Thermal properties Heat capacity

The heat capacity, C, of a system is the ratio of the heat

¾ Heat capacity added to the system, or withdrawn from the system, to the
• atomic vibrations, phonons resultant change in the temperature:
• temperature dependence
C = ΔQ/ΔT = dQ/dT [J/deg]
• contribution of electrons
¾ Thermal expansion ¾ This definition is only valid in the absence of phase
• connection to anharmonicity of interatomic potential transitions
• linear and volume coefficients of thermal expansion ¾ Usually C is given as specific heat capacity, c, per
¾ Thermal conductivity gram or per mol
• heat transport by phonons and electrons ¾ Heat capacity can be measured under conditions of
constant temperature or constant volume. Thus, two
¾ Thermal stresses distinct heat capacities can be defined:
⎛ δq ⎞
C V = ⎜ ⎟ - heat capacity at constant volume
⎝ dT ⎠ V
⎛ δq ⎞
C P = ⎜ ⎟ - heat capacity at constant pressure
⎝ dT ⎠ P

CP is always greater than CV - Why?

Hint: The difference between CP and Cv is very small for
solids and liquids, but large for gases.
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Heat capacity Temperature dependence of heat capacity

Heat capacity is a measure of the ability of the material to
Heat capacity has a weak temperature dependence at high
absorb thermal energy.
temperatures (above Debye temperature θD) but decreases
Thermal energy = kinetic energy of atomic motions + down to zero as T approaches 0K.
potential energy of distortion of interatomic bonds.
The higher is T, the large is the mean
atomic velocity and the amplitude of
Cv, J K-1 mol-1

atomic vibrations Æ larger thermal

energy

Vibrations of individual atoms in solids are not

independent from each other. The coupling of atomic
vibrations of adjacent atoms results in waves of atomic
displacements. Each wave is characterized by its
wavelength and frequency. For a wave of a given T/θD
frequency ν, there is the smallest “quantum” of vibrational
The constant value of the heat capacity of many simple solids is
energy, hν, called phonon. sometimes called Dulong – Petit law
Thus, the thermal energy is the energy of all phonons (or In 1819 Dulong and Petit found experimentally that for many
all vibrational waves) present in the crystal at a given solids at room temperature, cv ≈ 3R = 25 JK-1mol-1
temperature. This is consistent with equipartition theorem of classical
mechanics: energy added to solids takes the form of atomic
Scattering of electrons on phonons is one of the mechanisms
vibrations and both kinetic and potential energy is associated
responsible for electrical resistivity (Chapter 18) with the three degrees of freedom of each atom.
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 Temperature dependence of heat capacity Heat capacity of metals – electronic contribution
In addition to atomic vibrations (phonons), thermal excitation of
electrons can also make contribution to heat capacity.

To contribute to bulk specific heat, the valence electrons would have to

receive energy from the thermal energy, ~kT. Thus, only a small
fraction of electrons which are within kT of the Fermi level makes a
contribution to the heat capacity. This contribution is very small and
insignificant at room temperature.

The electron contribution to cv is proportional to temperature, cvel = γT

and becomes significant (for metals only) at very low temperatures
(remember that contribution of phonons cv ~ AT3 at T → 0K).
The low-T behavior can be explained by quantum theory. The
first explanation was proposed by Einstein in 1906. He
considered a solid as an ensemble of independent quantum
harmonic oscillators vibrating at a frequency ν. Debye advanced
the theory by treating the quantum oscillators as collective modes
in the solid (phonons) and showed that
cv ~ AT3 at T → 0K

Quantized energy levels

ΔE = hν
Energy

ΔE << kT - classical behavior Pn ~ e − ΔE/kT

ΔE ≥ kT - quantum behavior

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Heat capacity of various materials (at RT) Thermal expansion

Materials expand when heated and contract when cooled

l f − l0 Δl
= = α l (T f − T0 ) = α l ΔT
l0 l0
where l0 is the initial length at T0, lf is the final length at Tf

αl is the linear coefficient of thermal expansion

Similarly, the volume change with T can be described as

V f − V0 ΔV
= = αV (T f − T0 ) = αV ΔT
V0 V0
where αV is the volume coefficient of thermal expansion

For isotropic materials and small expansions, αV ≈ 3αl

Δl
V f = l 3f = (l0 + Δl ) = l03 + 3l02 Δl + 3l0 Δl 2 + Δl 3 ≈ l03 + 3l02 Δl = V0 + 3V0
3

l0
Δl V f − V0 ΔV Δl
V f ≈ V0 + 3V0 = ≈3 αV ΔT ≈ 3α l ΔT
l0 V0 V0 l0

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 Physical origin of thermal expansion Physical origin of thermal expansion

typical interatomic symmetric (harmonic) potential

interaction potentials are
asymmetric (anharmonic)

Potential Energy
Interatomic distance r
0
Potential Energy

Interatomic distance r
0

the average value of interatomic

separation does not change
increase of the average value of
interatomic separation
Thermal expansion is related to the asymmetric
(anharmonic) shape of interatomic potential. If the
Rising temperature results in the increase of the average interatomic potential is symmetric (harmonic), the average
amplitude of atomic vibrations. For an anharmonic value of interatomic separation does not change, i.e. no
potential, this corresponds to the increase in the average thermal expansion.
value of interatomic separation, i.e. thermal expansion.

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Thermal expansion of various materials Implications and applications of thermal expansion

Railway tracks
are built from
steel rails laid
with a gap
between the ends
tendency to expand upon
heating is counteracted by
contraction related to Thermostats based on bimetal strips made of two metals
ferromagnetic properties of with different coefficient of thermal expansion:
this alloy (magnetostriction)

Negative thermal expansion:

liquid water contracts when
heated from 0 to 4°C.
ZrVPO7, ZrW2O8, quartz at
very low T.

A bimetal coil from a thermometer reacts

The stronger the interatomic bonding (deeper the potential energy to the heat from a lighter, by Hustvedt,
curve), the smaller is the thermal expansion. Wikipedia
The values of αl and αV are increasing with rising T
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 Thermal conductivity Mechanisms of heat conduction
Thermal conductivity: heat is transferred from high to low Heat is transferred by phonons (lattice vibration waves)
temperature regions of the material. and electrons. The thermal conductivity of a material is
defined by combined contribution of these two
dT
q = −k - Fourier's law mechanisms:
dx k = kl + ke
where q is the heat flux (amount of thermal energy flowing where kl and ke are the lattice and electronic thermal
through a unit area per unit time) and dT/dx is the conductivities.
temperature gradient, and k is the coefficient of thermal Lattice conductivity: Transfer of thermal energy phonons
conductivity, often called simply thermal conductivity.
Electron conductivity: Free (conduction band) electrons
equilibrate with lattice vibrations in hot regions, migrate to
Units: q [W/m2], k [W/(m K)]
colder regions and transfer a part of their thermal energy
back to the lattice by scattering on phonons.
Note the similarity to the Fick’s first law for atomic
diffusion (Chapter 5): the diffusion flux is proportional to The electron contribution is dominant in metals and absent
the concentration gradient: in insulators.
dC
J = −D
dx Since free electrons are responsible for both electrical and
thermal conduction in metals, the two conductivities are
Non-steady state heat flow and atomic diffusion are related to each other by the Wiedemann-Franz law:
described by the same equation:
k
∂C ∂ 2C ∂T k ∂ 2T L=
=D = σT
∂t ∂x 2 ∂t c P ρ ∂x 2
where σ is the electrical conductivity and L is a constant

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Wiedemann-Franz law Effect of alloying on heat conduction in metals

The same factors that affect the electrical conductivity
k (discussed in Chapter 18) also affect thermal conductivity
L= in metals. E.g., adding impurities introduces scattering
σT centers for conduction band electrons and reduce k.

Cu-Zn alloy

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 Quest for good thermoelectric (TE) materials Quest for good thermoelectric (TE) materials
Thermoelectric conversion: conversion of thermal to Nanostructured materials - a chance to disconnect the linkage
electrical energy between the thermal and electrical transport by controlling
scattering mechanisms
An applied temperature
difference ΔT causes charge
carriers in the material
(electrons or holes) to diffuse
from the hot side to the cold
side, resulting in current flow
through the circuit and grain boundaries, interfaces – reduction of k, but also the
producing an electrostatic deterioration of carrier mobility (μ).
potential ΔV. nano/microcomposite (f): nanoparticles scatter phonon, while
microparticles can form a connected (percolating) network for
Figure of merit of TE material: electron transport.
ZT = (α2σ/k)T
The high
where σ, κ and α are the performance of
electrical conductivity, thermal these materials
conductivity, and Seebeck is related to
coefficient defined as nanostructure
Li et al., Nat. Asia Mater., 152, 2010
α = ∆V/∆T. engineering

Good TE material: High σ (low Joule heating), large Seebeck

coefficient (large ΔV), low k (large ΔT) are necessary.

ZT ≈ 3 is needed for TE energy converters to compete with

mechanical power generation and active refrigeration. Li et al.,
Nat. Asia Mater., 152, 2010
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Heat conduction in nonmetallic materials Temperature dependence of thermal conductivity

In insulators and semiconductors the heat transfer is by Thermal conductivity tend to decrease with increasing
phonons and, generally, is lower than in metals. It is temperature (more efficient scattering of heat carriers on lattice
sensitive to structure: vibrations), but can exhibit complex non-monotonous behavior.

¾ glasses and amorphous ceramics have lower k compared

to the crystalline ones (phonon scattering is more
effective in irregular or disordered materials).
¾ Thermal conductivity decreases with porosity (e.g.
foamed polystyrene is used for drinking cups).
¾ Thermal conductivity of polymers depends on the
degree of crystallinity – highly crystalline polymer has
higher k

Corn kernels have a hard moisture-sealed hull

and a softer core with a high moisture content.
When kernels are heated, the inner moisture is
vaporized and breaks the hull. The corn that
“pops” and is used to make popcorn have hulls
that are made from cellulose that is more
crystalline than “non-popping” corn kernels. As
a result, the hulls are good thermal conductors
(2-3 times better than corns that do not pop) and
are mechanically stronger (higher pressure can
build up before popping).

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 Thermal conductivity of various materials at RT Thermal conductivity of polymer nanofibers
Although, normally, polymers are thermal insulators (k ~ 0.1 Wm-1K-1),
it has been demonstrated in atomistic simulations [Henry & Chen, PRL
101, 235502, 2008] that thermal conductivity of individual polymer
chains can be very high. This finding has been supported by recent
experimental study of high-quality ultra-drawn polyethylene nanofibers
Diamond: 2310 with diameters of 50-500 nm and lengths up to tens of millimeters [Shen
et al., Nat. Nanotechnol. 5, 251, 2010] Æ it has been demonstrated that
Graphite: the nanofibers conducts heat just as well as most metals, yet remain
along c-axis: 2000 electrical insulators.
along a-axis: 9.5
Making the nanofibers: Pulling a thin thread of
material from a liquid solution - polymer
SiO2 molecules become very highly aligned.
crystalline
along c-axis: 10.4
along a-axis: 6.2
amorphous: 1.38

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Thermal conductivity of polymer nanofibers Thermal stresses

• can be generated due to restrained thermal
expansion/contraction or temperature gradients that
104 Wm-1K-1 lead to differential dimensional changes in different part
300 times higher of the solid body.
than k of bulk
polyethylene! • can result in plastic deformation or fracture.
In a rod with restrained axial deformation: σ = E αl ΔT
where E is the elastic modulus, αl is the linear coefficient
of thermal expansion and ΔT is the temperature change.

Stresses from temperature gradient

Rapid heating can result in strong temperature gradients Æ
Shen et al., Nat. Nanotechnol. 5, 251, 2010
confinement of expansion by colder parts of the sample.
The same for cooling – tensile stresses can be introduced in
a surface region of rapidly cooled piece of material.

Thermal stresses can cause plastic deformation (in ductile

Highly anisotropic unidirectional materials) or fracture (in brittle materials). The ability of
thermal conductivity: may be useful for
applications where it is important to
material to withstand thermal stresses due to the rapid
draw heat away from an object, such as cooling/heating is called thermal shock resistance.
a computer processor chip. Shock resistance parameter for brittle materials (ceramics):
σf k
TSR ∝ where σf is fracture strength of the material
Eα l
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 Restrained thermal expansion: Example problem Summary
Make sure you understand language and concepts:
A brass rod is restrained but stress-free at RT (20ºC).
Young’s modulus of brass is 100 GPa, αl = 20×10-6 1/°C ¾ anharmonic potential
At what temperature does the stress reach -172 MPa? ¾ atomic vibrations, phonons
¾ electron heat conductivity
l0
¾ electronic contribution to heat capacity
T0 ¾ heat capacity, CP vs. CV
¾ lattice heat conductivity
l0 Δl ¾ linear coefficient of thermal expansion
Tf Δl = ε th = α l (T f − T0 ) ¾ specific heat capacity
l RT
if thermal expansion is unconstrained ¾ thermal conductivity
¾ thermal expansion
l0 Δl
Δl ¾ thermal stresses
ε compress = −ε th = − ¾ thermal shock resistance
σ σ l RT
if expansion is constrained
¾ volume coefficients of thermal expansion

σ = Eε compress = − Eα l (T f − T0 ) = Eα l (T0 − Tf ) classical Dulong – Petit law

24.9
High T, Cv → 3R
σ − 172 ×106 Pa

Cv, J K-1 mol-1

T f = T0 − = 20 − = 106 o C
Eα l 100 ×109 Pa × 20 ×10-6 o C -1 quantum Debye model
Low T, Cv → 0

T
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