Chemistry 433 The Third Law of Thermodynamics
The third law of thermodynamics states that every substance
has a positive entropy, but at zero Kelvin the entropy is
Lecture 12 zero for a perfectly crystalline substance. The third law
introduces a numerical scale for the entropy. Stated
The Third Law succinctly:
S(0) = 0 for all perfectly ordered crystalline materials.
It is commonly said that all motion ceases at absolute zero.
Certainly all translation and rotation have ceased at absolute
NC State University zero. However, the nuclei still vibrate about their equilibrium
positions in so-called zero point motion. However, all
molecules are in their lowest vibrational state and entropy is
zero in any case provided there are no imperfections in the
crystal.
Residual Entropy CO: an Imperfect Crystal
The first statistical picture of entropy was that of Boltzmann. The molecule CO has a very small dipole moment and
The function W that represents the number of ways we can there is a finite chance that CO will crystallize as
distribute N particles into a number of states. Using the CO:CO:CO instead of CO:OC:CO. For each CO molecule
function W the entropy can be expressed as: there are two possible orientations of the molecule, therefore
S = kB ln W there are two ways each CO can exist in the lattice.
y
At zero Kelvin the system is in its lowest energy
gy state. For The number of ways y pper molecule is w = 2 for each CO.
a perfect crystal there is only one way to distribute the energy If we have N CO molecules there are wN ways or 2N ways
and W = 1, therefore S = 0. that all of the CO can be distributed. Therefore, the entropy
However, the entropy not equal to zero at T = 0 K if the at zero Kelvin is
substance is not a perfect crystal. Although the residual S = k ln W = k ln(wN) = Nk ln w = nR ln 2.
entropy in such cases is a small correction to the entropy The entropy at zero Kelvin is known as residual entropy.
calculated for chemical reactions it still leads to an important There are number of substances that show similar statistical
concept. variations in orientation that lead to a residual entropy.
Question Question
Suppose there are four ways the the molecule CFClBrI can Suppose there are four ways the the molecule CFClBrI can
be oriented in a crystal lattice at zero Kelvin. What is the be oriented in a crystal lattice at zero Kelvin. What is the
molar residual entropy? molar residual entropy?
A. 4R ln(2) A. 4R ln(2)
( )
B. 2R ln(4) ( )
B. 2R ln(4)
C. R ln(2) C. R ln(2)
D. R ln(4) D. R ln(4)
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Question Question
Which phrase best summarizes residual entropy? Which phrase best summarizes residual entropy?
A. the entropy of imperfect crystals A. the entropy of imperfect crystals
B. the entropy of the lowest energy state B. the entropy of the lowest energy state
C. the entropy of rotation C. the entropy of rotation
py of residues
D. the entropy py of residues
D. the entropy
The Temperature The temperature dependence of
Dependence of Entropy the heat capacity
We have seen calculations for the entropy change for processes.
However, it is also possible to calculate the absolute entropy. The third law of thermodynamics shows that
We can begin with the definition dS = dqrev/T. The heat Cp → 0 as T → 0 K.
transferred during a process at constant volume is It is necessary to treat Cp(T) as a function of temperature for
dqv,rev = CvdT. Thus, the entropy change at constant volume is: this reason alone. The Einstein and Debye theories of heat
capacity can be used to determine the functional form of the
T
ΔS = S(T) – S(0) =
CV(T)dT heat capacity of at these low temperatures. The Debye law
0 T states that the heat capacity depends on T3 near T = 0 K.
We have kept the equation general by showing Cv(T) as a
function of temperature. This calculation of the entropy is At temperatures close to T = 0, CV,m = aT3
valid only at constant V. At constant P we find an analogous
expression. Starting with the heat transferred, dqp,rev = CpdT. The constant a is an empirical constant. For practical calculation
We have T
CP(T)dT of the entropy experimental values can be used and the
ΔS = S(T) – S(0) =
0 T integrals are evaluated numerically.
Question Question
If there is no residual entropy then at T = 0 K we can state If there is no residual entropy then at T = 0 K we can state
that: that:
A. S > 0 and CP > 0 A. S > 0 and CP > 0
B. S = 0 and CP > 0 B. S = 0 and CP > 0
C. S > 0 and CP = 0 C. S > 0 and CP = 0
D. S = 0 and CP = 0 D. S = 0 and CP = 0
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Question Question
Consider the statement CP 0 as T 0. Which Consider the statement CP 0 as T 0. Which
consequence is valid. consequence is valid.
A. It is harder to heat matter near absolute zero, that is A. It is harder to heat matter near absolute zero, that is
it requires more energy per degree of temperature rise. it requires more energy per degree of temperature rise.
B. It is easier to heat matter near absolute zero,, that is B. It is easier to heat matter near absolute zero,, that is
it requires less energy per degree of temperature rise. it requires less energy per degree of temperature rise.
C. It gets easier to reach absolute zero because it is easier C. It gets easier to reach absolute zero because it is easier
cool matter at lower temperature. cool matter at lower temperature.
D. Both B and C are correct. D. Both B and C are correct.
Absolute Entropy Graphical representation
The absolute entropy can be calculated from 0 to any
temperature T using the integral of the function CP(T)/T.
If there is a phase transition between 0 and temperature T
we can also calculate the contribution to the entropy from
the transition.
Solid
Tfus
Cp(T)dT Δ fusH Tvap
Cp(T)dT Δ vapH T
Cp(T)dT
S(T) = + + + +
0
T Tfus Tfus
T Tvap Tvap
T
The heat capacity of each phase is different and the heat
capacities are also a function of temperature. Remember
that the heat capacity approaches zero and the temperature
Tfus
goes to zero so that the Cp is a strong function of T at very Cp(T)dT
S(T) =
low temperature. 0
T
Graphical representation Graphical representation
Liquid
Solid Solid
Tfus
Cp(T)dT Δ fusH
Tfus
Cp(T)dT Δ fusH Tvap
Cp(T)dT Δ vapH
S(T) = + S(T) = + + +
0
T Tfus 0
T Tfus Tfus
T Tvap
3
Graphical representation Graphical representation
Liquid Liquid
Solid Solid
Tfus
Cp(T)dT Δ fusH Tvap
Cp(T)dT Tfus
Cp(T)dT Δ fusH Tvap
Cp(T)dT Δ vapH
S(T) = + + S(T) = + + +
0
T Tfus Tfus
T 0
T Tfus Tfus
T Tvap
Graphical representation Graphical representation
Gas Gas
Liquid Liquid
Solid Solid
Tfus
Cp(T)dT Δ fusH Tvap
Cp(T)dT Δ vapH T
Cp(T)dT Tfus
Cp(T)dT Δ fusH Tvap
Cp(T)dT Δ vapH T
Cp(T)dT
S(T) = + + + + S(T) = + + + +
0
T Tfus Tfus
T Tvap Tvap
T 0
T Tfus Tfus
T Tvap Tvap
T
Absolute Entropies can be used to The standard reaction entropy
calculate Reaction Entropies
Entropies are tabulated in order to facilitate the calculation The standard reaction entropy, ΔrS , is the difference
of the entropy change of chemical reactions. For the between the standard molar entropies of the reactants
general reaction and products, with each term weighted by the
aA + bB → yY + zZ stoichiometric coefficient.
the standard entropy change is given by Δ r S ∅ = Σ νSm∅(p
(products)) – Σ νSm∅((reactants))
ΔrSo = yS
So[Y] + zS
So[Z] - aS
So[A] - bSo[B]
where the absolute entropies So are molar quantities. The standard state is for reactants and products at 1 bar
of pressure. The unit of energy used is J/mol-K.
Note the significant difference compared to enthalpy. There
is no such thing as an absolute enthalpy. Instead, we used IMPORTANT: Do not confuse entropy and enthalpy.
a reference of the elements in their standard states. In One common mistake is to set the entropies of elements
that case the enthalpy of formation was set arbitrarily to zero. equal to zero as one does for enthalpies of formation.
Since entropies are zero and T = 0 K we can use So as an Elements have an entropy that is not zero (unless the
absolute quantity. temperature is T = 0 K).
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An example: formation of H2O Question
We apply the absolute entropies of H2, O2 and H2O to the Consider the formation of CO2.
calculation of the entropy of reaction for: C(s) + O2(g) CO2(g)
2H2(g) + O2(g) 2 H2O(l)
The entropy change is: Which is correct?
ΔS = 2 S (H2O, l) - S(O2, g) - 2S(H2, g) A. ΔS = 0 (equilibrium)
= 2(70) - 2(131) - 205 J/mol-K B. ΔS = ΔH/T (phase transition)
= - 327 J/mol
J/mol-KK C ΔS = S(CO2, g) - S(O2, g) (S = 0 for solids)
C.
D. ΔS = S(CO2, g) - S(O2, g) - S(C, s) (reaction)
This result is not surprising when you consider that 3 moles
of gas are being consumed. A gas has a greater number
of translational degrees of freedom than a liquid.
On the other hand, it is difficult (at first) to understand how
a spontaneous reaction can have such a large negative
entropy.
Question The spontaneity of chemical reactions
Consider the formation of CO2.
C(s) + O2(g) CO2(g) The spontaneity of chemical reactions must be understood
by consideration of both the system and the surroundings.
Which is correct? This is one of the most subtle points of thermodynamics.
A. ΔS = 0 (equilibrium) The heat dissipated by the negative enthalpy change in the
B. ΔS = ΔH/T (phase transition) reaction to make water results in a large positive entropy
C ΔS = S(CO2, g) - S(O2, g) (S = 0 for solids)
C. changeg in the surroundings.
g In fact,, the reaction to make
D. ΔS = S(CO2, g) - S(O2, g) - S(C, s) (reaction) water proceeds with explosive force. The heat dissipated
in the surroundings ΔrH is also an entropy term. The entropy
change in the surroundings is:
∅
∅ Δ rH
Δ r Ssurr =
T
The entropy change of the surroundings is:
ΔrS = -(-572 kJ/mol)/298 K = + 1.92 x 103 J/mol-K
which is much larger than the negative entropy change of the
system (-327 J/mol-K).
Question Question
An endothermic reaction can be spontaneous if: An endothermic reaction can be spontaneous if:
A. ΔS > 0 A. ΔS > 0
B. ΔS < 0 B. ΔS < 0
C. ΔS = 0 C. ΔS = 0
D. none of the above D. none of the above