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**3 Assumptions made 205
**

and using eqn 11.28 we have

C

p

per mole =

f

2

+ 1

R, (19.23)

from which we may derive

γ =

C

p

C

V

=

(

f

2

+ 1)R

f

2

R

= 1 +

2

f

. (19.24)

We can summarize our results for the heat capacity of gases, per atom/molecule,

as follows:

Gas Modes f E γ

Monatomic translational only 3

3

2

k

B

5

3

Diatomic translational and rotational 5

5

2

k

B

7

5

Diatomic translational, rotational and vibrational 7

7

2

k

B

9

7

19.2.4 The heat capacity of a solid

In a solid, the atoms are held rigidly in the lattice and there is no pos-

sibility of translational motion. However, the atoms can vibrate about

their mean positions. Consider a cubic solid in which each atom is con-

nected by springs (chemical bonds) to six neighbours (one above, one

below, one in front, one behind, one to the right, one to the left). Since

each spring joins two atoms, then if there are N atoms in the solid, there

are 3N springs (neglecting the surface of the solid, a reasonable approx-

imation if N is large). Each spring has two quadratic modes of energy

(one kinetic, one potential) and hence a mean thermal energy equal to

2 ×

1

2

k

B

T = k

B

T. Hence the mean energy of the solid is

E = 3Nk

B

T, (19.25)

and the heat capacity is ∂E/∂T = 3Nk

B

. Because R = N

A

k

B

, the

molar heat capacity of a solid is then expected to be 3N

A

k

B

= 3R.

x

z

y

Fig. 19.6 In a cubic solid, each atom is

connected by chemical bonds, modelled

as springs, to six nearest neighbours,

two along each of the three Cartesian

axes. Each spring is shared between

two atoms.

19.3 Assumptions made

The equipartition theorem seems to be an extremely powerful tool for

evaluating thermal energies of systems. However, it does have some

limitations, and to discover what these are, it is worth thinking about

the assumptions we have made in deriving it.

206 Equipartition of energy

• We have assumed that the parameter for which we have taken the

energy to be quadratic can take any possible value. In the deriva-

tion, the variables x

i

could be integrated continuously from −∞

to ∞. However, quantum mechanics insists that certain quanti-

ties can only take particular ‘quantized’ values. For example, the

problem of a mass on a spring is shown by quantum mechanics

to have an energy spectrum which is quantized into levels given

by (n +

1

2

)ω. When the thermal energy k

B

T is of the same or-

der, or lower than, ω, the approximation made by ignoring the

quantized nature of this energy spectrum is going to be a very bad

one. However, when k

B

T ω, the quantized nature of the en-

ergy spectrum is going to be largely irrelevant, in much the same

way that you don’t notice that the diﬀerent shades of grey in a

newspaper photograph are actually made up of lots of little dots if

you don’t look closely. Thus we come to an important conclusion:

The equipartition theorem is generally valid only at high temper-

ature, so that the thermal energy is larger than the energy gap

between quantized energy levels. Results based on the equipar-

tition theorem should emerge as the high-temperature limit of

more detailed theories.

x

V x

x

Fig. 19.7 V (x) is a function which is

more complicated than a quadratic but

which has a minimum at x = x

0

.

• Everywhere we have assumed that modes are quadratic. Is that

always valid? To give a concrete example, imagine that an atom

moves with coordinate x in a potential well given by V (x), which is

a function which might be more complicated than a quadratic (see

for example Fig. 19.7). At absolute zero, the atom ﬁnds a potential

minimum at say x

0

(so that, for the usual reasons, ∂V/∂x = 0

and ∂

2

V/∂x

2

> 0 at x = x

0

). At temperature T > 0, the atom

can explore regions away from x

0

by borrowing energy of order

k

B

T from its environment. Near x

0

, the potential V (x) can be

expanded

3

as

3

Using a Taylor expansion; see Ap-

pendix B.

V (x) = V (x

0

) +

∂V

∂x

x

0

(x −x

0

) +

1

2

∂

2

V

∂x

2

x

0

(x −x

0

)

2

+· · · ,

(19.26)

so that using

∂V

∂x

x

0

= 0, we ﬁnd that the potential energy is

V (x) = constant +

1

2

∂

2

V

∂x

2

x

0

(x −x

0

)

2

+· · · , (19.27)

which is a quadratic again. This demonstrates that the bottom

of almost all potential wells tends to be approximately quadratic

(this is known as the harmonic approximation).

4 4

The argument that the bottom of al-

most all potential wells tends to be

approximately quadratic could fail if

(∂

2

V/∂x

2

)

x

0

turned out to be zero.

This would happen if, for example,

V (x) = α(x −x

0

)

4

.

If the temperature gets too high, the system will be able to access

positions far away from x

0

and the approximation of ignoring the

higher–order (cubic, quartic, etc.) terms (known as the anhar-

monic terms) in the Taylor expansion may become important.

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