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∂Ε ∂
∴ Molar specific heat at constant volume, Cv = = ( 3RΤ ) = 3R
∂Τ v ∂Τ
Experimental values of Cv of CV
most of the solids at ordinary or high
temperatures is very nearly equal to 3R
3R and is independent of temperature
in agreement with the classical theory , Experimental value
3
But experiments at low temperatures show that Cv is nearly proportional to T .and
Cv tends to zero as temperature tends to zero. Thus Dulong and Petit’s law is valid only at
high temperatures.
−Ei
ekT
.
6) This means that the number of oscillators with energy Ei is given by
− Ei
n i = C. exp ----------(1) where C is a constant.
kT
If n0 be the number of oscillators with zero energy then, n0 = c.e0 = c . Replacing C in eqn (1)
− Ei
by n0 , we get, n i = n 0 .e kT
--------------------------------------- (2)
where Ei is the energy in the ith state and Ei =i(hν). i = 0.1.2.3… etc.
3
N = n 0 + n 0 .e kT
+ n 0 .e kT
+ ......
−ε −2ε
= n 0 1 + e kT
+ e kT + .... ---(3)
1
[
But 1 + e + e
x 2x
+ e3 x ....] =
1 − ex
−ε − 2ε −3ε
1
∴ 1+ e kT +e kT + e kT + ............ = ……………….-Æ(i) . Using this in (3),
−ε
1 − e kT
n0
we get, N = −ε ---------------------------- (4)
1 − e kT
−ε
−ε
n ε .e kT
i.e.
E. 1 − e kT = 0 (using eqn. (i)). Rearranging this,
−ε
1 − e kT
−ε −ε
n ε .e kT n ε .e kT
∴ E= 0 2
i.e., Total energy E = 0 2
………………… (7)
−ε −ε
kT kT
1 − e 1 − e
E
∴ Average energy per oscillator <E> =
N
Substituting for N and E from eqns. (4) and (7) respectively, we get,
−ε
−ε 1 − e kT −ε
n ε .e kT = ε .e kT
< E >= 0 .
−ε
2
n0 −ε
kT
kT 1 − e
1 − e
ε.
i.e., < E > =
−ε
kT
1 −e
−ε −ε
kT
e e kT
ε
<E> = Using ε = hν / kT, we have
ε
kT
e − 1
hν
<E> = …………….…. (8)
hν
kT
e − 1
5
2
−θ E
3N 0 kθ E ∂Ε θE 3Rθ E
∴E = (or) CV = = 3R . .e T E = ……….(9)
θE ∂Τ v T θE
T T
e − 1 e − 1
θE
2
∂E θE eT
∴ Molar Specific heat at constant volume , CV = = 3 R ….Æ(10)
∂T V
2
T θE
e − 1
T
θE
CASE 1:- When temperature T is very high, such that T >> θE, then is very small.
T
θE 2 3
θ 1 θE 1 θE θE
∴e T
1+ E + + + ...... 1 + , neglecting higher powers.
T 2! T 3! T T
θE
θ
∴e T −1 E . Using this in eqn. (9), we get,
T
3Rθ E ∂E
E= = 3RT and hence CV = = 3R , the classical theory value.
θE ∂T V
( )
T
2
θ θ
CASE 2:- When temperature T is small, such that T << θE , then E E is very large.
T T
θE θE θE
e T
>> 1 and hence ∴ e T − 1 e T , neglecting 1. Using this in eqn. (9), we get,
6
3Rθ E
E=
θE
T
e
2
−θ E
∂Ε θE
∴ CV = = 3R . .e T
∂Τ v T
Thus, Einstein’s theory is able to explain the change and dependence of Cv on temperature at low
temperatures. Cv of the solid at low temperatures depends on temperature T and on θ E ie., the
characteristic frequency of vibration of the solid.
2
θ
In the above equation as T reduces, E CV
T
−θ E
increases while e T reduces. Since the
exponential reduction is much faster, value of Expt
3
is nearly proportional to T and Cv tends to zero T
as temperature tends to zero more slowly than that predicted by the Einstein’s theory.
Draw back of Einstein’s theory:
Einstein’s theory, in agreement with the experiment, established the change of Cv with
temperature. But fall in Cv with falling temperature is steeper than that observed in experiments.
This indicates that value of Cv calculated by Einstein’s theory are not accurate at low temperature.
This inaccuracy is due to the fact that the atoms in solids are assumed to be vibrating
independent of each other with the same frequency. This assumption is not correct.
7
1 2
given by Z (ν ).dν = 4πV 3 + 3 .ν 2 .dν ........(1)
cl ct
The total number of all possible modes of vibration is obtained by integrating the
8
equation (1) with limits between 0 and νD. But the total number of possible modes is 3N only.
νD
Therefore, ∫ Z (ν ).dν = 3N
0
i.e.,
νD
1 2 2
∫ 4π V c
0 l
3
+ .ν .dν = 3 N
ct3
ν
1 2 D
4π V 3 + 3 . ∫ ν 2 .dν = 3N
cl ct 0
1 2 ν D3 1 2 9N
4π V 3 + 3 . = 3 N (or) 4π V 3 + 3 = ......(2)
cl ct 3 cl ct ν D3
9N
Substituting this back into eqn (1), we have, Z (ν ).dν = .ν 2 .dν ........(3)
νD 3
From Planck’s quantum theory and Einstein’s theory of specific heat of solids, the average energy of
oscillators with frequency between ν and ν + dν is given by
hν
< E >= hν
. ∴Energy due to all the modes with frequency between ν and ν + dν is given by
e kT
− 1
9N hν 3
dE = Z(ν)dν.<E> i.e., dE = .dν
ν D3 hν
e kT
− 1
∴Total energy of the solid is given by
νD νD νD
9N hν 3 9 Nh ν3
E= ∫ dE = ∫ν 3
kThν
.dν i.e., E =
ν D3
. ∫ hν
.dν ......(4)
0 0 D
e − 1 0
e
kT
− 1
hν D kθ
Let = θ D , known as Debye temperature which is a characteristic of the solid.∴ν D = D
k h
9
hν kT kT
Also, let x = (or) ν= .x .....(i ) ∴ dν = .dx ....... (ii)
kT h h
hν D θ
When ν = 0, x = 0 and when ν = ν D , x = = D ......(iii)
kT T
Replacing the variable ν by x , changing the limits of the integral and substituting for ν D
3
θD kT 3 kT
h3 T x . .dx
h h
from the above equations, the eqn (4) becomes, E = 9 Nh.
k 3θ D 3
. ∫
0 ( e x − 1)
θD 3
x ..dx
9 NkT 4 T ................ (6). For 1 mole of the solid, N is replaced by the Avogadro number, N 0 .
E=
θD 3
.∫ ( e x − 1)
0
θD
4
9 RT T
x 3 .dx
As Nk = N0k =R for 1 mole, , the universal gas constant, it becomes, E =
θ D3
. ∫
0
ex −1
.......(7)
Now, E is the equilibrium thermal energy of 1 mole of the solid and its molar specific heat at
constant volume is given by Cv = (∂E / ∂T)V.
Case (i) : When the temperature T is very high, (i.e., T >> θD), x = ( hν/kT) is very small and hence
ex can be expanded as a power series in x. ∴ex = 1 + x + x2/2! + x3/3! + …..Neglecting the higher
powers this becomes, ex = 1 + x (or) (ex – 1) = x. Substituting this in (7)
θD θD
9 RT 4 θ D
4 T 3 4 T 3
9 RT x .dx 9 RT
E= ∫ = ∫ x .dx =
2
. . .
θ D3 0
x θ D3 0 θ D 3 3T 3
∂E
i.e., E = 3RT ∴Cv = = 3R, the classical value ( Dulong - Petit' s law)
∂T V
Thus, Cv is a constant = 3R at high temperature as in the case of theory & experiment.
Case (ii): Temperature T is very low (i.e., T << θD , TÆ0 ). In this case, (θD/T) is very large i.e.,
(θD/T) Æ ∝. Using this as the upper limit of the integral in eqn (7), the integral becomes a standard
integral whose value is given by π4/15.
9 RT 4 x 3 .dx
∞
9 RT 4 π 4
θ D 3 ∫0 e x − 1
i.e., E = . = .
θ D 3 15
3π RT 4 ∂E 12π R 3 ……………(8)
i.e., E = ∴ CV = = .T
5θ D 3
∂T V 5θ D 3
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Thermal conductivity:
Heat energy can be transmitted through crystals via the motion of phonons,
photons, free electrons or free holes, electron- hole pairs etc. The highest contribution
to thermal conduction in metals comes from free electrons. On the other hand, in
insulators almost the entire contributions to thermal conductivity comes from phonons.
dT
When there is a temperature gradient of across the two ends of a material, the
dx
dT
conductivity K is defined by the equation Q = K. where Q is the energy current density.
dx
[Thermal energy flowing per unit time across unit area].
From the kinetic theory of gases, it can be shown that the thermal conductivity of
an ideal gas in which a temperature gradient exists is given by
11
1
K= .V .λ.Cv ------------- (1)
3
Where V = average velocity of gas molecules
Cv = specific heat at constant volume of the gas and
λ = mean free length between successive collisions
This equation is more valid for a ‘phonon gas’ in an insulated solid as v, the velocity of
sound, is a constant for phonons.
The heat conduction by ‘phonon gas’ in solids is characterized by phonon flow.
Phonons are created at hot end and are annihilated at the cold end.
In equation (1), for thermal conductivity of insulators, v is the sound velocity and
Cv is the specific heat due to phonons given by Debye T 3 law:
Cv = α .T 3 where α is a constant.
1 2 EF
.m.VF 2 = EF or VF2 = ------------------ (2)
2 m
where V = VF is the velocity corresponding to energy E = EF
1
Using (2) and (3) in (1) i.e., in the eqn, K = .V .λ.Cv , we get
3
1 1 2E τ C
K= VF .VFτ .CV = VF 2τ CV = F V ………(4)
3 3 3m
Here Cv is the electronic specific heat Ce, viz. Cv = Ce
π 2 Nk 2
From the free electron theory, Ce = .T (kÆ Boltzmann Constant)
2 EF
Using this in (4) for CV, the expression for thermal conductivity K of metal reduces to
2 EFτ π 2 Nk 2 π 2 Nk 2τ
K= . .T = .T ……….(5)
3m 2 EF 3m
In the above expression, K appears to be proportional to temperature, T. But as τ is inversely
proportional to T, actually, K is independent of temperature. This is consistent with experimental
values of K.
Wiedermann-Franz law
Wiedermann and Franz found that the ratio of thermal conductivity K to the electrical conductivity σ
is the same for all metals at a given temperature. This can be shown as given below.
From the free electron theory, the electrical conductivity σ is given by
π 2k 2
L = 2 = 2.45 × 10−8 Watt.Ohm.Deg -2 …….(6).
3e
K π 2 Nk 2τ m π 2k 2
Using eqns. (5) and (6) the ratio (K/ σ) is found to be = .T . = 2 .T
σ 3m Ne τ 3e
2
K π 2k 2
Thus, = 2 .T . ……. (7). In deriving this Wiedermann-Franz law, it is assumed that mean
σ 3e
free path is the same for both electrical and thermal conductivities of the metal. Rearranging eqn.
K π 2k 2 π 2k 2
(7), we get, L = = 2 , where, L = 2 = 2.45 × 10−8 Watt.Ohm.Deg -2 is known as
σ T 3e 3e
Lorentz number which should be the same for all metals. I t was found to be in good agreement with
calculations.
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