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Morris
1. Introduction to thermodynamics
a. What is thermodynamics?
Thermodynamics is a description of material properties as a function of state. What do we mean by state?
A macroscopic state of a homogeneous material includes various physical properties. Some (but certainly
not all) of these properties are:
Temperature T
Energy U
Magnetic field H
Magnetism M
Composition x
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MSE 511 notes 2009 – J. R. Morris
PV = NkBT
N = number of atoms
kB = “Boltzmann‟s constant” = 1.381×10-23 J/K
Using Avagadro‟s number, NA = 6.022×1023 atoms/mole, we have
R = NA∙kB
An important note: The usage of the constants R and kB are because temperature is really an energy and
we have to convert from Kelvin to Joules.
Another important note: Temperature will be expressed almost always in Kelvin, not in Centigrade or
Fahrenheit.
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MSE 511 notes 2009 – J. R. Morris
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MSE 511 notes 2009 – J. R. Morris
This is the second law of thermodynamics. The equality holds only for reversible processes, where the
system is essentially in equilibrium during the change. In reality, the entropy may increase even when
there is no volume or energy change – a spontaneous increase in randomness.
In equilibrium, the energy is a function of the entropy S and the volume V:
U = U(S,V)
We may also rearrange this to write the entropy in terms of the energy and volume:
S = S(U,V).
We will commonly use these with partial derivatives:
The advantage: we don‟t need to know the history of the system to know its properties.
But what is this thing we call entropy?
The problem is that thermodynamics describes the collective behavior of many particles, and generally it
is not possible (or useful) to describe the behavior of each of these. On average, in equilibrium, their
behavior is described by only a few quantities. For example, we don‟t care too much about the energy of
each individual particle, only the total energy of the system. One macrostate (such as the total energy)
represents many possible microstates (energies of each particular particle). For a given total energy,
energy may flow within the system to allow more possibilities.
How many ways can we distribute the energy? Let (U) be the number of different possible ways of
distributing energy U in the system. For example, one particle could have a lot of kinetic energy, while
the rest have none. Or all particles could have exactly the same kinetic energies. These are two very
unlikely cases, amongst many possibilities.
The entropy per particle is defined to be
S = kB ln (U).
This connection is the heart of thermodynamics (and is engraved on Boltzmann‟s tombstone). It is not
obvious, but it works. For a given energy, the system evolves to a state with the most number of possible
states (i.e. it moves to the most likely state). In other words, for fixed energy, the system maximizes the
entropy. At constant volume with no heat flow, this gives
∆S ≥ 0 or, more generally, TdS ≥ đQ.
This is the “usual” statement of the second law, that entropy can only increase (or stay the same) if the
system is closed (∆Q=0). Again, if the process is reversible, TdS = đQ.
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MSE 511 notes 2009 – J. R. Morris
But, using the first law (with constant volume), this is simply
So: the condition that equilibrium is a maximum in entropy is equivalent to the temperatures being equal!
This is a “consistency” argument – what we defined ends up making some sense in the end. Similar
arguments under slightly different conditions are common.
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MSE 511 notes 2009 – J. R. Morris
Here, N! = N∙(N-1) ∙(N-2) ∙… However, this is not correct. This overcounts the possibilities, because it
is impossible to tell the difference between different A atoms. After they are placed, it is impossible to
tell which is the „first‟ and which is the „second‟. For NA=NB=2, this would give 12 arrangements, not 6.
Once the A atoms are placed, we must count the number of ways to re-arrange these on the same sites,
and divide this out. This number is simply NA!. So, the final result is
To calculate the entropy, we will use the fact that N, N A and NB are all large numbers. In this limit, we
may use Stirling’s approximation:
With some minor rearrangements, we may write the entropy per particle as
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MSE 511 notes 2009 – J. R. Morris
Self quiz: Is the entropy positive or negative? How can you tell from S = kB ln (U)? Does the
above equation for the ideal entropy of mixing satisfy this?
3. Basic applications of 1st & 2nd laws: heat capacity, Helmholtz & Gibbs free
energies
Now we have our basic tools: the first two laws of thermodynamics, and the statistical definition of
entropy. How do we use this? Again, let‟s ask a simple (but general question). Suppose we have a
system, and we want to increase its temperature by ∆T. How much heat must flow into the system? This
is the heat capacity of the system, defined as đQ/dT.
First, assume that the system is kept at constant volume. The first law may be written as
đQ = dU + PdV = dU for a constant volume process (dV=0).
The heat capacity at constant volume, CV, may then be written as
However, for liquids & solids, it is more common to use constant pressure measurements. What is the
heat capacity at constant pressure? At constant pressure, we have
đQ = dU + PdV = d(U+PV) (using dP=0).
The quantity H=U+PV is called the enthalpy. Using this, the constant pressure heat capacity, CP, may
then be written as
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MSE 511 notes 2009 – J. R. Morris
This is the mathematical statement that in a constant pressure process, the heat flow into the system is the
change in the enthalpy.
In general, for a reversible process,
dH = dU + VdP + PdV = TdS + VdP.
From this, we have
Now, let‟s consider a constant temperature process – again, this is a common condition. During a
reversible process, the work done by the system is dW = TdS – dU. For a constant temperature process,
we may write
-dW = d(U-TS) = dF
where F=U-TS is called the “Helmholtz free energy.” The reversible work done by a system during a
constant temperature process is the change in the Helmholtz free energy. If the system does work dW, the
free energy decreases.
For a non-reversible process, we have dF ≤ -dW. If no work is done (a constant volume process), then the
free energy will spontaneously decrease: ∆F ≤ 0. Thus, at a given temperature and volume, the system
will spontaneously move to a state of lowest Helmholtz free energy.
In general, dF = dU – TdS – SdT = – PdV – SdT, or
Note that because P>0 and S>0, the Helmholtz free energy F decreases with increasing volume
and with increasing temperature. From above, we can calculate the heat capacity CV from F:
In general, if we know F(V,T), we can calculate essentially all thermodynamic quantities, usually
from derivatives and other combinations. What about volume derivatives? The first derivative
gives –P, as noted above. The second derivative has a problem, though: Consider the quantity
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MSE 511 notes 2009 – J. R. Morris
Is this quantity extensive or intensive? F and V are both extensive, so in fact this is neither – it
scales as 1/V. But this is not useful. Let‟s define an intensive quantity instead, by scaling it
with the volume:
What is this quantity B? To understand this, consider a small, isothermal change in volume. The
volume strain is ∆V/V, and produces a change in pressure ∆P. Note that if ∆V>0, then ∆P<0 –
an expansion reduces pressure. We know from linear elasticity that the pressure change is
proportional to the volume strain, and this constant is the bulk modulus. It is also common (less
in materials science) to discuss the isothermal compressibility, defined as
Thus, the curvature of F, is proportional to the bulk modulus, and will be much larger
for a solid (which is hard to compress) than for a gas (which is much more compressible).
Self quiz: What is the compressibility and bulk modulus of an ideal gas? Evaluate this at T=273
K and P=101 kPa (roughly atmospheric pressure). Compare the bulk modulus of this with that of
steel (B=160×109 Pa) and with water (B=2.2×109 Pa).
Self quiz: Sketch the free energy vs. volume for a solid and for a gas. Note that a solid has a
well-defined volume at P=0, but a gas does not. Pay attention to the slope of the curve.
Now, what about a constant T, constant P process? Again, the second law gives
dU ≤ TdS – PdV
or dU – TdS + PdV ≤ 0.
For a constant temperature, constant pressure process, this gives
d(U-TS+PV) ≤ 0.
Defining the Gibb‟s free energy G=U – TS + PV = F + PV, this shows that G is a minimum under
constant temperature and pressure conditions. In equilibrium, the change is zero. Thus, the system
should evolve to minimize G at a given P and T. The differential form of G is
dG = VdP – SdT.
Therefore,
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MSE 511 notes 2009 – J. R. Morris
In this class, we will commonly use the Gibb‟s free energy, and simply call it the free energy.
Occasionally, we will also use the Helmholtz free energy.
There is a special property of G, when we consider how it scales with system size. If G(P,T,N) is
the free energy of a system with N particles, the free energy of a system with twice as many
particles is twice as much, for the same P and T. More generally,
G(P,T,N ) = N∙G(P,T,1) = Nµ(P,T)
where we have introduced the chemical potential µ. The chemical potential will play an
important role later on, when there is more than one type of atom. Note that the Helmholtz free
energy does not have an equivalent:
F(V,T,N) N∙F(V,T,1).
This can be seen by noting that there is a big difference between 10 23 atoms in a liter, and one
atom in a liter!
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MSE 511 notes 2009 – J. R. Morris
possible to cool a liquid below the melting point, or a gas below the boiling point, but the
system is then out of equilibrium.
The slopes are all negative. Why? The derivative (at constant pressure) is proportional
to –S, and entropy is always positive. Therefore, the slopes are negative. (They are also
curving downward, consistent with a positive heat capacity.)
Which phases have higher entropies? We immediately see that the slope of the liquid
line has a higher magnitude – and therefore has the higher entropy. This is intuitive – the
gas is very random, but high in energy. The solid phase has the lowest entropy.
Generally, at high temperatures, the Gibbs free energy is dominated by the entropy terms. At
low temperatures, the enthalpy dominates. The equilibrium phase is determined by balancing
these, minimizing G=H-PV.
Self-quiz: Carbon dioxide is an example of a substance that doesn‟t have a liquid phase at
atmospheric pressure: the solid phase (“dry ice”) transforms directly to a gas. Sketch the
graph of the Gibbs free energies, including the liquid phase. At some pressure, there will
be a temperature where all three phases can coexist. Sketch the Gibbs free energies vs. T
for this case.
For a phase transformation at constant pressure, there are some immediate important results.
Consider the case of melting: at Tmelt, we have Gliq =Gsol. This immediately implies
Hsol-TSsol = Hliq-TSliq.
However, we have already stated that the liquid entropy is higher than that of the solid phase:
∆S=Sliq-Ssol > 0.
Note that this immediately shows that we need to provide heat to melt the system, the latent heat:
L = ∆Q = Tmelt∆S.
However, to keep G constant, we must have
∆H = Hliq-Hsol = Tmelt∆S.
Thus, as the system moves to a higher energy, both the enthalpy and entropy increase. The
change in enthalpy is known as the latent heat L, and is equal to the heat of transformation.
Graphing this, we get something like the following:
Note the changes in entropy that occur at the phase
transformation. The enthalpy vs. temperature
would look very similar.
The discontinuities in entropy indicate a first-order
phase transformation (as they occur in a first
derivative in the free energy). There are other
phase transformations, such as second-order phase
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MSE 511 notes 2009 – J. R. Morris
transitions, where the entropy does not change at the transition, but its derivative (the heat
capacity, a second derivative of the free energy) is discontinuous. Magnetism and
superconductivity are two common examples of these. We will focus primarily on first-order
transitions.
Can we get transformations as a function of pressure? Of course:
this is sketched below for transformations from low pressure
(gas) through the liquid and solid phases. Again, this is sketched
using the thermodynamic relationships: The derivative
The volume always decreases with pressure, and so does the
slope. In this graph, there are a number of assumptions that are
not always true:
The liquid is assumed to have a larger volume (lower density)
than the solid phase. This is common, but is not always true.
Ice is less dense than water, which is why it floats.
The liquid is assumed to have a much smaller volume (and a
much higher density) than the gas. At high temperatures and pressures, this is not true.
Self quiz: Sketch this graph for water, where the density of the liquid is higher than that of the
solid.
In general, it is often useful to map out the transitions as a function of temperature and pressure.
A portion of this is shown here for water. The
melting point (“mp” in the figure) and the normal
boiling point (“nbp”) are labeled for atmospheric
pressure. The triple point (point A) occurs where
all three phases can exist.
Besides its immediate usefulness, these diagrams
provide some important information on the
underlying thermodynamic quantities, particularly
the free energy. Let us consider the line
connecting the solid and liquid phases. If we pick
a point on this line, (T,P) and (T+∆T,P+∆P), we
must satisfy
Gsol(T, P) = Gliq(T, P)
Gsol(T+∆T, P+∆P) = Gliq(T+∆T, P+∆P) Portion of the pressure-temperature phase
diagram for water, from
Assume that ∆T, ∆P are small. Then we can http://www.cbu.edu/~mcondren/water-
approximate the free energies by expanding in ∆T phase-diagram.jpg
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MSE 511 notes 2009 – J. R. Morris
Setting these expressions equal, and using Gsol(T, P) = Gliq(T, P), this becomes
Vsol∆P – Ssol∆T = Vliq∆P – Sliq∆T.
Rearranging, this becomes
∆P∆V = ∆T∆S
or
where ∆V=Vliq – Vsol and ∆S=Sliq – Ssol. Note that from above, the change in entropy is related to
the latent heat: L=T∆S. In the limit that ∆P and ∆T go to zero, this becomes
This is known as the Clausius-Clapeyron equation. While we have derived this for solid and
liquid phases, it applies to all lines in the P-T phase diagram. Also note that the latent heat and
the volumes are typically both normalized as quantities per mass, per mole, or per atom – as long
as they are done consistently, this equation still holds.
Again, let‟s examine the sign of the slope. By definition, the latent heat is positive, as is the
temperature. Therefore, if Vsol < Vliq,(the solid phase is denser than the liquid), then the slope is
positive. Conversely, if Vliq < Vsol,(the liquid phase is denser than the solid), then the slope is
negative.
Self quiz: For the water phase diagram above, let = N/V be the number of atoms per
volume (the number density). Do the densities satisfy gas>liq > sol ? How can you tell
from the phase diagram?
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MSE 511 notes 2009 – J. R. Morris
sealed container, partially filled. After some time, the water will be in equilibrium with the
vapor. This is a constant volume process at some fixed temperature; therefore, equilibrium must
minimize the Helmholtz free energy F(V,T). How do we determine equilibrium?
Again, let‟s begin by sketching the Helmholtz free energy vs. volume. This is done here for the
liquid & gas phase. Note that we must satisfy .
Therefore, the slope should be negative. For a liquid, the density
(or volume/atom) in the limit that P=0 is well defined, so there is
a place where the slope is zero. We can even consider what
happens if the volume of the liquid is greater than this (negative
pressure) but this can not be in true equilibrium. This is indicated
by the dotted line. For the gas, as the volume continues to
increase, the pressure continually drops. For an ideal gas,
P=NkBT/V. Notice also that the graphs curve upward: again, the
second derivative is related to the bulk modulus.
How do we describe coexistence from this graph? Suppose the
average volume per atom is close to the arrow shown in the above figure. The free energy of the liquid is
not stable, so the free energy of the gas looks appropriate. However, the system can have a lower free
energy, by having some atoms in the liquid phase (at a lower
volume per atom), and some in the gas phase (at a higher
volume per atom), maintaining the same average free
energy. To find out the coexisting Helmholtz free energy,
we construct a common tangent line as shown here. The
free energy can be as low as this value. With the addition of
this common tangent line, F(V,T) is everywhere sloping
downward, and continuous. The places where the line
intersect the liquid and gas curves shows the coexistence
volumes (or, more commonly quoted, the densities at
coexistence). The slope of the line gives the coexistence
pressure Pcoexist (at the given temperature), according to .
Note what happens as we compress the gas (isothermally). At first, the pressure simply increases. At
some point, the liquid begins to condense. As we decrease the volume further, the pressure does not
change, but more liquid appears. This continues until the system is completely liquid. Then, the pressure
will again rise.
We can complete the circle: let fliq be the Helmholtz free energy per atom, and the volume per atom of the
liquid be vliq. (This can be per mole or per mass just as well.) Similarly, let fgas and vgas be the same
quantities for the gas phase. It is not hard to see from the above graph that
fliq+Pcoexist vliq = fgas+Pcoexist vgas .
However, using G = F + PV, this is simply a statement that the Gibbs free energy per atom are the same
at coexistence. Equivalently, at coexistence, both phases have the same chemical potential µ.
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MSE 511 notes 2009 – J. R. Morris
If we have a liquid or solid in equilibrium with the gas, we can make use of the Clausius-Clapeyron to
calculate a relationship with the pressure. Let ∆Hvap be the heat of vaporization – how much energy it
takes to convert the phase to a vapor. From the Clausius-Clapeyron equation, assuming we are dealing
with a solid phase, we have
However, the volume per atom in the vapor is much greater than that of the solid – perhaps 100 times
larger. Therefore, we can neglect vsol. Using Pvvap=kBT this becomes
Rearranging, we have
Note that the heat of vaporization is here measured per atom. If this were measured per mole, this
becomes
Thus, a plot of (ln P) vs. (1/T) tends to give a straight line, whose slope gives a measure of the vapor
pressure.
Note that this does not only apply to solid-vapor conditions, but can also apply to adsorption. As an
example, for hydrogen storage, the goal is to find light materials with a heat of adsorption of 20-40
kJ/mol. This provides for a large adsorption, but not so large that it is difficult to get out again.
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MSE 511 notes 2009 – J. R. Morris
Practice problems:
1. Naphtalene melts at 353 K at 1 atm pressure with an enthalpy change of 19 kJ/mole. The volume
increase is 19×10-6 m3. What change in the melting temperature will be observed if the pressure
is raised by 100 atm? Note: 1 atm = 101.3 kPa.
2.
The vapor pressure vs. temperature of a liquid is given in the table. Calculate the enthalpy
change on vaporization at T=373 K.
12
10
T (K) 326.1 352.9 415.0 451.7
ln(P)
8
Pv (Pa) 131.6 657.9 13160 52632
6
4
0.002 0.0025 0.003 0.0035
1/T
3. The specific heat of water at 25 C is cp=4181 J/(kg∙K), while that of ice at 0C (the melting
temperature) is cp=2110 J/(kg∙K). The latent heat (or heat of fusion) is 3.34×105 J/kg. How
much heat must be supplied to bring one mole of ice from -10C to 10C, assuming that the heat
capacities are independent of T? Under certain conditions, water can be cooled considerably
below the freezing temperature without freezing (supercooled). Formulate an expression for the
latent heat vs. T. At what temperature does this go to zero? (Adapted from Pauling’s book).
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MSE 511 notes 2009 – J. R. Morris
5. The change in entropy when a metal melts is typically close to S≈R (per mole) or S≈kB (per
atom) (with an accuracy of about 15%). Estimate the change in volume that occurs when Fe
melts. Approximately how much heat (in Joules) must be supplied to melt one mole of Fe?
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MSE 511 notes 2009 – J. R. Morris
Here, V is the volume and A is the area, and the free energy per volume is gvol. The interfacial free energy
per area is indicated by . Let R be a characteristic size of our system, so that V~R3 and A~R2. In this
case,
(This holds only for cubic systems, but the results are more general.) The average free energy per volume
is then
When R is very large, the term /R can be ignored. However, for small volumes, this can not be ignored,
and even for large systems can control the microstructure evolution (which is dominated by interfaces).
Let us demonstrate the applicability of this for the case of the initial stages of crystal formation from the
liquid. Typically, a liquid can be cooled somewhat below the equilibrium melting temperature. The
liquid is then termed metastable: it is not the thermodynamically stable phase (as it has a higher free
energy than the solid), but can exist for measurable periods of time. To form the crystal, a small
crystalline region must form and grow. If there are no external causes for this, such as surfaces, cracks, or
other defects, then the nucleation is considered homogeneous; it can happen anywhere in the system with
the same probability. If, on the other hand, it is helped along by a defect, impurity, surface, or other
external cause, it is termed heterogeneous.
Again, we will treat the simplest case of homogeneous nucleation. If the interfacial free energy does not
depend on the orientation of the interface, then the nucleus will likely be spherical. The free energy
required to form the nucleus is
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MSE 511 notes 2009 – J. R. Morris
Here, ∆gvol=gsol-gliq is the difference in free energies per volume of the crystal. Note that we have usually
used values per mole or per atom, but here it is more convenient to discuss values per volume. Also note
that for T<Tm, ∆gvol is less than 0 – the free energy is reduced by forming the stable solid phase. Thus, for
large radii, Gnuc is less than zero, and the free energy can be lowered as long as R increases. However, for
small R, the interfacial free energy dominates, and the free energy increases as R increases. This is
shown roughly in the picture below. The maximum free energy G* of a nucleus can be found by
optimizing with respect to the radius. The resulting value is
Generally, the rates of transformation depend on the barrier according to a Boltzmann factor, so the
nucleation rate scales as exp(-G*nuc/kBT). A high interfacial free energy suppresses nucleation, while a
low interfacial free energy makes for easy nucleation.
We can get a better estimate of some of these quantities, assuming that the temperature is close to the
transition temperature. Near the transition,
The term ∆gvol(Tm) is zero, because the free energies are equal. Note that we can write this in terms of the
solid and liquid free energies (remember that these are per volume for now):
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MSE 511 notes 2009 – J. R. Morris
If this were the entire story, the rate of nucleation would continue to increase as the temperature drops.
However, this is not the case: if it were, it would be very difficult to form glasses. A more careful
treatment says that the nucleation rate (number of nuclei forming per volume, per time) is also
proportional to the diffusion rate; if
diffusion is slow, then the system is
slow to rearrange into a crystalline
arrangement. Diffusion typically
behaves roughly according to
D(T)=D0exp(-Ediff/kBT) where Ediff is
a positive energy associated with
the barrier to diffusion. The
quantity D(T)exp(-G*/kBT) is
therefore a product of a function
D(T) that decreases rapidly as T
decreases, multiplied by a function
exp(-G*/kBT) that is small near Tm
and increases rapidly as T
decreases. Thus, nucleation is slow
both at low T and near Tm. The
nucleation rate has a sharp peak at
some characteristic temperature. The graph at right has the characteristic shape of a “Time-Temperature-
Transformation” (“TTT”) diagram (with rotated axes) T
A more detailed treatment of nucleation would include other effects ignored here. Typical other topics
include:
Elastic terms: Typically, there is a change in volume at the transition, and this can result in an
additional elastic energy for forming the nucleus. In that case, not only will the energy of the
critical nucleus change, but sometimes also the shape of the nucleus.
Heterogeneous nucleation: If the interface between the nucleating phase and the wall of the
container is very low, then the energy of the nucleus can be much lower by forming a “bubble”
on the wall. This is particularly true if there is a crack in the container, so that there is little
interface between the nucleating phase and the metastable “parent” phase.
Practice problems:
1. Show that What is the radius R* of the critical nucleus?
2. Turnbull showed that for FCC metals, the interfacial free energy is approximately = ½ -1/3Lvol,
where is the number of atoms/volume in the solid phase. The rate of nucleation is proportional
to exp(-G*nuc/kBT). An observable nucleation rate may occur when G*nuc ≈50kBTm. Using this, and
estimating Lvol≈kBTm, estimate the maximum undercooling ΔT/Tm. Compare this to Turnbull‟s
observation that ΔT/Tm is typically no larger than 0.2.
3. (Adapted from Porter & Easterling, problem 4.4.) The nucleation rate is
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MSE 511 notes 2009 – J. R. Morris
Calculate the homogeneous nucleation rate in liquid copper at undercoolings of |T-Tm| = 180, 200
and 220 K, using the following data: Lvol=1.88x109 J/m3, Tm=1356 K, =0.177 J/m2, f0=1011/sec,
C0=6x1028 atoms/m3, and k=1.38x10-23 J/K. For each temperature, estimate the time it will take
for a 10 cm3 sample to form one critical nucleus. Repeat, assuming that is 10% smaller.
4. For slow vapor deposition on a surface, monatomic layers may nucleate as atoms accumulate.
The atoms lower their free energy by an amount g (per atom) by forming a layer, but the edge of
the layer has a positive step free energy s per atom. Assuming that the area occupied by an atom
is a2, and the length of the edge is equal to the number of atoms on the edge times a, write down
the free energy of a circular island of radius R. What radius gives the maximum energy? This is
the size of a critical nucleus. What is the energy of this critical nucleus, in terms of only g and s
(not R)?
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MSE 511 notes 2009 – J. R. Morris
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line. The two solvus lines show the compositions of the two phases, when they are in chemical
equilibrium.
An important issue is to determine the fraction of each phase, in a two-phase region. Suppose the
composition x is greater than the liquidus composition xL but less than the solidus composition xS (such as
shown by the point in the Ag-Cu figure). In otherwords, xL<x<xS. What is the fraction fL in the liquid
phase, what is the fraction fS in the solid phase? The simple expression that gives the answer to this is the
lever rule:
Note that these two expressions simply have the labels L and S reversed. This is called the “lever rule”
because if these represents fraction by weight, then the weight of the solid portion (proportional to fs)
times the length of the “arm” x-xS “balances” the weight of the liquid portion (proportional to fL) times the
length of its arm x-xL:
There is an important subtlety related to phase diagrams that must be mentioned. In the Ag-Cu figure
shown, the composition x is given by weight. This is very convenient for people making materials – the
x=50 wt-% composition means the same weights of Ag and Cu must be mixed. However, for showing
what crystal phases exist, it is often useful to know the composition by atomic fractions instead. For
example, salt crystals are really NaCl – the composition is 50 at-% Cl. Both conventions are used, and
the choice needs to be specified.
Given this, you should ask: are the fractions given by the lever rule by weight, or by atomic fraction? The
answer is simple: they are the same as the composition. If the compositions are all wt.-%, then the
fractions are by weight. On the other hand, if the compositions are atom-%, then the fractions are atomic
(or molar) fractions.
What other types of phase diagrams occur? The simplest is
the solid-solution phase diagram, such as that for Cu-Ni.
This is shown in the figure here (from www.copper.org).
There are two homogeneous regions, shown in blue: the
liquid region, and the solid phase, denoted by α. The α
phase is a nearly random mixture of Ni and Cu atoms on an
FCC lattice. On the phase diagram, there is a two-phase
region, shown in white, where the α phase coexists with the
liquid phase. The liquidus and solidus lines are labeled.
Suppose we have a composition x near 40 wt % Ni,
starting with the liquid phase, and cool. What transitions
occur? When the temperature reaches the liquidus line,
solid phase starts to form. As long as the temperature is
below the liquidus, but above the solidus, the system has
both phases present. The fraction in each phase is given by
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MSE 511 notes 2009 – J. R. Morris
the lever rule. Below the solidus, only the α phase is present. Note that this is different from the pure
system, where the liquid and solid phases are both present only at a single temperature (in equilibrium).
Now the melting process is “spread out” over a range of temperatures.
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MSE 511 notes 2009 – J. R. Morris
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MSE 511 notes 2009 – J. R. Morris
In this diagram, there are three major composition regions, characterized by different microstructures.
The highest carbon region, from 2 to 6.5 wt-% carbon, is “cast iron.” In this region, the microstructure is
primary iron or primary Fe3C, surrounded by eutectic composition. The iron transforms further, as
discussed later. In the composition range below 2 wt-%, the system will form pure iron (with carbon
additions), before subsequent transformations, avoiding the eutectic microstructure. This is termed
“steel.” At the eutectoid composition, the iron phase forms a very fine scaled microstructure (with
length scales defined by diffusion lengths in the solid phase). This microstructure is called “pearlite” in
this system, due to its characteristic appearance. (Note that the phrases “eutectic” and “eutectoid” apply
to many different phase diagrams, but
“pearlite” implies Fe-C.) If the system is
above 0.83% carbon (but below 2%), it is
“hyper-eutectoid” or “high carbon” steel.
Below 0.83% carbon, this is “hypo-eutectoid”
or “low carbon” steel. The presence of the
Fe3C significantly strengthens the iron, but is
best in small quantities (and kept to small
length scales).
At right is a micrograph from
http://www.msm.cam.ac.uk/phase-
trans/2006/old/old.html showing a “modern
hypereutectoid steel” with 1.85 % C (plus
minor additions). The large dark phase is the cementite phase (the first formed from the iron); the small
structure is the pearlite. [This image is originally from Munoz et al., Journal of Nuclear Materials 349, 1-
5 (2006)].
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MSE 511 notes 2009 – J. R. Morris
This is far from a full description of iron and steel, but serves as a very basic introduction. Important to
remember are why the different regions (cast iron, low-carbon steel, high-carbon steel) get their names,
and understand why the different microstructures form. There is a lot of terminology, but the most
important are the “eutectic” and “eutectoid” transformations that occur in many systems. The phrase
“pearlite” (as well as ferrite, austenite, and cementite) are important to those dealing with steel and iron
systems.
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MSE 511 notes 2009 – J. R. Morris
but there is another important result, from the way that the free energy G scales with the number of
particles. Specifically,
G = ANA + BNB + …
For a single component system, the chemical potential is just the Gibb‟s free energy per atom (or per
mole).
What happens when we mix two atom types A and B? From a thermodynamic point of view, it is useful
to define the partial molar free energies of the pure phases as
gA = GA/NA.
Here, GA is the Gibbs free energy of the pure A phase, and NA is the number of moles. Similarly,
gB=GB/NB.
When we combine the different types of atoms, we can write the total Gibbs free energy as
G = GA + GB + Gmix = NAgA + NBgB + Gmix
Where the term Gmix is the change in free energy from mixing. Again, the system will try to reach the
lowest Gibbs free energy – so if Gmix>0, then the A and B atoms will tend to separate. On the other hand,
if Gmix < 0, then the system will preferentially mix. It will be useful to do all of this on a molar basis, with
N=NA+NB being the total number of moles, and xA=NA/N being the atomic fraction of A atoms, and
xB=NB/N being the fraction of B atoms. Clearly, xA+xB=1. The molar free energy is then
g = xAgA + xBgB + gmix.
The terms gA are the “pure phase” free energies we considered in the first part – so we will not pay close
attention to those now. The mixing term is of most interest. Not surprisingly, there is an enthalpy
contribution and an entropy contribution:
gmix = hmix - Tsmix .
Of course, all of these quantities depend on temperature, pressure (which we will largely ignore), and
composition. The easiest to deal with is the entropy of mixing. If mixing is completely random, then the
entropy that we derived earlier is
This is the “ideal” entropy of mixing. (We wrote this per atom before; here, we write things per mole,
and use the ideal gas constant R instead of Boltzmann‟s constant kB). Note that because xA and xB are both
less than one, this term is always positive. If we write x=xB and xA=1-x, we can write this as
We sketched this before (around pg. 7). It is important to understand that the slope of this plot goes to
infinity as x → 0, and to minus infinity as x → 1. This means that a small change of composition can
dramatically increase the entropy. We will use this form throughout the rest of this, though it is only an
approximation. In reality, two atom types won‟t mix completely randomly – there will be some
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MSE 511 notes 2009 – J. R. Morris
preference for either some level of mixing (A atoms like to be near B atoms) or de-mixing (A-A and B-B
bonds are prefered over A-B bonds).
Let‟s consider a simple case: Suppose the enthalpy of mixing is zero: there is no enthalpy change from
mixing A and B atoms. This is a limiting case, but often useful. It is best for good “solid solution”
systems such as Cu-Ni. In this case, there is little correlation between the atoms, and the ideal entropy of
mixing is a good approximation. Neglecting hmix and using the above form for smix, we obtain the ideal
solution model for a mixture:
This ideal solution model is sufficient to understand many aspects of simple phase diagrams. Note that
the above expression is for a single phase, such as a single crystal phase, or a liquid phase. The entropy
of mixing term always favors mixing, so the free energy is lowered.
Let‟s sketch this, roughly, at different temperatures, for the Cu-Ni system. First, consider T=TmeltNi – at
high temperature, where the system is beginning to solidify. At this temperature, gNiliq=gNisol – for pure
Ni, the liquid and solid (FCC) free energies have the same value at the melting temperature. However, it
is above the melting temperature of Cu, so gCuliq < gCusol. In fact, gliq < gsol for all compositions except
pure Ni. This is shown schematically below. For both liquid and solid phases, the free energy is lowered
by mixing.
Now consider a slightly lower temperature, such that TmCu < T<TmNi. For Ni, the free energy of the solid
phase must be lower than that of the liquid: gNiliq>gNisol. For Cu, this is reversed: gCuliq<gCusol. Therefore,
the two curves must cross. This is shown in the middle figure above. It would be easy but wrong to
assume that the transition occurs at the composition where these cross. Why? Because these curves are
single-phase free energies. The system can, in a certain composition range, lower its free energy by
changing to two phases in coexistence. In the middle figure, the free energy at the composition where
gliq=gsol is higher than the average free energies of the „common tangent‟ shown. The system has the
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MSE 511 notes 2009 – J. R. Morris
lowest free energy by separating into a liquid with composition xliq and a solid with composition xsol.
These are the liquidus and solidus compositions at this temperature. This is analogous to the curves we
drew earlier for the Helmholtz free energy as a function of volume.
In general, if we have a free energy g(x) (at some temperature and pressure), and construct the tangent
line going through this curve at some value of x, the tangent line can be traced back to x=0 and x=1. It
can be easily shown that the intersections at these point are equal to the chemical potentials for atoms A
and B, respectively. That is to say, the intersections give the values A and B. So, for the common
tangent shown above, which meets both the liquid and solid curves, we must have Culiq = Cusol and Niliq
= Nisol , and these values can be obtained from where they meet the Cu and Ni axes, respectively. The
two phases, in equilibrium, have the same chemical potentials. This is a general condition for multiphase
equilibrium: all components must have the same chemical potential. If there are three phases in
equilibrium, all three curves have the same common tangent.
Finally, we consider the temperature T = TmCu. At this point, gCusol=gCuliq; however, for all other
compositions, the solid phase has the lowest free energy. This is shown at right in the figure above.
We can rewrite the “ideal solution” model in terms of the chemical potentials. Recall that the free energy
(per mole) is generally given by
g = xAA + xBB.
Comparing this to the above expression for the ideal solution model shows that
Aid = gA + RT ln xA
Bid = gB + RT ln xB .
These simple expressions give some estimate of the behavior of real solutions, and can be reasonably
accurate for some systems.
We obtained the ideal solution model using Hmix = 0. However, this is often a poor approximation. How
do we do better? With some idea on how Hmix changed with concentration, then a better approximation
can be made.
To get some idea, consider first a pure crystal phase. If the interactions between atoms are restricted to
near neighbors, and there are z neighbors per atom, then there are ½zN bonds in the system. Why ½ ?
Because each bond is shared by two atoms – so without this, we are double counting. If the enthalpy of a
bond is h, then the total enthalpy is
H = ½ zhN
Now, what happens if we have two types of atoms, A and B? There are now three types of bonds: A-A,
A-B, and B-B bonds. Note that the different types of bonds have different enthalpies. If the A and B
atoms are totally separate, then there are no A-B bonds, and the enthalpy may be written as
H = ½ zhAANA + ½ zhBBNB.
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MSE 511 notes 2009 – J. R. Morris
To find out about the enthalpy if the A and B atoms mix, we need to think about how they mix. An
ordered arrangement will be different than a random arrangement. The ideal entropy of mixing was
calculated by assuming complete randomness, so let us proceed using that. If atoms are arranged
randomly, then an A atom will usually have xAz neighbors that are A atoms, and xBz neighbors of type B.
Therefore, the enthalpy of one mole of A atoms will be
hA = ½ z (xAhAA + xBhAB).
hB = ½ z (xAhAB + xBhBB).
So, we‟ve written down expressions for the unmixed enthalpy, and the mixed enthalpy. What is most
useful is the change in enthalpy from mixing:
The term in brackets has a simple interpretation. If there is originally an A-A bond and a B-B bond, these
may be broken and combined to form 2 A-B bonds. The change in enthalpy is then 2hAB-hAA-hBB, exactly
the expression above.
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MSE 511 notes 2009 – J. R. Morris
There is a different approach to argue this form for hmix. In the limit that xA=0 or xB=0, the system is pure,
so the enthalpy of mixing must be zero. The simplest expression satisfying this is hmix = ΩmixxAxB. Other
terms may be added to generate different approximations, but this is the simplest term. In the usual
approximation, Ωmix is assumed to be independent of temperature, but this may also be changed.
Using this form of hmix, combined with the ideal entropy of mixing, we may write the Gibbs free energy
of mixing as
Use of this form is known as the regular solution model. In the limit that Ωmix=0, it reduces to the ideal
solution model.
Let‟s examine some behaviors of this expression. First, examine the plot of hmix shown in red here
(assuming a positive Ωmix). It looks similar to the
entropy of mixing, shown in green. However, the rise in
hmix near x=0 is not as steep as that for smix . If hmix>0,
then the enthalpy is minimized by keeping the system
separate. This is referred to as a “positive heat of
mixing.”
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MSE 511 notes 2009 – J. R. Morris
To write this as g = xAA + xBB, we use (xA+xB) = 1 to rewrite the enthalpy of mixing term as
A = gA + RT ln xA + Ωmix(1-xA)2
B = gB + RT ln xB + Ωmix(1-xB)2
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MSE 511 notes 2009 – J. R. Morris
This is done in analogy with the ideal solution model: Aideal = gA + RT ln xA. Thus, for an ideal solution,
the activity is the same as the composition. For a regular solution, we have
It is also common to define the activity coefficient as A=aA/xA; again, for an ideal solution, this is simply
A=1. For a regular solution, we have
Thus, the activity and the activity coefficient show how much the system deviates from ideality. If a
system is more “active,” i.e. >1, this implies that its chemical potential is higher than would be expected
simply from its concentration. This is the case when the enthalpy of mixing is positive. On the other
hand, if <1 (for a system with a negative heat of mixing), then it tends to be less reactive (or less
“active”) than would be expected for an ideal solution.
To examine this, consider the regular solution activity coefficients when x=xB≪1, and xA=1-x is nearly
one. In that case,
This says what we know intuitively: If a small amount of material B is dissolved in a large amount of A,
the chemical properties of element A are nearly unchanged, and the changes are simply due to the fact that
A is slightly diluted. If B does not want to mix with A (Ωmix>0), then the dissolved B elements are
somewhat more reactive (to try to stop mixing). On the other hand, if B is happy in A, then it will be less
reactive once dissolved.
These are well known expressions: the high-concentration result that A1 when xA1 is called “Raoult‟s
Law”; the low concentration result that Aconstant when xA≪1 is called “Henry‟s Law”. An important
note for Henry‟s law is that if Ωmix>0, then the constant is greater
than 1; similarly, if Ωmix<0, then the constant is less than one. The
ideal solution result is that the constant is identically equal to 1.
Raoult‟s law holds only for small concentrations. The enthalpy of mixing can be seen to be positive – the
activities are significantly larger than x for most concentrations.
A different situation occurs for Al-Si. The activity plots below show that again, there are significant
deviations from an “ideal” solution behavior in the liquid. However, now the activities are smaller than
the concentrations, indicating a negative enthalpy of mixing.
Practice problems:
1. Si melts at T=1687 K, with a change in entropy of 3.25 kB per atom.
A. What is the change in enthalpy on melting?
B. Si liquid is denser than crystalline Si. Will the melting temperature increase or decrease if
pressure is increased?
C. Derive the approximate expression Gsol(T)-Gliq(T)≈S(T-Tm), near the melting temperature.
D. A small amount of Al is added to the liquid, with an atomic concentration x. Write the
chemical potential Si of Si in the liquid at Tm, in terms of Gliq(Tm) for pure liquid Si. Assume
that the Al mixes ideally.
E. Using the results of parts C and D, estimate the liquidus temperature for x=10 at-% Al.
Assume that there is no Al
solubility in crystalline Si, so the
chemical potential for Si in the
solid phase does not depend on
concentration.
F. Using the measured liquid
activities given in the plot above,
explain whether the assumption of
ideal mixing is reasonable for part
D. Is the enthalpy of mixing in the
liquid phase positive or negative?
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MSE 511 notes 2009 – J. R. Morris
2. Below is the phase diagram of Al-Zn. Solid Al () has an FCC phase, and solid Zn () has an
HCP phase.
A. Is Zn more soluble in FCC Al, or is Al more soluble in HCP Zn? Is the enthalpy of mixing
positive or negative in the FCC phase? Explain.
B. Estimate the relative (atomic) percentages of and phase formed by the initial
solidification of the liquid with the eutectic composition.
C. Starting from pure phase with 40 atomic % Zn at T=400 ºC, what are the phases that form
as the system is cooled? Sketch the microstructure at T=300 ºC and at T=200 ºC.
D. Sketch the free energy of the andphases as a function of composition. Make separate
graphs for T=350 ºC, T=300 ºC, and T=250 ºC. Indicate the tie-line compositions.
E. (This part uses some material from the following section.)
With 40 atomic % Zn, suppose you wanted to form as much phase as possible from the
melt, at T=350 ºC. Would it be better to slowly cool the liquid, or quench it? Why?
385 ºC
282 ºC
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MSE 511 notes 2009 – J. R. Morris
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MSE 511 notes 2009 – J. R. Morris
Now suppose that the temperature is decreased slightly, so that the solid region grows. The new growth
is in equilibrium with the liquid at the new temperature. However, the already solidified region does not
change composition. Moreover, the liquid
phase is in equilibrium with the newly
solidified region. This can be seen here. The
newly solidified region at T2 has a different
composition than the first part. The key is that
as solidification progresses, the composition of
the solid and liquid regions change.
To make this more definite, consider the phase
diagram below. Solidification begins at T=T 1.
The initially solidified phase has the solidus composition. As the system is cooled to T 2, solidification
proceeds, but the composition of the solid phase changes through the system. The initially solidified
portion has less solute than the region solidified later. Where is this solute? It is in the liquid – so the
liquid is solute rich, compared to the equilibrium condition. This process continues as the temperature is
cooled.
Note that there is still a lever-rule relationship between the average concentration in the solid, <xsol>, and
the liquid concentration xliq. The average of the entire system is x. However, we can write the average
concentration in terms of the liquid and solid average
concentrations, and the fractions of the phase that are liquid
and solid:
x = <xsol>fsol + xliq fliq.
Using this, and fsol+fliq=1, we can derive the lever rule. Note
that because we have assumed that xliq>xsol, <xsol> must be less
than x as long as fliq is greater than zero. Once <xsol> = x, the
whole system must be solid.
At a temperature T3 where the equilibrium diagram gives
xsol(T3)=x, equilibrium should be a single, solid phase.
However, because the initially solidified regions have
concentrations less than x, the average concentration in the
solid region <xsol> is less than x. Thus, there is some liquid left. There is more solute in the liquid – so
there is still a liquid region, rich in solute. Thus, the system is not completely solidified at T3. The
average composition of the solid phase is always less than the total concentration. This means that the
system continues to solidify, with the liquid becoming richer in solute, down to the eutectic temperature.
At this point, the liquid has the eutectic composition, and further cooling results in eutectic solidification.
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MSE 511 notes 2009 – J. R. Morris
There are two main points here: first, the liquid does not fully solidify at the equilibrium temperature, but
can persist to lower temperatures. Secondly, some liquid solidifies with a eutectic microstructure – so
there is a two-phase region, even when the equilibrium state is single phase.
To examine this more thoroughly, let‟s plot the composition of the solid region as a function of position.
The first part has composition xsol(T1), some a little
further on has composition xsol(T2), etc. This is
shown in the figure at right.
How can this be made more rigorous? Assume that
the liquidus and solidus lines are straight lines, with
xsol=kxliq. The partition coefficient k is less than one.
Thus, the initially solidified region has a composition
xsol(T1)=kx (where x is the initial composition of the
liquid). If the fraction solidified increases by dfsol, then this region rejects some solute into the liquid.
This amount of rejection is equal to (xliq-xsol)dfsol. The change in the liquid phase composition is equal to
the fraction of liquid times the change in composition, fliqdxliq=(1-fsol)dxliq. Using the relation above, we
have
(1-k)xliq dfsol =fliqdxliq
Using fliq+fsol=1, we have dfsol= -dfliq, so
Note that k-1 is less than zero. This means that when fliq is small (the system is mostly solid), fliq(k-1) is
large, so the non-equilibrium result predicts that xliq is large as well. However, there is a limit: once xliq
reaches the eutectic composition, the remaining liquid can solidify rapidly. This is in agreement with the
arguments we made above.
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MSE 511 notes 2009 – J. R. Morris
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MSE 511 notes 2009 – J. R. Morris
Thermodynamic formulas:
First law:
dU = dQ – dW = dQ – PdV + i i dNi (Ni = number of atoms OR number of moles of type i )
dQ TdS
Other energies:
Enthalpy: H = U+PV
dH TdS + VdP
Helmholtz free energy: F = U – TS
dF = –SdT –PdV
Gibb’s free energy: G=H+PV=i i dNi
g = G/N = xAA + xBB
dG = VdP – SdT+ i i dNi
Gibb’s free energy for solutions, regular solution model (per particle):
G = xAGA+ xBGB + mixxAxB - TSmix (per mole or per atom)
Clausius-Clapeyron equation:
dP/dT = S/v
(v=volume/atom or volume/mole; S=entropy/atom or entropy/mole)
Constants:
kB = Boltzmann’s constant = 1.381x10-23 J/K
R = 8.316 J/K/mole
h = Planck’s constant = 6.626x10-34 J·s
NA= Avogadro’s number = 6.022x1023 atoms/mole
42