Sections 1 & 2: Spontaneous

Processes, Entropy, Laws of

Thermodynamics
Chapter 19: ChemicalThermodynamics
 Spontaneous Processes and Entropy
• First Law of Thermodynamics: Energy can neither be created nor
destroyed (a.k.a.: Conservation of Energy). This says, in essence,
that the total amount of energy in the universe is constant. Energy
can change forms, but all of it must be accounted for in any
chemical or physical process.
• This law answers such questions as:
• How much energy is involved in the change?
• Does energy flow into or out of the system?
• What form does the energy finally assume?
• Spontaneous Process: any process that occurs without
outside intervention. These processes may need a “push”
to get them started (activation energy), but once started,
they proceed without any further intervention. These
processes may be fast or slow – speed has nothing to do
with spontaneity.
Examples of spontaneous processes:
• A ball rolls down a hill, never up.
• Steel rusts in the open air, but never goes
back to iron metal and oxygen.
• Gas fills container uniformly. It does not
collect in one end of the container.
• Heat always flows from hot object to a cool
object, never reverse.
• Wood burns to form CO2 and H2O, but wood
is not formed when CO2 and H2O are heated
together.
• Below O 0C water freezes, and above O 0C, ice
melts.
Reversible v. Irreversible
• Processes that are spontaneous in one direction will not be spontaneous in the
reverse direction.
• Spontaneity has nothing to do with the rate of the process.
• Thermodynamics describes the direction and extent of reactions but does not
reference speed.
• A reversible process is one where the system can be restored to its original
condition with no change in the surroundings.
• An irreversible process is one that leaves the surroundings different when the
system is restored to its original condition.
• Reversible processes are those that reverse direction when a very small
(infinitesimal) change is made in some property of the system.
• All “real” processes are irreversible. Since spontaneous processes are real
processes, all spontaneous processes are irreversible.
• Energy has the tendency to “spread out”
 Entropy (S)
• A measure of the randomness or disorder of a
system.
• The driving force for a spontaneous process is
an increase in the total entropy of the universe.
• Entropy is a thermodynamic function that
describes the number of arrangements that
are available to a system. Nature proceeds
toward the states that have the highest
probabilities of existing.
• Positional Entropy: the probability of
occurrence of a particular state depends on the
number of ways (microstates) in which that
arrangement can be achieved:
• Ssolid < Sliquid << Sgas
Entropy and the Second Law of Thermodynamics
• Second Law of Thermodynamics: In
any spontaneous process there is
always an increase in the entropy of
the universe. In other words, the
entropy of the universe is always
increasing.
• For a given process or change to be
spontaneous, ∆Suniv must be
positive.
• ∆Suniv = ∆Ssys + ∆Ssurr
Temperature and Spontaneity
• Entropy changes in the surroundings are
primarily determined by heat flow
(remember, heat is the movement of thermal
energy from an area of higher TE toward an
area of lower TE).
• Exothermic reactions in a system at
constant temperature (isothermal) will
increase the entropy of the surroundings.
• Endothermic reactions in an isothermal
system will decrease the entropy of the
surroundings.
• The impact of the transfer of a given amount
of energy as heat to or from the surroundings
will be greater at lower temperatures.
• The sign of ∆S depends on the direction of
the heat (energy) flow:
exothermic = - ∆Ssystem,
endothermic = + ∆Ssystem.
• Nature tends to seek the lowest possible
energy.
• Entropy change is a state function,
depends only on the initial and final states
of a system

• (isothermal)
• Sample Exercise 19.2
Second Law of Thermodynamics

• For a reversible process, ΔS of the universe = 0

• For an irreversible process, ΔS of the universe will be greater
than 0.
• Therefore, the entropy of the universe increases for any
spontaneous process.