Bragg Equation
• n = 2 d sinΘ
• n must be an integer and is
assumed to be one unless Detector typically
otherwise stated. moves over range of 2
r
ecto
Θ angles
• Below is a sketch of the
de t y
X-ra
apparatus which we will not
go into.
2Θ
2Θ
X-ray source
Typically a Cu or Mo target Sample holder
1.54 or 0.8 Å wavelength
Orientation of diffracting planes
Bragg’s Equation
• n = 2 d sinΘ
• Below are the layers of atoms in a crystal. The
arrows represent light that is bouncing off of them.
The light has a known wavelength or . d is the
distance between the layers of atoms. Θ is the angle
that the light hits the layers.
Bragg Equation Example
n = 2 d sinΘ
If the wavelength striking a crystal at a 38.3°
angle has a wavelength of 1.54 Ǻ, what is the
distance between the two layers. Recall we
assume n = 1. You will need your calculator
to determine the sine of the angle.
1.54 Ǻ = 2 d sin 38.3°
this can be rearranged to d = λ / (2 Sin θB)
SO
= 1.54 Ǻ / ( 2 * Sin 38.3 ) = 1.24 Ǻ
Extra distance = BC + CD = 2d sin = n (Bragg Equation)
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 = 2 d sin
The given information is
n=1
= 14.170
= 0.154 nm = 154 pm
n 1 x 154 pm
d = = = 314.54 pm
2 sin 2 x sin14.17
It’s Importance
• The Bragg equation enables us to find
the dimensions of a unit cell. This gives
us accurate values for the volume of the
cell.
• As you will see in the following on unit
cells and the equations, this is how
density is determined accurately.
Spectroscopic Techniques
• Utilize the absorption or transmittance of
electromagnetic radiation (light is part of this,
as is UV, IR) for analysis
• Governed by Beer’s Law
A=abc
Where: A=Absorbance, a=wavelength-dependent
absorbtivity coefficient, b=path length, c=analyte
concentration
Spectroscopy
• Exactly how light is absorbed and reflected,
transmitted, or refracted changes the info and
is determined by different techniques
sample
Transmittance
spectroscopy
Reflected
spectroscopy
Raman
Spectroscopy
Light Source
• Light shining on a sample can come from
different places (in lab from a light, on a plane
from a laser array, or from earth shining on Mars
with a big laser)
• Can ‘tune’ these to any
wavelength or range of
wavelengths
IR image of Mars
Olivine is purple
Unit Cells
• While there are several types of unit cells, we
are going to be primarily interested in 3
specific types.
• Cubic
• Body-centered cubic
• Face-centered cubic
A crystalline solid possesses rigid and long-range order. In a crystalline solid, atoms,
molecules or ions occupy specific (predictable) positions.
An amorphous solid does not possess a well-defined arrangement and long-range
molecular order.
A unit cell is the basic repeating structural unit of a crystalline solid.
lattice At lattice points:
point • Atoms
• Molecules
• Ions
Unit Cell Unit cells in 3 dimensions
Shared by 8 unit cells Shared by 2 unit cells
1 atom/unit cell 2 atoms/unit cell 4 atoms/unit cell
(8 x 1/8 = 1) (8 x 1/8 + 1 = 2) (8 x 1/8 + 6 x 1/2 = 4)
When silver crystallizes, it forms face-centered cubic cells. The unit cell
edge length is 408.7 pm. Calculate the density of silver. Though not
shown here, the edge length was determined by the Bragg Equation.
m
d= V = a3 = (408.7 pm)3 = 6.83 x 10-23 cm3
V
Remember that there are 4 atoms/unit cell in a face-centered cubic cell
107.9 g 1 mole Ag
m = 4 Ag atoms x x = 7.17 x 10-22 g
mole Ag 6.022 x 1023 atoms
m 7.17 x 10-22 g
d= = = 10.5 g/cm3
V 6.83 x 10-23 cm3
This is a pretty standard type of problem to determine density from edge length.
A crystalline solid possesses rigid and long-range order. In a crystalline solid, atoms,
molecules or ions occupy specific (predictable) positions.
An amorphous solid does not possess a well-defined arrangement and long-range
molecular order.
A unit cell is the basic repeating structural unit of a crystalline solid.
lattice At lattice points:
point • Atoms
• Molecules
• Ions
Unit Cell Unit cells in 3 dimensions
Types of Solids
Ionic Crystals or Solids
• 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 Solids
Molecular Crystals or Solids
• Lattice points occupied by molecules
• Held together by intermolecular forces
• Soft, low melting point
• Poor conductor of heat and electricity
Types of Solids
Network or covalent Crystals or Solids
• Lattice points occupied by atoms
• Held together by covalent bonds
• Hard, high melting point
• Poor conductor of heat and electricity
carbon
atoms
diamond graphite
Types of Solids
Metallic Crystals or Solids
• Lattice points occupied by metal atoms
• Held together by metallic bond
• Soft to hard, low to high melting point
• Good conductor of heat and electricity
Cross Section of a Metallic Crystal
nucleus &
inner shell e-
mobile “sea”
of e-
Types of Crystals
Types of Crystals and General Properties
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
Crystalline Non-crystalline
quartz (SiO2) quartz glass
The Men Behind the Equation
• Rudolph Clausius
– German physicist and mathematician
– One of the foremost contributors to the science of
thermodynamics
– Introduced the idea of entropy
– Significantly impacted the fields of kinetic theory of gases and
electricity
• Benoit Paul Émile Clapeyron
– French physicist and engineer
– Considered a founder of thermodynamics
– Contributed to the study of perfect gases and the equilibrium of
homogenous solids
The Clausius- Clapeyron Equation
• In its most useful form for our purposes:
P1 H vap 1 1
ln ( )
P2 R T2 T1
In which:
P1 and P2 are the vapor pressures at T1 and T2 respectively
T is given in units Kelvin
ln is the natural log
R is the gas constant (8.314 J/K mol)
∆Hvap is the molar heat of vaporization
Useful Information
• The Clausius-Clapeyron models the change in vapor
pressure as a function of time
• The equation can be used to model any phase
transition (liquid-gas, gas-solid, solid-liquid)
• Another useful form of the Clausius-Clapeyron equation
is:
H vap
ln P C
RT
But the first form of this equation is the
most important for us by far.
Useful Information
• We can see from this form that the Clausius-Clapeyron
equation depicts a line
H vap H vap 1
ln P C Can be written as: ln P C
RT R T
which clearly resembles the model y=mx+b, with ln P representing y, C representing b,
1/T acting as x, and -∆Hvap/R serving as m. Therefore, the Clausius-Clapeyron models a
linear equation when the natural log of the vapor pressure is plotted against 1/T,
where -∆Hvap/R is the slope of the line and C is the y-intercept
Useful Information
H vap
ln P C
RT
We can easily manipulate this equation to arrive at the more familiar form of the
equation. We write this equation for two different temperatures:
H vap H vap
ln P1 C ln P2 C
RT1 RT2
Subtracting these two equations, we find:
H vap
H vap H vap 1 1
ln P1 ln P2
RT1 R2 R T2 T1
Common Applications
• Calculate the vapor pressure of a liquid at any
temperature (with known vapor pressure at a given
temperature and known heat of vaporization)
• Calculate the heat of a phase change
• Calculate the boiling point of a liquid at a nonstandard
pressure
• Reconstruct a phase diagram
• Determine if a phase change will occur under certain
circumstances
Shortcomings
• The Clausius-Clapeyron can only give
estimations
– We assume changes in the heat of vaporization
due to temperature are negligible and therefore
treat the heat of vaporization as constant
– In reality, the heat of vaporization does indeed
vary slightly with temperature
Real World Applications
• Chemical engineering
– Determining the vapor pressure of a substance
• Meteorology
– Estimate the effect of temperature on vapor
pressure
– Important because water vapor is a greenhouse
gas
An example of a phase diagram
