Statistical Thermodynamics

Introduction
Statistical thermodynamics provides the link between the microscopic properties of atoms and molecules (described by quantum mechanics) and their bulk (macroscopic) properties, many of which are well-described by classical thermodynamics. The molecular partition function, q, which describes the average number of quantum states accessible to a molecule at a given temperature is introduced, and expressions for the molar internal energy, entropy, and other thermodynamic state functions are derived. You should be familiar with the expressions for the various energy levels in a molecule (translational, rotational and vibrational) from previous courses and be condent using dierential calculus (especially the chain rule!)

Suggested Reading
Not a lot of imagination goes into the titles of books in this eld. 1. P. W. Atkins and J. de Paula, Atkins Physical Chemistry, any edition, OUP. 2. B. J. McClelland, Statistical Thermodynamics, Chapman and Hall, 1973. 3. D. A. McQuarrie, Statistical Thermodynamics, 1973. 4. A. Maczek, Statistical Thermodynamics, OUP Primer 58, 1998. 5. R. P. H. Gasser and W. G. Richards, An Introduction to Statistical Thermodynamics, World Scientic, 1995. 6. R. Bowley and M. Snchez, Introductory Statistical Mechanics, 2nd ed., a Oxford, 1999. 7. J. M. Seddon and J. D. Gale, Thermodynamics and Statistical Mechanics, RSC Tutorial Chemistry Texts, 2001. 8. K. A. Dill and S. Bromberg, Molecular Driving Forces, Garland, 2002. 9. K. Huang, Introduction to Statistical Physics, Taylor and Francis, 2001. Dont like any of these? Then maybe try one of those listed at http://stp.clarku.edu/books/.

Notation and Common Pitfalls

The magnitude of q and its meaning As mentioned above, the partition function, q, describes the average number of occupied quantum states at a given temperature. To appreciate the meaning of the size of q, compare the energy-level spacing with kB T , a measure of the amount of thermal energy available to the molecule. It is useful to recall that, in wavenumber units, kB T = 207 cm1 at T = 298 K. Therefore qtrans is usually huge, even at low temperatures since for a gas of molecules in a reasonably-sized (e.g. visible!) vessel the translational energy levels are very closely spaced. However, qvib 1 for many molecules at room temperature because the energy gap between the vibrational ground state (v = 0) and rst-excited state (v = 1) is typically 1000 cm1 . Zero-point energy From the denition of the canonical partition function, Q=
i

eEi /kB T ,

it is clear that Q depends on where the energies, Ei are measured from. In some contexts it is appropriate to measure them relative to the ground state (such that E0 = 0); in others, it may be decided to set the energy-zero somewhere else (so that E0 > 0). It doesnt really matter which is used, but be careful to state any macroscopic, thermodynamic quantities in the correct way. For example, if the energies used to calculate Q are measured relative to E0 = 0, the internal energy expression should be: U (T ) = U (0) + kB T 2 ln Q T ,
V

in which the zero-point energy is added on to the statistical thermodynamic expression for U .

Notes
Make your own notes for use in revision on the following topics. Dont hand them in. Microstates, congurations and their weights. Denition and signicance of the molecular partition function, q, and its factorization into translational, rotational, vibrational, and electronic components. Derivation of expressions for qtrans , qrot , and qvib and the approximations involved. The canonical partition function for non-interacting particles (distinguishable and indistinguishable). Determination of internal energy: in general and for an ideal gas.

 Determination of molar entropy: in general and for an ideal gas (the Sackur-Tetrode equation). Determination of molar entropy for a diatomic molecule. Determination of other thermodynamic properties from the partition function: Helmholtz free-energy, pressure, chemical potential. Application of statistical thermodynamics to chemical equilibrium: dissociation and ionization reactions (the Saha equation); Isotope-exchange reactions.

Question Sheet 1
1. Consider a small system consisting of N = 4 molecules: A, B, C and D, each of which is localized at a well-dened position in space. The molecules are all of the same chemical species and each has three nondegenerate energy levels: 0 = , 1 = 2 and 2 = 3. The system has a xed total energy, E = 8. All microstates of the system compatible with the xed E and N are equally probable. (a) How many congurations of the system are compatible with the xed total energy? Label each conguration by its set of distribution numbers, (n0 , n1 , n2 ). (b) How many physically-distinct ways are there of generating each of the congurations? (i.e. what is the weight of each conguration?) (c) Enumerate all possible microstates of the system associated with the most probable conguration. (d) Consider any particular conguration. What is the probability (i) that any of the microstates associated with this conguration will be observed; (ii) that a molecule will be found in each of the available quantum states? Repeat this procedure for the remaining compatible congurations. (e) Calculate the overall probability that a molecule selected at random from the system will be found in each of the three available quantum states. Compare these values with the results of (d)(ii) above if only the most probably conguration is considered. Clearly the most probable conguration does not completely dominate for an N = 4 molecule system. As N gets larger, it becomes overwhelmingly the most dominant conguration and this can be considered the equilibrium state of the system. 2. The weight function, W (n), for an arbitrary conguration, n (n0 , n1 , , ni , ), of a macroscopic system of N distinguishable particles is given by: W (n) = N! . i ni !

Show that if the system is in equilibrium the distribution number for quantum state i in the most probable conguration is n = i where q=
j

N ei , q

gj ej and =

1 . kB T

The sum in q is taken over energy levels; gj is the degeneracy of the jth energy level. Justify the following statement: the probability, Pi , that a molecule of the macroscopic system will be found in the state i is given by Pi = n /N . i

Hence show that the internal energy of the system, U (T ), is given by U (T ) = N kB T 2 ln q T

3. The population of an excited state of the oxygen atom relative to the ground state is 5.695 102 at 10,000 K and 5.840 103 at 5000 K. Assuming that spin-orbit coupling may be neglected, (a) Calculate the energy of this excited state relative to the ground state. (b) Given that the ground state is 3 P , determine which excited state (arising from the ground state electronic conguration) is under investigation. 4. Consider an isolated gas of N non-interacting atoms - a system of independent, indistinguishable particles. The atoms are contained in a cubical box of side 1 cm. (a) Suppose the gas contains N = 1020 Ar atoms. Calculate the values of the translational partition function, qtrans , and the de Broglie thermal wavelength, , at (i) T = 300 K, (ii) T = 100 K, (iii) T = 50 K. (b) In order that Maxwell-Boltzmann statistics be applicable to a system of independent, indistinguishable particles, qtrans N (i.e. the temperature of the system should be suciently large that the number of quantum states which are thermally accessible to a molecule ( qtrans ) should greatly exceed the number of molecules in the system. Show that this is equivalent to the condition that the mean interatomic separation, r = (N/V )1/3 , should be much greater than the thermal wavelength, . When becomes comparable to r, the quantum mechanical eects of indistinguishability become important: Boltzmann statistics are no longer applicable and the system is described by either Bose-Einstein or Fermi-Dirac statistics according to whether the particles are bosons or fermions respectively. (c) Verify for the example in (a) that Maxwell-Boltzmann statistics are indeed applicable at the temperatures considered. At what temperature does become equal to the mean interatomic separation of the Ar atoms? The (normal) boiling point of Ar is 87.3 K, so long before the quantum eects of indistinguishability become appreciable, interatomic interactions will in reality become important - i.e.our assumption that the atoms are non-interacting, or independent, will break down rst. (d) But now suppose the gas contains N = 5 1022 atoms of He - which has a relatively small mass. Calculate qtrans and at (i) T = 100 K, (ii) T = 20 K, (iii) T = 10 K. Assuming that the atoms can be regarded as independent, are Boltzmann statistics likely to be applicable at each of the temperatures considered? At what temperature does become equal to r? What implications do your results have for real He? The normal boiling point of He is 4.2 K; 3 He is a fermion and 4 He is a boson.

(e) Finally, suppose the gas contains N = 1022 electrons which we regard as non-interacting. (Obviously crude, but we might consider there to be an immobile and neutralizing background charge distribution which exactly cancels the electrons charge and which screens electron-electron interactions; this is a simple model of a metal). Are Maxwell-Boltzmann statistics adequate at (i) room temperature, (ii) T = 1000 K, (iii) T = 30, 000 K? 5. Consider a low-density gas of diatomic molecules. The vibrational contribution to the overall molecular partition function is given by

qvib =
v=0

ev

Assuming that the molecular vibrations can be represented adequately as simple harmonic, deduce a simple, closed expression for qvib . Obtain an expression for the probability that a molecule selected at random from the system will be found in any of its excited vibrational states. Calculate this probability for a gas of HCl molecules at T = 298 K. What are the implications of your result for the intensity of the hot bands in the infrared spectrum of (real) HCl? 0 (HCl) = 2856 cm1 . 6. This question is an exercise in obtaining thermodynamic functions using the canonical ensemble. The ensemble contains a very large number, N, of systems; each system has a volume, V , temperature, T , and contains N molecules. The total entropy, S, and total energy, E of the ensemble are given by S = kB ln W( ) and E =
i

Ei , i

where W( ) is the weight of the dominating conguration, ( , , , , ) 0 1 i and denotes the number of systems in the ensemble which are found i in quantum state i with energy Ei for the dominating conguration. (a) Using the canonical distribution for

, prove that i
E , T

S = kB ln Q +

where the canonical partition function, Q, is given by Q=

eEi /kB T .

S and E are the average entropy and internal energy per system respectively. (b) Show that the internal energy of a system is given by E = kB T 2 ln Q T ,
V

and that the Helmholtz free energy is A = kB T ln Q.

(c) Obtain a general expression for the pressure, p, of a system, and also for (S/V )T . (d) Consider an ideal monatomic gas - a collection of independent and indistinguishable particles. Starting from the general result derived in (c), together with the result for the molecular partition function, q, obtain an explicit expression for the pressure of the gas. Comment on your result. (e) Similarly, show that E(T ) E(0) = monatomic gas.
3 2 RT

for one mole of an ideal

(f) Prove from statistical mechanical considerations, starting from the results of part (a), that the change in entropy on expanding one mole of an ideal monatomic gas from a volume V1 to a volume V2 (at constant T ) is given by S = R ln V2 . V1

What does classical thermodynamics predict for S? (g) By consideration of A = kB T ln Q, derive an expression for the chemical potential of an ideal monatomic gas, and show it may be written in the form = + RT ln p , p

where p is standard pressure and is the standard chemical potential. 7. Derive the Sackur-Tetrode equation for the molar entropy of a monatomic gas. You may assume that Sm = NA kB ln q kB ln NA ! + NA kB T ln q T .
V

Account for the dierences between the values of Sm for the following gases at 1 bar and 298 K: He : 127 J K1 mol1 , Ne : 147 J K1 mol1 , Ar : 156 J K1 mol1 . How would your expression for Sm be modied if the gas consisted of diatomic molecules? The molar entropy of CO at 1 bar and 298 K is 198 J K1 mol1 . Estimate the bond length, r, of CO. [The literature value is r = 122 pm]

Question Sheet 2
1. Statistical mechanics gives the following result for the equilibrium constant, K(T ) of a gas-phase reaction: K(T ) =
J 0 qm,J J

NA

exp

E0 RT

(a) Outline the derivation of this equation, explaining carefully the meaning of the quantities appearing in it. Consider the thermal ionization of an atomic species, A, A A+ + e with ionization energy, I. For both A and A+ you need to retain only the lowest energy electronic state, 2S+1 L arising from the appopriate electronic conguration; the dierence in energy between the spinorbit components, J, of these states may be neglected. (b) Show that the equilibrium constant for this equation may be expressed as K(T ) = 2kB T 3 (T ) p g A+ I exp gA RT ,

where (T ) is the de Broglie thermal wavelength for the electron, and gA+ and gA denote respectively the degeneracies of the A+ and A electronic ground states. (c) Calculate K at T = 4000 K for the thermal ionization of carbon atoms. For C, I = 1086 kJ mol1 . (d) In assuming Boltzmann statistics, the above result for K(T ) eectively treats the electrons as classical particles. This is valid only if (T ) (V /Ne )1/3 where Ne /V is the number density of the electrons. For T = 4000 K and p/p = 104 , the fraction of ionized carbon atoms is 1.7 104 . Can the quantum mechanical nature of the electrons be neglected under these conditions? Explain your reasoning. 2. Consider the reactions H2(g) + I2(g) 2HI(g) D2(g) + I2(g) 2DI(g) (a) Show that the ratio of equilibrium constants is given by KH (qHI )2 (qD2 ) r E0 (H) r E0 (D) = exp KD (qDI )2 (qH2 ) RT ,

where r E0 (H) and r E0 (D) denote the T = 0 molar internal energy change for the appropriate reactions.

(b) Stating any assumptions made, show that the ratio of equilibrium constants can be simplied to mHI mD KH exp 1/2 KD mDI mH
1/2

r E0 (D) r E0 (H) RT

where mJ is the mass of species J. (c) The vibrational wavenumbers of HI and H2 are 2300 and 4400 cm1 respectively. Determine the ratio KH /KD at 1000 K. 3. Calculate the equilbrium constant of the reaction I2(g) 2I(g) at 800 K, using the following data for I2(g) : = 214.4 cm1 , B = 0.037 cm1 , and De = 1.542 eV. You may assume that only the ground electronic state of each state is thermally accessible. Explain how the calculation would be modied if you took into account the excited electronic state of the I atom arising from the ground electronic conguration. 4. Use statistical mechanics to account for the fact that the equilibrium constant for the reaction
35

Cl2 +37 Cl2 235 Cl37 Cl

is approximately 4 at high temperatures and is less than 4 at low temperatures.