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Spontaneous Process

A spontaneous process is one where a system moves to a lower energy state by releasing free energy. It will occur without an external energy input. Whether a process is spontaneous depends on factors like temperature and pressure that determine the appropriate free energy change (Gibbs or Helmholtz). A negative free energy change indicates spontaneity while a positive change means the process is non-spontaneous but the reverse may be. Entropy changes also provide information on spontaneity based on changes in the system and surroundings.

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218 views

Spontaneous Process

A spontaneous process is one where a system moves to a lower energy state by releasing free energy. It will occur without an external energy input. Whether a process is spontaneous depends on factors like temperature and pressure that determine the appropriate free energy change (Gibbs or Helmholtz). A negative free energy change indicates spontaneity while a positive change means the process is non-spontaneous but the reverse may be. Entropy changes also provide information on spontaneity based on changes in the system and surroundings.

Uploaded by

shalini kumari
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© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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Spontaneous process

A spontaneous process is the time-


evolution of a system in which it releases
free energy and it moves to a lower, more
thermodynamically stable energy
state.[1][2] The sign convention for free
energy follows the general convention for
thermodynamic measurements, in which a
release of free energy from the system
corresponds to a negative change in the
free energy of the system and a positive
change in the free energy of the
surroundings.

Depending on the nature of the process,


the free energy is determined differently.
For example, the Gibbs free energy is used
when considering processes that occur
under constant pressure and temperature
conditions whereas the Helmholtz free
energy is used when considering
processes that occur under constant
volume and temperature conditions.

Because spontaneous processes are


characterized by a decrease in the
system's free energy, they do not need to
be driven by an outside source of energy.

For cases involving an isolated system


where no energy is exchanged with the
surroundings, spontaneous processes are
characterized by an increase in entropy.

Overview
In general, the spontaneity of a process
only determines whether or not a process
can occur and makes no indication as to
whether or not the process will occur. In
other words, spontaneity is a necessary,
but not sufficient, condition for a process
to actually occur. Furthermore, spontaneity
makes no implication as to the speed at
which as spontaneous may occur.

As an example, the conversion of a


diamond into graphite is a spontaneous
process at room temperature and
pressure. Despite being spontaneous, this
process does not occur since the energy
to break the strong carbon-carbon bonds
is larger than the release in free energy.

Using free energy to


determine spontaneity
For a process that occurs at constant
temperature and pressure, spontaneity can
be determined using the change in Gibbs
free energy, which is given by:

where the sign of ΔG depends on the signs


of the changes in enthalpy (ΔH) and
entropy (ΔS). The sign of ΔG will change
from positive to negative (or vice versa)
where T = ΔH/ΔS.

In cases where ΔG is:

negative, the process is spontaneous


and may proceed in the forward
direction as written.
positive, the process is non-
spontaneous as written, but it may
proceed spontaneously in the reverse
direction.
zero, the process is at equilibrium, with
no net change taking place over time.

This set of rules can be used to determine


four distinct cases by examining the signs
of the ΔS and ΔH.

When ΔS > 0 and ΔH < 0, the process is


always spontaneous as written.
When ΔS < 0 and ΔH > 0, the process is
never spontaneous, but the reverse
process is always spontaneous.
When ΔS > 0 and ΔH > 0, the process
will be spontaneous at high
temperatures and non-spontaneous at
low temperatures.
When ΔS < 0 and ΔH < 0, the process
will be spontaneous at low temperatures
and non-spontaneous at high
temperatures.

For the latter two cases, the temperature


at which the spontaneity changes will be
determined by the relative magnitudes of
ΔS and ΔH.

Using entropy to determine


spontaneity
When using the entropy change of a
process to assess spontaneity, it is
important to carefully consider the
definition of the system and surroundings.
The second law of thermodynamics states
that a process involving an isolated
system will be spontaneous if the entropy
of the system increases over time. For
open or closed systems, however, the
statement must be modified to say that
the total entropy of the combined system
and surroundings must increase, or,

.
This criterion can then be used to explain
how it is possible for the entropy of an
open or closed system to decrease during
a spontaneous process. A decrease in
system entropy can only occur
spontaneously if the entropy change of the
surroundings is both positive in sign and
has a larger magnitude than the entropy
change of the system:

and

In many processes, the increase in entropy


of the surroundings is accomplished via
heat transfer from the system to the
surroundings (i.e. an exothermic process).

See also
Endergonic reaction reactions which are
not spontaneous at standard
temperature, pressure, and
concentrations.
Diffusion spontaneous phenomenon
that minimizes Gibbs free energy.

References
View full list of citations
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