Problems and Solutions: Physical Chemistry

CHAPTER
15 Statistical Mechanics
LAIDLER . MEISER . SANCTUARY

Physical Chemistry
Electronic Edition
Problems and Solutions

Chapter 15: Statistical Mechanics Permutations and Combinations:
Chapter 15
Permutations and Combinations:
15.1. Use Stirling’s formula to calculate and approximate value for ln(N!) and compare with the exact value for N=5, 10, 50, 100, 1,000
and 10,000!
Solution
Work out the following examples:
15.2. The number of possible arrangements of 4 objects (A B C D) among 4 positions (do not list them).
Solution
15.3. The number of possible arrangements of 3 objects (A B C) among 4 positions. List them all.
Solution
( x1 + x2 )
n
15.4. Use the binomial distribution to work out the binomial coefficients for for n=5. Arrange the numbers in Pascal’s
⎛4⎞ ⎛5⎞ ⎛5⎞
triangle. Work out the quantities ⎜ ⎟ ⎜ ⎟ and ⎜ ⎟ to check your entries.
⎝3⎠ ⎝3⎠ ⎝2⎠
Solution
15.5. Consider two sets of indistinguishable objects, {A A} and {B B B}. Work out and list the possible arrangements of these in 5
boxes, one object per box. Check your number against the formula.
n!
Prn ! =
∏ nc !
c
Solution
15.6. Work out the number of ways that the three objects (A B C) can be placed in 5 boxes, no more than one object per box. List all the
possibilities to confirm your number.
Solution
15-2
Chapter 15: Statistical Mechanics Quantum statistics
15.7. Work out the number of ways that the three objects (A A A) can be placed in 5 boxes, no more than one object per box. List all the
n!
Crn =
(n − r ) ! r !
Solution
15.8. Work out the number of ways that the two objects (A B) can be placed in 3 boxes with no restriction on the number of objects per
box. List all the possibilities to confirm your number.
Solution
15.9. Work out the number of ways that the two objects (A A) can be placed in 4 boxes without restriction on the number of objects per
Solution
15.10. When we remove the condition of distinguishability from the n objects of Eq.(A.5), we divide by n! to obtain Eq.(A.6). By
considering the simple case of 2 objects and 3 boxes, (same as problem 2g) show that it is improper similarly to divide Eq.(A.7) by
n! to obtain the desired result for Eq.(A.8).
Solution
15.11. A partially deuterated methane sample is analyzed and found to contain equal molar quantities of hydrogen and deuterium. On a
random basis, calculate the percentage of species CH4, CH3D, CH2D2, CHD3 ,CD4.
Solution
Quantum statistics
⎡ m! ⎤ ⎡ ( m + n −1) !⎤ ⎡ mn ⎤
15.12. Show that ln ⎢ ⎥ and ln ⎢ ⎥ both approach ln ⎢ ! ⎥ as n becomes large, provided that m>>n. (Use
⎣ n !(m − n) ! ⎦ ⎣ n !(m − 1) ! ⎦ ⎣n ⎦
Stirling’s formula and use the fact that m>>n, and m>>1).)
Solution
15-3
15.13. Show that the maximum entropy, S, is obtained when all the probabilities, pi are equal, where
n n
S = −∑ pi ln pi and ∑ pi = 1
i =1 i =1
(This shows us that complete lack of knowledge of which state the system is in results in the highest entropy. When all states are
equally likely, we have no preferential state, and this means the most random or highest entropy.)
Solution
15.14. Prove that for an N particle quantum state, the wave function must be either odd or even under the permutation of any two of the N
particles.
(This symmetry, of course, distinguishes bosons from fermions.)
Solution
15.15. A more accurate form of Stirling’s approximation is
ln N ! = N ln N − N + ln 2π N
In the stopcock opening and closing example, recalculate the effect of ΔS II → III using the above approximation and show that the
entropy change is negligible compared to ΔS I → II . Assume that the two volumes are equal, and consider what happens to this new
entropy change ΔS II → III < 0 as the number of particles goes to infinity
(Although we observe no noticeable change when we physically close the stopcock in going from state II to III, there is a change
due to our definition. This problem asks you to look into. The reason the change is negligible from our theory is because we are
dealing with an enormous number of particles, and can use Stirling’s approximation. However, if we had only a few particles, then
the effect of closing the stopcock would lead to a difference between the two states, II and III, i.e. the “entropy” would show a
decrease. This underscores the fact that we can not define entropy for a small number of particles because entropy is a statistical
quantity.)
Solution
15-4
N1 N
15.16. Using: = 2 prove the relationship:
V1 V2
⎡
( V1 / Vc ) ( V2 / Vc ) ( N1 + N 2 ) ! ⎥⎤ = ln ⎡ ( N1 ) N1 N 2 N2 ( N1 + N 2 ) ! ⎤⎥
N1 N2
ln ⎢ ⎢
⎢
⎢⎣ ( ( V1 / Vc )N + ( V2 / Vc )N ) ( N1 ) ! ( N2 ) ! ⎥⎦⎥
1 2
⎢⎣ ( N1 1 + N 2 2 )
N N
( N1 ) ! ( N 2 ) ! ⎥⎦
Solution
15.17. Without considering energy, calculate the statistical weights for 30 quanta distributed amongst 30 oscillators for the following
distributions of the quanta:
N 0 = 0, N1 = 30, N 2 → 29 = 0
N 0 = 1, N1 = 28, N 2 = 1, N 3 → 29 = 0
N 0 = 10, N1 = 10, N 2 = 10, N 3 → 29 = 0
(This is a problem of combinatorials, how many ways can 30 indistinguishable objects be distributed between 30 levels. For
oscillators, we usually label the lowest state by a “0”, so we go up to the 29th level. In general, there is usually degeneracy (more
than one state with the same energy) Here we are calculating the degeneracy for various possible energies. In case a) the energy is
30ε1 , for b) the energy is ε 0 + 28ε1 + 2ε 2 and for c) 10ε 0 + 10ε1 + 10ε 2 . The problem calculates the number of ways (the
statistical weight) that indistinguishable quantum can be arranged to give that particular energy.)
Solution
15.18. Show that Eq.Error! Reference source not found. satisfies FD and BE conditions of respectively no more that 1 particle, on the
average, in a state, and any number of particles in a state. Let x = exp ⎡⎣ ( ε α − μ ′ ) / k BT ⎤⎦
Solution
15-5
Chapter 15: Statistical Mechanics Transformations of statistical and thermodynamic functions
Transformations of statistical and thermodynamic functions

15.19. Starting from
S = k B ln Ω( E , V , N )
obtain the equation:
PV = k BT ln Ξ (T , V , μ )
where Ξ(T , V , μ ) is the grand partition function. Do NOT derive the ideal gas law (i.e. do not assume the particles do not interact).
(The grand partition function is one that is commonly used in chemical reactions.)
Solution
15.20. Derive expressions for the energy U=E, the entropy S the pressure P and the Helmholtz energy A, and the Gibbs energy G in terms
of the Canonical ensemble, Q.
Solution
15.21. Find the natural function for the isothermal-isobaric ensemble, Δ(T , P, N ) , i.e. for variables T, P and N.
Solution
15.22. Obtain an expression for CP in terms of the partition function Q for the system.
Solution
15.23. Obtain an expression for the pressure P in terms of the molecular partition function q, for (a) distinguishable molecules and (b)
indistinguishable molecules. Express the result in terms of the number of molecules N and also the amount of substance n.
Solution
⎡ ⎛ – hv ⎞ ⎤
15.24. The partition function for each degree of vibrational freedom is 1 / ⎢ 1 − exp ⎜ ⎟ ⎥ (Eq.Error! Reference source not found.).
⎣ ⎝ kBT ⎠ ⎦
Obtain from this expression the limiting value of the vibrational contribution to CV as T approaches infinity.
Solution
15-6
Chapter 15: Statistical Mechanics Partition functions
15.25. Chemical reactions often lead to the formation of products whose energy distributions show significant deviations from the
statistical distribution of Eq. 15.40. In a study of an elementary reaction with 16O1H radical as one of the products [Zhang, van
der Zande, Bronikowski, and Zare, J. Chem. Phys. 94, 2704(1994)], the following rotational distribution was observed for the OH(v
= 0) state (normalized such that ΣnJ/N = 1). Compare this to the statistical distribution expected from
Eq.Error! Reference source not found. at 298 K. The equilibrium bond distance of OH is 0.96966 Å.
J 7 8 9 10 11 12 13
nJ /N 0.0181 0.0232 0.0356 0.0475 0.0377 0.0762 0.1045
J 14 15 16 17 18 19 20
nJ /N 0.1266 0.1459 0.1466 0.1306 0.0907 0.0167 0.0000
Solution
Partition functions
15.26. Suppose that an array of harmonic oscillators has common frequency of ν = 1011 s-1. Calculate the ratio of the number of
th
oscillators in the 10 quantum state (n=9) to those in the ground state at 0 K, 300 K and 1000 K. The energy levels are given by
1
ε n = (n + )hν .
2
(This is a straight application of the Boltzmann distribution. Each energy level is non-degenerate.)
Solution
15.27. Calculate the average value of the energy per mole at the various temperatures for the oscillators in problem 17.
(This is best done by evaluating the partition function for harmonic oscillators and applying the general formula for ε .
Solution
15-7
⎛ 1⎞
15.28. The energy levels for a harmonic oscillator are given by ε n = ⎜ n + ⎟ hν .
⎝ 2⎠
2
a. Derive an expression for the mean-square fluctuation, σ E = E2 − E in energy for these oscillators.
b. Use ν = 1011 s -1 and the partition function from problem set 2 to evaluate the mean-square fluctuation.
c. Compare σ E to U = E .
d. What happens as the temperature is raised?

e. What happens as the number of particles increases?
(Fluctuations are generally negligible relative to macroscopic quantities but are important for many processes under certain
conditions, such as phase transitions.)
Solution
15.29. If the molecular partition function can be written as a product of factors, q = qtr ⋅ qint , then energy, entropy and the other
thermodynamic properties can be written as a sum of terms. Show that this is true for E, S and A.
Solution
h2
15.30. Calculate for helium in a one-dimensional box of a=10 cm and determine the energy level spacing for the first four levels.
8ma 2
Compare this with kBT. At what temperature are the energy levels spacing comparable in magnitude?
Solution
15.31. Calculate Θ v for H2 (frequency = 4162 cm-1) and I2 (frequency = 213.1 cm-1). Calculate qv for these gases at 300 K.
Solution
15.32. Starting with the molecular partition function, prove for diatomic molecules in the high temperature limit that the translational,
rotational and vibrational contributions to the heat capacity agree with the expression from equipartition.
Solution
15-8
15.33. Work out the heat capacity, Cv, at 300 K for the diatomic molecules listed below. Keep only the translational, rotational and
vibrational motion. Use table below for the rotational and vibrational temperatures. Only use the high temperature approximation if
it is valid. HCl, N2, O2, I2
qtr qr qv
HCl High temp. 19.73 1.0000016
N2 High temp. 104.89 1.0000146
O2 High temp. 144.92 1.00059
I2 High temp. 555.5 1.552
Solution
15.34. The high temperature limit of the rotational partition function for diatomics is
T
qr =
σΘ r
Give a brief explanation of the quantum mechanical origin of the symmetry number σ. Use equations where appropriate.
Solution
15-9
Chapter 15: Statistical Mechanics Partition Functions for Some Special Cases
15.35. Prove that the Einstein function for the vibrational contribution to the heat capacity, Eq.Error! Reference source not found. can be
written as,
2
⎛u u ⎞
( CV )Einstein = R ⎜ cos ⎟
⎝ 2 2⎠
where
hν Θ
u= = v.
k BT T
Show that the limiting value of Einstein function, Eq.Error! Reference source not found.,is the gas constant, R. (Recall that the
Einstein vibration is restricted to one frequency only so this is consistent with equipartition that states at high temperatures the
contribution to the heat capacity is equal to R for each degree or freedom. In this case, there is only one degree of freedom.)
Solution
Partition Functions for Some Special Cases

15.36. Starting with Eq. Error! Reference source not found. obtain an expression for the molar internal energy Um of an ideal monatomic
gas.
Solution
15.37. Calculate the molecular translational partition functions qt for (a) N2, (b) H2O, (c) C6H6 in a volume of 1 m3 at 300 K. In each case,
calculate also ln Qt,m, where Qt,m is the molar translational partition function.
Solution
15.38. The internuclear distance for N2 is 0.1095 nm. Determine the molecular rotational partition function qr and ln Q for N2 at 300 K.
Solution
15.39. Use the data in Table 15.3 (p. 807) to calculate, with reference to v = 0, the molecular vibrational partition function for CO2 at (a)
300 K and (b) 3000 K.
Solution
15-10
Chapter 15: Statistical Mechanics Partition Functions for Some Special Cases
15.40. Expressions such as the Sackur-Tetrode equation for the entropy contain a term ln (constant × T). At temperatures close to the
absolute zero this term has large negative values, and the expression therefore leads to a negative value of the entropy. Comment on
this.
Solution
15.41. Calculate the entropy of argon gas at 25 °C and 1 bar pressure.
Solution
15.42. From the data in Table 15.3, calculate, with reference to v = 0, the molecular vibrational partition function for Br2 at (a) 300 K and
(b) 3000 K.
Solution
15.43. Give the symmetry numbers of the following molecules: C3O2 (carbon suboxide), CH4, C2H4, C2H6 in the staggered conformation,
C2H6 in the eclipsed conformation, CHCl3, C3H6 (cyclopropane), C6H6 (benzene), NH2D, CH2Cl2.
Solution
15.44. Show that the rotational partition function for a linear molecule can be expressed as
qr = kBT/σBh
where B is the rotational constant defined by Eq.(13.63).
Solution
*15.45. Calculate the molar translational entropy of chlorine gas at 25 °C and 0.1 bar pressure.
Solution
*15.46. The carbon monoxide molecule has a moment of inertia of 1.45 × 10–46 kg m2 and its vibrational frequency is 6.50 × 1013 s–1.
Calculate the translational, rotational, and vibrational contributions to the molar entropy of carbon monoxide at 25 °C and 1 bar
pressure.
Solution
15-11
Chapter 15: Statistical Mechanics Equilibrium constants
15.47. Suppose that a system has equally spaced energy levels, the separation between neighboring levels being Δε . Prove that the fraction
of the molecules in state i, having energy ε i greater than the energy of the lowest level, is
⎛ – Δε ⎞ ⎛ –ε i ⎞
1 – exp ⎜ ⎟ exp ⎜ ⎟
⎝ kBT ⎠ ⎝ kBT ⎠
What is the limiting value of this fraction as T → ∞? Explain your answer.

Solution
*15.48. Deduce the following from the Sackur-Tetrode equation (Eq.Error! Reference source not found.), which applies to an ideal
monatomic gas:
a. The dependence of entropy on relative molecular mass Mr; also, obtain an expression for dSm/dMr.
b. The dependence of heat capacity CP on relative molecular mass.
c. The dependence of entropy on temperature; also obtain an expression for dSm /dT.
Solution
*15.49. Molecules absorbed on a surface sometimes behave like a two-dimensional gas. Derive an equation, analogous to the Sackur-
Tetrode Eq. Error! Reference source not found., for the molar entropy of such an adsorbed layer of atoms, in terms of the
molecular mass m and the surface area A. What would be the molar entropy if 1010 argon atoms were adsorbed on an area of 1 cm2 at
25 °C?
Solution
Equilibrium constants
15.50. Calculate the dissociation constant Kc for the reaction
O2 ( 3
Σ ) → 2O ( P)
3
at 1 000 K expressing the answer in mole l-1. Ignore nuclear degeneracy. Use the data from the table of Problem 51, along with the
value Λ o = 1.25 × 10−9 cm .
15-12
Solution
15.51. From the data in Table 15.5, calculate KP at 1000 K for the “water-gas” reaction
CO2(g) + H2(g) CO(g) + H2O(g)
Solution
15.52. Without making detailed calculations but by using symmetry numbers, estimate the equilibrium constants for the following
reactions:
a. 35Cl – 35Cl + 37Cl 35
Cl – 37Cl + 35Cl
b. 35Cl – 35Cl + 37Cl – 37Cl 235Cl – 37Cl
c. C35Cl4 + 37Cl C37Cl35Cl3 + 35Cl
d. N35Cl3 + 37Cl N37Cl35Cl2 + 35Cl
e. 35Cl2O + 37Cl 37
Cl35ClO + 35Cl
(Because of the similarity of the masses, these estimates will be quite accurate.)
D. M. Bishop and K. J. Laidler, J. Chem. Phys., 42, 1688(1965), have defined a statistical factor for a reaction as the number of
equivalent ways in which a reaction can occur. Thus for reaction (a) from left to right the statistical factor is 2, since the 37Cl atom
can abstract either of the two 37Cl atoms. For the reverse reaction the statistical factor r is 1, since the 35Cl atom can only abstract the
35
Cl atom in order to give the desired products. If two identical molecules are involved, the statistical factor must be taken as the
1
number of equivalent products divided by 2; thus for reaction (b) from right to left the statistical factor is .
2
Bishop and Laidler proved that the ratio l/r of statistical factors is always equal to the ratio σAσB/σYσZ of symmetry numbers. Verify
that this is true for the given reactions.
This statistical factor procedure is useful in providing a simple insight into the factors that appear in equilibrium constants.
Solution
15-13
*15.53. Calculate the equilibrium constant at 1000 °C for the dissociation

I2 2I
given the following information: moment of inertia of I2 = 7.426 × 10–45 kg m2, wavenumber for I2 vibration = 213.67 cm–1, ∆U0 =
148.45 kJ mol–1. The I atom is in a 2P3/2 state; neglect higher states.
Solution
*15.54. Calculate the equilibrium constant KP for the dissociation
Na2 2Na
at 1000 K, using the following data: internuclear separation in Na2 = 0.3716 nm, vibrational wavenumber ν = 159.2 cm–1, ∆U0 =
70.4 kJ mol–1. The Na atom is in a 2S1/2 state; neglect hiher states.
Solution
*15.55. Calculate the equilibrium constant KP at 1200 K for Cl2 2Cl, from the following data: internuclear separation in Cl2 = 199 pm,
–1 –1
wavenumber for vibration = 565.0 cm , ∆U0 = 240.0 kJ mol . The ground state of Cl is a doublet, 2 P3 1 , the
,
2 2
separation between the states being 881 cm–1.

Solution
15.56. Calculate the isotopic ratio KH/KD at 300 K for the reactions
H2 2H and D2 2D
Take the zero-point energies of H2 and D2 to be 26.1 kJ mol–1 and 18.5 kJ mol–1, respectively.
Solution
15-14
Chapter 15: Statistical Mechanics Transition state theory
Transition state theory

15.57. On the basis of transition-state theory, make rough estimates of the preexponential factors at 300 K for the following types of gas
reactions:
a. A bimolecular reaction between an atom and a diatomic molecule, with the formation of a linear activated complex.
b. A bimolecular reaction between two diatomic molecules, the activated complex being nonlinear with one degree of restricted
rotation.
c. A bimolecular reaction between two nonlinear molecules, the activated complex being nonlinear with no restricted rotation.
d. A trimolecular reaction between three diatomic molecules, the activated complex being nonlinear with one degree of restricted
rotation.
Take the translational partition functions (for three degrees of freedom) to be 1033 m–3, the rotational functions for each degree of
freedom to be 10, the function for a restricted rotation to be 10, and the vibrational functions to be unity. Express the calculated
preexponential factors in molecular units (m3 s–1) and in molar units (dm3 mol–1 s–1).
Solution
15.58. The rate constant for the reaction
2NO + O2 → 2NO2
has been found to be proportional to T–3. Suggest an explanation for this behavior.
Solution
15.59. Deduce the temperature dependency of the preexponential factor of the following types of reactions, where A represents an atom, L
a linear molecule, and N a nonlinear molecule:
A + L; A + N; L + L; L + N; N + N
Solution
15-15
15.60. The rate of the reaction

O+ + N2 → NO+ + N
has been found over a certain temperature range to be proportional to T–0.5 (M. McFarland et al., J. Chem. Phys., 59, 6620(1973).
How can this be explained in terms of simple transition-state theory?
Solution
15.61. For the case of two atoms giving a product, A + B [AB]‡ → Product, show that transition-state theory yields essentially the
same expression for the rate constant as the collision theory expression of Eq. (9.76).
Solution
15.62. In mass-spectrometric experiments, P. Kebarle and coworkers (J. Chem. Phys., 52, 212(1970) have found that under certain
conditions the rate constant for the reaction
N + + N 2 + N 2 → N 3+ + N 2
is proportional to T–2.5. Suggest an explanation for this behavior.

Solution
15.63. On the basis of transition-state theory, and assuming the vibrational partitions to be temperature-independent, deduce the
temperature dependence of the preexponential factor for each of the following reactions:
a. 2ClO → Cl2 + O2
b. NO + O3 → NO2 + O2
c. NO2 + F2 → NO2F + F
d. 2NOCl → 2NO + Cl2
e. 2NO + Br2 → 2NOBr
Solution
15-16
15.64. Benzaldehyde is oxidized by permanganate in aqueous solution. Suppose that the aldehydic hydrogen atom is replaced by a
deuterium atom; what can be said on the basis of transition-state theory about the kinetic isotope ratio kH/kD at 25 °C? The
wavenumber of the aldehydic C—H vibration is 2900 cm–1.
Solution
15.65. A transition-state theory study of the reaction O(3P) + HCl generated the following information at T = 600 K:
Reactants
O qt 1.767 × 1032 m–3 (for 3 degrees of freedom)

32 –3
HCl qt 6.084 × 10 m (for 3 degrees of freedom)
qr 39.40 (for 2 degrees of freedom)
ν0 2991.0 cm–1
Transition state (bent)
qt 1.050 × 1033 m–3 (for 3 degrees of freedom)

qr 1730 (for 3 degrees of freedom)
ν1 1407.9 cm–1
ν2 266.8 cm–1
The maximum of the reaction path is at 45.97 kJ mol–1. Calculate the rate constant at this temperature.
(Note: Some interesting problems on transition-state theory involving the use of a computer are to be found in S. J. Moss and C. J.
Coady, J. Chem. Ed., 60, 455(1983).)
Solution
15-17
Chapter 15: Statistical Mechanics Essay questions
Essay questions
15.66. The molar entropy of a gas increases with the temperature and with the molecular weight. Give a physical explanation of these two
effects.
15.67. Explain the factors that influence the magnitudes of partition functions, and comment on the magnitudes of the molecular partition
functions for translational, rotational, and vibrational energy. What characteristics of a molecule will lead to a high value of (a) qt,
(b) qr, and (c) qv?
15.68. Discuss the assumptions and limitations of conventional transition-state theory. Mention briefly procedures that have been used to
overcome some of the limitations.
15.69. On the basis of the treatment of equilibrium constants in terms of partition functions, explain the factors that account for the effects
of isotopic substitution.
15-18
Chapter 15: Statistical Mechanics Solutions
Solutions
15.1. Use Stirling’s formula to calculate and approximate value for ln(N!) and compare with the exact value for N=5, 10, 50, 100, 1,000
and 10,000!
Solution:
Given: Stirling’s formula, several values of N.
Required: calculate and approximate value for ln(N!)
We can use the stirling’s formula from Eq. 15.25 to solve for the approximate value of ln(N!) :
nn
ln n ! = n ln n − n or n ! =
en
Note that the above formula works best if n is greater than 10.
N exact ln(N!) stirling's formula Error (%)
5 4.787492 3.047 36.35
10 15.10716 13.026 13.78
50 148.478 145.601 1.94
100 363.739 360.517 0.89
1000 5912.123 5907.755 0.07
10000 81959.46 82103.4 0.0018
15-19
ABS ( ln( N !) − ( N ln N − N ) )
Error =
ln( N !)
23
(Note: 10,000! is considerably less than (6.023 x 10 )! whence Stirling’s formula is essentially exact.)
Back to Problem 15.1 Back to Top
15-20
15.2. The number of possible arrangements of 4 objects (A B C D) among 4 positions (do not list them).
Solution:
Given: 4 objects (A B C D)
Required: the number of possible arrangements
The four objects are distinguishable, so there are P44 = 4! = 24 arrangements.
15-21
15.3. The number of possible arrangements of 3 objects (A B C) among 4 positions. List them all.
Solution:
Given: 3 objects (A B C)
Required: the number of possible arrangements among 4 positions
4!
P34 = = 24
(4 − 3)!
ABC_ AB_C A_BC _ABC

ACB_ AC_B A_CB _ACB
BAC_ BA_C BAC_ _BAC
BCA_ BC_A B_AC _BAC
CAB_ CA_B C_AB _CAB
CBA_ CB_A C_BA _CBA
15-22
( x1 + x2 )
n
15.4. Use the binomial distribution to work out the binomial coefficients for for n=5. Arrange the numbers in Pascal’s
⎛4⎞ ⎛5⎞ ⎛5⎞
triangle. Work out the quantities ⎜ ⎟ ⎜ ⎟ and ⎜ ⎟ to check your entries.
⎝3⎠ ⎝3⎠ ⎝2⎠
Solution:
Given: see above
Required: binomial coefficients
( x1 + x2 )5 = x15 + 5 x14 x2 + 10 x13 x22 + 10 x12 x23 + 5 x1 x24 + x25
Work out Pascal’s triangle:

1
1 2 1
1 3 3 1
1 4 6 4 1
1 5 10 10 5 1
Prn n! ⎛n⎞ ⎛ 4⎞ ⎛ 5⎞ ⎛5⎞

Use Crn = = = ⎜ ⎟ to check the entries and spot check Pascal’s Triangle: ⎜ ⎟ = 4 ⎜ ⎟ = 10 and ⎜ ⎟ = 10 etc.
Prr
(n − r )!r ! ⎝ r ⎠ ⎝ 3⎠ ⎝ 3⎠ ⎝ 2⎠
15-23
15.5. Consider two sets of indistinguishable objects, {A A} and {B B B}. Work out and list the possible arrangements of these in 5
boxes, one object per box. Check your number against the formula.
n!
Prn ! =
∏ nc !
c
Solution:
Given: {A A}, {B B B}, one object per box
Required: list all possible arrangements that can be placed in 5 boxes
n! 5!
Prn! = → P55! = = 10
∏ nc !
c
3!2!
BBBAA ABBAB
AABBB BABBA
BAABB ABABB
BBAAB BBABA
ABBBA BABAB
15-24
15.6. Work out the number of ways that the three objects (A B C) can be placed in 5 boxes, no more than one object per box. List all the
Solution
Given: (A B C), one object per box
m! 5!
Pnm = → P35 = = 60
(m − n)! (2)!
ABC_ _ A_BC_ _ABC_ A_ _BC AB_ _C AB_C_ A_B_C _ _ABC _A_B_C _AB_C
Now permute each of these ten columns 6 times keeping the empty boxes straight, AS ABOVE:
ABC_ _ etc.
ACB_ _
BAC_ _
BCA_ _
CAB_ _
CBA_ _
15-25
15.7. Work out the number of ways that the three objects (A A A) can be placed in 5 boxes, no more than one object per box. List all the
n!
Crn =
(n − r ) ! r !
Solution:
Given: (A A A), one object per box
n! 5!
Crn = → C35 = = 10
(n − r )!r ! (5 − 3)!3!
AAA_ _ A_ _ AA
_ AAA _ A _A _ A
_ _ AAA A _AA_
_A_AA AA _ _ A
_AA_ A AA _ A _
15-26
15.8. Work out the number of ways that the two objects (A B) can be placed in 3 boxes with no restriction on the number of objects per
Solution:
Given: (A B), no restriction on the number of objects per box
N = m n → 32 = 9
AB _ _ _ AB
_ AB _ B_A
_ _ AB BA_
A_B _BA
AB_
15-27
15.9. Work out the number of ways that the two objects (A A) can be placed in 4 boxes without restriction on the number of objects per
Solution:
Given: (A A), no restriction on the number of objects per box
N=
( m + n − 1)! → ( 4 + 2 − 1)! = 10
n !(m − 1)! 2!3!
AA _ _ _ _AA_
_ AA _ _ __AA
_ _ AA _ A_A_
_ _ _ AA A__A
AA__ _A_A
15-28
15.10. When we remove the condition of distinguishability from the n objects of Eq.(A.5), we divide by n! to obtain Eq.(A.6). By
considering the simple case of 2 objects and 3 boxes, (same as Problem 15.8) show that it is improper similarly to divide Eq.(A.7)
by n! to obtain the desired result for Eq.(A.8).
Solution:
Given: 2 objects, 3 boxes
Required: see above
m! m!
N = Pnm = Eq.(A.5) for distinguishable → Eq.(A.6) for indistinguishable
(m − n)! (m − n)!n !
Can we do the same for:

mn
Eq.(A.7) N = m n for distinguishable → N = for indistinguishable?
n!
The answer is no. We must use: N =
( m + n − 1)!
n !(m − 1)!
Show this for the case of 2 objects and 3 boxes:
mn 32
Wrong: N = → = 4.5
n! 2!
Correct: N =
( m + n − 1)! → ( 3 + 2 − 1)! = 6
n !(m − 1)! 2!(3 − 1)!
AA _ _ A_A
_ AA _ _AA
_ _ AA AA_
It will be seen from this problem that mn/n! is a number lying between m!/(n!(m-n)!) (Eq.(A.6) and (m+n-1)!/n!(m-1)!, Eq.(A.8). When
arrangements that differ between the two ways of counting, (due to distinguishability), represent a negligible part of the total number of
arrangements, the difference between the ways of counting becomes unimportant.
15-29
15.11. A partially deuterated methane sample is analyzed and found to contain equal molar quantities of hydrogen and deuterium. On a
random basis, calculate the percentage of species CH4, CH3D, CH2D2, CHD3 ,CD4.
Solution:
Given: see above
Required: calculate % of species CH4, CH3D, CH2D2, CHD3 ,CD4 on a random basis.
Let the probability of an H appearing by PH and a D appearing as PD. These probabilities are take as equal and PH= PD=0.5.
There can be up to 4 bonds, so we have:
( PH + PD ) 4 = PH4 + 4 PH3 PD1 + 6 PH2 PD2 + 4 PH1 PD3 + PD4
The chance of 4 H is PH4 =1/16

The chance of 3 H and 1 D is 4 PH3 PD1 =1/4
The chance of 2 H and 2 D is 6 PH2 PD2 =6/16=3/8
The chance of 1 H and 2 D is 4 PH1 PD3 =1/4
The chance of 4 D is PD4 =1/16
15-30
⎡ m! ⎤ ⎡ ( m + n −1) !⎤ ⎡ mn ⎤
15.12. Show that ln ⎢ ⎥ and ln ⎢ ⎥ both approach ln ⎢ ! ⎥ as n becomes large, provided that m>>n. (Use
⎣ n !(m − n) ! ⎦ ⎣ n !(m − 1) ! ⎦ ⎣n ⎦
Stirling’s formula and use the fact that m>>n, and m>>1).)
Solution:
Given: see above
Required: see above
⎡ m! ⎤ ⎡ m(m − 1)(m − 2)...(m − n + 1) ⎤

ln ⎢ ⎥ = ln ⎢ ⎥⎦
⎣ n !(m − n)!⎦ ⎣ n!
⎡ ⎡ m(m − 1)(m − 2)...(m − n + 1) ⎤ ⎤ ⎡ m(m − 1)(m − 2)...(m − n) ⎤
→ lim ⎢ ln ⎢ ⎥ ⎥ = ln ⎢ ⎥⎦
n →∞
⎣ ⎣ n! ⎦⎦ ⎣ n!
⎡ n times
⎤
⎢ m ⋅ m ⋅ m... ⋅ m ⎥ ⎡ mn ⎤
→= ln ⎢ ⎥ = ln ⎢ ⎥
⎢ n! ⎥ ⎣ n! ⎦
⎣ ⎦
and
⎡ ( m + n − 1) !⎤ ⎡ (m + n − 1)(m + n − 2)...(m − 2) (m − 1)! ⎤

ln ⎢ ⎥ = ln ⎢ ⎥
⎣ n !(m − 1)! ⎦ ⎣⎢ n ! (m − 1)! ⎦⎥
⎡ ⎡ n − 2 terms
⎤⎤
⎢ ⎢ (m + n − 1)(m + n − 2)...(m − 2) ⎥ ⎥ ⎡ mn−2 ⎤
= lim ⎢ln ⎢ ⎥⎥ = ln ⎢ n! ⎥
n →∞
m >> n ⎢
n! ⎣ ⎦
⎢ ⎥⎥
⎣ ⎣ ⎦⎦
⎡ mn ⎤
⎯⎯⎯n →∞
→ ln ⎢ ⎥
m >> n ⎣ n! ⎦
15-31
Alternately we can start with Eqs.(15.56) and (15.59) to obtain Eq.(15.60):
⎡ ⎛ N ⎞ ⎛g ⎞⎤
ln Ω BE = ∑ ⎢ + g j ln ⎜1 + j ⎟ + N j ln ⎜ j + 1⎟ ⎥
j ⎢
⎜ g j ⎟⎠ ⎜N ⎟⎥
⎣ ⎝ ⎝ j ⎠⎦
⎡ ⎛ N ⎞ ⎛g ⎞⎤
ln Ω D = ∑ ⎢ ± g j ln ⎜1 ± j ⎟ + N j ln ⎜ j ± 1⎟ ⎥
j ⎢
⎜ g j ⎟⎠ ⎜N ⎟⎥
⎣ ⎝ ⎝ j ⎠⎦
⎡ ⎛g ±N ⎞⎤
∑j ⎢ N j + N j ln ⎜⎜ j N j
g j >> N j
⎯⎯⎯→ ⎟⎟ ⎥
⎣⎢ ⎝ j ⎠ ⎦⎥
= ∑ ⎡⎣ N j + N j ln ( g j ± N j ) − N ln ( N j ) ⎤⎦
j
⎛ N ⎞
We have used: g j ln ⎜1 ± j ⎟ ≅ ± N j by expanding the natural logarithm, ln (1 ± x ) ≅ ± x for small x. Once again, neglect g relative to
⎜ g j ⎟⎠ j
⎝
N which gives Eq2.(15.60) and (15.61),
j
ln Ω D = ∑ ⎡⎣ N j ln ( g j ) − N j ln ( N j ) + N j ⎤⎦
j
This result is of tremendous importance in permitting us to ignore the restrictions of Bose-Einstein and Fermi-Dirac quantum statistics when
the number of accessible quantum states (the m boxes) far exceed the number of molecules (the n objects).
15-32
15.13. Show that the maximum entropy, S, is obtained when all the probabilities, pi are equal, where
n n
S = −∑ pi ln pi and ∑ pi = 1
i =1 i =1
(This shows us that complete lack of knowledge of which state the system is in results in the highest entropy. When all states are
equally likely, we have no preferential state, and this means the most random or highest entropy.)
Solution:
Given: see above
Required: prove the above expression for equal probabilities
To solve for this problem, we can use the Lagrange multipliers. Take the derivative with respect to each probability subject to the
n
condition, ∑p
i =1
i = 1 . For maximum entropy, we set the results equal to zero:
⎛ ∂S ⎞
⎜ ⎟ = − ln pi − 1 + α = 0
⎝ ∂pi ⎠ p j , j ≠i
+ ln p1 = α − 1
so, + ln p2 = α − 1 hence all the pi’s must be equal and pi = exp (α − 1)
+ ln p3 = α − 1
n
Since ∑p
i =1
i = 1 then
n n n
1 = ∑ pi = ∑ exp (α − 1) = exp (α − 1) ∑1 = n exp (α − 1)
i =1 i =1 i =1
so
15-33
⎛1⎞ 1
ln ⎜ ⎟ = α − 1 so pi =
⎝n⎠ n
15-34
15.14. Prove that for an N particle quantum state, the wave function must be either odd or even under the permutation of any two of the N
particles.
(This symmetry, of course, distinguishes bosons from fermions.)
Solution:
Given: N particle quantum state
Required: prove the above
Let Ψ (1, 2,3,....N ) be an N particle state. Now permute two particles:
Pij Ψ (1, 2,3,.i... j...N ) = aΨ (1, 2,3,. j...i...N )
but two permutations must get us back to the same state that we started from,
Pij Pij Ψ (1, 2,3,. j...i...N ) = a 2 Ψ (1, 2,3,.i... j...N )
The only way this can happen is if a 2 = 1 or a = ±1 .
15-35
15.15. A more accurate form of Stirling’s approximation is
In the stopcock opening and closing example, recalculate the effect of ΔS II → III using the above approximation and show that the
entropy change is negligible compared to ΔS I → II . Assume that the two volumes are equal, and consider what happens to this new
entropy change ΔS II → III < 0 as the number of particles goes to infinity
(Although we observe no noticeable change when we physically close the stopcock in going from state II to III, there is a change
due to our definition. This problem asks you to look into. The reason the change is negligible from our theory is because we are
dealing with an enormous number of particles, and can use Stirling’s approximation. However, if we had only a few particles, then
the effect of closing the stopcock would lead to a difference between the two states, II and III, i.e. the “entropy” would show a
decrease. This underscores the fact that we can not define entropy for a small number of particles because entropy is a statistical
quantity.)
Solution:
Given: altered version of Stirling’s approximation
Required: the effect of ΔS II → III
The expression from the notes using the usual form of Stirling’s approximation is:
⎧⎪ ( N1 ) N1 ( N 2 ) N2 ( N1 + N 2 ) !⎫⎪
ΔS II → III = A ln ⎨ ⎬
⎩⎪ ( N1 + N 2 )
N1 + N 2
N1 ! N 2 ! ⎭⎪
⎧⎪ N1 ln N1 + N 2 ln N 2 + ( N1 + N 2 ) ln ( N1 + N 2 ) − N1 − N 2 ⎫⎪
= A⎨ ⎬=0
⎪⎩ − ( N1 + N 2 ) ln ( N1 + N 2 ) − N1 ln N1 + N1 − N 2 ln N 2 + N 2 ⎪⎭
15-36
We note that all the terms cancel. If we use the better approximation for Strirling’s approximation,
we get:
⎧⎪ ( N1 ) N1 ( N 2 ) N2 ( N1 + N 2 ) !⎫⎪
ΔS II → III = A ln ⎨ ⎬
⎪⎩ ( N1 + N 2 )
N1 + N 2
N1 ! N 2 ! ⎪⎭
⎪⎧ N1 ln N1 + N 2 ln N 2 + ( N1 + N 2 ) ln ( N1 + N 2 ) − N1 − N 2 + ln 2π ( N1 + N 2 ) ⎫⎪
= A⎨ ⎬
⎪⎩ − ( N1 + N 2 ) ln ( N1 + N 2 ) − N1 ln N1 + N1 − ln 2π N1 − N 2 ln N 2 + N 2 − ln 2π N 2 ⎪⎭
= A ln
( N1 + N 2 )
2π N1 N 2
Let us assume that V1=V2.so N1=N2= N/2 giving
( N1 + N 2 ) N = N A ln
1 2
( 2N / 2) A 2N A 2
A ln
2π N1 N 2 = 2π ( N / 2 )
2
= ln
2 πN 2
= ln
2 πN
A 2 A⎛ 2 ⎞
write this as: ln = ⎜ ln − ln N ⎟
2 πN 2 ⎝ π ⎠
15-37
This shows that there is a decrease in entropy for large N, but this is negligible. The correction from this shows a decrease in entropy of
− A ln N when the stopcock is closed. If we plug in A=k, then we get
− A ln N = −k ln N = − (1.38 ×10−23 ) ln ( 6.23 ×1023 ) = − (1.38 ×10−23 ) 55 = −7.6 ×10−22
which is negligible. Suppose we had 1010 moles, the calculation would change to:
− A ln N = −k ln N = − (1.38 ×10−23 ) ln ( 6.23 × 1033 ) = − (1.38 ×10−23 ) 78 = −10.7 × 10−22
which is still negligible.
15-38
N1 N
15.16. Using: = 2 prove the relationship:
V1 V2
⎡
( V1 / Vc ) 1 ( V2 / Vc ) 2 ( N1 + N 2 ) ! ⎥⎤ = ln ⎡ ( N1 ) N1 N 2 N2 ( N1 + N 2 ) ! ⎤⎥
N N
ln ⎢ ⎢
⎢⎣ (
⎢ ( V / V ) N1 + ( V / V ) N2
1 c 2 c ) ( N1 ) ! ( N2 ) ! ⎥⎥⎦ ⎢⎣ ( N1 1 + N 2 2 )
N N
( N1 ) ! ( N 2 ) ! ⎥⎦
Solution:
N1 N
Given: = 2
V1 V2
Required: prove the above relationship
Cancel the Vc’s:
⎡ (V1 / Vc ) N1 (V2 / Vc ) N2 ( N1 + N 2 ) !⎤ ⎡⎛ V N1 + N2 ⎞ (V1 ) N1 (V2 ) N2 ( N1 + N 2 ) !⎤

ln ⎢ ⎥ = ln ⎢⎜ cN1 N2 ⎟ ⎥
⎢⎣ (V1 / Vc + V2 / Vc ) ⎢⎣⎝ Vc Vc ⎠ (V1 + V2 )
N1 + N 2 N1 + N 2
N1 ! N 2 ! ⎥⎦ N1 ! N 2 ! ⎥⎦
⎡ (V1 ) N1 (V2 ) N2 ( N1 + N 2 ) !⎤
= ln ⎢ ⎥
⎢⎣ (V1 + V2 )
N1 + N 2
N1 ! N 2 ! ⎥⎦
Now consider only the powers (since the factorials remain):
⎡ (V1 ) N1 (V2 ) N2 ⎤
ln ⎢ N1 + N 2 ⎥
= N1 ln V1 + N 2 ln V2 − ( N1 + N 2 ) ln (V1 + V2 )
⎣⎢ (V1 + V2 ) ⎦⎥
Use N1V2 = N 2V1 to get
15-39
⎛ N 2V + N 22V1 ⎞
= N1 ln V1 + N 2 ln V2 − ( N1 + N 2 ) ln ⎜ 1 2 ⎟
⎝ N1 N 2 ⎠
Now write out all the terms as a sum of ln’s:
= N1 ln V1 + N 2 ln V2 − ( N1 + N 2 ) ln ( N12V2 + N 22V1 ) + N1 ln N1 + N1 ln N 2
+ N 2 ln N1 + N 2 ln N 2
Now we can use the fact that N1V2 = N 2V1 to get
= N1 ln V1 + N 2 ln V2 − ( N1 + N 2 ) ln ( N1V2 { N1 + N 2 } ) + N1 ln N1 + N1 ln N 2
+ N 2 ln N1 + N 2 ln N 2
and expand the terms:
= N1 ln V1 + N 2 ln V2 − ( N1 + N 2 ) ln ( N1V2 ) − ( N1 + N 2 ) ln ( N1 + N 2 )
+ N1 ln N1 + N1 ln N 2 + N 2 ln N1 + N 2 ln N 2
= N1 ln V1 + N 2 ln V2 − ( N1 + N 2 ) ln ( N1 ) − ( N1 + N 2 ) ln (V2 ) − ( N1 + N 2 ) ln ( N1 + N 2 )
= N1 ln V1 + N 2 ln V2 − N1 ln N1 − N 2 ln N1 − N1 ln V2 − N 2 ln V2 − ( N1 + N 2 ) ln ( N1 + N 2 )
collect and cancel terms:
15-40
= N1 ln V1 + N 2 ln V2 − N1 ln N1 − N 2 ln N1 − N1 ln V2 − N 2 ln V2 − ( N1 + N 2 ) ln ( N1 + N 2 )
= N1 ln V1 − N1 ln V2 + N1 ln N 2 + N 2 ln N 2 − ( N1 + N 2 ) ln ( N1 + N 2 )
⎛V ⎞
= N1 ln ⎜ 1 ⎟ + N1 ln N 2 + N 2 ln N 2 − ( N1 + N 2 ) ln ( N1 + N 2 )
⎝ V2 ⎠
V1 N1
Using =
V2 N 2
⎛N ⎞
= N1 ln ⎜ 1 ⎟ + N1 ln N 2 + N 2 ln N 2 − ( N1 + N 2 ) ln ( N1 + N 2 )
⎝ N2 ⎠
= N1 ln N1 − N1 ln N 2 + N1 ln N 2 + N 2 ln N 2 − ( N1 + N 2 ) ln ( N1 + N 2 )
= N1 ln N1 − N1 ln N 2 + N1 ln N 2 + N 2 ln N 2 − ( N1 + N 2 ) ln ( N1 + N 2 )
= N1 ln N1 + N 2 ln N 2 − ( N1 + N 2 ) ln ( N1 + N 2 )
⎡ N N1 N N2 ⎤
= ln ⎢ 1 2
N1 + N 2 ⎥
⎣⎢ ( N1 + N 2 ) ⎦⎥
which is in the form we want.

15-41
15.17. Without considering energy, calculate the statistical weights for 30 quanta distributed amongst 30 oscillators for the following
distributions of the quanta:
N 0 = 0, N1 = 30, N 2 → 29 = 0
N 0 = 1, N1 = 28, N 2 = 1, N 3 → 29 = 0
N 0 = 10, N1 = 10, N 2 = 10, N 3 → 29 = 0
(This is a problem of combinatorials, how many ways can 30 indistinguishable objects be distributed between 30 levels. For
oscillators, we usually label the lowest state by a “0”, so we go up to the 29th level. In general, there is usually degeneracy (more
than one state with the same energy) Here we are calculating the degeneracy for various possible energies. In case a) the energy is
30ε1 , for b) the energy is ε 0 + 28ε1 + 2ε 2 and for c) 10ε 0 + 10ε1 + 10ε 2 . The problem calculates the number of ways (the
statistical weight) that indistinguishable quantum can be arranged to give that particular energy.)
Solution:
Given: see above
Required: statistical weights
The number of ways of producing the energies of these distributions is simply:
N!
30
∏N
i =1
i
a. N 0 = 0, N1 = 30, N 2→29 = 0
N! 30!
→ =1
30
0!⋅ 30!⋅ 0!⋅ ....0!⋅
∏N
i =1
i
15-42
b. N 0 = 1, N1 = 28, N 2 = 1, N 3→29 = 0
N! 30!
→ = 30 ⋅ 29 = 870
30
1!⋅ 28!⋅1!⋅ ....0!⋅
∏N
i =1
i
c. N 0 = 10, N1 = 10, N 2 = 10, N 3→29 = 0
N! 30!
→ = 29 ⋅ 26 ⋅ 23 ⋅ 22 ⋅ 21⋅19 ⋅17 ⋅13 ⋅11⋅ 5 = 1.8503323 ×1012
30
10!⋅10!⋅10!⋅ ....0!⋅
∏N
i =1
i
15-43
15.18. Show that Eq.Error! Reference source not found. satisfies FD and BE conditions of respectively no more that 1 particle, on the
average, in a state, and any number of particles in a state. Let x = exp ⎡⎣ ( ε α − μ ′ ) / k BT ⎤⎦
Solution:
Given: x = exp ⎡⎣ ( ε α − μ ′ ) / k BT ⎤⎦
Required: show above statement

The expression for BE (-) statistics and FD (+) statistic is
BE
1 1
= ≡ Z FD
( x)
exp ⎡⎣( ε α − μ ′ ) / k BT ⎤⎦ ∓ 1 x
e ∓1
Since the range of x is ± ∞ , we have for FD statistics, (+) sign:
Z FD (−∞) = 1; Z FD (0) = 1/ 2; Z FD (∞) = 0;
For BE statistics, (-) sign:
Z BE (−∞) = 1; Z BE (0) = ∞; Z BE (∞) = 0;
Hence the average population of an eigenstate for fermions cannot exceed 1 while there is no restriction on the average population of an
eigenstate for bosons.
15-44
15.19. Starting from
S = k B ln Ω( E , V , N )
obtain the equation:
PV = k BT ln Ξ (T , V , μ )
where Ξ(T , V , μ ) is the grand partition function. Do NOT derive the ideal gas law (i.e. do not assume the particles do not interact).
(The grand partition function is one that is commonly used in chemical reactions.)
Solution:
Given: S = k B ln Ω( E , V , N )
Required: derive PV = k BT ln Ξ(T , V , μ )
Grand Canonical ensemble: change variable N to μ, and E to T :
We have already changed the variables from S = k ln Ω( E ,V , N ) , see Eq.(15.107), E to T, giving –A/T, so now, using the Legendre
transformation,
A
− = k B ln Q(T ,V , N ) →
T
⎡
⎢ A ∂
⎛ −A
Φ (T , V , μ ) = ⎢ − − ⎜
( T ) ⎞⎟ ⎤
⎥ ⎡ A 1 ⎛ ∂A ⎞
N ⎥ = ⎢− + ⎜
⎤ A 1
N ⎥ = − + μN
⎜ ⎟ ⎟
T ∂N T T ⎝ ∂N ⎠T ,V , μ ⎥⎦ T T
⎢⎣ ⎝ ⎠T ,V , μ ⎥⎦ ⎢⎣
Following the same procedure, we get,
A 1 E μ
k ln Ξ(T , V , μ ) = Φ (T , V , μ ) = − + μN = − + S + N
T T T T
15-45
To identify the function that is natural for the grand canonical ensemble, note that the Gibbs energy for a one-component system is,
G = N μ = H − TS = E + PV − TS (a)
divide by T and rearrange,
μ E PV
N = + −S (b)
T T T
Comparing Eq.(a) with Eq.(b) shows that,
PV
= k B ln Ξ(T ,V , μ )
T
15-46
15.20. Derive expressions for the energy U=E, the entropy S the pressure P and the Helmholtz energy A, and the Gibbs energy G in terms
of the Canonical ensemble, Q.
Solution:
Given: U = E, S, P, A, G, Q
Required: derivation
We have:
A = −k BT ln Q(T ,V , N )
and
dA = − Sdt − PdV
using
⎛ ∂A ⎞ ⎛ ∂A ⎞
⎜ ⎟ = −P ⎜ ⎟ = −S
⎝ ∂V ⎠T ⎝ ∂T ⎠V
gives
⎛ ∂A ⎞ ⎛ ∂ ln Q ⎞
S = −⎜ ⎟ = kT ⎜ ⎟ + k B ln Q
⎝ ∂T ⎠V ⎝ ∂T ⎠V
⎛ ∂A ⎞ ⎛ ∂ ln Q ⎞
P=⎜ ⎟ = k BT ⎜ ⎟
⎝ ∂V ⎠T ⎝ ∂V ⎠T
and from A=E-TS
⎛ ∂ ln Q ⎞
E = k BT 2 ⎜ ⎟
⎝ ∂T ⎠V
15-47
finally the Gibbs energy is
⎛ ∂ ln Q ⎞
G = A + PV = −k BT ln Q +k BTV ⎜ ⎟
⎝ ∂V ⎠T
15-48
15.21. Find the natural function for the isothermal-isobaric ensemble, Δ (T , P, N ) , i.e. for variables T, P and N.
Solution:
Given: isothermal-isobaric
Required: natural function
We have:
S = k B ln Ω(U ,V , N ) = Φ(U ,V , N ) microcanonical ensemble

→ Φ (T ,V , N ) = k B ln Ω(T , V , N ) ≡ k ln Q(T ,V , N ) canonical ensemble
→ Φ (T ,V , μ ) = k B ln Ω(T ,V , μ ) ≡ k ln Ξ(T ,V , μ ) grand canonical ensemble
→ Φ(T , P, N ) = k B ln Ω(T , P, N ) ≡ k ln Δ(T , P, N ) isothermal-isobaric ensemble
We know that the natural function of the variables T ,V , N is –A/T, so all we have to do is apply the Legendre transformation for V to T,
A ⎛ ∂ (−A /T ) ⎞ A 1 ⎛ ∂A ⎞
Φ (T , P, N ) = − −⎜ ⎟ P=− + ⎜ ⎟ P
T ⎝ ∂P ⎠T ,V , N T T ⎝ ∂P ⎠T ,V
A 1 ⎛ A + PV ⎞ G
=− − VP = − ⎜ ⎟=−
T T ⎝ T ⎠ T
so, as no surprise the isothermal-isobaric ensemble is
G
Φ (T , P, N ) = − = k B ln Ω(T , P, N ) ≡ k B ln Δ(T , P, N )
T
or
G = −k BT ln Δ(T , P, N )
15-49
15.22. Obtain an expression for CP in terms of the partition function Q for the system.
Solution:
Given: Cp, Q
Required: see above
⎛ ∂H ⎞
We know that C p = ⎜ ⎟ ,
⎝ ∂T ⎠ P
⎛ ∂ ln Q ⎞
and that H − U 0 = kBT 2 ⎜ ⎟ + NkBT
⎝ ∂T ⎠V
if U 0 = 0 , substitution of the above expression into the expression for C p will yield:
⎛ ∂H ⎞
Cp = ⎜ ⎟
⎝ ∂T ⎠ P
⎛ ⎡ 2 ⎛ ∂ ln Q ⎞ ⎤⎞
⎜ ∂ ⎢ kBT ⎜ ⎟ + NkBT ⎥ ⎟
⎝ ∂T ⎠V
Cp = ⎜ ⎣ ⎦⎟
⎜ ∂T ⎟
⎜⎜ ⎟⎟
⎝ ⎠P
⎪⎧ ∂ ⎡ ⎫
2 ⎛ ∂ ln Q ⎞ ⎤ ⎪
Cp = ⎨ ⎢ kBT ⎜ ⎟ ⎥ ⎬ + NkB
⎩⎪ ∂T ⎣ ⎝ ∂T ⎠V ⎦ ⎭⎪ P
15-50
15.23. Obtain an expression for the pressure P in terms of the molecular partition function q, for (a) distinguishable molecules and (b)
indistinguishable molecules. Express the result in terms of the number of molecules N and also the amount of substance n.
Solution:
Given: P, q, N, n
Required: see above
From Eq. 3.118,
⎛ ∂A ⎞ ⎛ ∂ ln Q ⎞
P = −⎜ ⎟ = kBT ⎜ ⎟
⎝ ∂V ⎠T ⎝ ∂V ⎠T
a. From Eq. 15.45 for distinguishable molecules
Q = qN
Take the natural logarithm on both sides yield:

ln Q = N ln q
Therefore,
⎛ ∂ ln Q ⎞
P = kBT ⎜ ⎟
⎝ ∂V ⎠T
⎛ ∂ ( N ln q ) ⎞
P = kBT ⎜ ⎟
⎝ ∂V ⎠T
⎛ ln q∂N + N ∂ ln q ⎞
P = kBT ⎜ ⎟
⎝ ∂V ⎠T
⎛ ∂ ln q ⎞
P = NkBT ⎜ ⎟
⎝ ∂V ⎠T
⎛ ∂ ln q ⎞
P = nRT ⎜ ⎟
⎝ ∂V ⎠T
15-51
b. From Eq. 15.47 for indistinguishable molecules,
qN
Q=
N!
Take the natural logarithm on both sides yield:
ln Q = ln q N − ln N !
ln Q = N ln q − N ln N + N
⎛ ∂ ln Q ⎞
Similarly to a., we will substitute the above expression into P = kBT ⎜ ⎟ , and will yield the same answer as a.:
⎝ ∂V ⎠T
⎛ ∂ ln Q ⎞
P = kBT ⎜ ⎟
⎝ ∂V ⎠T
15-52
⎡ ⎛ – hv ⎞ ⎤
15.24. The partition function for each degree of vibrational freedom is 1 / ⎢ 1 − exp ⎜ ⎟ ⎥ (Eq.Error! Reference source not found.).
⎣ ⎝ kBT ⎠ ⎦
Obtain from this expression the limiting value of the vibrational contribution to CV as T approaches infinity.
Solution:
⎡ ⎛ – hv ⎞ ⎤
Given: 1 / ⎢ 1 − exp ⎜ ⎟ ⎥ ,T → ∞
⎣ ⎝ kBT ⎠ ⎦
Required: limiting value of the vibrational contribution to CV

In the limit as T → ∞ the vibrational partition function becomes
1 kBT
=
⎛ hν ⎞ hν
1 − ⎜1 − ⎟
⎝ kBT ⎠
Then
U m − U 0,m = RT
and
CV , m = R = 8.3145 J K −1 mol−1
15-53
15.25. Chemical reactions often lead to the formation of products whose energy distributions show significant deviations from the
statistical distribution of Eq. 15.40. In a study of an elementary reaction with 16O1H radical as one of the products [Zhang, van
der Zande, Bronikowski, and Zare, J. Chem. Phys. 94, 2704(1994)], the following rotational distribution was observed for the OH(v
= 0) state (normalized such that ΣnJ/N = 1). Compare this to the statistical distribution expected from
Eq.Error! Reference source not found. at 298 K. The equilibrium bond distance of OH is 0.96966 Å.
J 7 8 9 10 11 12 13
nJ /N 0.0181 0.0232 0.0356 0.0475 0.0377 0.0762 0.1045
J 14 15 16 17 18 19 20
nJ /N 0.1266 0.1459 0.1466 0.1306 0.0907 0.0167 0.0000
Solution:
Given: v = 0, ΣnJ/N = 1, T = 298 K, d OH = 0.96966 Å
Required: comparison to statistical distribution

The reduced mass of 16O1H is
1.0078 g mol−1 ×15.9949 g mol−1 1 kg

μ=
(1.0078 + 15.9949 ) g mol−1 6.022 ×1023 mol−1 1000 g
μ = 1.574 335 324 × 10−27 kg
The moment of inertia is
I = (1.574 335 324 × 10−27 kg )( 0.96966 ×10−10 m ) = 1.480 253 857 ×10−47 kg m 2
2
The rotational partition function is
qr =
2 IkBT
=
(
2 1.480 253 857 ×10−47 kg m 2 ) (1.381×10 −23
m 2 kg s −2 K −1 ) ( 298 K )
( 6.626 ×10 )
−34 2
2
m 4 kg 2 s −2
qr = 0.277 506 523 at T = 298 K
15-54
J ( J + 1) 2
Now, using Eq. 15.40 with g J = 2 J + 1 , and ε J = , we write

2I
nJ 2 J + 1 ⎡ − J ( J + 1) 2
) ⎤⎥ .
= exp ⎢
N qr ⎢⎣ 2 IkBT ⎥⎦
A plot of this fraction as a function of J along with the experimental distribution is shown in the accompanying figure.
15-55
15.26. Suppose that an array of harmonic oscillators has common frequency of ν = 1011 s-1. Calculate the ratio of the number of
oscillators in the 10th quantum state (n=9) to those in the ground state at 0 K, 300 K and 1000 K. The energy levels are given by
1
ε n = (n + )hν .
2
(This is a straight application of the Boltzmann distribution. Each energy level is non-degenerate.)
Solution:
1
Given: ν = 1011 s-1, n = 9, T = 0 K, 300 K, 1000 K, ε n = (n + )hν
2
Required: ratio of the number of oscillators
⎛ ⎛ 1⎞ ⎞
exp ⎜ − β ⎜ 9 + ⎟ hν ⎟
N10 exp(− βε 9 ) ⎝ ⎝ 2⎠ ⎠
= = = exp ( − β 9hν )
N 0 exp(− βε 0 ) ⎛ ⎛1⎞ ⎞
exp ⎜ − β ⎜ ⎟ hν ⎟
⎝ ⎝2⎠ ⎠
⎛ 9hν ⎞ ⎛ 9 ( 6.623 × 10−34 J s )(1011 s -1 ) ⎞
= exp ⎜ − ⎟ = exp ⎜⎜ − ⎟
⎝ k BT ⎠ ⎝ (1.38 × 10 −23
J K -1
) T ⎟
⎠
⎛ 9 ( 6.623 × 10−34 J s )(1011 s -1 ) ⎞ ⎛ 3.8874 ×102 K -1 ⎞
= exp ⎜ − ⎟ = ex p ⎜− ⎟
⎜
⎝ (1.38 × 10 −23
J K -1
) T ⎟
⎠ ⎝ T ⎠
15-56
N10 (T ) ⎛ 3.8874 × 102 K -1 ⎞

= exp ⎜ − ⎟
N0 ⎝ T ⎠
N10 (0) ⎛ 3.8874 × 102 K -1 ⎞
= exp ⎜ − ⎟
N0 ⎝ 0 ⎠
N10 (0)
=0
N0
N10 (300) ⎛ 3.8874 × 102 K -1 ⎞
= exp ⎜ − ⎟ = exp ( −1.129 )
N0 ⎝ 300 ⎠
N10 (300)
= 0.274
N0
N10 (1000) ⎛ 3.8874 ×102 K -1 ⎞
= exp ⎜ − ⎟ = exp ( −0.38874 )
N0 ⎝ 1000 ⎠
N10 (1000)
= 0.678
N0
15-57
15.27. Calculate the average value of the energy per mole at the various temperatures for the oscillators in problem 17.
(This is best done by evaluating the partition function for harmonic oscillators and applying the general formula for ε .
Solution:
Given: problem 17
Required: average value of the energy per mole
You need to know the following sum:
∞
1
∑
n =0
exp ( − xn ) =
(1 − exp(− x) )
1
Now calculate the partition function for the case that the energy is: ε n = (n + )hν
2
q = ∑ exp ⎡⎣ − ( ε i − ε 0 ) / ( k BT ) ⎤⎦ = ∑ exp [ −nhνβ ]

i n
so
1
q=
(1 − exp(−hνβ ) )
Now use:
1 dq d ln q
ε − εo = − =−
q dβ dβ
15-58
1 dq 1 d ⎛ 1 ⎞ 1⎛ exp ( −hνβ ) ⎞
= ⎜⎜ ⎟⎟ = ⎜⎜ −hν ⎟
q d β q d β ⎝ (1 − exp(− hνβ ) ) ⎠ q ⎝ (1 − exp(−hνβ ) ) ⎟⎠
2
1 ⎛ 1 ⎞⎛ exp ( −hνβ ) ⎞ hν
⎜⎜ ⎟⎟ ⎜⎜ −hν ⎟⎟ = −
q ⎝ (1 − exp(−hνβ ) ) ⎠ ⎝ (1 − exp(−hνβ ) ) ⎠ (1 − exp(hνβ ) )
so
1 dq hν
ε − εo = − =
q d β ( exp(hνβ ) − 1)
or
hν hν
ε = +
2 ( ( exp(hνβ ) − 1) )
15-59
hν hν hν hν
ε (T ) → ε (0) = + = +
2 ( exp(∞) − 1) 2 ∞
6.623 ×10−23
= = 3.31×10 −23 J molecule -1 (zero point energy)
2
hν hν hν 6.623 × 10−23 J molecule-1
ε (300) = + = +
2 ( ( exp(hνβ ) − 1) ) 2 (
exp(6.623 × 10−23 J / (1.38 ×10−23 J K -1 ⋅ 300 K )) − 1 )
hν 6.623 ×10−23 J molecule-1 hν 6.623 × 10−23 J molecule-1
= + = +
2 (1.0161 − 1) 2 0.0161
= ( 0.0331×10−21 + 4.173 ×10−21 ) =4.206 ×10−21 J molecule-1
hν hν hν 6.623 × 10−23 J molecule-1

ε (1000) = + = +
2 ( ( exp(hνβ ) − 1) ) 2 ( )
exp(6.623 × 10−23 J / (1.38 ×10−23 J K -1 ⋅1000 K )) − 1 E = N ε
hν 6.623 ×10 J molecule
−23
hν 6.623 × 10 J molecule
-1 −23 -1 E (0) = 19.5 J mol-1
= + = +
2 (1.0048 − 1) 2 0.0048 E (300) = 2.533 kJ mol-1
= ( 0.00331× 10−20 + 1.3798 × 10−20 ) =1.383 × 10−20 J molecule-1 E (1000) = 8.329 kJ mol-1
15-60
⎛ 1⎞
15.28. The energy levels for a harmonic oscillator are given by ε n = ⎜ n + ⎟ hν .
⎝ 2⎠
2
a. Derive an expression for the mean-square fluctuation, σ E = E2 − E in energy for these oscillators.
b. Use ν = 1011 s -1 and the partition function from problem set 2 to evaluate the mean-square fluctuation.
c. Compare σ E to U = E .
d. What happens as the temperature is raised?

e. What happens as the number of particles increases?
(Fluctuations are generally negligible relative to macroscopic quantities but are important for many processes under certain
conditions, such as phase transitions.)
Solution:
⎛ 1⎞
Given: ε n = ⎜ n + ⎟ hν
⎝ 2⎠
Required: see above
⎛ E ⎞
∑E j exp ⎜ − j ⎟
a. E =
j ⎝ k BT ⎠
q
or
⎛ Ej ⎞ ⎛ Ej ⎞
E ∑ exp ⎜ − k T ⎟ = ∑ E j exp ⎜ − ⎟
j ⎝ B ⎠ j ⎝ k BT ⎠
Differentiate with respect to T,
15-61
⎛ ∂E ⎞ E ⎛ Ej ⎞ ⎛ Ej ⎞
⎜ ⎟ +
⎝ ∂T ⎠V , N Qk BT
2 ∑E j exp ⎜ − ⎟ = ∑ E j exp ⎜ −
2
⎟
j ⎝ k BT ⎠ j ⎝ k BT ⎠
or
2 2
E2 − E = E− E = σ E2 = k BT 2CV
σ E = k BT 2CV
so the ratio of energy fluctuation to the average energy is
σE (k BT 2CV )1/ 2
=
E E
b. From Eq.(15.128)
⎛ ⎞
⎛ ∂E ⎞ Nk B ⎜ ∂ 2 ln q ⎟
CV = ⎜ ⎟ = 2 ⎜
T ⎜ ∂ 1 2 ⎟⎟
⎝ ∂T ⎠V
⎝ T ⎠V ( )
therefore
⎛ ⎞ ⎛ 2 ⎞
Nk B2T 2 ⎜ ∂ 2 ln q ⎟ ⎜ ∂ ln q ⎟
σ E = k BT CV =
2
= kB N ⎜
T 2 ⎜⎜ ∂ 1 2 ⎟⎟ 2 ⎟
⎝ ( ) T ⎠V ⎝ ( )
⎜∂ 1
T ⎠V
⎟
From Eq.(15.155), we have
1
q=
(1 − exp(−hνβ ) )
Differentiating twice wrt 1/T,
15-62
⎛ hν ⎞
⎛ 2 ⎞ 2 exp ⎜ − ⎟
⎜ ∂ ln q ⎟ ⎛ hν ⎞ ⎝ k BT ⎠
⎜ 1 2 ⎟ =⎜k ⎟
( )
3
⎜∂ ⎟ ⎝ B⎠ ⎛ ⎛ hν ⎞ ⎞
⎝ T ⎠V ⎜ 1 − exp ⎜ − ⎟⎟
⎝ ⎝ k BT ⎠ ⎠
this gives
⎛ hν ⎞
⎛ 2 ⎞ exp ⎜ − ⎟
⎜ ∂ ln q ⎟ ⎝ 2 k BT ⎠
σ E = k BT 2CV = k B N⎜ 2 ⎟
= hν N
( )
3/ 2
⎜∂ 1 ⎟ ⎛ ⎛ hν ⎞ ⎞
⎝ T ⎠V ⎜ 1 − exp ⎜ − ⎟⎟
⎝ ⎝ k BT ⎠ ⎠
or in numbers:
⎛ hν ⎞
exp ⎜ − ⎟
⎝ 2k BT ⎠ = 6.623 ×10−23 J N exp ( −2.4 / T )
σ E = hν N
⎛ ⎛ 3hν ⎞ ⎞ (1 − exp(−4.799 / T ) )
3/ 2
⎜1 − exp ⎜ − ⎟⎟
⎝ ⎝ 2 k BT ⎠ ⎠
c. We can calculate the average energy,
hν hν Nhν Nhν
ε = + → E =N ε = +
2 ( ( exp(hνβ ) − 1) ) 2 ( ( exp(hνβ ) − 1) )
giving
Nhν ( 6.023 × 10 molecule )( 6.623 ×10 J molecule )

23 −23 -1
E = +
2 (
exp(6.623 × 10−23 J / (1.38 ×10−23 J K -1 ⋅ T K )) − 1 )
⎛ 39.9 J ⎞
E = n ⎜19.9 J + ⎟
⎝ exp(4.799 / T ) − 1 ⎠
15-63
where n is the number of moles. Therefore the the ratio is
⎡ −23 exp ( −2.4 / T ) ⎤

⎢ 6.623 × 10 J ⎥
(1 − exp(−4.799 / T ) )
3/ 2
σE N ⎢ ⎥
=
E n ⎢ ⎛ 39.9 J ⎞ ⎥
⎢ ⎜19.9 J + exp(4.799 / T ) − 1 ⎟ ⎥
⎢⎣ ⎝ ⎠ ⎥⎦
which shows that the fluctuations are very small.

d. Clearly at T=0 K the exponentials in the numerator vanish, while the denominator shows the second term vanishes. As T increases,
these terms become important. If you want to expand the exponentials in 1/T, then you will see what happens at high temperature,
but that is not necessary for the problem.
e. From the above equation,
⎛ hν ⎞
exp ⎜ − ⎟
σ E = k BT 2CV = σ E = hν N ⎝ 2 k BT ⎠
3/ 2
⎛ ⎛ hν ⎞ ⎞
⎜1 − exp ⎜ − ⎟⎟
⎝ ⎝ k BT ⎠ ⎠
It is clear that the fluctuations increase as the square root of N. Parts d. and show us that fluctuations increase with temperature and
density.
15-64
15.29. If the molecular partition function can be written as a product of factors, q = qtr ⋅ qint , then energy, entropy and the other
thermodynamic properties can be written as a sum of terms. Show that this is true for E, S and A.
Solution:
Given: q = qtr ⋅ qint
Required: show that E, S, and A can be written as a sum of terms
⎛ ∂ ln q ⎞ 2 ⎛ ∂ ln ( q1q2 ) ⎞
E − Eo = RT 2 ⎜ ⎟ = RT ⎜ ⎟
⎝ ∂T ⎠V ⎝ ∂T ⎠V
⎡⎛ ∂ ln q1 ⎞ ⎛ ∂ ln q2 ⎞ ⎤
E − Eo = RT 2 ⎢⎜ ⎟ +⎜ ⎟ ⎥ = E1 + E2 − E1o − E2 o
⎣⎝ ∂T ⎠V ⎝ ∂T ⎠V ⎦
For the entropy and the Hemlholtz energy you have to decide where the factorial goes. Therefore we write q = qtr qint
⎡ ⎛ ∂ ln qtr qint ⎞ ⎤
S = Nk B ⎢ln qtr qint − ln N + 1 − ⎜ ⎟ ⎥
⎣ ⎝ ∂ ln T ⎠V ⎦
⎡ q ⎛ ∂ ln qtr ⎞ ⎛ ∂ ln qint ⎞ ⎤
= Nk B ⎢ln tr qint + 1 − ⎜ ⎟ −⎜ ⎟ ⎥
⎣ N ⎝ ∂ ln T ⎠V ⎝ ∂ ln T ⎠V ⎦
⎡ q ⎛ ∂ ln qtr ⎞ ⎤ ⎡ ⎛ ∂ ln qint ⎞ ⎤
= Nk B ⎢ln tr + 1 − ⎜ ⎟ ⎥ − Nk B ⎢ln qint −⎜ ⎟ ⎥
⎣ N ⎝ ∂ ln T ⎠V ⎦ ⎣ ⎝ ∂ ln T ⎠V ⎦
⎡ q ⎛ ∂ ln qtr ⎞ ⎤ ⎡ ⎛ ∂ ln qint ⎞ ⎤
= Nk B ⎢ln tr − ln N + 1 − ⎜ ⎟ ⎥ − Nk B ⎢ ln qint − ⎜ ⎟ ⎥
⎣ N ⎝ ∂ ln T ⎠V ⎦ ⎣ ⎝ ∂ ln T ⎠V ⎦
= Str + Sint
⎡ q ⎤ ⎡ q ⎤
A = − Nk BT ⎢ ln + 1⎥ = − Nk BT ⎢ln tr + 1⎥ − Nk BT ln qint
⎣ N ⎦ ⎣ N ⎦
= Atr + Aint
15-65
From here on, you can put in the qint as a product and the energies, entropy and free energies become a sum.
15-66
h2
15.30. Calculate for helium in a one-dimensional box of a=10 cm and determine the energy level spacing for the first four levels.
8ma 2
Compare this with kBT. At what temperature are the energy levels spacing comparable in magnitude?
Solution:
Given: a=10 cm
h2
Required: value of , energy level spacing, compare energy level spacing with kBT, temperature at which the energy levels spacing are
8ma 2
comparable
( 6.626 ×10−34 J-s )

2
h2
=
8ma 2 8 × 4 × 1.673 ×10−27 kg × ( 0.1)2 m 2
h2
= 8.2 × 10−40 J
8ma 2
n2h2
Energy levels:
8ma 2
n energy (J) difference(J) degrees K
1 8.2 × 10−40
24.6 ×10−40 1.8 × 10−16
2 32.8 ×10−40
41× 10−40 3 × 10−16
3 73.8 ×10−40
57 ×10−40 4 ×10−16
4 131. ×10−40
15-67
The thermal energy is kBT, and the energy splitting for the translational energy is of the order of 10−16 K. That is, only at temperatures below
about 10-16 K are these states not in the high temperature approximation. Therefore at any reasonable temperature, the translation energy
levels are all occupied and are in the classical limit (high T).
15-68
15.31. Calculate Θv for H2 (frequency = 4162 cm-1) and I2 (frequency = 213.1 cm-1). Calculate qv for these gases at 300 K.
Solution:
Given: for H2 : frequency = 4162 cm-1, for I2 : frequency = 213.1 cm-1, T = 300 K
Required: Θv , qv
1
qv =
⎛ Θ ⎞
1 − exp ⎜ − v ⎟
⎝ T ⎠
hν ( 6.626 ×10 J-s )( 4162 cm -1 )( 3 ×1010 cm s -1 )

−34
Θv = =
For H2, kB (1.381×10 −23
J K -1 )
Θv = 5990 K
1 1
qv = = = 5859
⎛ 5990 ⎞ 1 − 0.9998293
1 − exp ⎜ − ⎟
⎝ 300 ⎠
hν ( 6.626 × 10 J-s )( 213.1 cm -1 )( 3 ×1010 cm s -1 )

−34
For I2, Θv = = = 306.7 K

kB (1.381×10 −23
J K -1 )
1
qv = = 1.562
⎛ 306.7 ⎞
1 − exp ⎜ − ⎟
⎝ 300 ⎠
15-69
15.32. Starting with the molecular partition function, prove for diatomic molecules in the high temperature limit that the translational,
rotational and vibrational contributions to the heat capacity agree with the expression from equipartition.
Solution:
Given: see above
Required: see above
This is for diatomics.
⎛ ∂ ln qtr ⎞ Lk BT 2 ⎛ ∂qtr ⎞
Etr − Eo = Lk BT 2 ⎜ ⎟ =
⎝ ∂T ⎠V q ⎜⎝ ∂T ⎟⎠V
3/ 2 3/2
Lk BT 2 ⎛ 2π mk B ⎞ 3 1/2 Lk BT 2 ⎛ 2π mk B ⎞ 3 1/2
Etr − Eo = ⎜ ⎟ T = 3/2 ⎜ ⎟ T
q ⎝ h2 ⎠ 2 ⎛ 2π mk B T ⎞ ⎝ h
2
⎠ 2
⎜ 2 ⎟
⎝ h ⎠
Lk BT 2 3 1/2 2
Lk T 3 3 3
Etr − Eo = T = B = Lk BT = RT
T 3/2 2 T 2 2 2
T
Rotation: qr =
σΘ r
Lk BT 2 ⎛ ∂qr ⎞ Lk BT 2 1 ⎛ ∂T ⎞
Er − Eo = ⎜ ⎟ = ⎜ ⎟
qr ⎝ ∂T ⎠V ⎛ T ⎞ σΘr ⎝ ∂T ⎠V
⎜ ⎟
⎜ σΘ r ⎟
⎝ ⎠
Lk BT 2
Er − Eo = = Lk BT = RT
T
T
Vibration: qv =
Θv
15-70
Lk BT 2 ⎛ ∂qv ⎞ Lk BT 2 1 ⎛ ∂T ⎞
Ev − Eo = ⎜ ⎟ = ⎜ ⎟
qr ⎝ ∂T ⎠V ⎛ T ⎞ Θv ⎝ ∂T ⎠V
⎜ ⎟
⎜ Θv ⎟
⎝ ⎠
Lk BT 2
Ev − Eo = = Lk BT = RT
T
15-71
15.33. Work out the heat capacity, Cv, at 300 K for the diatomic molecules listed below. Keep only the translational, rotational and
vibrational motion. Use table below for the rotational and vibrational temperatures. Only use the high temperature approximation if
it is valid. HCl, N2, O2, I2
qtr qr qv
HCl High temp. 19.73 1.0000016
N2 High temp. 104.89 1.0000146
O2 High temp. 144.92 1.00059
I2 High temp. 555.5 1.552
Solution:
Given: T = 300 K, above table
Required: Cv
v K r K re Å Do eV
HCl 4140 15.2 1.275 4.43
N2 3340 2.86 1.095 9.76
O2 2230 2.07 1.204 5.08
I2 310 0.054 2.667 1.54
Translantional:
15-72
3/ 2
⎛ 2π mk BT ⎞ V
qt = ⎜ ⎟ V= From question 1, these are all high temperature so we can take the contribution to the heat capacity as
⎝ h
2
⎠ Λ3
3
R
2
Rotational:
∞
j ( j + 1)Θr h2
qr = ∑ (2 j + 1) exp(− where Θ r =
j =0 T 8π 2 k B I
or at high temperatures:
T
qr =
σΘ r
If we look at the table, we can see that the largest rotational temperature is 15.2 K. Hence only for HCl might we have a deviation from the
high temperature approximation. So for HCl we have:
∞
⎛ j ( j + 1) × 15.2 ⎞ ⎛ 2 ×15.2 ⎞ ⎛ 6 ×15.2 ⎞
qr = ∑ (2 j + 1) exp ⎜ − ⎟ = 1 + 3exp ⎜ − ⎟ + 5exp ⎜ − ⎟ ...
j =0 ⎝ 300 ⎠ ⎝ 300 ⎠ ⎝ 300 ⎠
j =1 j =2 j =3 j =4 j =5 j =6 j =7 j =8 j =9 j=10
= 1 + 2.7109 + 3.6893 + 3.8110 + 3.2671 + 2.4058 + 1.5480 + 0.8787 + 0.4427 + 0.1987 + 0.079..
= 20.03
If we compare this with the high temperature limit, we get:
T 300
qr = = = 19.73 Therefore for the rotational motion, HCl is in the high temperature limit at 300 K. Hence all the others are in the
Θ r 15.2
high temperature limit too.
Vibrational:
15-73
−1
⎛ ⎛ Θ ⎞⎞
qv = ⎜ 1 − exp ⎜ − v ⎟ ⎟ We can just plug in the values and calculate the result (see next table):
⎝ ⎝ T ⎠⎠
−1
⎛ ⎛ 4140 ⎞ ⎞
qv = ⎜ 1 − exp ⎜ − ⎟ ⎟ = 1.0000016 etc. (see table) Clearly all but I2 are close to “1” meaning that the vibrational contributions are not in
⎝ ⎝ 300 ⎠ ⎠
the high temperature approximation.
To calculate the heat capacity for each, the contribution from translational and rotational is the same, being the high temperature
approximation:
tranlational
Rotational
3 5
CV = R + R = R which is good for HCl, N2 and O2. For I2, we have to do a bit more work:
2 2
From Eq.(9.38):
⎛ ⎞
⎛ ∂E ⎞ Lk B ⎜ ∂ 2 ln q ⎟ Lk B ⎛ ∂ 2 ln q ⎞
CV = ⎜ ⎟ = 2 ⎜ 2 ⎟
= 2 ⎜ 2 ⎟
where x=T-1.
⎝ ∂T ⎠V T ⎜ ∂ 1
⎝ T ⎠V
⎟ ( )
T ⎝ ∂x ⎠V
This is the calculation for the contribution from vibration to the heat capacity of I2.
15-74
Lk B ⎛ ∂ 2 ln qv ⎞ Lk B ∂ ⎛ ∂ ln qv ⎞ Lk B ∂ 1 ⎛ ∂qv ⎞
CV = 2 ⎜ ⎟ = 2 ⎜ ⎟ = 2 ⎜ ⎟
T ⎝ ∂x ⎠V T ∂x ⎝ ∂x ⎠V T ∂x qv ⎝ ∂x ⎠V
2
⎛ ⎞
Lk B ∂ 1 ⎛ ∂ ⎡ 1 ⎤ ⎞ Lk B ∂ 1 ⎜ −Θv e −Θv x ⎟
= 2 =
T ∂x qv ⎜⎝ ∂x ⎢⎣1 − e −Θv x ⎥⎦ ⎟⎠ T 2 ∂x qv ⎜⎜ 1 − e −Θv x 2 ⎟⎟
⎝ ( ) ⎠
⎛ ⎞
Lk B ∂ ⎛ −Θv e −Θv x ⎞ Lk Θ ∂ ⎛ 1 ⎞ Lk Θ −Θv eΘv x ⎟
= 2 ⎜ ⎟ = − B2 v ⎜ Θx ⎟ = − B2 v ⎜
⎝ (
T ∂x ⎜ 1 − e −Θv x ) ⎟
⎠
T (
∂x ⎜ e − 1
⎝
v
) ⎟
⎠
T (
⎜ Θv x
⎝ e −1 ⎠ )
2
⎟
⎛ ⎞ Lk 310 2 ⎛
=
Lk B Θv2 ⎜ eΘv x ⎟ = B( ) ⎜ e310 / 300 ⎞⎟ = 0.8524 R
(
T 2 ⎜ e Θv x − 1 ) ⎟ ( 300 ) ⎜ ( e310 / 300 − 1) ⎟
2 2 2
⎝ ⎠ ⎝ ⎠
5
Hence the heat capacity of I2 is CV = R + 0.8524 R =3.3524R=27.87 J K-1 Mol-1
2
Experimentally, the heat capacities of HCl, N2, and O2 are very close to 2.5R. This shows that the at 300 K the calculations are correct if
the vibrational contributions are ignored. In contrast for Iodine, has contributions from the vibrational parts. Unfortunately it is a solid at
300 K and does not boil until over 400 K, so we do not have data at 300 K. On the other hand, above the boiling point you can see that the
heat capacity of iodine will be 3.5 R, since the vibrational contributions will then be in high temperature limit.
15-75
15.34. The high temperature limit of the rotational partition function for diatomics is
T
qr =
σΘ r
Give a brief explanation of the quantum mechanical origin of the symmetry number σ. Use equations where appropriate.
Solution:
T
Given: qr =
σΘ r
Required: explanation
Symmetry restrictions due to permutation symmetry lead to the sum over rotational states omitting certain values. For homonuclear
diatomics, one half of the states are missing. For example, O162 (Hill page 469) has a rotational partition function of,
1
qrn = ∑ ... ⎯⎯⎯⎯⎯
high temperature
→ ∑ ...
j = even 2 all j values
This explains the quantum mechanical origin of the symmetry number = 2.
15-76
15.35. Prove that the Einstein function for the vibrational contribution to the heat capacity, Eq.Error! Reference source not found. can be
written as,
2
⎛u u ⎞
( CV )Einstein = R ⎜ cos ⎟
⎝ 2 2⎠
where
hν Θ
u= = v.
k BT T
Show that the limiting value of Einstein function, Eq.Error! Reference source not found.,is the gas constant, R. (Recall that the
Einstein vibration is restricted to one frequency only so this is consistent with equipartition that states at high temperatures the
contribution to the heat capacity is equal to R for each degree or freedom. In this case, there is only one degree of freedom.)
Solution:
Given: see above
Required: see above
The vibrational contribution to the heat capacity, Eq.(15.166)
2
⎛Θ ⎞ eΘ E / T
CV = R ⎜ E ⎟ 2
⎝ T ⎠ ⎡⎣eΘE / T − 1⎤⎦
u 2 eu u2
CV = R 2
=R 2
⎡⎣ eu − 1⎤⎦ ⎡⎣eu / 2 − e −u / 2 ⎤⎦
1 2
where u = Θ E / T . Using cosechu = = u − u gives,
sinh u e − e
2
u2 4 ⎛u u⎞
CV = R 2
= R ⎜ cosech ⎟
4 ⎡e − e ⎤
u / 2 − u / 2
⎝2 2⎠
⎣ ⎦
15-77
15-78
15.36. Starting with Eq. Error! Reference source not found. obtain an expression for the molar internal energy Um of an ideal monatomic
gas.
Solution:
Given: Eq. 15.156
Required: obtain expression for Um
Einstein’s expression is:
u 2 exp ( u )
( )
CV =R
( exp ( u ) − 1)
Einstein 2
hν E Θ E
where u = = so as T → ∞ , u → 0 , and exp ( u ) → 1 except for the denominator,
k BT T
u 2 exp ( u ) u2
( )
CV =R T →0
⎯⎯⎯ →R =R
( exp ( u ) − 1) (1 + u − 1)
Einstein 2 2
15-79
15.37. Calculate the molecular translational partition functions qt for (a) N2, (b) H2O, (c) C6H6 in a volume of 1 m3 at 300 K. In each case,
calculate also ln Qt,m, where Qt,m is the molar translational partition function.
Solution:
Given: V = 1 m3, T = 300 K
Required: molar translational partition functions, ln Qt,m
From Eq. 15.86, we know that
( 2π mkBT )
32
V
qt = 3
h
( 2π ×1.381×10 × 300 ) m/kg
−23 32
( )
32
qt =
( 6.626 × 10 ) −34 3
qt = 1.444 ×1070 ( m/kg )

32
15-80
a. For N2:
2 × 14.0067 g mol−1 × 10−3 kg g −1

m=
6.022 × 1023 mol−1
m = 4.651 843 241× 10−26 kg
( 2π ×1.381×10 )
−23 32
× 300 × 4.651 843 241×10−26
qt =
( 6.626 ×10 )−34 3
qt = 1.449 ×1032
For N indistinguishable molecules,
ln Q = N ln q − N ln N + N
Here N = 6.022 × 1023
ln Qt , m = 6.022 ×1023 × ln (1.449 ×1032 ) − 6.022 × 1023 × ln ( 6.022 × 1023 )
+ 6.022 ×1023
ln Qt , m = 1.222 388 923 ×1025
ln Qt , m = 1.223 ×1025
b. For H2O:
18.015 g mol−1 × 10−3 kg g −1

m=
6.022 × 1023 mol−1
15-81
m = 2.991 531 053 × 10−26 kg
( 2π ×1.381×10 )
−23 32
× 300 × 2.991 531 053 ×10−26
qt =
( 6.626 ×10 )−34 3
qt = 7.47 ×1031
ln Qt , m = 6.022 ×1023 × ln ( 7.47 ×1031 ) − 6.022 × 1023 × ln ( 6.022 × 1023 )
+ 6.022 × 1023
ln Qt , m = 1.182 489 333 × 1025
ln Qt , m = 1.182 ×1025
c. For C6H6:
78.114 g mol−1 ×10−3 kg g −1

m=
6.022 ×1023 mol−1
m = 1.297 143 806 × 10−25 kg
( 2π ×1.381×10 )
−23 32
× 300 × 1.297 143 806 × 10−26
qt =
( 6.626 ×10 )−34 3
qt = 6.746 × 1032
ln Qt , m = 6.022 ×1023 × ln ( 6.746 ×1032 ) − 6.022 ×1023 × ln ( 6.022 ×1023 )
+ 6.022 ×1023
ln Qt , m = 1.315 011 864 ×1025
ln Qt , m = 1.315 ×1025
15-82
15.38. The internuclear distance for N2 is 0.1095 nm. Determine the molecular rotational partition function qr and ln Q for N2 at 300 K.
Solution:
Given: d = 0.1095 nm, T = 300 K
Required: qr, lnQ
14.0067 g mol−1 × 10−3 kg g −1

Mass of N atom =
6.022 × 1023 mol−1
Mass of N atom = 2.325 921 621×10−26 kg
Moment of inertia of N2
1
I = × 2.325 921 621×10−26 × ( 0.1095 ×10−9 )
2
2
I = 1.394 419 086 × 10−46 kg m 2
The symmetry number is 2.
8π 2 (1.394 419 086 ×10−46 )(1.381× 10−23 ) ( 300 )

qr =
2 ( 6.626 × 10−34 )
2
qr = 51.947 556 65
qr = 51.9
ln Qr = L ln qr
ln Qr = ( 6.022 × 1023 ) ln ( 51.947 556 65 )
ln Qr = 2.378 831 327 × 1024
ln Qr = 2.38 ×1024
15-83
15.39. Use the data in Table 15.3 (p. 807) to calculate, with reference to v = 0, the molecular vibrational partition function for CO2 at (a)
300 K and (b) 3000 K.
Solution:
Given: Table 15.3, v = 0
Required: molecular vibrational partition function for CO2
The molecular vibrational partition function is
2
⎛ ⎞
1 1 ⎜ 1 ⎟
qv = × ⎜ ⎟
⎛ −1890 ⎞ ⎛ −3360 ⎞ ⎜ ⎛ −954 ⎞ ⎟
1 − exp ⎜ ⎟ 1 − exp ⎜ ⎟ ⎜ 1 − exp ⎜ ⎟⎟
⎝ T ⎠ ⎝ T ⎠⎝ ⎝ T ⎠⎠
2
⎛ ⎞
1 1 ⎜ 1 ⎟
a. qv = × ⎜ ⎟
⎛ −1890 ⎞ ⎛ −3360 ⎞ ⎜ ⎛ −954 ⎞ ⎟
1 − exp ⎜ ⎟ 1 − exp ⎜ ⎟ ⎜ 1 − exp ⎜ ⎟⎟
⎝ 300 ⎠ ⎝ 300 ⎠ ⎝ ⎝ 300 ⎠ ⎠
qv = 1.001 839 683 × 1.000 013 674 × 1.088 662 816
qv = 1.090 680 524
qv = 1.09
2
⎛ ⎞
1 1 ⎜ 1 ⎟
b. qv = × ⎜ ⎟
⎛ −1890 ⎞ ⎛ −3360 ⎞ ⎜ ⎛ −954 ⎞ ⎟
1 − exp ⎜ ⎟ 1 − exp ⎜ ⎟ ⎜ 1 − exp ⎜ ⎟⎟
⎝ 3000 ⎠ ⎝ 3000 ⎠ ⎝ ⎝ 3000 ⎠ ⎠
qv = 2.139 457 549 × 1.484 295 694 × 13.477 045 2
qv = 42.797 537 98
qv = 42.8
15-84
15.40. Expressions such as the Sackur-Tetrode equation for the entropy contain a term ln (constant × T). At temperatures close to the
absolute zero this term has large negative values, and the expression therefore leads to a negative value of the entropy. Comment on
this.
Solution:
Given: see above
Required: comment on the observed phenomenon
The Sackur-Tetrode equation is based on Eq. 15.86 for the translational partition function. This expression was obtained by replacing a
summation (Eq. 15.83) by an integration (Eq. 15.84), a procedure that is valid only if the spacing between the translation levels is much
smaller than kBT . This approximation is not valid at extremely low temperatures, and the Sackur-Tetrode equation then is inapplicable.
15-85
15.41. Calculate the entropy of argon gas at 25 °C and 1 bar pressure.

Solution:
Given: T = 25 °C, P = 1 bar
Required: entropy
From the Sackur-Tetrode equation (Eq. 15.88),
S / J K −1 mol−1 = 108.74 + 12.47 ln M r
For argon, M r = 39.948 and therefore,
S / J K −1 mol−1 = 108.74 + 45.98 = 154.7

S = 154.7 J K −1 mol−1
15-86
15.42. From the data in Table 15.3, calculate, with reference to v = 0, the molecular vibrational partition function for Br2 at (a) 300 K and
(b) 3000 K.
Solution:
Given: Table 15.3, v = 0
Required: molecular vibrational partition function
The value of θ v is 470 K and thus,
1
qv =
⎛ −470 K ⎞
1 − exp ⎜ ⎟
⎝ T ⎠
a. At T = 300 K,
1
qv =
⎛ −470 K ⎞
1 − exp ⎜ ⎟
⎝ 300 K ⎠
qv = 1.263 806 81
qv = 1.26
b. At T = 3000 K,
1
qv =
⎛ −470 K ⎞
1 − exp ⎜ ⎟
⎝ 3000 K ⎠
qv = 6.896 028 941
qv = 6.90
15-87
15.43. Give the symmetry numbers of the following molecules: C3O2 (carbon suboxide), CH4, C2H4, C2H6 in the staggered conformation,
C2H6 in the eclipsed conformation, CHCl3, C3H6 (cyclopropane), C6H6 (benzene), NH2D, CH2Cl2.
Solution:
Given: see above
Required: symmetry numbers
15-88
15-89
15.44. Show that the rotational partition function for a linear molecule can be expressed as
qr = kBT/σBh
where B is the rotational constant defined by Eq.(13.63).
Solution:
Given: see above
Required: see above
The rotational constant is
h
B=
8π 2 I
We know that
8π 2 IkBT
qr =
σ h2
Therefore, we can substitute the expression for B into the above equation and yield:
kBT
qr =
σ Bh
15-90
*15.45. Calculate the molar translational entropy of chlorine gas at 25 °C and 0.1 bar pressure.
Solution:
Given: T = 25 °C, P = 1 bar
Required: molar translational entropy
LkBT
We use Eq. 15.88 with Vm = :
P
5 ⎡⎛ 2π mkBT ⎞3 2 kBT ⎤
S m = R + R ln ⎢⎜ 2 ⎟ ⎥
2 ⎢⎣⎝ h ⎠ P ⎥⎦
2 × 35.45 g mol−1 × 10−3 kg g −1

For Cl2, m = −1
1.177 349 718 × 10−25 kg
6.022 × 10 23
mol
P = 0.1 bar = 1.00 × 104 Pa
Plug the values into the expression for Sm, we get:
5
S m = × 8.3145 J K −1 mol−1 + 8.3145 J K −1 mol−1
2
⎡⎛ 32
⎤
⎢
× ln ⎢⎜
2π × 1.177 349 718 × 10 −25 ⎞
⎟ (1.381× 10−23 × 298.15 ) ⎥
⎥
⎜
⎢⎣⎝ ( 6.626 ×10 )
−34 2 ⎟
⎠
1.00 ×104
⎥⎦
S m = 20.786 25 J K −1 mol−1 + 8.3145 J K −1 mol−1
× ln ( 2.187 125 651×1063 × 4.117 451 5 × 10−25 )
S m = 20.786 25 J K −1 mol−1 + 745.777 858 7 J K −1 mol−1
S m = 766.564 108 7 J K −1 mol−1
Sm = 766.6 J K −1 mol−1
15-91
*15.46. The carbon monoxide molecule has a moment of inertia of 1.45 × 10–46 kg m2 and its vibrational frequency is 6.50 × 1013 s–1.
Calculate the translational, rotational, and vibrational contributions to the molar entropy of carbon monoxide at 25 °C and 1 bar
pressure.
Solution:
Given: I = 1.45 × 10−46 kg m 2 , ν = 6.50 × 1013 s –1 , T = 25 °C, P = 1 bar
Required: translational, rotational, and vibrational contributions to the molar entropy

The translational entropy is given by the Sackur-Tetrode equation (Eq. 15.90)
St , m / J K −1 mol−1 = 108.74 + 12.47 ln ( M r )
Here, Mr is the relative molecular mass of the compound

For carbon monoxide, the relative molecular mass is
M r = 12.00 + 16.01 = 28.01 g mol−1
Therefore,
St , m / J K −1 mol−1 = 108.74 + 12.47 ln ( 28.01)

St , m = 150.297 043 J K −1 mol−1
St ,m = 150.3 J K −1 mol−1
The rotational partition function is
8π 2 IkBT
qr =
h2
8π 2 ×1.45 × 10−46 kg m 2 ×1.381× 10−23 m 2 kg s −2 K −1 × 298.15 K
qr =
( 6.626 ×10 )−34 2
m 4 kg 2 s −2
qr = 107.370 101 5
15-92
The rotational entropy is
⎛ ∂ ln Qr ⎞
S r = kBT ⎜ ⎟ + kB ln Q
⎝ ∂T ⎠V
⎛ ∂ ln qr ⎞
S r ,m = RT ⎜ ⎟ + R ln qr since Qr = qr
N
⎝ ∂T ⎠V
S r ,m = R + R ln qr
S r ,m / J K −1 mol−1 = 8.3145 + 8.3145ln107.370 101 5

S r ,m = 47.195 444 68 J K −1 mol−1
Sr ,m = 47.2 J K −1 mol−1
Since ν = 6.50 × 1013 s –1 , the spacing between vibrational energy levels is
hν = 6.626 × 10−34 × 6.50 × 1013 = 4.3069 × 10−20 J

hν 4.3069 × 10−20 J
=
kBT 1.381×10−23 m 2 kg s −2 K −1 × 298.15 K
hν
= 10.460 111 07
kBT
1
qv = = 1.000 028 658
1 − exp ( −10.460 111 07 )
qv ≈ 1
The vibrational energy is therefore negligible.

15-93
15.47. Suppose that a system has equally spaced energy levels, the separation between neighboring levels being Δε . Prove that the fraction
of the molecules in state i, having energy ε i greater than the energy of the lowest level, is
⎛ – Δε ⎞ ⎛ –ε i ⎞
1 – exp ⎜ ⎟ exp ⎜ ⎟
⎝ kBT ⎠ ⎝ kBT ⎠
What is the limiting value of this fraction as T → ∞? Explain your answer.

Solution:
Given: see above
Required: limiting value as T → ∞, explanation
The fraction of molecules in the i-th level is
⎛ −ε ⎞
exp ⎜ i ⎟
⎝ kBT ⎠
⎛ −ε ⎞ ⎛ −ε ⎞ ⎛ −ε ⎞
1 + exp ⎜ 1 ⎟ + exp ⎜ 2 ⎟ + exp ⎜ 3 ⎟ + ...
⎝ kBT ⎠ ⎝ kBT ⎠ ⎝ kBT ⎠
⎛ −ε ⎞
exp ⎜ i ⎟
= ⎝ kBT ⎠
⎛ −Δε ⎞ ⎛ −2Δε ⎞ ⎛ −3Δε ⎞
1 + exp ⎜ ⎟ + exp ⎜ ⎟ + exp ⎜ ⎟ + ...
⎝ kBT ⎠ ⎝ kBT ⎠ ⎝ kBT ⎠
⎡ ⎛ −Δε ⎞ ⎤ ⎛ −εi ⎞
= ⎢1 − exp ⎜ ⎟ ⎥ exp ⎜ ⎟
⎣ ⎝ kBT ⎠ ⎦ ⎝ kBT ⎠
The limiting value of this fraction when T → ∞ is zero; this is because the molecules are now distributed evenly among an infinite number
of levels.
15-94
*15.48. Deduce the following from the Sackur-Tetrode equation (Eq.Error! Reference source not found.), which applies to an ideal
monatomic gas:
a. The dependence of entropy on relative molecular mass Mr; also, obtain an expression for dSm/dMr.
b. The dependence of heat capacity CP on relative molecular mass.
c. The dependence of entropy on temperature; also obtain an expression for dSm /dT.
Solution:
Given: ideal monatomic gas
Required: deduction from the Sackur-Tetrode equation
3
a. S m = constant + R ln M r (1)
2
dSm 3 R
= ( 2)
dM r 2 M r
b. The heat capacity of CP is ( ∂H ∂T ) P = ( ∂S ∂ ln T ) P and therefore does not depend on M r . The Sackur-Tetrode equation can be
written as
5
S m = constant + R ln T ( 3)
2
and therefore
5
CP , m = R ( 4)
2
There is no dependence on M r .
15-95
c. From Eq. (3),
dSm 5 R
= (5)
dT 2 T
15-96
*15.49. Molecules absorbed on a surface sometimes behave like a two-dimensional gas. Derive an equation, analogous to the Sackur-
Tetrode Eq. Error! Reference source not found., for the molar entropy of such an adsorbed layer of atoms, in terms of the
molecular mass m and the surface area A. What would be the molar entropy if 1010 argon atoms were adsorbed on an area of 1 cm2 at
25 °C?
Solution:
Given: see above, 1010 argon atoms, A = 1 cm 2 , T = 25 °C
Required: derivation for the molar entropy, molar entropy
For two-dimensional translational motion,
2π mkBTA
qt =
h2
⎛q⎞ ⎛ A ⎞
ln Q = N ln ⎜ ⎟ + N = N ln ⎜ 2 2π mkBT ⎟ + N
⎝N⎠ ⎝ Nh ⎠
⎛ ∂ ln Q ⎞
S + kBT ⎜ ⎟ + kB ln Q
⎝ ∂T ⎠ A
1 ⎛ A ⎞
S m = RT × + R + R ln ⎜ 2 2π mkBT ⎟
T ⎝ Nh ⎠
⎛ 2π mkBTA ⎞
S m = 2 R + R ln ⎜ 2 ⎟
⎝ Nh ⎠
39.948 g mol−1 ×10−3 kg g −1

For Ar, m = −1
= 6.633 676 519 ×10−26 kg
6.022 ×10 23
mol
If 1010 molecules are absorbed on an area of 1 cm2 at 25 °C ,
15-97
S m = 2 × 8.3145 J K −1 mol−1 + 8.3145 J K −1 mol−1 ln ⎡⎣ 2π × 6.633 676 519 × 10−26 kg
1.381× 10−23 m 2 kg s −2 K −1 ×10−4 m 2 × 298.15 K ⎤

× ⎥
10 × ( 6.626 × 10 ) m kg s
10 −34 2 4 2 −2 ⎥
⎦
S m = 16.629 J K −1 mol−1 + 8.3145 J K −1 mol−1 ln ( 3.908 947 05 × 107 )
S m = 161.977 798 4 J K −1 mol−1
Sm = 162.0 J K −1 mol−1
15-98
15.50. Calculate the dissociation constant Kc for the reaction
O2 ( 3
Σ ) → 2O ( P)
3
at 1 000 K expressing the answer in mole l-1. Ignore nuclear degeneracy. Use the data from the table of Problem 51, along with the
value Λ o = 1.25 × 10−9 cm .
Solution:
Given: T = 1 000 K , table of Problem 51, Λ o = 1.25 × 10−9 cm
Required: Kc
The calculation here is
For our case:
O2 2O
EOo 2 = − D0 = −5.08 eV
qO2 ⎛ D ⎞
K 1p = exp ⎜ − o ⎟
qO2 N ⎝ kT ⎠
qO2 = qt qr qv qe and qO = qt qe
3/ 2 triplet state degeneracy

⎛ 4π mO2 k BT ⎞ ⎛ T ⎞⎛ 1 ⎞
qO2 = qt qr qv qe = ⎜ ⎟ ⎜ ⎟⎜ −Θv / T ⎟× 3
⎝ h2 ⎠ ⎝ 2Θ r ⎠⎝ 1− e ⎠
15-99
3/ 2
⎛ ⎞
⎜ 4π × 32 × 1.673 ×10−27 ×1.381×10−23 × 1000 ⎟
qO2 =
⎜ ( 6.626 ×10−34 ) ⎟
2
⎝ ⎠
triplet state degeneracy
⎛ 1000 ⎞ ⎛ 1 ⎞
×⎜ ⎟⎜ −2230 /1000 ⎟
× 3
⎝ 2 × 2.07 ⎠ ⎝ 1 − e ⎠
qO2 = ( 6.6129 × 1020 )

3/ 2
( 241.54 )( 9.23)( 3) = 1.137 ×1035 m-3
and
1
qO = qt qe = 3 ( 3) = 6.788 ×1016 m-3
⎛ −9 m ⎞
⎜1.25 ×10 cm × 0.01 ⎟
⎝ cm ⎠
so
qO2 ⎛ D ⎞
K 1p = exp ⎜ − o ⎟=
qO2 N ⎝ k BT ⎠
⎛ ( 6.788 × 1016 ) ⎞ ⎛ ( m -3 )2 ⎞
2
=⎜ ⎟⎜ ⎟
⎜ (1.137 × 1035 )( 6.022 × 1023 ) ⎟ ⎜ m -3 ⎟
⎝ ⎠⎝ ⎠
⎛ 5.08 eV ×1.602 ×10-19 J eV -1 ⎞
× exp ⎜ − ⎟
⎝ 1.381× 10−23 ×1000 ⎠
2.555×10−26
3
l 6 m
= (1.34 ×10 ) exp ( −58.929 ) = 3.43 × 10 molecule
−25 −51
× 10 -1
m3 l
−51 −27
= 3.43 ×10 molecule = 2.063 × 10 mol
-1 -1
This is K 1p , to get K c1 = K 1p × ( RT )
−1
15-100
15.51. From the data in Table 15.5, calculate KP at 1000 K for the “water-gas” reaction
CO2(g) + H2(g) CO(g) + H2O(g)
Solution:
Given: Table 15.5, T = 1000 K
Required: KP
ΔH 298
o
= −110.53 − 241.82 + 393.51 = 41.16 kJ mol −1 ( from Table 15.5 )
Δ ( H 298
o
− H 0o ) = 8.665 + 9.902 − 8.468 − 9.360 = 0.739 kJ mol−1
ΔH 0o = 41.16 − 0.739 = 40.421 kJ mol−1
ΔG1000
o
= 40 420 − 1000 ( 204.18 + 196.83 − 226.54 − 137.07 ) = 3020 J mol −1
3020
ln K P = − = −0.363 220 879
8.3145 × 1000
K P = 0.695 432 809
K P = 0.695
15-101
15.52. Without making detailed calculations but by using symmetry numbers, estimate the equilibrium constants for the following
reactions:
a. 35Cl – 35Cl + 37Cl 35
Cl – 37Cl + 35Cl
b. 35Cl – 35Cl + 37Cl – 37Cl 235Cl – 37Cl
c. C35Cl4 + 37Cl C37Cl35Cl3 + 35Cl
d. N35Cl3 + 37Cl N37Cl35Cl2 + 35Cl
e. 35Cl2O + 37Cl 37
Cl35ClO + 35Cl
(Because of the similarity of the masses, these estimates will be quite accurate.)
D. M. Bishop and K. J. Laidler, J. Chem. Phys., 42, 1688(1965), have defined a statistical factor for a reaction as the number of
equivalent ways in which a reaction can occur. Thus for reaction (a) from left to right the statistical factor is 2, since the 37Cl atom
can abstract either of the two 37Cl atoms. For the reverse reaction the statistical factor r is 1, since the 35Cl atom can only abstract the
35
Cl atom in order to give the desired products. If two identical molecules are involved, the statistical factor must be taken as the
1
number of equivalent products divided by 2; thus for reaction (b) from right to left the statistical factor is .
2
Bishop and Laidler proved that the ratio l/r of statistical factors is always equal to the ratio σAσB/σYσZ of symmetry numbers. Verify
that this is true for the given reactions.
This statistical factor procedure is useful in providing a simple insight into the factors that appear in equilibrium constants.
Solution:
Given: above reactions
Required: equilibrium constants
The symmetry numbers are given below the molecules (They are 1 for atoms.) and the statistical factors are shown above and below the
arrows; for simplicity 35 Cl is written as Cl and 37 Cl as Cl*.
15-102
*15.53. Calculate the equilibrium constant at 1000 °C for the dissociation

I2 2I
given the following information: moment of inertia of I2 = 7.426 × 10–45 kg m2, wavenumber for I2 vibration = 213.67 cm–1, ∆U0 =
148.45 kJ mol–1. The I atom is in a 2P3/2 state; neglect higher states.
Solution:
Given: above reaction, T = 1000 °C , I2 = 7.426 × 10–45 kg m2, wavenumber for I2 vibration = 213.67 cm–1, ∆U0 = 148.45 kJ mol–1, 2P3/2
state
Required: equilibrium constant
Mass of I atom,
126.90 g mol−1 × 10−3 kg g −1

m= −1
= 2.107 273 331×10−25 kg
6.022 × 10 23
mol
From Eq. 15.86, the translational partition function for the I atom, with V = 1 m3 , is
( 2π mkBT )
32
V
qt = 3
h
( 2π × 2.107 273 331×10 )

32
−25
kg ×1.381× 10−23 m 2 kg s −2 K −1
q ( I) =
( 6.626 ×10 )
t
−34 3
m 6 kg 3 s −3
( )
32
× 1273.15 K × 1 m3
qt ( I ) = 1.221× 1034
The degeneracy of the ground state is
⎛3⎞
2⎜ ⎟ +1 = 4
⎝2⎠
15-103
Thus
qt ( I ) = 4 × 1.221× 1034 = 4.884 × 1034
For the iodione molecule,
( 2π × 2 × 2.107 273 331×10 )

32
−25
kg × 1.381×10−23 m 2 kg s −2 K −1
q (I ) =
( 6.626 ×10 )
t 2
−34 3
m 6 kg 3 s −3
( )
32
× 1273.15 K ×1 m3
qt ( I 2 ) = 23 2 qt ( I ) = 3.453 × 1034
From Eq. 15.95,
2 IkBT
qr =
σ h2
8π 2 × 7.426 × 10−45 kg m 2 × 1.381× 10−23 m 2 kg s −2 K −1 ×1273.15 K
qr ( I 2 ) =
2 ( 6.626 × 10−34 )
2
m 4 kg 2 s −2
qr ( I 2 ) = 1.174 ×104
15-104
And from Eq. 15.102,
1
qv =
⎛ −hν ⎞
1 − exp ⎜ ⎟
⎝ kBT ⎠
1
qv ( I 2 ) =
⎛ −6.626 ×10 × 21 367.0 × 2.998 ⎞
−34
1 − exp ⎜ −8 −23 ⎟
⎝ 10 ×1.381×10 ×1273.15 ⎠
1
qv ( I 2 ) =
1 − 0.785 520 326
qv ( I 2 ) = 4.662 446 486
The molecular partition function for I 2 is thus
qI2 = 3.453 ×1034 ×1.174 × 104 × 4.662 446 486

qI2 = 1.890 072 814 × 1039
qYy qZz − ∑ v ⎛ −ΔU 0 ⎞

K° = a b N exp ⎜ ⎟
qA qB ⎝ RT ⎠
From Eq. 15.140, the molecular equilibrium constant, K, is
K° =
( 4.884 ×10 )
34 2
⎛ −148 450 × 1273.15 ⎞
exp ⎜ ⎟
1.890 072 814 × 10 39
⎝ 8.3145 ⎠
K ° = (1.262 038 998 × 1030 )( 8.120 × 10−7 )

K ° = 1.025 362 665 ×1024
Its value in molar units is
1
K c = 1.025 362 665 ×1024 molecule m −3 × molecule−1 mol
6.022 ×10 23
K c = 1.702 694 562 mol m = 1.702 694 562 × 10−3 mol dm −3

−3
15-105
At T = 1273.15 K, 1 mol dm −3 = 105.8 bar
105.8 bar
K P = 1.702 694 562 ×10−3 mol dm −3 ×
1 mol dm −3
K P = 0.180 257 057 bar
K P = 0.180 bar
(The experimental value obtained by Starck and Bodenstein in 1910 was 0.165 atm = 0.167 bar.)
15-106
*15.54. Calculate the equilibrium constant KP for the dissociation

Na2 2Na
at 1000 K, using the following data: internuclear separation in Na2 = 0.3716 nm, vibrational wavenumber ν = 159.2 cm–1, ∆U0 =
70.4 kJ mol–1. The Na atom is in a 2S1/2 state; neglect hiher states.
Solution:
Given: T = 1000 K , internuclear separation in Na2 = 0.3716 nm, vibrational wavenumber ν = 159.2 cm–1, ∆U0 = 70.4 kJ mol–1, 2S1/2 state
Required: KP
Mass of Na atom is:
22.99 g mol−1 × 10−3 kg g −1

m= −1
= 3.817 668 549 × 10−26 kg
6.022 ×10 23
mol
⎛1⎞
The electronic partition function is 2 ⎜ ⎟ + 1 = 2 .
⎝2⎠
The molecular partition function for Na is
2 × ( 2π × 3.817 668 549 × 10−26 × 1.381× 10−23 ×1000 )

32
q ( Na ) =
( 6.626 ×10 ) −34 3
q ( Na ) = 1.311×1033
For Na2,
( 2π × 2 × 3.818 ×10 ×1.381×10 ×1000 )

−26 −23 32
qt ( Na 2 )=
( 6.626 ×10 ) −34 3
qt ( Na 2 ) = 1.854 ×1033 ( = q ( Na ) × 2 )
t
15-107
Moment of inertia of Na2 is,
3.817 668 549 ×10−26 × ( 0.3716 ×10−9 )

2
I=
2
−45
I = 2.636 072 43 ×10 kg m 2
8π 2 × 2.636 ×10−45 × 1.381×10−23 ×1000

qr ( Na 2 ) =
2 × ( 6.626 ×10−34 )
2
qr ( Na 2 ) = 3273.466 428
1
qv ( Na 2 ) =
⎛ −159.2 × 2.998 × 1010 × 6.626 ×10−34 ⎞
1 − exp ⎜ ⎟
⎝ 1.381×10−23 ×1000 ⎠
qv ( Na 2 ) = 4.885 909 311
Thus, the partition function of Na2 at 1000 K is
= 1.854 ×1033 × 3273.466 428 × 4.885 909 311

= 2.965 261 662 × 1037
The molecular equilibrium constant is
K=
(1.311×10 ) 33 2
⎛ −70 400 ⎞
exp ⎜ ⎟
2.965 261 662 × 10 ⎝ 8.3145 × 1000 ⎠
37
K = 1.218 742 727 ×1025
1
K c = 1.218 742 727 × 1025 molecule m −3 × molecule −1 mol
6.022 × 10 23
K c = 20.238 172 16 mol m = 0.020 238 172 16 mol dm −3

−3
At T = 1000 K, 1 mol dm −3 = 83.1 bar
15-108
83.1 bar
K P = 0.020 238 172 16 mol dm −3 ×
mol dm −3
K P = 1.681 792 106 bar
K P = 1.68 bar
15-109
*15.55. Calculate the equilibrium constant KP at 1200 K for Cl2 2Cl, from the following data: internuclear separation in Cl2 = 199 pm,
–1 –1
wavenumber for vibration = 565.0 cm , ∆U0 = 240.0 kJ mol . The ground state of Cl is a doublet, 2 P3 1 , the
,
2 2
separation between the states being 881 cm–1.

Solution:
Given: T = 1200 K , internuclear separation in Cl2 = 199 pm, wavenumber for vibration = 565.0 cm–1, ∆U0 = 240.0 kJ mol–1,
2
P3 1 , separation between states = 881 cm-1.
,
2 2
Required: KP
Mass of Cl atom is
35.45 g mol−1 × 10−3 kg g −1

m= −1
= 5.886 748 589 ×10−26 kg
6.022 × 10 23
mol
Translational partition function for the Cl atom with V = 1 m3 , is
( 2π × 5.886 748 589 ×10 ×1.381×10 ×1200 )

−26 −23 32
Q ( Cl ) =
( 6.626 ×10 )
t
−34 3
Qt ( Cl ) = 1.651×1033
The degeneracy of the 2 P3 2 state is 4; that of the 2 P1 2 is 2; the electronic partition function is thus,
⎛ −ε ⎞
Qe ( Cl ) = 4 + 2 exp ⎜ ⎟
⎝ kBT ⎠
⎛ −881× 2.998 ×1010 × 6.626 ×10−34 ⎞
Qe ( Cl ) = 4 + 2 exp ⎜ ⎟
⎝ 1.381×10−23 ×1200 ⎠
Qe ( Cl ) = 4.695 654 774
15-110
The complete partition function for the Cl atom is thus
Q ( Cl ) = 1.651× 1033 × 4.695 654 774

Q ( Cl ) = 7.752 526 032 ×1033
For the Cl2 molecule,
qt ( Cl2 ) = 23 2 qt ( Cl ) = 4.669 733 183 ×1033
The moment of inertia of Cl2 is
1 1
mCl r 2 = × 5.886 748 589 × 10−26 × (1.99 × 10−10 ) kg m 2
2
I = μr 2 =
2 2
I = 1.165 605 654 × 10−45 kg m 2
The rotational partition function of Cl2 ( σ = 2 ) is
8π 2 × 1.165 605 654 ×10−45 × 1.381×10−23 ×1200

qr ( Cl2 ) =
2 ( 6.626 × 10−34 )
2
qr ( Cl2 ) = 1736.934 508
The vibrational partition function is
1
qr ( Cl2 ) =
⎛ −565 × 2.998 ×1010 × 6.626 ×10−34 ⎞
1 − exp ⎜ ⎟
⎝ 1.381× 10−23 × 1200 ⎠
qr ( Cl2 ) = 2.032 545 566
The molecular partition function of Cl2 is thus,
15-111
q ( I 2 ) = 4.669 733 183 ×1033 ×1736.934 508 × 2.032 545 566

q ( I 2 ) = 1.648 601 918 ×1037
The molecular equilibrium constant is thus
K=
( 7.752 526 032 ×10 ) 33 2
⎛ −240 000 ⎞
exp ⎜ ⎟
1.648 601 918 ×10 37
⎝ 8.3145 ×1200 ⎠
K = 1.303 447 699 ×1020
Its value in molar units is
1
K c = 1.303 447 699 ×1020 molecule m −3 × molecule −1 mol
6.022 × 10 23
K c = 2.164 476 419 × 10−4 mol m = 2.164 476 419 ×10−7 mol dm −3
−3
At 1200 K, 1 mol dm −3 = 99.8 bar
99.8 bar
K P = 2.164 476 419 ×10−7 mol dm −3 ×
mol dm −3
K P = 2.160 147 466 ×10−5 bar
K P = 2.16 ×10−5 bar
15-112
15.56. Calculate the isotopic ratio KH/KD at 300 K for the reactions
H2 2H and D2 2D
Take the zero-point energies of H2 and D2 to be 26.1 kJ mol–1 and 18.5 kJ mol–1, respectively.
Solution:
Given: T = 300 K, E0,H2 = 26.1 kJ mol−1 , E0,D2 = 18.5 kJ mol−1
Required: KH/KD
The equilibrium constant, K H , is
qH2 ⎛ −E ⎞
exp ⎜ 0 ⎟
qH2 ⎝ RT ⎠
qH (translational only) involves m1.5

H
qH 2 (translational and two degrees of rotational freedom) involves mH2.5 . The preexponential factor in the expression for the equilibrium is
thus proportional to m0.5 . The isotope ratio is thus
15-113
KH ⎛ 1 ⎞
0.5
⎡ − ( 26.1 + 18.5 ) kJ mol−1 ⎤
= ⎜ ⎟ exp ⎢ ⎥
KD ⎝ 2 ⎠ ⎣ RT ⎦
KH ⎛ 1 ⎞
0.5
⎡ −44 600 J mol−1 ⎤
= ⎜ ⎟ exp ⎢ ⎥
KD ⎝ 2 ⎠ −1 −1
⎢⎣ 8.3145 J K mol × 300 K ⎥⎦
KH
= 0.707 106 781×1.716 471 994 ×10−8
KD
KH
= 1.213 728 986 × 10−8
KD
KH
= 1.21× 10−8
KD
15-114
15.57. On the basis of transition-state theory, make rough estimates of the preexponential factors at 300 K for the following types of gas
reactions:
a. A bimolecular reaction between an atom and a diatomic molecule, with the formation of a linear activated complex.
b. A bimolecular reaction between two diatomic molecules, the activated complex being nonlinear with one degree of restricted
rotation.
c. A bimolecular reaction between two nonlinear molecules, the activated complex being nonlinear with no restricted rotation.
d. A trimolecular reaction between three diatomic molecules, the activated complex being nonlinear with one degree of restricted
rotation.
Take the translational partition functions (for three degrees of freedom) to be 1033 m–3, the rotational functions for each degree of
freedom to be 10, the function for a restricted rotation to be 10, and the vibrational functions to be unity. Express the calculated
preexponential factors in molecular units (m3 s–1) and in molar units (dm3 mol–1 s–1).
Solution:
Given: above gas reactions, T = 300 K , translational partition function = 1033 m-3, rotational functions = 10, function for rectricted rotation
= 10, vibrational functions = 1
Required: estimates of the preexponential factors
kBT
At 300 K, = 6.25 × 1012 s −1 , which for present purposes is rounded to 6 × 1012 s −1.
h
a. For the atom the partition function is 1033 m −3 . The diatomic molecule has three degrees of translational freedom (which will be
written as t 3 ), two degrees of rotational freedom ( r 2 ), and one of vibrational freedom ( v ). Its partition function is thus
1033 ×102 = 1035 m −3 .
The linear triatomic activated complex has t 3 , r 2 , and υ 3 , and its partition function is
1033 ×102 = 1035 m −3
The estimated preexponential factor is
15-115
kBT q 12 −1 1035 m −3
= 6 ×10 s
h qA qB 1033 ×1035 m −6
kBT q
= 6 × 10−21 m3 s −1
h qA qB
Multiplication by 6 × 1023 mol−1 and by 1000 dm3 m −3 gives
A = 4 × 106 dm3 mol−1 s −1
b. Diatomic molecule A: t 3 r 2υ
qA = qB = 1033 × 100 = 1035 m −3
Activated complex: t 3 r 3 ( rr )υ 4 (One vibration has been replaced by a restricted rotation [ rr ] .)
q = 1033 × 104 = 1037 m −3
Thus
1037 m −3
A = 6 × 1012 = 6 ×10−21 m −3 s −1
(10 )
35 2
A = 6 × 10−21 m −3 s −1 × 6 × 1023 mol−1

A = 3600 m −3 mol−1 s −1
A = 4 × 106 dm −3 mol−1 s −1
c. (The numbers of vibrational modes are now unspecified, but this makes no difference since they are unity.)
Reactants A and B: t 3 r 3 q = 1033 × 103 = 1036 m −3
Activated compex: t 3 r 3 q = 1036 m −3
15-116
1036
A = 6 × 10 12
= 6 ×10−24 m −3 s −1
(10 )
36 2
A = 4 × 103 dm3 mol−1 s −1
d. Reactants A, B, and C: t 3 r 3 q = 1036 m −3
Activated complex: t 3 r 3 ( rr ) q = 1037 m −3
1037
A = 6 × 1012 = 6 ×10−59 m −6 s −1
(10 )
36 3
A = 4 × 10−29 dm3 mol−1 s −1
15-117
15.58. The rate constant for the reaction

2NO + O2 → 2NO2
has been found to be proportional to T–3. Suggest an explanation for this behavior.
Solution:
Given: above reaction, rate constant ∼ T −3
The fact that there is no exponential dependence suggests that E0 = 0 . The temperature dependence arises entirely from the preexponential
terms. For each of the three linear reactants there are three degrees of translational freedom and two of rotation, and they vary with
temperature as (see Table 15.4)
T 1.5T = T 2.5
The activated complex is presumably nonlinear, and if there is no restricted rotation the temperature dependence is as
T 1.5T 1.5 = T 3
The preexponential factor is thus proportional to
T3
T× = T −3.5
(T )
2.5 3
To explain the dependence on T −3 we must allow the activated complex to have one degree of restricted rotation, so that its partition
function is proportional to
T 1.5T 1.5T 0.5 = T 3.5
The preexponential factor is then proportional to
15-118
T 3.5
T× = T −3
(T )
2.5 3
We can postulate an activated complex of the following structure
with restricted rotation about the O—O bond.
15-119
15.59. Deduce the temperature dependency of the preexponential factor of the following types of reactions, where A represents an atom, L
a linear molecule, and N a nonlinear molecule:
A + L; A + N; L + L; L + N; N + N
Solution:
Given: above types of reactions
Required: temperature dependency of the preexponential factor
The temperature dependencies of the partition function are as follows:
A: t3 : T 1.5
L: t 3 r 2 : T 1.5T = T 2.5
N: t 3 r 3 : T 1.5T 1.5 = T 3
The nonlinear activated complexes have partition functions proportional to T 1.5T 1.5 = T 3 . The temperature dependencies for the various
types of reactions are therefore as follows:
TT 3
A + L: 1.5 2.5
=T0
T T
TT 3
A + N: 1.5 3
= T −0.5
T T
TT 3
L + L: 2.5 2.5
= T −1
T T
TT 3
L + N: 2.5 3
= T −1.5
T T
TT 3
N + N: = T −2
T 3T 3
15-120
15.60. The rate of the reaction

O+ + N2 → NO+ + N
has been found over a certain temperature range to be proportional to T–0.5 (M. McFarland et al., J. Chem. Phys., 59, 6620(1973).
How can this be explained in terms of simple transition-state theory?
Solution:
Given: above reaction, reaction rate ∼ T −0.5
For the preceding problem it was shown that for an atom reacting with a linear molecule, the preexponential factor is proportional to T 0 if
TT 2.5
the activated complex is nonlinear. If the activated complex is linear the temperature dependence is 1.5 2.5
= T −0.5 . It thus appears that the
T T
activated complex is linear, and that the temperature dependence is due entirely to the preexponential factor.
15-121
15.61. For the case of two atoms giving a product, A + B [AB]‡ → Product, show that transition-state theory yields essentially the
same expression for the rate constant as the collision theory expression of Eq. (9.76).
Solution:
Given: above reaction
Required: prove the above statement
Starting with Eq. 15.152, we get
⎛k T ⎞ q
‡
⎛ −E ⎞
k =⎜ B ⎟ exp ⎜ 0 ⎟ ,
⎝ h ⎠ qA qB ⎝ kBT ⎠
where
⎡ 2π ( mA + mB ) kBT ⎤⎦
32
⎛ 2 IkBT ⎞
q =⎣
‡
⎜ 2 ⎟
h3 ⎝ ⎠
( 2π mA kBT ) ( 2π mB kBT )
32 32
qA = ; qB =
h3 h3
⎛ m m ⎞
Substituting the partition functions in the first equation, where I = ⎜ A B ⎟ ( rA + rB ) = μ d AB
2 2
, and simplifying, we get
m
⎝ A + mB ⎠
12
⎛ 8π kBT ⎞ ⎛ − E0 ⎞
k =d 2
⎜ ⎟ exp ⎜ ⎟,
⎝ μ ⎠
AB
k T
⎝ B ⎠
Which, when multiplied by the Avogadro constant (and also multiplying the numerator and denominator of the argument of the exponential
term with the Avogadro constant), is essentially the same as Eq. (9.76).
15-122
15.62. In mass-spectrometric experiments, P. Kebarle and coworkers (J. Chem. Phys., 52, 212(1970) have found that under certain
conditions the rate constant for the reaction
N + + N 2 + N 2 → N 3+ + N 2
is proportional to T–2.5. Suggest an explanation for this behavior.

Solution:
Given: above reaction, reaction rate ∼ T −2.5
The partition function for the ion N + is proportional to T 1.5 , while that for N 2 is proportional to T 2.5 . If the activated complex is nonlinear,
its partition function is proportional to T 3 . The temperature dependence of the preexponential factor is thus, according to transition-state
theory,
TT 3
= T −2.5 ,
T 1.5
(T )
2.5 2
The results can therefore be explained in terms of a nonlinear complex, with E0 = 0 .
15-123
15.63. On the basis of transition-state theory, and assuming the vibrational partitions to be temperature-independent, deduce the
temperature dependence of the preexponential factor for each of the following reactions:
a. 2ClO → Cl2 + O2
b. NO + O3 → NO2 + O2
c. NO2 + F2 → NO2F + F
d. 2NOCl → 2NO + Cl2
e. 2NO + Br2 → 2NOBr
Solution:
Given: above reactions
Required: deduce temperature dependence of the preexponential factor
The activated complexes will be assumed in all cases to be linear and to have no restricted rotation. If an activated complex is linear, the
temperature dependence decreases by 0.5, while each degree of restricted rotation increases the dependence by 0.5.
TT 3
a. = T −1
(T )2.5 2
TT 3
b. 2.5 3
= T −1.5
T T
TT 3
c. 3 2.5
= T −1.5
TT
TT 3
d. = T −2
(T )3 2
15-124
TT 3
e. = T −0.5
(T )
1.5 3
15-125
15.64. Benzaldehyde is oxidized by permanganate in aqueous solution. Suppose that the aldehydic hydrogen atom is replaced by a
deuterium atom; what can be said on the basis of transition-state theory about the kinetic isotope ratio kH/kD at 25 °C? The
wavenumber of the aldehydic C—H vibration is 2900 cm–1.
Solution:
Given: above information, T = 25 °C, λ = 2900 cm −1.
Required: see above
The two molecules differ only by isotopic substitution and will have different vibrational frequencies for the bond where substitution
occurs. We make the reasonable assumption that the change in nuclear mass will not affect the electronic energy and therefore the force
constant, k, will remain the same. The only difference occurs when the reduced mass of the two forms enter the equations. The reduced
mass is given by Eq. 13.94 or 13.118, from which the reduced mass of the deuterated form is found to be smaller than that of the form with
the normal hydrogen.
Then from Eq. 13.123, the smaller value of μD makes v0 for the deuterated bond greater than v0 for the hydrogen bond. Consequently, the
bond energy of the deuterated form is greater than that of the hydrogen form. This has the effect of putting the deuterated form at a lower
potential energy than the hydrogen form, and therefore causing a greater expenditure of energy to promote the deuterated form to the
activated state. Therefore the C—H cleavage is greater than that of the C—D bond for the same energy input and the reaction rate of the
C—H form should be faster.
15-126
15.65. A transition-state theory study of the reaction O(3P) + HCl generated the following information at T = 600 K:
Reactants
O qt 1.767 × 1032 m–3 (for 3 degrees of freedom)

32 –3
HCl qt 6.084 × 10 m (for 3 degrees of freedom)
qr 39.40 (for 2 degrees of freedom)
–1
ν0 2991.0 cm
Transition state (bent)
qt 1.050 × 1033 m–3 (for 3 degrees of freedom)

qr 1730 (for 3 degrees of freedom)
ν1 1407.9 cm–1
ν2 266.8 cm–1
The maximum of the reaction path is at 45.97 kJ mol–1. Calculate the rate constant at this temperature.
(Note: Some interesting problems on transition-state theory involving the use of a computer are to be found in S. J. Moss and C. J.
Coady, J. Chem. Ed., 60, 455(1983).)
Solution:
Given: T = 600 K, above information,
Required: rate constant
Since the vibrational partition functions are not given, we calculate them below:
15-127
−1
⎡ ⎛ −hc × 2991.0 ⎞ ⎤
qHCl
v = ⎢1 − exp ⎜ ⎟ ⎥ = 1.000 784 342,
⎣ ⎝ kBT ⎠⎦
−1
⎡ ⎛ −hc ×1407.9 ⎞ ⎤
q = ⎢1 − exp ⎜
‡
v1 ⎟ ⎥ = 1.035 752 093,
⎣ ⎝ k BT ⎠⎦
−1
⎡ ⎛ −hc × 266.8 ⎞ ⎤
q = ⎢1 − exp ⎜
‡
v2 ⎟ ⎥ = 2.120 407 02.
⎣ ⎝ kBT ⎠⎦
Now, the quantity E0 appearing in the exponent of Eq. 15.152 has to be evaluated. This is the energy difference between the zero point
energy of the reactants and that of the transition state,
1
E0 = 45 970 + Lhc (1407.9 + 266.8 − 2991.0 ) = 38 097 J mol−1.
2
Therefore, we calculate
⎛ kBT ⎞ (1.050 × 10 ) (1730 )(1.035 752 093 × 2.120 407 02 )

33
⎛ −38 097 ⎞
k =⎜ ⎟ exp ⎜ ⎟
⎝ h ⎠ (1.767 × 10 )( 6.084 × 10 ) ( 39.4 )(1.000 784 342 )
32 32
⎝ RT ⎠
k = 5.677 833 797 × 10−21 m3 s −1
k = 5.678 ×10−21 m3 s −1
The translational partition functions are calculated for unit volume and hence, although strictly speaking, their units are simply m -3 , we may
interpret this to mean “state m -3 ” or molecules m -3 .
15-128

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CHAPTER

LAIDLER . MEISER . SANCTUARY

Problems and Solutions

N 0 = 10, N1 = 10, N 2 = 10, N 3 → 29 = 0

Transformations of statistical and thermodynamic functions

obtain the equation:

d. What happens as the temperature is raised?

HCl High temp. 19.73 1.0000016

N2 High temp. 104.89 1.0000146

O2 High temp. 144.92 1.00059

I2 High temp. 555.5 1.552

Partition Functions for Some Special Cases

What is the limiting value of this fraction as T → ∞? Explain your answer.

b. 35Cl – 35Cl + 37Cl – 37Cl 235Cl – 37Cl

c. C35Cl4 + 37Cl C37Cl35Cl3 + 35Cl

d. N35Cl3 + 37Cl N37Cl35Cl2 + 35Cl

*15.53. Calculate the equilibrium constant at 1000 °C for the dissociation

separation between the states being 881 cm–1.

Transition state theory

15.60. The rate of the reaction

is proportional to T–2.5. Suggest an explanation for this behavior.

d. 2NOCl → 2NO + Cl2

e. 2NO + Br2 → 2NOBr

O qt 1.767 × 1032 m–3 (for 3 degrees of freedom)

Transition state (bent)

qt 1.050 × 1033 m–3 (for 3 degrees of freedom)

Given: Stirling’s formula, several values of N.

Required: calculate and approximate value for ln(N!)

N exact ln(N!) stirling's formula Error (%)

5 4.787492 3.047 36.35

10 15.10716 13.026 13.78

50 148.478 145.601 1.94

100 363.739 360.517 0.89

1000 5912.123 5907.755 0.07

10000 81959.46 82103.4 0.0018

Back to Problem 15.1 Back to Top

The four objects are distinguishable, so there are P44 = 4! = 24 arrangements.

Back to Problem 15.2 Back to Top

ABC_ AB_C A_BC _ABC

Back to Problem 15.3 Back to Top

( x1 + x2 )5 = x15 + 5 x14 x2 + 10 x13 x22 + 10 x12 x23 + 5 x1 x24 + x25

Work out Pascal’s triangle:

Prn n! ⎛n⎞ ⎛ 4⎞ ⎛ 5⎞ ⎛5⎞

Back to Problem 15.4 Back to Top

Back to Problem 15.5 Back to Top

Back to Problem 15.6 Back to Top

Back to Problem 15.7 Back to Top

Back to Problem 15.8 Back to Top

Back to Problem 15.9 Back to Top

Can we do the same for:

Back to Problem 15.10 Back to Top

There can be up to 4 bonds, so we have:

( PH + PD ) 4 = PH4 + 4 PH3 PD1 + 6 PH2 PD2 + 4 PH1 PD3 + PD4

The chance of 4 H is PH4 =1/16

Back to Problem 15.11 Back to Top

⎡ m! ⎤ ⎡ m(m − 1)(m − 2)...(m − n + 1) ⎤

⎡ ( m + n − 1) !⎤ ⎡ (m + n − 1)(m + n − 2)...(m − 2) (m − 1)! ⎤

Alternately we can start with Eqs.(15.56) and (15.59) to obtain Eq.(15.60):

Back to Problem 15.12 Back to Top