THE SECOND AND THIRD LAWS

CRITERIA OF SPONTANEITY
(1) A spontaneous change is one-way or unidirectional.
- For reverse change to occur, work has to be done.
(2) For a spontaneous change to occur, time is no factor.
- A spontaneous reaction may take place rapidly or very slowly.
(3) If the system is not in equilibrium state (unstable), a spontaneous change is inevitable.
- The change will continue till the system attains the state of equilibrium.
(4) Once a system is in equilibrium state, it does not undergo any further spontaneous
change
in state if left undisturbed.
- To take the system away from equilibrium, some external work must be done on the
system.
(5) A spontaneous change is accompanied by decrease of internal energy or enthalpy
(ΔH).
- It implies that only such reactions will occur which are exothermic.
- But the melting of ice and evaporation of rain water are endothermic processes which
proceed spontaneously.
- Clearly, there is some other factor in addition to ΔH which governs spontaneity. It is
the second law of thermodynamics which introduces this new factor that is called
entropy.

SECOND LAW OF THERMODYNAMICS

Entropy
- Measure of the degree of disorder or randomness.
- Entropy is an extensive property
- Entropy is a state function.

- The second law of thermodynamics states that: whenever a spontaneous process takes
place, it is accompanied by an increase in the total energy of the universe:
-
“The entropy of an isolated system increases in the course of a spontaneous change:
ΔStotalt > 0”
ΔSuniv = ΔSsyst + ΔSsurr

Thermodynamically irreversible processes (like cooling to the temperature of the surroundings

and the free expansion of gases) → spontaneous processes → increase in total entropy.
The second law, as stated above, tells us that when:
o irreversible = spontaneous process = ΔSuniv > 0

o reversible = ΔSuniv = 0 (constant)

Units Of Entropy = 1 eu (cal mol–1 K–1) = 4.184 J mol–1 K–1

Thermodynamic Implications:
Kelvin-Planck statement:
“No process is possible in which the sole result is the absorption of heat from a reservoir and
its complete conversion into work”
Rudolf Clausius statement:
“Heat does not flow spontaneously from a cool body to a hotter body.”
Trouton’s rule:
“Wide range of liquids give approximately the same standard entropy of vaporization (about
85 J/K mol) “
- The explanation of Trouton’s rule is that a comparable change in volume occurs when
any liquid evaporates and becomes a gas.
- Hence, all liquids can be expected to have similar standard entropies of vaporization.

Change in Entropy
1. Change In Entropy of The Surroundings

2. Change In Entropy for an Adiabatic Change

∆ Ssur = 0
- This expression is true however the change takes place, reversibly or irreversibly,
provided no local hot spots are formed in the surroundings.
- That is, it is true so long as the surroundings remain in internal equilibrium.
- If hot spots do form, then the localized energy may subsequently disperse
spontaneously and hence generate more entropy.

3. Change of Entropy in Reactions

4. The entropy changes for the isothermal expansion of a perfect gas

5. Phase Transitions

Exothermic
- If the phase transition is exothermic (ΔtrsH < 0, as in freezing or condensing),
then the entropy change of the system is negative. This decrease in entropy is
consistent with the increased order of a solid compared with a liquid and with the
increased order of a liquid compared with a gas.
- The change in entropy of the surroundings, however, is positive because energy
is released as heat into them, and at the transition temperature the total change in
entropy is zero.
Endothermic
o If the transition is endothermic (ΔtrsH > 0, as in melting and vaporization), then
the entropy change of the system is positive, which is consistent with dispersal of matter
in the system.
o The entropy of the surroundings decreases by the same amount, and overall the
total change in entropy is zero.

6. Standard Molar Entropies of Ions in Solution

- A positive entropy means that an ion has a higher molar entropy than H+ in water
and a negative entropy means that the ion has a lower molar entropy than H+ in
water.

7. ∆S at different conditions

8. Calorimetric Measurement of Entropy

-It is established in Topic 3A that the entropy of a system at a temperature T is related to
its entropy at T = 0 by measuring its heat capacity Cp at different temperatures and
evaluating the integral in eqn 3A.19
-The entropy of transition (ΔtrsH/Ttrs) for each phase transition between T = 0 and the
temperature of interest must then be included in the overall sum.
-For example, if a substance melts at Tf and boils at Tb, then its molar entropy above its
boiling temperature is given by:
Boltzmann Formula / Statistical Entropy
- The entry point into the molecular interpretation of the Second Law of thermodynamics is
Boltzmann’s insight, first mentioned in Foundations B, that an atom or molecule can
possess only certain values of the energy, called its ‘energy levels’.
- The continuous thermal agitation that molecules experience at T > 0 ensures that they are
distributed over the available energy levels.
- Boltzmann also made the link between the distribution of molecules over energy levels and
the entropy.
-
- Boltzmann proposed that the entropy of a system is given by:

where k = 1.381 × 10−23 J K−1 and W is the number of microstates

o If W = 1, which corresponds to one microstate (only one way of achieving a
given energy, all molecules in exactly the same state), then S = 0 because ln 1
= 0.
o If W > 1 and S > 0.

Microstates - The number of ways in which the molecules of a system can be arranged
while keeping the total energy constant.
. “A more disorderly distribution of matter and a greater dispersal of energy
corresponds to a greater number of microstates associated with the same total energy”

Ex. In particular, for a gas of

particles in a container, the energy
levels become closer together as
the container expands. As a result,
more microstates become possible,
W increases, and the entropy
increases, exactly as we inferred
from the thermodynamic definition
of entropy.
Gas Power Cycles – Use the change in properties of a gaseous system in order to convert
heat or work to a desired output.
CARNOT CYCLE
- A Carnot cycle, which is named after the French engineer Sadi Carnot, consists of four
reversible stages .
- most efficient cycle -composed of four steps
Step 1→2: Reversible isothermal
expansion
Step 2→3: Reversible adiabatic
expansion
Step 3→4: Reversible isothermal
compression
Step 4→1: Reversible adiabatic
compression

1. Reversible isothermal expansion from A to B at Th; the entropy change is qh/Th, where qh is
the energy supplied to the system as heat from the hot source.
2. Reversible adiabatic expansion from B to C. No energy leaves the system as heat, so the
change in entropy is zero. In the course of this expansion, the temperature falls from Th to Tc,
the temperature of the cold sink.
3. Reversible isothermal compression from C to D at Tc. Energy is released as heat to the cold
sink; the change in entropy of the system is qc/Tc; in this expression qc is negative.
4. Reversible adiabatic compression from D to A. No energy enters the system as heat, so the
change in entropy is zero. The temperature rises from Tc to Th.

The total change in entropy around the cycle is the sum of the changes in each of these four
steps:
“We note that any reversible cycle can be approximated as a collection of Carnot cycles and the
integral around an arbitrary path is the sum of the integrals around each of the Carnot cycles “

Calculation Parameters of Carnot cycle

A. Carnot Heat Engine

- Converts heat into usable work with the release of residual heat.

- A heat engine takes heat energy from high temperature reservoir and
concerts some of it into work, returning the unconverted heat to a low
temperature sink.
- Heat engine runs on a periodic cycle process that can yield work
continuously.

Carnot Theorem – Every perfect engine working reversibly between the

same temperature limits has the same efficiency, whatever be the working
substance

“All reversible engines have the same efficiency regardless of their construction”
“ No heat engine, no matter how well constructed, can convert all the heat from the high T
reservoir into work”
Thermodynamic Temperature
- Suppose we have an engine that is working reversibly between a hot source at a
temperature Th and a cold sink at a temperature T, then we know from eqn 3A.10 that:
B. Carnot Refrigerator
- Converts work in order to remove certain amount of heat.

C. Carnot Heat Pump

- Converts work in order to supply certain amount of heat; similar to refrigerator.

PHASE CHANGE
- Occurs at constant pressure (isobaric)
THIRD LAW
“The entropy of all perfect crystalline substances is zero at T = 0”

- The entropy of a substance varies directly with temperature. The lower the temperature, the
lower the entropy.

- For a perfect crystalline structure and at absolute zero temperature, the number of
permutations is just one.

Nernst Heat Theorem

“The entropy change accompanying any physical or chemical transformation
approaches zero as the temperature approaches zero: ΔS → 0 as T → 0 provided all
the substances involved are perfectly ordered.”

GIBBS FREE ENERGY

- Thermodynamically, a system has reached equilibrium if the change in Gibbs free energy ,
is zero.

Helmholtz energy/ Work Function, A

A=U −TS (3C.7)

- A = wrev
A decrease in the work function in any process at constant temperature gives the maximum
work that can be obtained from the system during any change.
criteria of spontaneous change as: dAT,V ≤0
Gibbs-Helmholtz Equation
- Used to determine the dependence of K in different temperatures
CLAUSIUS INEQUALITY
- When a change in the system occurs and there is a transfer of energy as heat between the
system and the surroundings, the Clausius inequality reads:

- We can develop this inequality in two ways according to the conditions (of constant volume
or constant pressure) under which the process occurs:

1. @ Constant Volume
- First, consider heating at constant volume. Then, in the absence of additional (non-
expansion) work, we can write dqV = dU; consequently:

- Because T > 0, at either constant internal energy (dU = 0) or constant entropy (dS = 0)
this expression becomes, respectively:

o The first inequality states that, in a system at constant volume and constant
internal energy (such as an isolated system), the entropy increases in a
spontaneous change. That statement is essentially the content of the Second
Law.

o The second inequality is less obvious, for it says that if the entropy and volume
of the system are constant, then the internal energy must decrease in a
spontaneous change.

o Do not interpret this criterion as a tendency of the system to sink to lower energy.
It is a disguised statement about entropy and should be interpreted as implying
that if the entropy of the system is unchanged, then there must be an increase in
entropy of the surroundings, which can be achieved only if the energy of the
system decreases as energy flows out as heat.

2. @ Constant Pressure
- When energy is transferred as heat at constant pressure, and there is no work other
than expansion work, we can write dqp = dH and obtain:

o The entropy of the system at constant pressure must increase if its enthalpy
remains constant (for there can then be no change in entropy of the
surroundings).
o Alternatively, the enthalpy must decrease if the entropy of the system is constant,
for then it is essential to have an increase in entropy of the surroundings.
Thermodynamic Relations, and Free Energies

MAXWELL RELATIONS