1 Introduction

Definition of statistical thermodynamics

Statistical thermodynamics, or statistical mechanics, is the
study of the microscopic behaviors of thermodynamic
systems using statistical methods and probability theory.

The essential problem in statistical thermodynamics is to

determine the distribution of a given amount of energy E
over N particles in a system. The macroscopic properties,
such as thermodynamic energy, heat capacity, etc., can be
calculated in terms of partition functions.
Statistical thermodynamics is a bridge of connecting between
macroscopic and microscopic properties of a system.
There are two kinds of systems

Interacting system (dependent subsystems)

Non-interacting system (Independent
subsystems , for instance, ideal gas)
Two kinds of particles

Identical particles, or indistinguishable

particles (such as gaseous molecules), is
also called non-localized particles.

Distinguishable particles (Such as the atoms in

crystal), is also called localized particles.
2. Distribution and microstate

2.1 Distribution of energy levels

We call the occupation number ni the number of distribution in
energy level i.
For example, a distribution of 6 identical particles among 9
units of energy must satisfy with the conditions

N ni 6
i

U ni i 9
i
3. Distribution of energy levels cont..

The total number of ways of distribution is 26.

 2.2 Distribution of states

The number of particles occupied in a microscopic quantum state is

called the number of distribution of states.

One distribution j of energy levels has a certain number of

microstates Wj, the sum of all Wj is the total number of microstates
of a system. That is.

=

2.2 Distribution of states cont
There are 16 ways of distribution of four
distinguishable particles in two identical boxes.
2.3 Distinguishable particles

Consider N distinguishable (terbedakan) or

localized particles distribute into N non degenerate
energy levels.
= . . = !
Now consider another kind of distribution that the numbers of
particles occupied in different energy levels are denoted as n1,
n2, , ni. All the energy levels are still nondegenerate.

! ! !
= = = =
1!2!3!! !
!

Konfigurasi seketika subsistem Konfigurasi seketika makrosistem

2.3 Distinguishable particles cont
Three different distributions
of six particles. The
exchanges of particles in the
same energy level do not
create new microstate
because every energy level
has only one quantum state.
The numbers of microstates
for three distributions are

6! 6! 6!
WA 6 WB 60 WC 180
1!5! 3!2!1! 2!2!1!1!
2.4The Method of the Most Probable Distribution

The distribution peaks sharply about its maximum as N increases.

To obtain ensemble properties, we replace the weighted average by the

most probable distribution.

To find the most probable distribution we need to find the maximum of W

subject to the constraints of the ensemble.

This requires two mathematical tools, Stirlings approximation and

Lagranges method of undermined multipliers.
 Stirlings Approximation

This is an approximation for the logarithm of the factorial of large numbers.

The results is easily derived by approximating the sum by an integral.

ln N ! N ln N N
 Lagranges Method of
Undetermined Multipliers

Extremize the function f ( x1 , , xn ) subject to the constraint g ( x1 , , xn ) 0.

n
f
The function has an extremum if f x j 0.
j 1 x j
n
g
The constraint condition is satisfied at all points, so g x j 0.
j 1 x j

This relation connects the variations of the variables, so only n-1 of them are
independent. We introduce a parameter l and combine the two relations into

n f g


j 1 x j
l
x j
x j 0.

Lets pick variable xm as the dependent one. We choose l such that
 f g
l 0
xm xm

This allows us to rewrite the previous equation in the form

n f g

j m x j
l
x j
x j 0.

Because all the variables in this equation are independent, we can vary them
arbitrarily, so we conclude
f g
l 0 for all j m
x j x j

Combined with the equation specifying l, we have

f g
l 0 for all j
x j x j

Notice that Lagranges method doesnt tell us how to determine l.

 The Boltzmann Factor

where a and b are Lagrange multipliers. Using the expression for W,

applying Stirlings approximation and evaluating the derivative we find

j / kT
nj = N( ) n j le
It can be shown that
ni e bEi Boltzmann Distribution
Pi
b 1/ k BT N e bE j
j
(Probability function for
energy distribution)
At a temperature T the probability that a system is in a state with quantum
mechanical energy Ej is

b Ej
e
Pj
Q

Q e
b Ej
(b 1/ kBT ) canonical partition function
j
 3. Boltzmann distribution
For a large number of noninteracting particles
j / kT
n j le nj = N( )

= 1.3810-23 J K-1, Boltzmann constant. is proportional

coefficient. The population can also be expressed in the form of
energy level distribution (gi = jumlah/tingkat degenerasi)
i / kT
ni l gi e
The total number is

N n j le
j / kT
N ni l gi e i / kT

j j i i
 3. Boltzmann distribution cont
N N
then l
e
j / kT
i
g e
i
i / kT

j
Define the particle partition function

q e
j / kT
q gi e i / kT

j i
then
N j / kT N i / kT
nj e ni gi e
q q
The distribution that obeys these equations is called the Boltzmann
distribution. The equations are also known as Boltzmann
distribution law.
4. Computations of the partition function

5.1 Some features of partition functions

(1) at T=0, the partition function is equal to the
degeneracy of the ground state.
i
q gi e

kT lim q g 0
T 0
i
(2) When T is so high that for each term i/kT=0,
lim q
T
q = fungsi partisi molekul, yaitu memberikan indikasi jumlah
keadaan rata-rata yang dapat dicapai secara termal oleh
molekul pada temperatur sistem tersebut
 4.1 Some features of partition functions cont

(3) factorization property If the energy is a sum of those from

independent modes of motion, then
q qt qr qv qe qn
i t , i r , i v , i e , i n ,i
g i g t , i g r , i gv , i g e , i g n , i
The partition functions for 5 mode motions are expressed as
t ,i r ,i v ,i

qt gt ,i e kT
; qr g r ,i e kT
; qv g v ,i e kT

i i i
e ,i e ,i

qe ge,i e kT
; qe ge,i e kT

i i
4.1 Some features of partition functions cont

t ,i r,i
q [ g t,i exp( )] [ g r,i exp( )]
i kT i kT
v,i e,i
[ g v,i exp( )] [ g e,i exp( )]
i kT i kT
n,i
[ g n.i exp( )]
i kT
qt qr qv qe qn
4.2 Zero-point energy

zero-point energy is the energy at ground state or

the energy as the temperature is lowered to
absolute zero.
Suppose some energy level of ground state is 0,
and the value of energy at level i is i, the energy
value of level i relative to ground state is

i 0
i
0

Taking the energy value at ground state as zero,

we can denote the partition function as q0.
4.2 Zero-point energy cont
i0
0
q gi e
0 kT

i q e kT q
0

t ,0 / kT r ,0 / kT v ,0 / kT
q e
0
t qt ; q e
0
r qr ; q e
0
v qv
e ,0 / kT n ,0 / kT
q e
0
e qe ; q e
0
n qn
Since t,00, r,0=0, at ordinary temperatures.

q qt , q qr
0
t
0
r
4.2 Zero-point energy cont
The vibrational energy at ground state is

v,0 h 1
2
therefore
h /2 kT
q e
0
v qv
the number of distribution in any levels does not
depend on the selection of zero-point energy.
N i / kT N ( i0 0 )/ kT N i0 / kT
ni gi e 0 0 / kT gi e 0 gi e
q q e q
4.3 Translational partition function

Energy level for translation

h n 2 2
nz2n y2
i ,t ( 2 2)
x
2
8m a b c
The partition function

t ,i
qt gt ,i exp( )
i kT
 4.3 Translational partition function cont

h 2 nx2 n y2 n 2
qt exp 2 2 2 / kT
z

nx 1 n y 1 nz 1 8m a b c

h2 2

h2 2

h2 2
exp 2 x
n exp 2 y
n exp 2 z
n
nx 1 8mkTa ny 1 8mkTb nz 1 8mkTc
qt , x qt , y qt , z

h2 2

h 2
2
exp
qt , x exp 2 y
qt , y n
2 x
n n y 1 8mkTb
nx 1 8mkTa

h2 2
qt , z exp 2 z
n
nz 1 8mkTc
Take qt,x as an example
2 2
h n
qt, x exp( ) x
2
nx 1 8mkT a
2
h
exp(a n )2 2
x ( 2
a
2

nx 1 8mkTa
For a gas at ordinary temperature 2<<1, the summation
converts into an integral.

qt,x exp(a n )dnx 2 2
x
0
 1 12

a x 2
From mathematic relations in Appendix e dx ( )
0 2 a
1 2 mkT 1
qt,x ( ) 2 ( a
1
2
)
2a h 2

q t,y In like manner,

q t,z
2 mkT 3 2
qt ( 2
) a bc
h
2 mkT 3 2
( 2
) V
h
 Example Calculate the molecular partition
function q for He in a cubical box with sides 10cm
at 298K.
Solution The volume of the box is V=0.001m3.
The mass of the He molecule is
0.004/(6.0221023)=6.646610-27kg. Substituting
these numbers and the proper natural constants,
we have
3/2
2 6.6466 10 1.38 10
27 23
298
q 34 2 0.001 7.820 1027
(6.626 10 )
For ideal gas,

M nRT NkT
m V
L p p

T K
3 5
2
8.2052 107 N M 1
2

kg mol
qt
p
Pa
 4.4 Rotational partition function
The rotational energy of a linear molecule is given by
r = J(J+1)h2/82I and each J level is 2J+1 degenerate.
h2
r J ( J 1) J 0
1
2
8 I 2

r ,i

h2
qr g r ,i e kT
(2 J 1) exp J ( J 1) 2
i J 0 8 IkT
define the characteristic rotational temperature

h2
r 2
8 Ik
4.4 Rotational partition function cont

J ( J 1) r
qr (2 J 1) exp( )
J 0 T
r<<T at ordinary temperature, The summation can be
approximated by an integral

qr (2 J 1) exp J ( J 1)r / T dJ
0
Let J(J+1)=x, hence J(2J+1)dJ=dx, then

qr exp( xr / T )dx T r 8 IkT h 2 2
0
4.4 Rotational partition function cont

For a homonuclear diatomic molecule, such as O2, it comes back

to the same state after only 180o rotation.

T 8 2 IkT
qr
r h 2

where is called the symmetry number. is the number of

indistinguishable orientations that a molecule can exhibit by
being rotated around symmetry axis. It is equal to unity for
heteronuclear diatomic molecules and is equal to 2 for
mononuclear diatomic molecules.
For HCl, = 1; and for Cl2, = 2.
 4.5 Vibrational partition function

Vibrational energies for one dimensional oscillator are

1
v (v )h v 0,1, 2,
2
Vibration is non-degenerate, g=1. The partition function is

v ,i

1
qv gv ,i e kT
exp v h / kT
i v 0 2
 4.5 Vibrational partition function cont

Define the characteristic vibrational temperature

h
v , v
k
v 3 v 5 v
qv exp( ) exp( ) exp( )
2T 2T 2T
v v 2 v
exp( ) [1 exp( ) exp( ) ]
2T T T
4.5 Vibrational partition function cont

Characteristic vibrational temperatures are usually

several thousands of Kelvins except for very low
frequency vibrational modes.

v,H 5986K
2

v,CO 3084K

v,O 2239K
2

we cannot use integral instead of summation in the calculation

of vibrational partition function.
4.5 Vibrational partition function cont

v v
At low T 1 exp( ) 1 according
T T
to mathematics
1
when x 1 1 x x
2

1 x
v /2T
v /2T 1 e 1
qv e v /T
v /2T v /2T
1 x 1 e e e
4.5 Vibrational partition function cont

take the ground energy level as zero,

qv0 exp v,0 / kT qv 1

1 exp( h )
kT
For NO, the characteristic vibrational temperature is
2690K. At room temperature v/T is about 9;
the qv0 1 , indicating that the vibration is almost in the
ground state.
 4.6 Electronic and nuclear partition function

e,0 e,1
qe ge,0 exp( ) ge,1 exp( )
kT kT
e,0 ge,1 e,1 e,0
ge,0 exp( )[1 exp( ) ]
kT ge,0 kT

( e,1 e,0 ) 400 kJ mol , -1

Energy difference is large, so electrons are generally at ground

state, all terms except first one in the summation expression is
negligible.
e,0 e ,0 / kT
qe ge,0 exp( ) q e0
e qe ge,0
kT
4.6 Electronic and nuclear partition function cont

If the quantum number of total angular momentum

for electronic motion is j, the degeneracy is (2j+1).
Then the electronic partition function can be
written as
q 2 j 1
e
0

A rare exception is halide atoms and NO molecule.

The difference between the ground state and the
first excited state of them are not so large, the
second term in the summation has to be
considered.
 Nuclear motion

Nuclear motion is always in the ground state at ordinary

chemical and physical process because of large energy
difference between ground and first excited state. Its
partition function has the form of
n,0
qn g n,0 exp( )
kT
q gn,0 2I 1
0
n

where I is a quantum number of nuclear spin.

 Thermodynamic Properties of the Canonical Ensemble

Postulate:
The ensemble average

j j e
1 b Ej
P E Q E j Q 1E U ( N ,V , T )
j j

is the observable internal energy.

From the above,

ln Q 2 ln Q
U k T
b
B
N ,V T N ,V

U 1 U 2
ln Q
cv 2 kB b
2
2
constant-volume heat capacity
T N ,V k BT b N ,V b N ,V
 Separable Systems

The partition function for a system of two types of noninteracting particles,

described by the Hamiltonian

H H (1) H (2)

with energy eigenvalues

E jk (1)
j k
(2)

is
Q Q(1)Q(2)

If the energy can be written as a sum of various (single-particle-like)

contributions, the partition function is a product of the corresponding
components.
 Distinguishable vs. Indistinguishable Particles

The partition function for a system of N distinguishable particles is

Q qN

where q is the partition function of one particle.

The partition function for a system of N indistinguishable particles is

Q q N /N !
 Partition Function for Polyatomic Molecules

The Hamiltonian of a molecule is often approximated by a sum of

translational, rotational, vibrational and electronic contributions:

H H trans H rot H vib H elec

Within this approximation the molecular partition function is

q q trans q rot q vib q elec

 Translational Partition function

Atom in box of volume V:

3

2 mk BT 2

q trans
(V , T ) V

2
h

Translational energy of an ideal gas:

3
U trans
(V , T ) RT
2

Translational contribution to the heat capacity of an ideal gas:

3
c trans
v R
2
 Electronic Partition function

There is no general expression for electronic energies, thus one cannot write an
expression for the electronic partition function. However, electronic excitation
energies usually are large, so at ordinary temperatures

q elec (V , T ) 1
 Vibrational Partition Function for Diatomic Molecule

vvib v 12 (harmonic oscillator approximation)

e b /2 evib / 2T
q vib
b
vib / T
, "vibrational temperature"
1 e 1 e
vib
kB

Vibrational energy of diatomic molecule:

1 1
U vib N b
2 e 1

Vibrational contribution to heat capacity of diatomic molecule:

vib e vib / T
2

cvvib R

T 1 e vib / T
2

As T , cvvib R
 Rotational Partition Function for Diatomic Molecule
2
J ( J 1)
Jrot (rigid rotor approximation, (2J +1)-fold degeneracy)
2I

8 2 IkBT T h2
q rot , rot 2 "rotational temperature"
h 2
rot 8 IkB

Rotational energy of diatomic molecule:

U rot NkBT

Rotational contribution to heat capacity of diatomic molecule:

cvrot R
Symmetry factors:
If there are identical atoms in a molecule some rotational operations result in
identical states. We introduce the symmetry factor to correct this
overcounting.

T
q rot

rot

For homonuclear diatomic molecules at high temperature =2.

 Polyatomic Molecules

n atoms, 3n degrees of freedom.

Nonlinear molecules:
3 Translational degrees of freedom a
3 Rotational degrees of freedom q vib
q vib
j ,
j 1
3n-6 Vibrational degrees of freedom

3n 5 (linear)
a
Linear molecules: 3n 6 (nonlinear)
3 Translational degrees of freedom
2 Rotational degrees of freedom
3n-5 Vibrational degrees of freedom
 Rotational partition function for linear polyatomic molecules

T h2
q rot
, rot 2
rot 8 IkB

Symmetry factor:
The number of different ways the molecule can be rotated into an
indistinguishable configuration.

Asymmetric molecules: 1 (e.g. COS)

Symmetric molecules: 2 (e.g. CO2 , HC CH)
 Rotational partition function for nonlinear polyatomic molecules

Rotational properties of rigid bodies: three moments of inertia IA , IB , IC .

I A I B IC spherical top (e.g. CH 4 )

I A I B IC symmetric top (e.g. NH3 )
I A I B IC asymmetric top (e.g. H 2O)

8 Ik BT 2 2

Spherical top: q rot

h 2
1

8 I A k BT 8 I C k BT
2 2 2

Symmetric top: q rot

h2 h 2

1 1 1

8 I A k BT 8 I B k BT 8 I C k BT
2 2 2 2 2 2

Asymmetric top: q rot

h2

h 2
h 2

The symmetry factor equals the number of pure rotational elements (including the
identity) in the point group of a nonlinear molecule.
 The Normal Mode Transformation

3n

p 2
H i +V (r1 ,r2 , ) (Cartesian atomic coordinates)
i 1 2mi

Expand the potential in a Taylor series about the minimum through quadratic terms:

1 3n 3n 1 T
V
2 i 1 j 1
x K x
i ij j
2
x K x ( xi =ri - ri min Cartesian displacement coordinates)

2V
where Kij force constant matrix
xi x j

We will show in a simple way how one can obtain an independent mode form by doing a
coordinate transformation. In practice, the normal mode transformation proceeds after the
Hamiltonian in expressed in internal coordinates.
 Transform to mass-weighted Cartesian coordinates qi mi xi

pi2 1 2 3n
1 2 1 3n 3n
Then = pi and H pi qi Kij q j
2m 2 i 1 2 2 i 1 j 1

2V 12 12 V
2
Kij mi m j
qi q j xi x j

Introduce normal mode coordinates Qi (with conjugate momenta Pi ): U Q q

q K q QT U T K U Q Q T Q

UT K U , or K U U

U is the orthogonal matrix of eigenvectors, L is the diagonal matrix of eigenvalues.

3n
1 2 1 3n 2 2
Now H Pi i Qi
i 1 2 2 i 1
 The Equipartition Principle

Every quadratic term in the Hamiltonian of a system contributes kBT to the

internal energy U and kB to the heat capacity cv at high temperature.

1
p 2
1
Translation in one dimension: H (one quadratic term) k B
2 m 2
2
1 d 1
Rotation about an axis: H (one quadratic term) k B
2 d 2 2
(linear molecules: 2 such terms, nonlinear molecules: 3 such terms)
1
p 2
1
Vibration: H m 2 x 2 (two quadratic terms) k B
2 m 2

Diatomic molecule: 3 kB
Linear triatomic molecule: 6 kB
Nonlinear triatomic molecule: 6 kB
THE FIRST LAW OF THERMODYNAMICS

The first law is about conservation of energy

(in the form of work and heat)
 Mechanical Work

Expansion of a gas

removing pins
m h
piston held
down by pins
Pi , Vi Pf , V f

Work performed by the gas: w Pext V Convention: work done on the

system is taken as positive.
Infinitesimal volume change: w Pext V

Vf
Mechanical work: w Pext (V )dV
Vi
 Reversible Processes

A process is called reversible if Psystem= Pext at all times. The work expended to
compress a gas along a reversible path can be completely recovered upon reversing
the path.

When the process is reversible the path can be reversed, so expansion and
compression correspond to the same amount of work.
To be reversible, a process must be infinitely slow.

A process is called reversible if Psystem= Pext at all times.

Vf
w P(V )dV
Vi
Reversible Isothermal Expansion/Compression of Ideal Gas

P
P

Pi Vf
w nRT ln
Vi
Pf

V
Vi Vf

Reversible isothermal compression: minimum possible work

Reversible isothermal expansion: maximum possible work
 Exact and Inexact Differentials

A state function is a property that depends solely on the state of the system. It does not
P
depend on how the system was brought to that state.
When a system is brought from an initial to a final state, the change in a state function is
independent of the path followed.
An infinitesimal change of a state function is an exact differential.

Internal energy U : state function

dU : exact differential
f
i
dU U f U i U , independent of the path

Work and heat are not state functions and do not correspond to exact differentials.
Of the three thermodynamic variables, only two are independent. It is convenient to
choose V and T as the independent variables for U.
 The First Law

The sum of the heat q transferred to a system and the work w performed on it equal
P
the change U in the systems internal energy.

U q w

Postulate: The internal energy is a state function of the system.

Work and heat are not state functions and do not correspond to exact differentials.

PdV
dU dq
Work and Heat along Reversible Isothermal Expansion
for an Ideal Gas, where U=U(T)
P reversible VC
P constant-pressure TB TA
VA
V
PA
A B reversible wAC nRTA ln C
isothermal VA
wBC 0
wAB PA VB VA
PC C

V VC
VA VC U AC 0 q AC nRTA ln
VA
TC
qBC U BC cV dT
TB

TB
U AB cV dT
TA

q AB U AB wAB cV dT PA VB VA
TB

TA
 Free Expansion

P
Suddenly remove the partition

No work, no heat! U 0

U
dU cV dT dV U U (T ) T 0
V T

U
For real, non-ideal gases these hold approximately, and is small.
V T
 Adiabatic Processes
A process is called adiabatic if no heat is transferred to or out of the system.
U wad , dU dwad
P
dU cV dT PdV
P reversible
constant-pressure nRT
dV (ideal gas)
V
A B reversible isothermal
PA
If cV(T) is known, this can be used to determine
PC C T (and thus also P) as a function of V.
D For a monatomic ideal gas,
V
VA VC cV 23 nR independent of T
reversible adiabatic
3

TD VA
2

Adiabatic cooling!

TA VD

Gases heat up when compressed adiabatically.

(This is why the pump used to inflate a tire becomes hot during pumping.)
 Enthalpy

H U PV
P
VdP enthalpy function
dH dU PdV VdP dq

H
Heat capacity at constant pressure: cP =
T P

Ideal gas: cP cV nR

Heat transferred at constant pressure is enthalpy change.

Reversible Adiabatic Expansion of Ideal Gas Revisited

c dT PdV c dT VdP 0
dq V P

cV dT PdV , cP dT VdP
cP
d ln V d ln P
cV
V2 P1
If cP / cV is constant (e.g., monatomic ideal gas),
V1 P2

5 5
For a monatomic ideal gas, cP nR,
2 3
5
PV const.
3
 ENTROPY AND THE SECOND LAW

Processes evolve toward states of minimum energy and maximum disorder.

These two tendencies are in competition.

The second law is about entropy and its role in determining whether a
process will proceed spontaneously.
 Entropy

A statement of the second law:

P
No process is possible whose sole effect is the absorption of heat from a reservoir and
the conversion of this heat into work.

Postulate:
There exists a state function S called the entropy. This is such that, for a reversible
process,

dq
dS
T
dS 0
.
1/T is the integrating factor for dq

S has units of R (or kB). For a reversible process, dU TdS PdV

Isolated system is a system that cannot exchange any matter or energy with the
environment.

PThe second law: The entropy of an isolated system never decreases.

A spontaneous process that starts from a given initial condition always leads to the
same final state. This final state is the equilibrium state.
 Entropy of an Ideal Gas

nRT
dU cV dT TdS PdV TdS dV
V
dT dV
dS cV nR
T V
T V V
S cV (T ) d ln T nR d ln V f (T ) f (T0 ) nR ln
T0 V0 V0
S (T ,V ) independent of the path!

nRT
dH cP dT TdS VdP TdS dP
P
dT dP
dS cP nR
T P
T P P
S cP (T ) d ln T nR d ln P g (T ) g (T0 ) nR ln
T0 P0 P0
S (T , P )
 The Clausius Principle

The Clausius principle states that

No process is possible whose sole result is the transfer of heat from a cooler body to a
hotter body.
The Clausius principle is another statement of the second law.

dU dU A dU B 0 (isolated system)
A B dU A dU B 1 1
dS dSA dSB dU A
TA TB TA TB

According to Clausius principle, if TA > TB then heat will flow from A to B, i.e.,

dS 0

A spontaneous process evolves in the direction of increasing entropy.

Reversible vs. Spontaneous (Irreversible) Processes

0.
In an isolated system dq

dq
Reversible process: dS .
T

dq
Spontaneous (irreversible) process: dS .
T

dq
In general, dS .
T

A reversible adiabatic process is an isentropic process, dS = 0.

 The Caratheodory Principle

This is yet another statement of the second law. It states that

In the neighborhood (however close) of any equilibrium state of a system (of any
number of thermodynamic coordinates) there exist states that cannot be reached by
reversible adiabatic processes.
Caratheodorys statement is equivalent to the existence of the entropy function.

Family of isentropic (constant S)

surfaces that dont intersect.
S1
S2
S3
V
Proof of Existence of Non-Intersecting Adiabatic Surfaces

Suppose B can be reached from A by a reversible adiabatic process. Lets suppose C

can also be reached from A via a reversible adiabatic process.

P Consider the process A B C A.

A U A B C A 0 qB C wA B ,C A
qBC 0 (heat absorption)
wA B ,C A qB C 0
C
B

So in this cycle there is heat absorbed that is converted into work. This is in
contradiction with the second law. We arrived at this contradiction by assuming
there are two reversible adiabatic processes starting from point A.
 The Carnot Cycle
P
A AB: reversible isothermal at temperature T1
BC: reversible adiabatic
B
CD: reversible isothermal at temperature T2 < T1
DA: reversible adiabatic
D
C U ABCDA 0 q AB qCD w 0
V (the system does work)

w q
Efficiency of Carnot engine: 1 CD
q AB q AB

B
dq q q qCD T
Entropy changes: S AB AB , SCD CD S AB 2
A T T1 T2 q AB T1

1
T2
1 (unless T2 0) One can never utilize all the thermal energy given to the
T1 engine by converting it into mechanical work.
 The Internal Combustion Engine
In the gasoline engine, the cycle involves six processes, four
of which require motion of the piston and are called strokes.
The idealized description of the engine is the Otto cycle.

1. Intake stroke. A mixture of gasoline vapor and air is

drawn into the cylinder (EA).
P
2. Compression stroke. The mixture of gasoline vapor and
air is compressed until its pressure and temperature rise C
considerably (AB).
3. Ignition. Combustion of the hot mixture is caused by an
electric spark. The resulting combustion products attain
D
a very high pressure and temperature, but the volume
remains unchanged (BC). B
4. Power stroke. The hot combustion products expand and
push the piston out, thus expanding adiabatically (CD). E A
5. Valve exhaust. An exhaust valve allows some gas to V
escape until the pressure drops to that of the atmosphere
(DA).
6. Exhaust stroke. The piston pushes almost all the
remaining combustion products out of the cylinder (AE).
 Thermodynamics of the Otto Cycle
P
C Reversible adiabatic compression AB: TAVA 1 TBVB 1

BC is reversible absorption of heat qh from a series of

D reservoirs whose temperatures range from TB to TC :
TC
B qh cV dT .
TB

E A If we assume cV is constant, qh cV (TC TB ).

V

Reversible adiabatic expansion CD: TCVC 1 TDVD 1 or TCVB 1 TDVA 1

DA is reversible rejection of heat qc to a series of reservoirs whose temperatures range

TA
from TD to TA : qc cV dT cV (TD TA ).
TD

1
q T T V
1 c 1 D A 1 B VB / VA : compression ratio
qh TC TB VA
 Other Ideal Gas Engines

See http://www.ac.wwu.edu/~vawter/PhysicsNet/Topics/ThermLaw2/Entropy/GasCycleEngines.html

copied in 444-web-page/Ideal Heat Engine Gas Cycles.htm

 Entropy of Reversible Isothermal Expansion
of an Ideal Gas

Reversible isothermal expansion: dq sys dU sys d wsys

But dU sys 0 dq sys PdV

dq
2 V2 PdV V2 dV V2
Ssys sys
nR nR ln 0
1 T V1 T V1 V V1
The heat entering the system was absorbed from the environment. Then

dq env dq sys Senv Ssys , Suniv 0.
Entropy of Spontaneous Expansion of an Ideal Gas

Spontaneous expansion: q sys U sys wsys 0

Entropy is a state function, so the entropy change of the system has the
same value as that during a reversible (isothermal) expansion:
V2
Ssys nR ln 0
V1
Because no heat is absorbed from the environment,

dq env 0 Senv 0, S univ 0.

The entropy of the system increased, but the entropy of the environment
remained unchanged.
 Statistical Mechanical Definition of Entropy

Sensemble kB ln W

Completely ordered ensemble: a1 1, a2 a3 0 Sensemble 0

Maximum disorder: a1 a2 a3 (set that maximizes W )

1
Ssys Sensemble
A
 1 A !
Ssys Sensemble Use W and apply Stirling's approximation.
A aj !
j

ln W lnA ! ln a j ! A lnA A a j ln a j a j
j j

Sensemble k BA lnA k B a j ln a j
j

aj
Use populations pj
A
Sensemble k BA lnA k B A p j lnA p j
j

k BA lnA k BA p
j
j lnA k BA p
j
j ln p j

Ssys kB p j ln p j
j
 Pure and Mixed States

If all replicas of our system in a particular ensemble are in the same state n, i.e.,

pn 1, pi n 0 then S 0. This is called a pure ensemble.

Note: the quantum state n need not be an eigenstate of the Hamiltonian.

If the members of the ensemble are in different quantum states, i.e.,

pi 1 for all i, then S 0. This is called a mixed ensemble.

The canonical ensemble is a mixed ensemble.

 Entropy of the Canonical Ensemble
pi Q 1e b Ei

S k B Q 1 e b Ei b Ei ln Q k B b U k B ln Q
i

U
S k B ln Q
T

ln Q
From U k BT 2 it follows that
T N ,V

ln Q
S k BT k B ln Q
T N ,V
 Entropy of Monatomic Ideal Gas

ln Qtrans
S k BT k B ln Qtrans
T N ,V

ln Qtrans 3N
. Using Stirling's approximation to ln N !,
T N ,V 2 T

2 mk T 2 V
3
5
S nR nR ln B

h N A
2
2
 Molecular Interpretation of Work and Heat

b Ej
dU p j dE j E j dp j
e
U pjEj, pj
j Q j j

variation of energy levels change populations without

without changing populations; changing energy eigenvalues;
can be done by changing can be done by heating
the volume. or cooling

E
dU p j j dV E j dp j PdV dq
j V N j

Q b E j E j
Q e j ,
b E
b e V
j V N ,b j N

E j ln Q E dp
P p j k BT dq j j
j V N V N ,b j
Example: Monatomic ideal gas

3N

1 2 m 2
ln Q N
Q V N

N ! h2 b V N , b V

N T
P k BT nR ideal gas law!
V V

We see that the ideal gas law is obtained by using relations obtained for a gas of non-interacting
particles.
 The Boltzmann Factor:
Determination of the Lagrange Multiplier

S k B p j ln p j dS k B ln p j dp j dp j k B ln p j dp j
j j j

because dp
j
j 0

dS k B b E j ln Q dp j b k B E j dp j b k B dq
dq

j j T

1
b kB
T
 THE THIRD LAW

The third law is about the impossibility of attaining the absolute zero of
temperature in a thermodynamic system.
 Entropy as a Function of Temperature

P U S
dU TdS PdV cV T
T V T V

T2
S (T2 ) S (T1 ) cV (T )d ln T under constant V
T1

H S
dH TdS VdP c T

P
T P T P

T2
S (T2 ) S (T1 ) cP (T )d ln T under constant P
T1
 The third law:
Absolute zero is not attainable via a finite series of processes.

P according to the Nernst-Simon statement,

or,

The entropy change associated with any isothermal reversible process of a condensed
system approaches zero as the temperature approaches zero.

cV
dS dT at constant V
T
Crystals: cV T 3 as T 0 dS T 2 dT as T 0

S kB p j ln p j
j

The entropy of a system that has a non-degenerate ground state vanishes at the absolute
zero.
 First-Order Phase Transitions

Many thermodynamic variables are discontinuous across first-order phase transitions.

P

S
T
Phase I

T0
cPII (T )dT

H
T

(constant P)
cPI (T )dT
0
T0
Phase II

T0 T
 Helmholtz and Gibbs Free Energies

A U TS Helmholtz free energy

dA TdS PdV TdS SdT SdT PdV
A A(T ,V )

G A PV U TS PV Gibbs free energy

dG SdT PdV PdV VdP SdT VdP
G G (T , P )

Reversible isothermal process under constant volume: dA = 0

Reversible isothermal process under constant pressure: dG = 0
 Legendre Transforms
It is often desirable to express a thermodynamic function in terms of different
independent variables. Most often this new desirable variable is the first
derivative of a fundamental function with respect to one of its undesirable
independent variables; for example,

U U ( S ,V )
U
dU TdS PdV , P
V S
We are seeking a general tool for finding a new function that contains the
same information as the original fundamental thermodynamic function, but
where the undesirable variable has been eliminated in favor of the
desirable one. In the previous example,

We seek a new function H H ( S , P) that is equivalent

to U but which depends on the variable P rather than V .
 General Theory of Legendre Transformation

f Given a function f (x), we seek an

equivalent function (i.e., one containing
the same information as f ) whose
independent variable is df /dx.
The curve f (x) can be reconstructed from
the family of its tangent lines.
x
A tangent line can be specified by its slope f (new independent variable)
and intercept .
f
Notice f f x f ( x) Legendre tranform of f
x

We solve f ( x) for x and substitute in the above relation to obtain

( x). This is possible if f is single-valued, i.e., f 0 at all x.
 Application of Legendre Transform Theory

U
T
S V
U U ( S ,V ) A A(T ,V ) U TS
dU TdS PdV dA SdT PdV

U A
P P
V S V T

G G (T , P) A ( P)V
H H ( S , P) U ( P)V
H TS U TS PV
dH TdS VdP H
T dG SdT VdP
S P
 Maxwells Relations

f ( x1 , x2 )
df y1dx1 y2 dx2 y2 y1


1 x2 2 x1
x x
f f
y1 y2
x1 x2 x2 x1

Conversely, if the Maxwell relation is satisfied, one can conclude that df is

an exact differential.
 Examples

dU TdS PdV
U U T P
T P
S V V S V S S V

dA SdT PdV
A A S P
S , P
T V V T V T T V

dH TdS VdP dG SdT VdP

T V S V

P S S P P T T P
 Applications of Maxwells Relations

Entropy of a gas:

S S
dS dT dV
T V V T
S P
At constant T , dS dV dV
V T T V
V2 P
S2 S1 dV along an isothermal process
V1
T V
P nR V2
Ideal gas: S2 S1 nR ln
T V V V1
Internal energy of a gas:

U S P
dU TdS PdV P T P T
V T V T T V
U P
At constant T , dU dV P T dV
V T T V
V2 P
U 2 U1 P T dV along an isothermal process
V1
T V

We may choose a sufficiently large value of V1 such that U1 is given by

the ideal gas law, then calculate the internal energy at a different volume
where the gas does not exhibit ideal behavior.
 Pfaffian Forms

Extensive variable Intensive variable Work

V (gas volume) -P -P dV

L (wire length) F (force) F dL

A (film area) S (surface tension) -S dA

M (magnetic dipole moment) H (magnetic field) H dM

dU TdS Yi dX i Pfaffian form

i

X i : extensive variable
Yi : intensive variable
 PHASE EQUILIBRIUM

What is the equilibrium state of a multi-component system?

 Phase Diagrams
Water

Carbon Dioxide
(Typical Case)

Phase transitions (melting, freezing, boiling, sublimation, etc.)

 Chemical Potential

Intensive variable m such that dwchem m j dn j "chemical work"
j

(The sum is over all components of a system and nj are the mole numbers.)

dU TdS PdV m j dn j U H
j mi
n S ,V ,n n S , P ,n
dH TdS VdP m j dn j i j i
i j i

j
A G
dA SdT PdV m j dn j

i T ,V ,n j i i T , P ,n j i
n n
j

dG SdT VdP m j dn j
j

Pure substance: G( P, T , n) n g ( P, T ) m g ( P, T )

The chemical potential of a pure substance is the molar Gibbs free energy.
 General Conditions of Equilibrium

An isolated system tends to attain the state of maximum entropy with respect
to its internal (extensive) degrees of freedom, subject to the given external
constraints.
dS = 0, d2S < 0

Consequence:
The thermodynamic potentials attain minimum values with respect to their
internal extensive variables at equilibrium, subject to the given external
constraints.
 I. Thermal Equilibrium
Constraints:
A B V A const., V B const., U U A U B const.
"Internal variable": U A
rigid, diathermal wall
impermeable to matter

U A U A ( S A ,V A ) and S S A (U A ,V A ) S B (U B ,V B )

Since the volumes cannot change,

S A S A S A S A
dS dU A
dU B
dU A

U V A U V B U V A U V B
A B A B

S 1
From dU TdS PdV we find and therefore
U V T
1 1
dS A B dU A
T T
At equilibrium dS 0 for any dU A . It follows that T T
A B
 II. Thermal and Mechanical Equilibrium
Constraints:
A B V V A V B const., U U A U B const.
"Internal variables": U A , V A
movable, diathermal wall
impermeable to matter

S A S A S A S A
dS dU A
dV A
dU B
dV B

U V A V U A U V B V U B
A A B B

S A S A S A S A A
A
B dU
A
A
B dV
U V A U V B V U A V U B
S 1 S P
From dU TdS PdV we find , and therefore
U V T V U T
1 1 P A PB A
dS A B dU A B dV .
A

T T T T
At equilibrium dS 0 for any dU A , dV A . It follows that T A T B , P A PB
 III. Equilibrium with Respect to Matter Flow

Rigid, diathermal
wall permeable to substance 1
A B
Internal variables: U A , n1A

S A S A S B S B
dS A
dU A
A dn A
B
dU B
B dn B

1 1
U V ,n1
A A 1 V ,U
n A A U V ,n1
B B 1 V ,U
n B B

S m1
dU TdS PdV m j dn j
j
1 U ,V
n T

1 1 m1A m1B A
dS A B dU A B dn1
A

T T T T

At equilibrium T A T B , m1A m1B

 1st Order Phase Transitions:
The Clausius-Clapeyron Equation

P
Phase I
B
A
A
Phase II

T
d m I m BI m AI S I dT V I dP
d m II m BII m AII S II dT V II dP

dP S III
V II
V I
dP S II
S dT
I

dT V III

dP H
Clapeyron equation
dT T V
Liquid-to-vapor transition

dP
S l g 0, V l g 0 0
dT
Increase in pressure causes conversion to the higher-density liquid phase.

Solid-to-liquid transition

S sl 0
dP
If V sl 0 then 0
dT
dP
If V sl 0 then 0. This is the case with water.
dT

The Clapeyron equation is an expression of Le Chateliers principle.

Approximation for liquid-vapor phase transition:

RT
Vg V l, V g (ideal gas), so
P

1 dP H l g
Clausius-Clapeyron approximation
P dT RT 2
Statistical Mechanical Calculation of Chemical Potential

G A
m
n P ,T n T ,V

ln Q ln Q
A U TS k BT
2
T k BT k B ln Q
T N ,V T N ,V

A k BT ln Q

ln Q ln Q
m k BT RT
n T ,V N T ,V
 Chemical Potential of Ideal Gas
qN
Q ln Q N ln q ln N ! N ln q ( N ln N N )
N!

ln Q q
ln
N N

n V k BT
PV nRT N A RT Nk BT
NA N P

q k BT q
m RT ln RT ln k BT RT ln P
V P V

q k BT P P
m RT ln 0
RT ln , or m m0 RT ln
V P P0 P0

P0 standard pressure (105 Pa)

SOLUTIONS
We consider a two-component system with mole numbers n1 and n2.

dG VdP SdT m1dn1 m 2 dn2

dG m1dn1 m 2 dn2 at constant P and T

Imagine increasing the mole numbers from 0 to their final values by varying a
dimensionless parameter l:

dn1 n1d l , dn2 n2 d l

n1 n2 1
G m1dn1 m 2 dn2 ( m1n1 m 2 n2 )d l m1n1 m 2 n2
0 0 0

G G1 G2 G1n1 G2 n2
Gi : partial molar free energies
Gi mi
The partial molar free energy is the chemical potential of the substance, i.e., an
intensive variable. However, the partial molar free energies generally depend on
the mole fraction n1 /(n1 n2 ) . This is so because the partial derivatives

G
mi

i T , P ,n
n
j i

are functions of all the variables, including nj.

Using a similar procedure we can write

V V1 V2 V1n1 V2 n2 (Vi : partial molar volumes)

The partial molar volumes depend on the mole fraction of the particular substance
in the solution and are not additive when substances are mixed! This statement
applies generally to any extensive variable. Of course extensive variables still
scale linearly with the total number of moles, provided the mole fraction of each
substance remains fixed.
 Euler Relations

The internal energy U is a function of extensive variables, U U ( S ,V , n1 , n2 , ).

Based on the previous remarks, U is a homogeneous first order property, i.e.,

U (l S , lV , l n1 , l n2 , ) lU ( S ,V , n1 , n2 , )

Differentiating with respect to l,

U ( S ,V , n1 , n2 , ) U (l S , lV , l n1 , l n2 , )
l
U (l S , lV , l n1 , l n2 , ) (l S ) U (l S , lV , l n1 , l n2 , ) (lV )

(l S ) l (lV ) l
U (l S , lV , l n1 , l n2 , ) (l n1 )

(l n1 ) l
This is true for any value of l. For l = 1,

U (l S , lV , l n1 , l n2 , ) lU ( S ,V , n1 , n2 , )

U U U
S V n1 U
S V n1

U TS PV mi ni
i

This is called Eulers relation for the internal energy.

Other Euler relations:

H U PV H TS mi ni
i

A U TS A PV mi ni
i

G A PV G mi ni
i
 The Gibbs-Duhem Relation

Differentiating the Euler relation for dG,

dG m j dn j n j d m j
j j

Using the relation

dG SdT VdP m j dn j
j

we obtain the Gibbs-Duhem relation

SdT VdP n j d m j 0
j
This result can also be obtained from the Euler relation for dU:

dU TdS SdT PdV VdP m j dn j n j d m j

j j

Using the relation

dU TdS PdV m j dn j
j

we find

SdT VdP n j d m j 0
j

For a one-component system we recover the known result

SdT VdP nd m dG
 Phase Equlibrium in Multicomponent Systems

n1g , n2g
Two-component liquid at equilibrium with its vapor.
At constant P and T,

n1l , n2l G G
dG l dn1 g
l
dn1g
n1 P ,T ,n2l ,n1g ,n2g n1 P ,T ,n1l ,n2l ,n2g
G G
l dn2 g
l
dn2g
n2 P ,T ,n1l ,n1g ,n2g n2 P ,T ,n1l ,n2l ,n1g

G
Since dn1l dn1g 0, dn2l dn2g 0, and l m l
1, etc.
n1 P ,T ,n2l ,n1g ,n2g

m1l m1g , m 2l m 2g
Assuming the vapor behaves as an ideal gas, the chemical potential of substance
j in the solution is

Pj
m m m (T ) RT ln
l
j
g
j
0
j
P0

For the pure substance j,

Pj*
m lj* m gj * m 0j (T ) RT ln
P0
because m 0j (T ) doesn't depend on mole fractions. It follows that

Pj
m m RT ln
l
j
l*
j
Pj*
 Ideal Solutions and Raoults Law

If the partial vapor pressure of each component in a solution obeys the relation

Pj x j Pj*

nj
where x j is the mole fraction of component j in the liquid phase,
n
i
i

the solution is called ideal. Ideal solutions follow Raoults law,

m sol
j m j RT ln x j
*

Here m sol
j is the chemical potential of (liquid) component j in the solution

and m *j is the chemical potential of the pure substance.

 Vapor Pressure of Ideal Two-Component Solutions

P P1 P2 x1P1* x2 P2* x1P1* (1 x1 ) P2* x1 ( P1* P2* ) P2* (linear in x1 )

P The mole fraction of

*
P
1 component 1 in the liquid
P phase is
P1
P2* P P2*
x1 *
P2 P1 P2*
0 x1 1
Calculate the mole fraction y1 of component 1 in the vapor phase at a given
value P of the vapor pressure using Daltons law of partial pressures:

P1
y1 (Dalton's law)
P
x1 P1* P P2* P1* P1* P2*
* * *
1
x1 P1 x2 P2 P1 P2 P P1 P2
* * *
P

liquid-vapor coexistence
x1 depends linearly on P. P1*
P vs. x1
y1 depends nonlinearly
(hyperbolically) on P (and on x1 )! P2* P vs. y1

0 1
x1 or y1
How much liquid vs. vapor is there at a pressure PC, given that the overall mole
fraction of component 1 is x1B ?

Mole fractions in liquid and vapor phases:

n1l n1l n1g n1g
x lE
l, y g
F
g or n1l nl x1E , n1g n g y1F
n1 n2 n n1 n2 n
1 l 1 g

n1l n1g
x l
B
x1B nl n g n1l n1g nl x1E n g y1F
n ng
1

A
n x x
l B
1
E
1 n y
g F
1 x B
1 "lever rule" P1*
B
P vs. x1 E
C F
D
*
P2
P vs. y1

0 x1 or y1 1
 Non-Ideal Solutions

Pj x j Pj*
P

P1* P1*
P
P
P1
P1
P2* P2* P2
P2

0 x1 1 0 x1 1

attractive interactions between repulsive interactions between

different molecules dominate different molecules dominate

Pj x j Pj* as x j 1 only
 Temperature-Composition Diagrams

P
vapor
Tb vs. y1 T1*

T2* Tb vs. x1
liquid
0 1

Substance labeled 2 is assumed to have a lower boiling point. The vapor is

richer than the solution in the more volatile substance 2, thus y1 < x1..

Fractional distillation exploits this principle.

 Azeotropes

P
vapor T1*
Tb vs. y1

T2*
Tb vs. x1
liquid
0 x1 1

Fractional distillation cannot separate the two components.

 Activity

For any solution (ideal or not),

Pj
m m RT ln
l
j
l*
j
Pj*
Pj
For ideal solutions *
xj
P j

Pj
For nonideal solutions *
a j "activity of component j in the solution"
Pj

m lj m lj* RT ln a j
 Solid-Liquid Solutions

A: water
B: water + sugar
A B
Solutions separated by membrane
permeable to water only.

m Aj m Bj for every substance that appears on both sides and

m wA m w*
m wB m w* RT ln aw

These cannot be equal with aw 1 unless m wA m wB .

The only way for this to happen is to have P A P B .
 Osmotic Pressure

m wA (T , P) m w* (T , P)
A B m wB (T , P ) m w* (T , P ) RT ln aw

Pw m w* P
aw * . But V *
w , so m w* (T , P ) m w* (T , P) Vw ( P)dP
Pw P T P

Assuming Vw is independent of pressure for the liquid,

P
P
Vw ( P)dP Vw so Vw RT ln aw 0
For a dilute solution aw xw 1 xs
ln aw ln(1 xs ) xs Vw RTxs
ns
xs Vw RTns
nw
It follows that the osmotic pressure of dilute solutions is given by the relation

cRT
 Additional Definitions

Coefficient of Thermal Expansion

1 V
a
V T P

Isothermal Compressibility Factor

1 V
T
V P T
KINETIC THEORY OF GASES
 Root-Mean-Square Velocity

u u x , u y , u z velocity vector of a gas molecule

p2 3
From the equipartition principle, k BT
2m 2

1
3k BT
u 2 2
urms
m
 Velocity Distribution

Recall that the probability of having translational energy

E m u x2 u y2 u z2
1
2

is given by the Boltzmann factor

m ux2 u 2y uz2 / 2 kBT
P( E ) e

The probability of having a velocity component ux in the x direction is Gaussian:

m mu x2 / 2 k BT
px (u x ) e
2 k BT

k BT
From this, u x 0 and u 2
x u x2 px (u x )
m
 The Maxwell-Boltzmann Distribution

Calculate the probability distribution f (u) for a molecule to have a velocity

modulus
u u u u
1
2 2 2 2
x y z

by converting to spherical polar coordinates and integrating over angles:

3
2 m mu 2 / 2 kBT
2

f (u )du u du sin d
2
d e
0 0
2 kBT

m 2 mu 2 / 2 kBT
2

f (u ) 4 ue
2 k BT

8k BT 8k B T
Average speed: u u f (u )du u
m m
 Most Probable Speed

The maximum of the Maxwell-Boltzmann distribution lies at

d
f (u ) 0
du
which is satisfied for

2 k BT
ump
m
 Velocity Distribution and Reaction Rates

The shape of the Maxwell-Boltzmann distribution has important implications

for chemical reactions. Even though the maximum of the curve depends
weakly on temperature, the fraction of molecules with velocities higher than a
critical value depends exponentially on the temperature. Thus a relatively
small increase of temperature can have a large effect on the rate of a chemical
reaction.
REACTION RATES
 Chemical Reactions

A A BB CC D D

1 d [A] 1 d [B] 1 d [C] 1 d[D]

k[A]a [B]b
A dt B dt C dt D dt

Exponents: reaction order

d [A]
First order reactions: k[A] [A] [A]0 e kt
dt
d [A] 1 1
Second order reactions: k[A]2
kt
dt [A] [A]0
 1st Order Reactions
k
A B
k

d [A] d [B]
k [A]+k [B]
dt dt

Steady state (dynamic equilibrium):

d [A] [B]eq k
0 K
dt [A]eq k

At all times, [A] [B] [A]0

k [A]eq k [B]eq k [A]0 [A]eq k k [A]eq k [A]0

At all times, [A] [B] [A]0

Steady state (dynamic equilibrium):

d [A] [B]eq k
0 K
dt [A]eq k

k [A]eq k [B]eq k [A]0 [A]eq k k [A]eq k [A]0

d [A]
k [A] k [A]0 [A] k k [A] k k [A]eq
dt
k k [A] [A]eq
d [A]

dt
[A] [A]eq k k [A] [A]eq
d
dt

[A] [A]eq [A]0 [A]eq e ( k k )t

 Temperature Dependence of Rate Constants

In most cases under common conditions, k A e Ea / RT Arrhenius equation

Ea : activation energy

reactants Eb
products

reaction coordinate
 Transition State Theory

Assumption: All trajectories that reach the barrier top lead to products.

p


dx dp e b H ( x , p )
m
( x xb ) ( p)
k TST


dx

dp e b H ( x , p )

p
b p 2 /2 m b Eb p e b Eb
m 0
b H ( xb , p )
Numerator = dp e dp e e
0 m b
Denominator = Qrcl (partition function of reactants)
Assuming the potential is harmonic about the minimum,

p2 1
b m02 ( x x0 )2
2
dx dp e 2 m 2
Q cl

b0
r

0 b E
k TST e b

Taking into account degrees of freedom orthogonal to the reaction coordinate,

k BT Q b Eb
k TST e
h Qr

Q : partition function of stable modes at the transition state
Qr : partition function of reactants
 Corrections to Classical Transition State Theory

1. Recrossing of transition state region (negative corrections)

2. Quantum mechanical effects (primarily tunneling)

ln k

activated crossing

tunneling regime

1/T
Tunneling
 Preliminaries
P(E)
classical
1
E
?
Vb quantum
mechanical
0
Vb E

Ptunneling (E) exp 1 2m[V ( x) E]dx

Tunneling is important in the kinetics of light particles

(primarily e-, H, H+, D,)
Tunneling effects are sensitive to isotopic substitution
 Time evolution in double wells
Symmetric double well in a
dissipative medium: quenched
tunneling oscillations
1

very small
0.5
splittings

0
Isolated symmetric
double well: constant
-0.5
amplitude tunneling
oscillations
-1
Asymmetry quenches 0 4 8 12 16
t
tunneling
 Finite temperature reaction rates
En / kBT
Generally, Pc(T ) e Pmc(En)
n

microcanonical
thermally averaged

Arrhenius rate plot

Classical rate theory:
V / kBT
kcl(T ) Ae b

log k
Tunneling dominates at kqm
low temperatures, where
the classical rate goes to kcl
zero.
1/T
 Early history
1927 Hund suggested that quantum mechanical tunneling may
play an important role in some chemical reactions.

1928 Fowler and Nordheim observed velocities of electrons

emitted by metals that were too small.

e- V(r)

R. H. Fowler and L. Nordheim, Proc. Roy. Soc. A 119, 173 (1928)

1932 The discovery of deuterium provided ample evidence for
quantum tunneling and motivated theoretical and
experimental work on isotope effects.
p+ n p+

1933 Kinetic information from ortho/para-H2 interconversion

revealed considerable deviations from Arrhenius
behavior indicative of tunneling
1934 Observation of tunneling splittings in NH3
1956 H+/D+ abstraction from 2-ethoxycarbonylcyclopentanone
Chemical bonding, conjugated systems
and band structure
V(r)
R

*
b

conduction
valence
Electron tunneling in biomolecules

Quantum paths for the tunneling

electron in ruthenium-modified
myoglobin. The heme and
ruthenium redox centers are
separated by 28 Angstroms.

KA. Kuki A. and P. G. Wolynes, Science 1987, 236, 1647-1652.

 Exciton tunneling in
molecular aggregates

Exciton tunneling in
symmetric molecular
aggregates leads to a type
of band structure and
delocalized states.
Nuclear tunneling in electron transfer

Fe2+ Fe3+ + e-

R. A. Marcus,
1992 Nobel Prize in Chemistry.
 Tunneling of atoms

scattering predissociation
bimolecular reactions unimolecular decay

enhancement
of tunneling

asymmetric symmetric
isomerizations isomerizations
 Tunneling effects in
bimolecular reactions

A+BC AB+C H+H2 H2+H

D+H2 HD+H

(observed through interconversion

of ortho- and para-forms)
RBC

Potential surface curvature

(corner cutting)

RAB
 Tunneling effects in
molecular spectroscopy

Tunneling leads to splitting of Inversion of NH3

rovibrational levels in symmetric
isomerizations. The splitting is
observed spectroscopically in the
microwave region.

1.3cm1

C. E. Cleeton and N. H. Williams,

Phys. Rev. 45, 234 (1934).
H tunneling in
hydrogen-bonded
molecules

3,7-dichlorotropolone
 Tunneling in enzymes

Tunneling plays a significant role in hydrogen transfer

at enzyme active sites.

Motion of the primary (1) and

secondary (2) hydrogens in the
reaction of alcohol dehydrogenase.

A. Kohen, R. Cannio, S. Bartolucci and J.P. Klinman (1999), Nature 399, 496-499.
 Tunneling in the condensed phase
kqm kqm
TST

5 4

Classical rate theory: 3 activated dynamics

3

log
V / kBT

2 kcl(T ) Ae b
2 deep
1 tunneling

0 1
0 1 2 3 0 1 2 3
/ m / m

Intermediate T Low T
Rotational tunneling in crystals
At low temperatures (4-50K)
the rotation of ammonium ions
in ionic salts is dominated by
tunneling.

H. L. Strauss, Acc. Chem. Res. 30, 37-42 (1997).

Competing effects in kinetics
Diffusion of H and D in crystalline Si

conventi
onal
TST
TST for 1-
dim.
adiabatic
potential quant
um

Inverse isotope effect!

 Theoretical treatments of tunneling

Full solution of the quantum mechanical wave equation

Instanton theory (tunneling in imaginary time / inverted
potential)
Tunneling corrections to classical trajectory calculations from
semiclassical expressions
Quantum mechanical solution of simplified models (master
equations, harmonic bath approximations,)
Path integral or quantum Monte Carlo calculations in select
situations (e.g., tunneling splittings)
 Scanning Tunneling Microscopy

A tip is scanned over a surface at a distance of a few atomic

diameters in a point-by-point and line-by-line fashion. At each
point the tunneling current between the tip and the surface is
measured. The tunneling current decreases exponentially with
increasing distance and thus, through the use of a feedback loop,
the vertical position of the tip can be adjusted to a constant
distance from the surface.

Gerd Binnig and Heinrich Rohrer, IBM

Research Laboratory, Zurich, shared the
Physics Nobel prize in 1986 for their
discovery of STM.
 Imaging surfaces

Unreconstructed (110) Ni surface

Cu surface (electron standing

waves on surface steps)
Cr impurities on a Fe (001) Zig-zag chain of Cs atoms
surface on the GaAs(110) surface.
 Nanoengineering with STM

Stadium quantum corral:

Spelling atom in
Fe on Cu
Japanese. Fe on Cu
STABILITY CRITERIA AND PHASE TRANSITIONS
 Concavity of the Entropy
Imagine a system whose entropy function S
of a system has the shape shown in the
figure. Consider two identical such
systems, each with internal energy U0 and
entropy 2S(U0). Suppose we remove
energy U from the first system and put
it in the second system. The new entropy
will be

S (U U ) S (U U ) 2S (U ) U0 - U U0 U0 + U U

Since this rearrangement of the energy results in a larger entropy, it should occur
spontaneously if the two systems are connected through a diathermal wall. This way
the system will break up into two systems of different thermodynamic properties. This
process is a phase transition.

The instability leading to phase separation is a consequence of the assumed convex

shape of S over a range of U. In stable thermodynamic systems the entropy function is
a concave function, i.e., d 2 S < 0 with respect to the extensive variables U and V.
 Stability Conditions for Thermodynamic Potentials

The concavity condition for the entropy implies the convexity of the internal energy
function with respect to its extensive variables S and V, as illustrated in the figure.

Adapted from H. B. Callen, Thermodynamics and

an Introduction to Thermostatistics, 2nd Edition.

V
The other thermodynamic potentials are functions of extensive as well as intensive
variables. Because intensive variables are introduced through negative terms in the
Legendre transform of the internal energy, the resulting thermodynamic potentials
are concave functions of their intensive variables (but they are still convex functions
of their extensive variables). For example,

2 A 2G
2 0, 2 0
V T T P

A consequence of the first of these relations is

P A
2
2 0 T 0
V T V T

V
 First Order Phase Transitions

G or U
Failure of stability criteria:
If the fundamental thermodynamic
function of a system is unstable,
fluctuations may take the system over the
local maximum, and the system breaks up
into more than one phases.

S or V
Second Order Phase Transitions and Critical Phenomena

The two stable minima responsible for a first order phase transition coalesce at the
critical point, giving rise to a second order phase transition.

G or U

Critical phenomena are

accompanied by huge density
fluctuations, which give rise to
the observed critical
opalescence.

S or V
SUPERFLUIDITY AND BOSE-EINSTEIN CONDENSATION
 The History of Superfluid 4He

1908: 4He was first liquified (5.2 K).

Unusual properties were observed: strange flow, expansion upon cooling below 2.2
K.

1928: Sharp maximum in the density with a discontinuity in slope at ~2.2 K. Two phases.

1932: The specific heat diverges at 2.17 K; the curve has a l shape (lambda transition).
Normal and superfluid phases identified.

1930s-1940s:
Remarkable transport properties of superfluid 4He studied extensively.
Viscosity drops by many orders of magnitude; the system flows through capillaries.
The superfluid forms extended thin films over large surfaces.
The superfluid does not rotate upon rotating its container.
It appears the superfluid flows without friction!
 The Phenomenon of Superfluidity

A group of phenomena including:

Frictionless flow
Persistent current
Heat transfer without a thermal gradient
 Bose-Einstein Condensation (BEC)

Einstein predicted that if a gas of bosons were cooled to a sufficiently low temperature, all the
atoms would gather in the lowest energy state.

In 1995, Cornell and Wieman produced the first condensate of 2000 Rb atoms at 20 nK.
Ketterle produced a condensate of Na with more atoms and observed interference patterns.

BEC is intimately connected with superfluidity, but is not a necessary condition for this group
of phenomena.

Recent Nobel prizes:

2001: Cornell, Wieman and Ketterle for BEC
2003: Leggett for theory of superfluids
N0
Condensate fraction: n0
N
(N0: number of particles in the zero momentum state)

In the strongly interacting 4He superfluid the condensate fraction is small (about 7% at T = 0)
 The Quantum-Classical Isomorphism

A single quantum mechanical particle is isomorphic to a necklace of N classical beads

that are connected with one another via harmonic springs and which experience a
potential equal to 1/N of the actual potential felt by the quantum particle.

Quantum statistical effects of identical bosons or fermions manifest themselves in the

exchange of beads, which causes the necklaces of different particles to cross-link.
A snapshot of 4He at 1.2 K. Each 4He atoms is represented in the simulation through
20 pair-propagator beads. The blue beads correspond to linked necklaces.
The End