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Lecture Thermodynamic Basics of Physical Chemistry
Lecture Thermodynamic Basics of Physical Chemistry
When temperature indeed approaches zero degrees the gas properties changes and
Eq. (1.2) is no longer valid but the measurements under normal conditions still give a
very good definition of the absolute zero temperature using extrapolation.
The pressure, P, of the
Fig. 1. Volume vs. Temperature gas is defined using the force
0.04
per the unit area acting from
P= 1 atm the gas to the walls of the
container. To hold gas at the
0.03 given volume we need to apply
the certain force to the walls to
resist to its expansion. Solids
V (m3)
0.02 P= 2 atm
and liquids usually stay at the
0
T0 = -273.15 C given volume but if we try to
P = 3 atm compress them reducing their
volume they will act with the
0.01
strong backwards pressure. In
P = 4 atm
the laboratory conditions the
pressure of material is
0 determined by the atmospheric
-300 -200 -100 0 100 200
pressure acting on them
T (0C) uniformly. The atmospheric
pressure can be measured with the help of barometer.
The SI unit for pressure is 1 N/m2 and it is also called 1Pa. The atmospheric
pressure is about 105 times higher.
Sample problem: What is the pressure equilibrating the gravity of 760 mm Hg? The
density of Hg is 13594 kg/m3.
The quantity of the matter is another important characteristics, which can be
determined by the mass of the homogeneous material of interest (not mixture). The molar
mass representing the product of Avogadro’s number to the molecular mass is used for
the unit quantity (one mole). Then the quantity of the matter is determined by the ratio of
its mass to the molar mass n=m/M. The SI unit for the quantity of matter is one mole.
Thus we introduced four characteristics of macroscopic material including
volume, temperature, pressure and quantity (V, T, P, n). There is a common believe that
knowing any of these three parameters and the state of the matter we can determine the
fourth one. For the gases under normal conditions (atmospheric pressure) the
interrelationship of parameters is given with a very high accuracy by the ideal gas
equation, which can be written in the form
PV = nRT. (1.3)
-1 -1
The universal gas constant R is defined as R=8.3144598 J mol K .
Van der Waals suggested the generalization of this equation for smaller volumes
and/or higher pressures in the form
Statistical Thermodynamics, Lecture 1 4
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
! an 2 $
# P + 2 & (V − nb) = nRT. (1.4)
" V %
Van der Waals parameters a and b for some gases are given in the end of these notes.
This equation can be rewritten for a one mole of the gas in the form
a RT
P=− 2 + , (1.5)
V V −b
where V is the molar volume. The first term reflects the attractive interaction at long
distances between molecules. Its dependence on the volume comes from the distance
dependence of their dispersive interaction. The subtraction of the parameter b from the
volume reflects the subtraction of the minimum volume corresponding to the condensed
phase. It is practically impossible to compress the gas to smaller volume because of the
electronic repulsion.
To see how important are related corrections to the ideal gas equation one can
calculate the change in the gas mass density in Eq. (1.4) compared to Eq. (1.3) for some
gas, say CO2.
What can we learn from ideal gas laws? First of all one can express mass density
ρ in the ideal gas as
PM
ρ0 = , (1.6)
RT
where M is the molar mass of a given gas. So knowing pressure, temperature and the
chemical formula of molecules one can find the gas density. Does this really work? Let
us check that for some gas. For molecular oxygen this density is known experimentally to
be ρ=1.429 g/L=1.429 kg/m3 at standard temperature and pressure (STP) in accordance
with the Wikipedia page https://en.wikipedia.org/wiki/Oxygen. What are the standard
temperature and pressure? Standard temperature is defined as zero degrees Celsius (0 0C),
which translates to 32 degrees Fahrenheit (32 0F) or 273.15 degrees kelvin (273.15 K).
This is essentially the freezing point of pure water at sea level, in air at standard pressure.
Definition of the standard pressure is time sensitive. Before 1982 it was one atmosphere
that is 101325 Pa (N/m2), while after 1982 it becomes exactly 105Pa or 1 bar. Knowing
the gas constant R=8.314 and the molar mass of oxygen 2*15.999 g = 31.998 g =
0.031998 kg one can estimate the gaseous oxygen density as 1.4090 kg/m3. It is close to
the right number but not exactly there and differs by around 2%. If, however I use the old
definition of STP (before 1982) I would be getting ρ=1.427 kg/m3 which is about ten
times more accurate. Perhaps the numbers in Wikipedia are given for the old SPT
definitions.
The Van der Waals equation should give better approach to reality. Let us see
how can we improve the present estimate? Using the definition ρ=M/V for the one mole
one can obtain the following cubic equation for the gas mass density
ab 3 a 2
ρ − ρ + ( RT + Pb) ρ − MP = 0.
M2 M
It is hard to solve the qubic equation exactly in any reasonable form. One can construct
an approximate solution assuming that Van der Waals corrections to pressure and volume
(-a/V2 and b) are much smaller than actual pressure and volume. Then one can seek for
the solution in the form
Statistical Thermodynamics, Lecture 1 5
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
MP
ρ = ρ0 + ρ1, ρ0 = , ρ0 >> ρ1.
RT
Substituting this form into the cubic equation and keeping only linear term in ρ1 one can
find the Van der Waals correction ρ1 in the form
⎛ ab 3 a 2 ⎞
⎜ − 2 ρ0 + ρ0 − Pbρ0 ⎟ ⎡ a b a b⎤
ρ1 = M M
⎝ ⎠
= ρ0 ⎢− 2
+ 2
− ⎥.
RT ⎣ PV0 V0 PV0 V0 ⎦
Using Van der Waals gas parameters for oxygen a=1.378 L2atm/mol2 = 0.1378
m6Pa/mol2, b=0.03183 L/mol=3.183*10-5m3/mol one can estimate ρ0+ρ1=1.4294 kg/m3.
This result matches available data within the experimental accuracy. The root of the cubic
polynomial can be found numerically and it does not deviate from the above estimate.
Sample problem: What pressure should be applied to the gas at room temperature to
have the van Der Waals correction to the density of order of 10% of the density. How big
is this pressure for a gaseous oxygen?
The ideal gas equation results in the interesting conclusion that the volume per the
mole, VM=RT/P (0.0224 m3 STP), does not depend on the specific gas properties (molar
mass, etc). This reflects the fact that the volume per the molecule in an ideal gas at given
temperature and pressure does not depend on specific molecules. As we know the
temperature determines the kinetic energy per the molecule. Independence of pressure on
the specific molecules reflects the fact that its determined by the kinetic energy of
molecules only.
The above observation helps to generalize the ideal gas equation for the gas
mixture. The number of moles n in the ideal gas equation for the gas mixture should
given by the sum of the numbers of moles of all participating gases
PV = (n1 + n2 +... + nk )RT.
Fig. 1. Illustration of the work made on the material. It can be expressed either as
d’Wext=Fdx or as d’Wext=(F/A)Adx = -PdV
How to apply these concepts to the ideal gas? The molecules in ideal gas interacts
very weakly with each other, so the total energy should be expressed as the product of the
number of molecules N and typical molecular energy which is the same as the product of
molar energy multiplied by the number of moles. Consequently U=nUM(T). The energy
change due to heating can be described by the differential change
dU=ndUM(T)/dT=nCVdT where nCV is the gas heat capacity at constant volume and CV is
the molar specific heat, which is the heat capacity of one mole. If the heat capacity is
approximately temperature independent then the gas energy can be expressed as
Statistical Thermodynamics, Lecture 1 7
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
U=c+CVT=U0+CV(T-T0), where U0 is the reference energy at the reference temperature
T0. The heat capacity increases proportionally to the quantity of matter. It is convenient to
introduce the specific heat per unit mass that is given by the ratio of the molar heat
capacity and the molar mass, cV=CV/M. The heat capacity expresses the amount of heat
which should be delivered to the gas at constant volume to raise its temperature by 1K.
The practical measurements are usually performed at constant pressure, rather
than volume. Under those conditions it is convenient to introduce the specific heat at
constant pressure. In this regime the energy (heat) transferred to the gas is used to raise
the gas internal energy (temperature) by CV(Tf-Ti) where Ti and Tf are initial and final
temperatures and to expand gas performing the work P(Vf-Vi)=R(Tf-Ti). Because of the
energy conservation the total energy transferred to the gas is given by (CV+R) (Tf-Ti).
Consequently, the heat capacity at constant pressure is given by CP=CV+R.
Molar specific heats of ideal gases at sufficiently high temperature can be defined
using the equipartition principle for the gas energy. This principle suggests the same
molar energy RT/2 or RT for each degree of freedom. For monatomic molecules (n=1) all
three degrees of freedom correspond to translational motion having each the energy
RT/2. The total energy then is 3RT/2 and for the molar specific heats we got CV=3R/2
and CP=5R/2.
For n-atomic molecules of non-linear shape the number of degrees of freedom can
be count as following. The total number is 3n because each atom has three directions to
go. Three of them correspond to the translational motion and three to rotational having
total energy 3RT. The remaining 3n-6 degrees of freedom are vibrational. Each
vibrational degree of freedom under classical conditions (high enough temperature)
possess the energy RT including RT/2 for kinetics and RT/2 for potential energies.
Consequently the total energy is U=(3n-3)RT and the specific heats are given by CV=(3n-
3)R and CP=(3n-2)R. If the molecule has a linear shape then the number of rotational
degrees of freedom is 2 so the number of vibrational degrees of freedom is 3n-5.
Consequently the energy is U=(3n-5/2)RT and the specific heats are given by CV=(3n-
5/2)R and CP=(3n-3/2)R.
Ideal and Van der Waals gas equations permits us to describe the work done on
gas. For instance if the gas is placed in container equilibrated thermally with the
environment, that is having the same temperature, the work to compress the gas from the
volume V1 to some smaller volume V2 can be evaluated integrating the first law of
thermodynamics as
V2 V2
W = − ∫ P dV = − ∫ nRT dV / V = nRT ln(V1 / V2 ),
V1 V1
V2 nRTdV V2 dV ⎛ V − nb ⎞ an 2 an 2
WVdW = − ∫ + ∫ an 2 2 = nRT ln ⎜ 1 ⎟+ − .
C.
V1 Second law
V − nb V1 ofVthermodynamics.
⎝ V2 − nb ⎠ V1 V2
To compress the gas the external pressure should exceed the equilibrium internal pressure
Pin(V) so the total work can be separated into two parts (V2<V1)
V2 V2
Wc = − ∫ Pin (V )dV − ∫ (Pex (V ) − Pin (V ))dV . (1.11)
V1 V1
The work for the backwards process can be represented in a similar manner
V2 V2
Wd = ∫ Pin (V )dV + ∫ (Pex (V ) − Pin (V ))dV , (1.12)
V1 V1
with the important difference that the external pressure for the decompression process
should be smaller than the internal pressure. Consequently, first terms in Eqs. (1.11),
(1.12) are equal and of the opposite sign so they compensate each other if the
compression-decompression cycle is performed, while second terms are positive in both
cases representing the heating of the system. The difference between actual external and
equilibrium pressures is responsible for the irreversibility of the system evolution in the
cycle. If the external pressure approaches the internal equilibrium pressure the
irreversible part disappears though the compression decompression takes longer and
longer in time. In the limit of infinitely slow (adiabatic) process external pressure is
getting equal to the internal pressure and the process becomes reversible. According to
the above definition of entropy it should not change in such a process.
The energy increase during the cycle represents the heat transferred to the system,
because the volume finally did not change. In the limit of adiabatically slow reversible
process there is no heat transferred to the system and mechanical works compensate each
other in forward and backwards paths.
One can represent the entropy change in the standard mathematical form of the
full differential as
⎛ ∂S ⎞ ⎛ ∂S ⎞
dS = ⎜ ⎟ dE + ⎜ ⎟ dV . (1.13)
⎝ ∂E ⎠V ⎝ ∂V ⎠ E
Statistical Thermodynamics, Lecture 1 9
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
We assumed no change in the number of particles. Eq. (1.13) is the multivariable calculus
generalization of the standard equation df=(df/dx)dx. To prove the validity of this
substitution one can take derivatives of the function change in the left hand side and the
linear function in the right hand side, which will lead to the identities. If we need
coincidence with the accuracy to square terms one can reexpress this like
df=(df/dx)dx+(1/2)(d2f/dx2)dx2+..
Sample problem. Write expression accurate to the cubic term in dx.
Sample problem. Write expression accurate to the quadratic terms for two variable
functions.
Assume that we consider the reversible process with the external pressure equal to
the internal pressure P=Pin. In any case according to the first law of thermodynamics one
can express the entropy change using Eq. (2) as
" ∂S % " ∂S % " ∂S %
dS = $ ' d 'Q − $ ' Pin dV + $ ' dV. (1.14)
# ∂U &V # ∂U &V # ∂V &U
As we defined above the entropy should not change in the reversible process where on
the other hand d’Q=0 as we have just established and pressure must be equal to the
equilibrium pressure.
Then using the definition of entropy we got
1 # ∂S &
dS = − Pin dV + % ( dV = 0. (1.15)
T $ ∂V 'U
This results in the identity
" ∂S % P
$ ' = in , (1.16)
# ∂V &E T
which completes the definition of the entropy. The change of entropy with the change of
energy and volume can be expressed as
dU Pin dV
dS = + . (1.17)
T T
Consequently we can rewrite the first law of thermodynamics in the form
dU = −Pin dV + TdS.
(1.18)
The first term represents reversible work corresponding to the adiabatic process limit,
while the second part describes the heat transfer to the system.
Consequently, one can express the change in entropy in terms of the heat
transferred to the system in the case of constant volume as
d 'Q
dS = . (1.19)
T
The latter equation is directly associated with the second law of thermodynamics. It tells
us that for thermally isolated system the spontaneous change of entropy is always
positive or zero (see the example with piston). Another example of spontaneous increase
of entropy is associated with two bodies with different temperatures placed in thermal
contact. The heat dQ transferred to the cold body is equal to the heat removed from the
hot body (energy conservation). The system entropy change can be expressed as the
entropy raise of the first body dQ/Tl and entropy reduction of the second body –dQ/Th.
The total entropy change dQ(1/Tl-1/Th) is positive since Th>Tl.
Statistical Thermodynamics, Lecture 1 10
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
In other words I would say that the laws of thermodynamics define two
fundamental extensive parameters of the macroscopic system. One of them must be
conserved (energy) and one must grow when the processes are irreversible (entropy).
The important property of the system is its specific heat C, which we will usually
use as a heat capacity per one mole of matter. It represents the differential measure of the
amount of heat needed to raise the temperature, which can be expressed as dQ/dT. Since
the heat can be transferred under different conditions two situations should be considered
separately of constant volume (gas in container) or constant pressure (standard laboratory
conditions with atmospheric pressure). In both cases we can define specific heats
differently as the specific heat at constant volume, CV, or at constant pressure, CP, as
" ∂Q % " ∂S %
CV = $ ' = T $ ' ,
# ∂T &V # ∂T &V
(1.20)
" ∂Q % " ∂S %
CP = $ ' = T $ ' .
# ∂T &P # ∂T &P
Guess which of two should be larger?
Sample problems. Calculate the entropy of ideal gas assuming that CV is a volume
independent constant. What would happen with the temperature and entropy of ideal gas
in case if the container size increasing twice either adiabatically or instantaneously?
According to the first law of thermodynamics the gas energy change can be expressed in
terms of entropy and volume changes as dU=TdS-PdV. The energy of ideal gas is
expected to be volume independent because of the absence of molecular interactions.
Accordingly, it can be expressed as dU=CVdT. Then the differential of entropy takes the
form dS=CVdT/T+PdV/T. Using the ideal gas equation one can rewrite this result as
dS=CVdln(T)+nRdln(V)=d(CVln(T)+nRln(V)). Consequently the entropy can be
approximated by S=A+ CVln(T)+nRln(V), where A is volume independent constant. As
the alternative one can use the reference entropy S0 at certain reference volume V0 and
temperature T0 in the form S(V, T)=S0+ CVln(T/T0)+nRln(V/V0).
To evaluate the Chemical potential for ideal gas one has to express the internal energy
U=nCV(T-T0)+U0 in terms of volume V and entropy
S=nS0(V0/n,T0)+nCVln(T/T0)+nRln(V/(nV0)). The temperature can be expressed in terms
of entropy using the definition of entropy and for the internal energy we get
⎡ S − nR ln(V / (nV0 )) ⎤
U = nU 0 (S0 ,V0 ) − nCV T0 + nCV T0 exp ⎢ ⎥.
⎣ nCV ⎦ (2.7)
Using the definition of the chemical potential in Eq. (2.6) we get the definition of the
chemical potential in the form
⎡ S R ⎤ U − TS + PV
µ = U 0 (S0 ,V0 ) − CV T0 + CV T + CV T ⎢− + ⎥=
⎣ nCV CV ⎦ n . (2.8)
The numerator in this expression is called the Gibbs free energy and this is a very general
definition of the chemical potential as a molar Gibbs free energy. Using previously
obtained expressions for the internal energy and entropy of ideal gas one can express the
chemical potential in terms of any two parameters of interest.
One can use the expression of the chemical potential in terms of the derivative of
entropy with respect to the quantity of matter at fixed internal energy and volume.
Employing the ideal gas equation and assuming U=U0+CVT we get
! dU nRdV $ ! U − nu0 $ !V $
dS = # + & → S = nCV ln # & + nR ln # & + ns0 = ns =
" T V %n " n % "n%
! RT $
= nCV ln (CV T ) + nR ln # & + ns0 .
" P %
Calculate internal energy and entropy for Van der Waals gas at given temperature
and volume.
This tricky calculation can be performed using the fact the second derivative of
internal energy of Van der Waals gas with respect to volume and temperature is equal to
zero, which justifies separation of two those dependencies. To prove that, consider the
partial derivative of energy with respect to the volume at constant temperature. This
derivative can be evaluated using the first thermodynamic law and entropy differential
definition as
Statistical Thermodynamics, Lecture 1 16
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
⎛ ∂S ⎞ ⎛ ∂S ⎞
dU = −PdV + TdS = −PdV + T ⎜ ⎟ dV + T ⎜ ⎟ dT.
⎝ ∂V ⎠T ⎝ ∂T ⎠V
Consequently, one can express the derivative of interest as
⎛ ∂U ⎞ ⎛ ∂S ⎞
⎜ ⎟ = −P + T ⎜ ⎟ .
⎝ ∂V ⎠T ⎝ ∂V ⎠T
Using the Maxwell identity
⎛ ∂P ⎞ ⎛ ∂S ⎞
⎜ ⎟ =⎜ ⎟ .
⎝ ∂T ⎠V ⎝ ∂V ⎠T
and Van der Waals equation one gets
⎛ ∂U ⎞ TR a
⎜ ⎟ = −P + = 2.
⎝ ∂V ⎠T V −b V
Consequently, the internal energy can be expressed as U=-a/V+U(T), where the second
term does not depend on the volume. Its dependence can be expressed as U=U0+CV(T-
T0)-a/V. Using the definition of entropy derivative with respect to temperature
⎛ ∂S ⎞ CV
⎜ ⎟ =
⎝ ∂T ⎠V T
one can then obtained the expression for entropy in the form S(V, T)=S0+
CVln(T/T0)+nRln((V-b)/(V0-b)).
Additional requirements for the true entropy maximum should include the certain
conditions for its second derivatives. Indeed, all first derivatives should be equal zero in
the maximum. However this is necessary but insufficient condition for true maximum.
For the single variable function the second derivative in the maximum must be non-
positive. Otherwise this is minimum rather than maximum.
The second order expansion for the entropy change can be evaluated in terms of
thermodynamic variables as
Statistical Thermodynamics, Lecture 1 17
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
1 # ∂(S) & 1 # ∂2 S & 1 # ∂2 S &
Δ 2 S = % 2 ( ΔU 2 + % 2 ( ΔV 2 + % 2 ( Δn 2 +
2 $ ∂U ' 2 $ ∂V ' 2 $ ∂n '
1# ∂ S &2
1# ∂ S & 2
1 # ∂2 S & 1 # ∂2 S &
+ % ( ΔUΔV + % ( ΔVΔU + % ( ΔUΔn + % ( ΔUΔn +
2 $ ∂U∂V ' 2 $ ∂U∂V ' 2 $ ∂U∂n ' 2 $ ∂n∂U '
1 # ∂2 S & 1 # ∂2 S &
+ % ( ΔVΔn + % ( ΔVΔn =
2 $ ∂V∂n ' 2 $ ∂n∂V '
1 # ∂(1 / T ) & 2 1 # ∂(P / T ) & 2 1 # ∂(µ / T ) & 2
= % ( ΔU + % ( ΔV − % ( Δn +
2 $ ∂U ' 2 $ ∂V ' 2 $ ∂n '
1 # ∂(1 / T ) & 1 # ∂(P / T ) & 1 # ∂(1 / T ) & 1 # ∂(µ / T ) &
+ % ( ΔUΔV + % ( ΔVΔU + % ( ΔUΔn − % ( ΔUΔn +
2 $ ∂V ' 2 $ ∂U ' 2 $ ∂n ' 2 $ ∂U '
1 # ∂(P / T ) & 1 # ∂(µ / T ) &
+ % ( ΔVΔn − % ( ΔVΔn =
2 $ ∂n ' 2 $ ∂V '
ΔU *# ∂(1 / T ) & # ∂(1 / T ) & # ∂(1 / T ) & -
= ,% ( ΔU + % ( ΔV + % ( Δn/ +
2 +$ ∂U ' $ ∂V ' $ ∂n ' .
ΔV *# ∂(P / T ) & # ∂(P / T ) & # ∂(P / T ) & -
+ ,% ( ΔV + % ( ΔU + % ( Δn/ +
2 +$ ∂V ' $ ∂U ' $ ∂n ' .
Δn *# ∂(µ / T ) & # ∂(µ / T ) & # ∂(µ / T ) & -
− ,% ( Δn + % ( ΔU + % ( ΔV / =
2 +$ ∂n ' $ ∂U ' $ ∂V ' .
1
= [ ΔUΔ(1 / T ) + ΔVΔ(P / T ) − ΔnΔ(µ / T )].
2
To investigate the system stability with respect to its volume and temperature
changes at fixed quantity of matter (Δn=0, something should be fixed because there is
always instability with respect to proportional changes of volume, energy and number of
particles) one can represent second order term in Eq. (3.19) in terms of temperature and
volume changes as
Statistical Thermodynamics, Lecture 1 18
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
1
Δ 2 S = − ( ΔTΔS − ΔPΔV ) =
2T
(3.21)
ΔT 2 ΔTΔV ⎛⎛ ∂S ⎞ ⎛ ∂P ⎞ ⎞ ⎛ ∂P ⎞ ΔV 2
= −CV − ⎜⎜ ⎟ − ⎜ ⎟ ⎟ + ⎜ ⎟ .
2T 2 2 ⎝⎝ ∂V ⎠T ,n ⎝ ∂T ⎠V ,n ⎠ ⎝ ∂V ⎠T ,n 2T
The expression has to be non-positive for true entropy maximum. This leads to three
basic thermodynamics inequalities for diagonal terms
⎛ ∂P ⎞
CV ≥ 0, ⎜ ⎟ ≤ 0. (3.22)
⎝ ∂V ⎠T ,n
Off diagonal term can be evaluated to zero later Maxwell identities.
The common sense treatment of these inequalities is straightforward. Indeed, in
case of a negative heat capacity the small heat transfer from the system of interest to the
outside world will raise the temperature of the system and should stimulate more heat
transfer outside of the system making the present situation unstable. In case of positive
derivative of pressure vs. volume the small increase of volume leads to an increase in the
internal pressure, which will lead to further expansion.
Alternatively one can express Eq. (3.21) in terms of entropy and changes as
ΔS 2 ⎛ ∂V ⎞ ΔP 2
Δ2S = − +⎜ ⎟ (3.23)
2CP ⎝ ∂P ⎠S,µ 2T
Here the new thermodynamic inequalities can be derived including the positiveness of the
heat capacity at constant pressure CP>0.
Sample problem: obtain thermodynamic inequalities for the ideal gas assuming that it
can be characterized by temperature dependent specific heat CV(T) taken at constant
volume.
4. Phase equilibriums.
At the first order phase transition point several phases of the same matter can
coexist with each other. The stability conditions for the whole material does not change
requiring maximum entropy/minimum energy in the stable state so for two phases in
touch (say ice and water) temperatures, pressures and chemical potentials must be the
same. This results in the Clausius-Clapeyron equation for the line separating phases in the
P-T plane. In terms of chemical potentials one can define equilibrium using equivalence
of the chemical potential differentials along the phase border, which yields
The graph shows the pressure volume dependence for CO2. At large volume
RT/v>>a/v2àv>>a/(RT) the gas behave like ideal gas obeying the dependence P=RT/v.
Then if temperature is sufficiently low meaning a/RT >>b the pressure decreases with
decreasing the volume, which conflicts with the thermodynamics inequality (2.11).
Therefore is case of three possible values of volume corresponding to one pressure (the
intersections with the horizontal straight line in the graph) only solutions one the
solutions at the edges are stable, while the solution in the middle is unstable. Increase of
pressure towards this domain leads to the jump from the gas phase (most right solution)
to the liquid phase (most left solution).
Let us first determine the regime where discontinuous transition exists.
Depending on the temperature the graph can have or not have domains where the
horizontal line crosses it more than once. The second line from the top represents the
crossover regime between the two where there is always only one intersection and more
than pone intersections are possible. This crossover line has the inflection point where
both first and second derivatives of pressure over volume are equal zero.
One can determine the crossover line using the inflection point equations
Statistical Thermodynamics, Lecture 1 22
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
2a RT
P' = 3 − = 0,
v (v − b)2
(4.5)
6a 2RT
P '' = − 4 + = 0.
v (v − b)3
Solving two equations together we got v=3b and P=a/(27b2) at the inflection point
realized at the temperature Tc=8a/(27bR). This inflection point is called critical point
where the transition liquid gas is continuous (second order like transition) but still exists.
This temperature is higher than the typical laboratory temperatures. For instance
for water it is given by 656 K, which is much higher than the boiling temperature at the
atmospheric pressure. The pressure of 220Atm should be in the related critical point.
Actual temperature and pressure at the critical point for water T=647K and P=218atm are
not far from Van der Waals theory predictions.
The continuous transition occurring between liquid and gas at the critical point is
the example of the second order phase transition, while the discontinuous transition at
lower temperature represents the first order transition. Consider the discontinuous
transition within the Van der Waals model.
In this case the pressure derivative with the respect to volume in Eq. (4.5)
approaches zero at two positive values of volume approaching first local maximum Pmax
at v=vmax and then local minimum Pmin at v=vmin. At pressures P>Pmax the only liquid
phase is stable and can exist, while at P<Pmin only gas phase is stable and can exist. At the
intermediate pressures Pmin<P<Pmax Eq. (4.4) for the volume has three solution and only
two of them vmin(P) and vmax(P) are stable with respect to the thermodynamic inequality,
while the middle solution is unstable and cannot exist. Considering two stable solutions
one should choose more stable which possesses the minimum Gibbs free energy. The
difference in Gibbs free energies is convenient to express using Helmholtz free energies
as
vmax
ΔG = ΔA + P(vmax (P) − vmin (P)) = − ∫ P(v)dv + P(v
max (P) − vmin (P)). (4.6)
vmin
This difference in Gibbs free energies can be represented as the difference between two
areas formed by intersections of the horizontal line of constant pressure with P(v)
dependence in the graph (B-A). If B>A a liquid phase is more stable because it has
smaller Gibbs free energy. Otherwise the gas phase is preferable. The second phase
possessing larger Gibbs free energy is metastable (undercooled gas or overheated liquid).
It turns out though that overheated liquid boils to form the gas. The pressure where
A+B=0 corresponds to the equilibrium point between liquid and gas phases which can
exist at only one pressure at given temperature.
Equations describing phase transition point for Van der Waals gas can be
formulated algebraically evaluating analytically integrals in Eq. (4.6) and using the
pressure volume relationship as
Statistical Thermodynamics, Lecture 1 23
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
a a #v −b&
ΔG = − − RT ln % max ( + P(vmax − vmin ) = 0;
vmin vmax $ vmin − b '
(4.7)
a RT a RT
P=− 2 + =− 2 + .
vmin vmin − b vmax vmax − b
The solution of these equations for water boiling temperature using matlab code
(T=258.1677865506905;x = roots([P -P*b-Rgas*T a -a*b]); a/min(x)-a/max(x)-
Rgas*T*log((max(x)-b)/(min(x)-b))+P*(max(x)-min(x))) yields water boiling
temperature as low as 258K which disagrees remarkably with its actual value of 373.15
K. For Kr Van der Waals model gives reasonable prediction of 100K boiling temperature
compared to 120K actual temperature at 1 Atm. Why does it fail for water?
5. Chemical equilibrium
The chemical potential is important for considering the chemical reactions in the mixtures
of different materials. The analysis of mixtures is particularly needed to describe
solutions and chemical reactions there. Then one can define an energy as a function of the
quantities ni (moles) of materials U(S, T, N1, N2, … Nk). One can define the chemical
potential for each component similarly to the previous definitions as
⎛ ∂E ⎞
µ i = ⎜⎜ ⎟⎟ . (5.1)
∂N
⎝ i ⎠ S ,V , N k k ≠i
Since for the bulk material under consideration the energy should scale proportionally to
other extensive parameters, U(λ S, λV, λ N1,..λ N k ) = λU(S,V, N1,..N k ). we can similarly
express the energy as
k
U(S,V, n1,..nk ) = TS − PV + ∑ µi ni . (5.2)
i=1
One can similarly define the Gibbs free energy as
k
G(T, P, n1,..nk ) = U − TS + PV = ∑ µi ni . (5.3)
i=1
As was derived earlier at constant temperature and pressure the direction of spontaneous
system evolution is determined by the reduction of the Gibbs free energy. This is what we
need to know to use the Gibbs free energy Eq. (5.3) for understanding reaction
equilibriums.
Consider some reaction occurring at fixed pressure P and temperature T of the
environment. The very general reaction equation can be written in the form
Nr Np
In the course of chemical reaction the changes in quantities of products and reactants are
proportional to their stoichiometric coefficients with positive signs for products and
negative signs for reactants. Accordingly the change in the Gibbs free energy can be
expressed as
dG ∝ −∑ µi pi + ∑ µ j rj . (5.6)
p p
The reaction proceeds spontaneously if the sum of the product chemical potentials
weighted by stoichiometric coefficients is smaller than that for reactants. In the opposite
case the reaction goes backwards. Chemical equilibrium between products and reactants
takes place if the following equation is satisfied
∑µ p = ∑µ r .
i i i i
(5.7)
p r
This is the condition for the chemical equilibrium.
To apply the concept of the chemical equilibrium to the practical reactions we
begin the consideration with the mixture of ideal gases. The chemical potentials of ideal
gases within the mixture do not depend on each other because of the absence of
interaction between them. As it was derived earlier one can express the chemical
potential of the ideal gas as
µ (T,V ) = µ (T,V0 ) − RT ln(V / n). (5.8)
We did not use the pressure dependence here because the total pressure is not quite
relevant for the individual component. However it is convenient to use partial pressure,
defined for each component i as
n
Pi = P i , n = n1 + n2 +...nk . (5.9)
n
Then the chemical potential of each component can be conveniently expressed as
!P $
µi (T, P) = µi (T, P0 ) + RT ln # i &. (5.10)
" P0 %
If we use the atmospheric pressure for P0 then the first term in Eq. (5.10) is defined at
normal pressure while the second term is expressed in terms of activity ai, which can be
defined for the ideal gas as
P
ai = i . (5.11)
Patm
Consequently the chemical potential can be expressed in terms of activity as
µ (T , P) = µ 0 (T ) + RT ln(ai ). (5.12)
It is important to notice that if activity of certain material goes to zero the chemical
potential approaches negative infinity. This is a consequence of very high entropy for
small density of material, which gives to each individual molecule a large volume to
occupy. Therefore the reaction always equilibrates at finite quantities of participating.
Statistical Thermodynamics, Lecture 1 25
Alex Burin; aburin@tulane.edu; 1-504 862 3574;
Israel 508
If we substitute Eq. (5.12) into the chemical equilibrium equation (5.7) one can express it
in the form
⎛ a pp11 ⋅ a pp22 ... ⎞
− ΔG0 = RT ln⎜ r1 r2 ⎟.
⎜ a ⋅ a ... ⎟
⎝ r1 r 2 ⎠ (5.13)
ΔG0 = ∑ µ i 0 pi − ∑ µ i 0 ri .
p r
This equation expresses the law of mass action. Activities are equal pressures expressed
in atmospheric units. One can introduce the equilibrium constant of the reaction at the
atmospheric pressure as
a pp11 ⋅ a pp22 ... Ppp11 ⋅ Ppp22 ...
K p (T ) = r1 r2 = r1 r2 . (84)
a r1 ⋅ a r 2 ... Pr1 ⋅ Pr 2 ...
Eq. (83) can then be expressed as
(
− ΔG0 = RT ln K p (T ) ..) (5.15)
Sample problem. Write the expression for the equilibrium constant of the reaction
2CO(g)+O2(g)=2CO2(g). What is its absolute value? If we had initially only CO2 at the
atmospheric pressure what would be the equilibrium pressures of gases? What if we had
initially 2 moles of CO and one of O2? What if one mole of each?
One can express the equilibrium constant of the reaction using the concentrations (mole
densities) of reactants and products c=P/(RT), expressed in some standard units of mol/L.
The concentration dependent equilibrium reaction constant can be expressed as
c pp11 ⋅ c pp22 ...
K c (T ) = r1 r2 . (5.16)
c r1 ⋅ c r 2 ...
Sample problem. What is the relationship of Kp and Kc for the reaction given above at
room temperature?