REVIEW
Thermodynamics and living organisms: We are all law-abiding citizens
The first two laws of thermodynamics are important to understanding biochemical
reactions. The first law states that energy can neither be created nor destroyed,
and the second law states that the entropy, or disorder, of the universe must
increase with every process. Willard Gibbs derived a formula that aids us in
understanding how thermodynamic principles govern chemical reactions:
DG = DH
– TDS |
Where:
DG = Gibbs Free Energy Change
DH = Enthalpy change
DS = Entropy change
T = Temperature |
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The Gibbs Free Energy Change of a reaction (DG)
tells us whether a reaction is thermodynamically possible. Reactions with a
negative DG are spontaneous, meaning they
have a reasonable probability of occurring naturally, without energy input.
REACTION
SPONTANEITY |
Sign of DG |
Column 2 |
Positive (+) DG |
Nonspontaneous |
DG = 0 |
At equilibrium |
Negative (–) DG |
Spontaneous |
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Keep in mind that the DG function does not
impact the rate, or speed, of a reaction. Reactions with large negative DG
values may still occur very slowly.
Because the DG of a reaction varies with
reactant and product concentrations, temperature, and pressure, biochemists agreed
on standard conditions for reporting DG values.
The standard conditions are 1 atmosphere of pressure, a temperature of 298 K,
and reactant and product concentrations of 1 M, with the exception of H+,
which may be present at physiological concentrations (neutral pH). The standard
free energy change of a reaction is denoted by DG°´.
The DG of a reaction is related to the standard
free energy change for the reaction, DG°´,
by the following relationship:
DG |
= |
DG°´ |
+ |
RT ln |
[C][D] |
|
[A][B] |
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Where:
R is the gas constant (8.3145 J mol–1K–1)
T is the temperature (in Kelvin) |
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Since DG = 0 at equilibrium and the ratio
of products to reactants is the equilibrium constant Keq, it follows
that
Thus, DG°´ is the driving force
that pushes reactants and products toward equilibrium.
The Thermodynamics Police: No violation of the laws of thermodynamics have
ever been observed
There is an argument that has circulated for years that purports to prove that
the theory of evolution is incorrect because it violates the laws of thermodynamics.
In this argument, evolution (the theory that the complex plants and animals
that inhabit the Earth today evolved from simple, self-replicating molecules)
is said to violate the second law of thermodynamics, because the entropy of
a highly ordered animal is much lower than the entropy of a simple molecule.
Thus, the story goes, the molecules that make up living organisms have moved
from a state of disorder to a state of order over millions of years, a clear
violation of the law that states that entropy is always increasing.
The problem with this line of reasoning is that it treats a living organism
as a closed system that does not interact with its environment. Reactions that
increase the order of one part of the system are always offset by an increase
of disorder in another part of the system, and it takes energy to produce order
(anyone who has ever tried to keep a room clean can attest to that!). Thus,
our bodies grow at the expense of the order of the food we ingest, ice cubes
are formed in the freezer at the expense of heat released by the refrigerator,
and cans are stacked on the shelf as our muscles break down glucose to do the
work. We are citizens of the universe; the biochemical reactions within our
bodies follow the laws of thermodynamics.
Example 7: Perpetual motion
Your friend, an engineering major, tells you that for her class project she
will try to build a perpetual-motion machine. How can you use your knowledge
of thermodynamics to convince her to change her project before she flunks
the course?
Answer
Perpetual motion machines can succeed only if energy useful for doing work
continually circulates through the machine, keeping it running forever without
energy input. From studying the laws of thermodynamics through the formula
DG = DH
– TDS, you know that in
any process, some useful energy is always lost to an increase in entropy of
the system. Thus, if the process is repeated often enough, eventually all
the useful energy in the system will be consumed. This makes a perpetual motion
machine impossible, because it could work only if the machine never lost any
usable energy during its operation.
You have completed this exercise.
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