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Entropy

THERMODYNAMIC DEFINITION OF
ENTROPY

The thermodynamic definition of entropy


concentrates on the change in entropy, dS, that
occurs as a result of a physical or chemical
change (in general, as a result of .a process)
The definition is motivated by the idea that a
change in the extent to which energy is
dispersed depends on how much energy is
transferred as heat.

THERMODYNAMIC DEFINITION OF
ENTROPY

The
thermodynamic
definition of
entropy is based
on the
expression:

For a measurable
change between
two states i and f
this expression
integrates to:

THERMODYNAMIC DEFINITION OF
ENTROPY

That is, to calculate the difference


in entropy between any two states of
a system, we find a reversible path
between them, and integrate the
energy supplied as heat at each
stage of the path divided by the
temperature at which heating occurs.

THERMODYNAMIC DEFINITION OF
ENTROPY

Furthermore, because the temperature of the


surroundings is constant whatever the change, for
a measurable change.

That is, regardless of how the change is brought


about in the system, reversibly or irreversibly, we
can calculate the change of entropy of the
surroundings by dividing the heat transferred by
the temperature at which the transfer takes place.

Calculating the entropy change in the


surroundings.

To calculate the entropy


change in the surroundings
when 1.00 mol H2O(l) is
formed from its elements
under standard conditions at
298 K, we use H = 286
kJ from Table 2.7. The
energy released a heat is
supplied
to
the
surroundings, now regarded
as
being
at
constant
pressure, so qsur = +286 kJ.

Calculating the entropy


change in the
surroundings

Therefore,
ssur

= 2.86 105
J

298 K
ssur = +960 J
K1

This
strongly
exothermic reaction
results
in
an
increase
in
the
entropy
of
the
surroundings
as
energy is released
as heat into them.

Other way is to define


entropy change of the
system
alone.

dStotal = dSsystem +
dSsurroundings

After complete cycle:


Total heat supplied is:
Total work output is:
U = 0, so Q = W

So: Either W and Q must be negative: work is done


to the system and heat is extracted from it or W
and Q must be zero.
Thus: W = Q 0, or
Hence:
What if the cycle is reversible?
So: W = Q 0, So:
Hence: In order to be consistent with the first result,

Example of increasing entropy

Take a room and an ice cube as an


example. Let's say that the room is the
isolated system. The ice will melt and the
total entropy inside the room will increase.
This may seem like a special case, but it's
not. All what I'm really saying is that the
room as whole is not at equilibrium
meaning that the system is exchanging
heat, etc insideitself increasing entropy.