm
General molar mass plan: Find grams, find mols, put grams over mols.
To find grams: find volume and
multiply by density.
An unknown metal is found to have a density of 7.8748 g/mL and to crystallize in a body centered cubic
lattice. The edge of the unit cell is 0.28664 nm. Calculate the atomic mass of the metal.
To find grams: find volume and
L= 0.28664 nm
multiply by density.
An unknown metal is found to have a density of 7.8748 g/mL and to crystallize in a body centered cubic
lattice. The edge of the unit cell is 0.28664 nm. Calculate the atomic mass of the metal.
An unknown metal is found to have a density of 7.8748 g/mL and to crystallize in a body centered cubic
lattice. The edge of the unit cell is 0.28664 nm. Calculate the atomic mass of the metal.
L= 0.28664 nm
General molar mass plan: Find grams, find mols, put grams over mols.
Example 2:
• Chromium crystallizes with a body-centered cubic unit cell. The radius of a
chromium atom is 125 pm. Calculate the density of solid crystalline chromium in
g/mL.
Chromium crystallizes with a body-centered cubic unit cell. The radius of
Example a chromium atom is 125 pm. Calculate the density of solid crystalline
chromium in g/mL.
Plan: Find mass of unit cell, find volume of
unit cell, put mass over volume.
Chromium crystallizes in a bcc unit cell. The radius of a Cr atom is 125 pm.
Calculate the density of solid crystalline Cr in g/mL.
Plan: Find mass of unit cell, find
volume of unit cell, put mass over
volume.
mas
s
Chromium crystallizes with a body-centered cubic unit cell. The radius of a chromium atom is 125 pm.
Calculate the density of solid crystalline chromium in g/mL.
Plan: Find mass of unit cell, find volume
of unit cell, put mass over volume.
mass
volume
Chromium crystallizes with a body-centered cubic unit cell. The radius of a
chromium atom is 125 pm. Calculate the density of solid crystalline
chromium in g/mL.
Wrap-up
• Based on the problem solving techniques we’ve learned here be sure that you can:
• Calculate the density of a metal based on information given about the unit cell.
• Calculate the unit cell based on information given.
• Calculate cell length based on given information.
• Calculate molar mass based on given information.
Network Covalent Solids:
Carbon and Silicates
Learning Outcomes
• Have a general familiarity with various forms of carbon.
• Have a general familiarity with various forms of silicate.
Graphite vs Diamond
Carbon
Buckminsterfullerene
• Can be other sizes.
• Clusters “stuck” together with dispersion forces.
• C60 is generally soft
Carbon Nanotubes:
• Lightweight and strong
• 100x stronger than steel
• 1/16 as dense.
• Many many possibilities
• Possible for electronic devices
• Great for lightweight material needs
• X-rays, biosensors, small chipset,
bendable electronics, space elevator
Silicates: Silicon and Oxygen
• Silicon bonds to 4 oxygen (tetrahedral shape on
each).
• If quartz is heated and cools quickly, before it
can crystallize, it becomes amorphous glass.
Review
• Many allotropes of many carbon and silicates exist.
• Common carbon allotropes are diamond, graphite, carbon nanotubes, and
buckminsterfullerene.
• Silicates are made up of tetrahedral Si bound to oxygens
