Specific heat capacity of solids

Solids are forms of matter having characteristics like strong forces of intermolecular
interaction, rigidity, proper shape, structure, etc. Solids can be heated, so the capacity of
specific heat for solids can be determined. The SI unit of specific heat capacity is J/Kg/K.

The specific heat capacity of solids is defined as the amount of energy provided to a unit
mass of any solid substance so that its temperature is raised by 1°C.

To determine the specific heat capacity, we will have to make use of the law of equipartition
of energy. This law states that for a system in thermal equilibrium, there will be a certain
amount of average energy for each degree of freedom a molecule has.

For example, a gas molecule moving in three-dimensional space has three coordinates, so the
value of the degree of freedom for that molecule would be 3.

Let us consider any solid having N atoms. Each atom is allowed to move freely but only in
one coordinate axis or 1D space. The expression for the total energy U is given as:

U = 3kbTNA= 3RT

We will use the equation for the first law of thermodynamics given below:

ΔQ = ΔU+P ΔV

The first law states: “Energy cannot be created or destroyed, it can only be converted from
one form to another.”

Here, PV can be eliminated as the volume change is negligible for solids.

Therefore, the expression for molar specific heat capacity (heat capacity calculated for one
mole of solid) will be:

C= ΔQ / ΔT= ΔU /ΔT

C = 3R = 24.94 J/K-1 mol -1

C here is the molar specific heat capacity

Q is the heat given and ∆T is the temperature change.

Heat capacity is more or less an intrinsic property. This means that it is an attribute of any
particular substance. The heat capacity is calculated with the help of a Calorimeter. The bomb
calorimeter always indicates constant volume values. Another type of calorimeters known as
the coffee cup calorimeters is associated with finding heat capacity at constant pressure.
Introduction

Heat capacity is calculated of the heat energy needed to amplify the temperature of an object
via an indeed temperature interval. Heat capacity is a wide property since its value is
proportional to the amount of material in the object; for instance, a bathtub of water has a
greater heat capacity than a cup of water. Heat capacity is generally conveyed in units of J/K
(or J K-1). For example, one could write that the gasoline in a 55-gallon drum has an standard
heat capacity of 347 kJ/K.

Definition of Heat Capacity

The heat capacity of a material, C, is amplify in internal energy of a substance U per unit
raise in temperature T:

C = (∂U/∂T)

Heat capacity is mathematically described as the ratio of a tiny amount of heat δQ added to
the body, to the equivalent tiny enhance in its temperature dT:

For thermodynamic systems through more than one physical dimension, the above
explanation doesn't give a single, unique amount unless a meticulous infinitesimal path
through the system's phase space has been described (this means that one requires to know at
all times where all parts of the system are, how much mass they have, and how fast they are
moving). This information is utilized to account for different ways that heat can be stored as
kinetic energy (energy of motion) and potential energy (energy stored in force fields), as an
object increases or contracts. For all real systems, the path through such modifies must be
explicitly explained, because the value of heat capacity based on that path from one
temperature to an additional, is chosen. Of particular helpfulness in this context are the values
of heat capacity for steady volume, CV, and stable pressure, CP. Such will be described
below.

Heat Capacity of Compressible Bodies

The state of an easy compressible body through fixed mass is described via 2 thermodynamic
parameters such as temperature T and pressure p. Consequently as revealed above, one might
distinguish between heat capacity at constant volume, CV, and heat capacity at steady
pressure, Cp:

Where

Cv = ( Δq/ δT)v = T( δS/ δT)v

Cp = ( δQ/ Δt)p = T( Δs/ δT)p

δQ is the infinitesimal amount of heat added,

dT is the subsequent rise in temperature.

The increment of internal energy is the heat added and the work added:

dU = TdS - pdV

So the heat capacity at constant volume is

Cv = (δU/δT)v

The enthalpy is defined by H = U + PV. The increment of enthalpy is

dH = dU + (pdV + V dp)

which, after replacing dU with the equation above and cancelling the PdV terms reduces to?

dH = TdS + Vdp

So the heat capacity at constant pressure is

Cp = ( δH/ δT)p

As we know that this last 'definition' is a bit circular, because the idea of "enthalpy" itself was
discovered to be a estimate of heat absorbed or generated at constant pressures (the situations
in that chemists generally work). As such, enthalpy merely accounts for the extra heat that is
generated or absorbed via pressure-volume work at steady pressure.

Therefore, it isn't surprising that constant-pressure heat capacities might be described in terms
of enthalpy, because "enthalpy" was described in the 1 st place to build this so. Analogous
expressions for precise heat capacities at steady volume and at stable pressure are:

Cv = ( δu/ δT)v

Cp = ( δh/ δT)p

Where u = specific internal energy and h = specific enthalpy. Such intensive quantities can be
expressed on a per mole basis or on a per mass basis, as long as constancy is preserved all
through the equation.

Relation between Specific Heat

Measuring the heat capacity at steady volume can be prohibitively hard for liquids and solids.
That is, small temperature transforms classically need huge pressures to preserve a liquid or
solid at constant volume implying the enclosing vessel must be almost rigid or at least
extremely strong. In its place it is easier to calculate the heat capacity at steady pressure
(allowing the material to enlarge or contract as it wishes) and solve for the heat capacity at
constant volume using mathematical associations derived from the basic thermodynamic
laws. Starting from the fundamental Thermodynamic relation one can illustrate,
Cp - Cv = α2T/αβT

where,

α is the coefficient of thermal expansion,

βT is the isothermal compressibility, and

ρ is density.

For an ideal gas, if ρ is expressed as molar density in the above equation, this equation
reduces simply to Mayer's relation,

Cp,m - Cv,m = R

Where Cp,m and Cv,m are intensive property heat capacities conveyed on a per mole basis at
steady pressure and stable volume, correspondingly.

Specific heat capacity

The specific heat capacity of a substance on a per mass basis is

C= δC/δm'

Which in the absence of phase transitions is equivalent to

c = Em = C/m = C/ρV'

Where C is the heat capacity of a body made of the material in question,

m is the mass of the body,

V is the volume of the body, and

Ρ = m/V

is the density of the material.

For gases, and as well for other substances under high pressures, there is require to
differentiate between dissimilar boundary conditions for the processes under consideration
(because values differ significantly between different conditions). Typical procedures for that
heat capacity may be described contain isobaric (constant pressure, dp = 0) or isochoric
(constant volume, dV = 0) processes. The equivalent specific heat capacities are expressed as

Cp = (δc/ δm)p

Cv = (δC/δm)v

A related parameter to c is Cv -1, the volumetric heat capacity. In engineering practice, C v for
solids or liquids frequently signifies a volumetric heat capacity, rather than a constant-volume
one. In these cases, the mass-specific heat capacity (exact heat) is frequently explicitly
written through the subscript m, as Cm. Of course, from the above associations, for solids one
writes

C m = C/m = cV/ Ρ.

For pure homogeneous chemical compounds by established molecular or molar mass or a

molar quantity is established, heat capacity as an intensive property can be expressed on a per
mole basis instead of a per mass basis via the subsequent equations equivalent to the
per mass equations:

Cp,m = (δC/δn)p= molar heat capacity at constant pressure

Cv,m = (δC/δn)v= molar heat capacity at constant volume

Where n = number of moles in the body or thermodynamic system. One may term to such a
'per mole' quantity as molar heat capacity to differentiate it from precise heat capacity on a
per mass basis.

Dimensionless heat capacity

The dimensionless heat capacity of a material is

C* = C/nR = C/NK

Where

C is the heat capacity of a body made of the material in question (J/K)

n is the amount of matter in the body (mol)

R is the gas constant (J/(K·mol) N is the number of molecules in the body. (Dimensionless)

k is Boltzmann's constant (J/(K·molecule)

Solid phase
Fig: The Dimensionless Heat Capacity Divided via three, as a Function of Temperature as
Predicted by the Debye model and by Einstein's Earlier Model

The horizontal axis is the temperature separated via the Debye temperature. As we know that,
as supposed, the dimensionless heat capacity is zero at absolute zero, and increases to a value
of 3 as the temperature becomes much larger than the Debye temperature. The horizontal line
above the plots corresponds to the classical limit of the Dulong-Petit law.

For issue in a crystalline solid phase, the Dulong-Petit law, that was computed empirically,
states that the mole-specific heat capacity supposes the value 3 R. Indeed, for solid metallic
chemical components at room temperature, molar heat capacities range from about 2.8 R to
3.4 R (beryllium being a notable exception at 2.0 R).

The theoretical maximum heat capacity for superior multi-atomic gases at higher
temperatures as well approaches the Dulong-Petit limit of 3 R, so long as this is computed per
mole of atoms, not molecules. The cause is that gases through extremely huge molecules, in
theory have approximately the similar high-temperature heat capacity as solids, lacking only
the (small) heat capacity contribution that comes from potential energy that can't be stored
between divide molecules in a gas. The Dulong-Petit "limit" consequences from the
equipartition theorem, and as these is only valid in the standard limit of a microstate
continuum that is an elevated temperature limit. For light and non-metallic elements, in
addition to most of the ordinary molecular solids depend on carbon compounds at standard
ambient temperature, quantum results might as well play a significant role, as they do in
multi-atomic gases. Such outcomes generally join to provide heat capacities lower than 3 R
per mole of atoms in the solid, even though heat capacities computed per mole of molecules
in molecular solids might be more than 3R. For instance, the heat capacity of water ice at the
melting point is about 4.6 R per mole of molecules, but only 1.5 R per mole of atoms. The
lower number consequences from the 'freezing out' of possible vibration modes for light
atoms at correctly low temperatures, just as in many gases. Such results are seen in solids
more often than liquids: for instance the heat capacity of liquid water is once more close to
the theoretical 3 R per mole of atoms of the Dulong-Petit academic maximum.

For a more modern and exact analysis of the heat capacities of solids, particularly at low
temperatures, it is helpful to employ the thought of phonons.
A Classical Approach to Heat Capacity

A good deal of insight might be attained from an extremely easy model of a solid. Consider
the solid to be a 3 dimensional lattice of atoms in that the atoms are held near equilibrium
positions via forces. If the force on an atom is proportional to its digression from its
equilibrium position then it is termed a harmonic oscillator. For zero deviation the force is
zero so the force for tiny deviations is proportional to the deviation. Therefore any these solid
can be believed to be composed of harmonic oscillators. In a cubic lattice the atoms can
oscillate in three directions.

The standard energy E of a harmonic oscillator in one dimension is kT, where k is

Boltzmann's constant. In 3 dimensions the average energy is 3kT. If there are N atoms in the
lattice then the internal energy is U= N(3kT). Let A be Avogadro's number (6.025×1023).
Then separating and multiplying the equation of U by A gives

U = (N/A)(3AkT)

The ratio (N/A) is the number of moles of the substance, n, and Ak is denoted as R. Thus

U = n(3RT)

so

UM = (U/n) = 3RT

The heat capacity per unit mole of a substance at constant pressure is then defined as

Cp = (∂UM/∂T)

and thus from the above Cp = 3R

The value for Cp of 3R is about 6 calories per degree Kelvin. This is identified as the Dulong
and Petit value. It is a good approximation for the calculated values for solids at room
temperatures (300°K). At low temperatures the Dulong and Petit value isn't a good
approximation. Below is exposed the heat capacity of metallic silver as a function of
temperature.
Fig: Heat Capacity for Silver at Different Temperatures

The shape of the curve for T near zero is of interest. It appears to be proportional to a power
of T, say T² or T³.

A Quantum Mechanical Derivation of Heat Capacity

According to Planck's law for the distribution of energy for an ensemble (collection) of
harmonic oscillators the average energy E is given by

E = hω/[exp(hω/kT) - 1]

Where h is Planck's constant h divided by 2*pi; and ω is the characteristic frequency

(circular) of the oscillators. This frequency is in the nature of a parameter for the substance
and has to be determined empirically.

For temperature such that kT is much larger than hω the denominator becomes approximately
hω/kT so E is approximately kT.

In general though

U = NE = N3hω/[exp(hω/kT) - 1]

UM = 3Ahω/[exp(hω/kT) - 1]

and therefore

Cp = -3Ahω/[exp(hω/kT) - 1]²[exp(hω/kT)](-hω/kT²)

With a little rearrangement this can be put into the form

Cp = 3R (hω/kT) ²exp(hω/kT)/[exp(hω/kT) - 1]²

Now if the numerator and denominator are separated via [exp(hω/kT)]² the consequence is
Cp = 3R(hω/kT)²exp(-hω/kT)/[1 - exp(-hω/kT)]²

The attempt to attain the limit of this expression as T→0 generates the ambiguous result of
∞/∞. The application of l'Hospital's Rule 2 time's finally produces the consequence that the
limit of Cp is zero as T→0.

The Heat Capacity Function for Low Temperatures

As mentioned above the empirical heat capacity curve for silver seems to be proportional to
T² or T³ for tiny values of T. The graph of the quantum mechanical heat capacity function
obtained above specifies that for values of T near zero the heat capacity function is zero and
flat.

Fig: Heat Capacity for Solids at Different Temperatures

To examine the behaviour of the heat capacity function for small T it simplify matters let
hω/k, that has the dimensions of temperature, be signified as θ. This parameter is sometimes
termed the Einstein temperature since it was Einstein who 1 st formulated this line of analysis.
(Einstein was far more adept at realizing the implications of the quantization of energy
establish via Planck than Planck himself.) The heat capacity function is then:

Cp = 3R (θ/T)²exp(-θ/T)/[1 - exp(-θ/T)]²

Matters can be made even simpler through replacing θ/T with z. Then

Cp = 3Rz²exp (-z)/[1 - exp(-z)]²

and

ln(Cp) = ln(3R) + 2ln(z) - z - 2ln[1 - exp(-z)]

This means that ln (Cp) →-∞ as z→+∞; i.e., Cp→0 as T→0.

Limit using l'Hospital's Rule

Cp = 3R(hω/kT)²exp(-hω/kT)/[1 - exp(-hω/kT)]²

The term [1 - exp(-hω/kT)]² approaches the limit of 1 as T→0 so let us ignore that term. Thus

Cp = 3R(hω/kT)²/exp(hω/kT)

and to simplify matters let hω/k, which has the dimensions of temperature, be denoted as θ.
Then

Cp = 3R(θ/T)²/exp(θ/T)

When T goes to zero the above term goes to ∞/∞. By l'Hospital's Rule we should consider the
limit of the derivatives of the numerator and denominator. Therefore

3R(2(θ²)(-1/T³)/(exp(θ/T)(-θ/T²) = 6Rθ(1/T)/exp(θ/T)

Which, as T→0, goes to ∞/∞

Therefore l'Hospital's rule must be applied again, which gives

6Rθ (-1/T²)/(exp(θ/T)(θ/T²) = 6R/exp(θ/T) which has a limit of zero as T→0.

Therefore Cp → 0 as T→0.

Heat Capacity at Absolute Zero

From the definition of entropy

TdS = δQ

We can compute the absolute entropy via integrating from zero kelvin temperature to the
final temperature Tf

S(Tf) = ∫t=0 Tf SQ/T = ∫0 Tf δQ/dT*dT/T = ∫0Tf C(T)* dT/T

The heat capacity must be zero at zero temperature in order for the above integral not to yield
infinite absolute entropy, therefore violating the third law of thermodynamics. One of the
strengths of the Debye model is that (unlike the preceding Einstein model) it predicts the
proper mathematical form of the approach of heat capacity toward zero, as absolute zero
temperature is approached.

Tutorsglobe: A way to secure high grade in your curriculum (Online Tutoring)

Expand your confidence, grow study skills and improve your grades.

Since 2009, Tutorsglobe has proactively helped millions of students to get better grades in
school, college or university and score well in competitive tests with live, one-on-one online
tutoring.
Using an advanced developed tutoring system providing little or no wait time, the students
are connected on-demand with an expert at [Link] Students work one-
on-one, in real-time with a tutor, communicating and studying using a virtual whiteboard
technology. Scientific and mathematical notation, symbols, geometric figures, graphing and
freehand drawing can be rendered quickly and easily in the advanced whiteboard.

Free to know our price and packages for online chemistry tutoring. Chat with us or submit
request at info@[Link]