THE SECOND LAW OF THERMODYNAMICS

Rolling a large boulder uphill is work. So is cleaning your room

or mowing the lawn. You know intuitively that any activity that

requires you to expend energy is a form of work. A physicist

defines work more generally as displacement of an object against

some force—rolling that boulder uphill against the force of

gravity, for example, or moving an electron against the force that

attracts it to an atomic nucleus. The biologist’s definition of work

is even broader, encompassing activities such as the synthesis of

organic molecules, moving solutes across cellular membranes,

osmosis, muscle contraction, and the dynamics of ecosystems. In

effect, virtually any activity that consumes energy can be considered

work. It should not be too surprising, then, that a biologist’s

principal concern with energy is whether or not that energy is

available to do work.

This view simplifies things to the extent that it leaves only

two kinds of energy—energy that can do work and energy that

can not do work. Energy that is available to do work is called

free energy or Gibbs free energy in honor of J. W. Gibbs, a 19th

century physical chemist who introduced the concept. Free

energy is assigned the symbol G. This book is about photosynthesis

and respiration, so let’s talk about free energy in the

context of these two reactions. In the simplest possible terms,

photosynthesis and respiration can be expressed as a reversible

chemical reaction:

A Short Course in Bioenergetics 29

Respiration

C6H1206 + 602 <—————————> 6CO2 + 6H2O + Energy

Glucose Carbon dioxide

Photosynthesis

A molecule of glucose has a relatively high free energy, while

the free energy of its equivalent in the form of six molecules of

carbon dioxide and water is much lower. We don’t need to know

the absolute free energy values for glucose or for carbon dioxide

plus water. Only the difference in free energy (expressed as ÆG)

between the two states is important because that is the energy

that is available to do work.

The difference in free energy between the energy of glucose

and the energy of carbon dioxide plus water amounts to 2,869 kJ

(686 kcal) per mole (the atomic weight of a substance, expressed

in grams). When plants synthesize glucose from carbon dioxide

and water, this amount of energy must be obtained from somewhere

else in order to make up the difference in free energy. In

photosynthesis, this energy is supplied by light. When one mole

of glucose is broken down to carbon dioxide and water, the 2,869

kJ of energy is released. This is the amount of energy that is available

to do work. When energy is consumed in a reaction, as it is

in photosynthesis, the value of ÆG is positive. When energy is

released, as it is in respiration, the value of ÆG is negative.

A reaction that proceeds with a release of free energy (ÆG negative)

is called an exergonic reaction. A reaction that requires an

input of free energy (ÆG positive) to make it happen is called an

endergonic reaction. Put another way, an exergonic reaction is one

in which the free energy of the products is less than the free energy

of the reactants; an endergonic reaction is one in which the free

energy of the products is greater than the free energy of the reactants.

Only exergonic reactions will occur spontaneously. Solutes

will always flow from a region of higher concentration to a region

30 Photosynthesis and Respiration

of lower concentration and heat will always flow from a warm

body to a cold body. The oxidation of glucose to carbon dioxide

and water is a spontaneous reaction, but the reverse reaction is

not. Despite the large quantities of carbon dioxide and water in

the atmosphere, they have never been known to spontaneously

recombine to form glucose.

Every time work is done or energy is converted from one form

to another, some of the energy inevitably ends up in a form that

is not available to do any further work. This form of energy is

called entropy. Entropy is an obscure concept, usually described as

a measure of disorder or randomness in a system. Whenever work

is done, such as when gasoline is burned in an automobile engine,

some of the energy is lost as heat that eventually dissipates into

the environment. The energy of the gasoline is distinctly non-random—

it is right there in the tank—but the heat generated as the

gasoline is burned eventually becomes uniformly distributed

throughout the universe.

As another example, consider a sugar molecule such as

glucose. Glucose is highly ordered—we can predict with a fair

degree of certainty the location of the six carbon atoms in the

molecule at any given time. Therefore, the entropy of glucose is

low. Those same six carbon atoms in the form of six individual

carbon dioxide molecules, however, are free to randomize

throughout the environment and their position at any point in

time would be highly unpredictable. Therefore, the entropy level

of the individual carbon dioxide molecules is high.

One consequence of thermodynamic laws is that spontaneous

reactions always lead to an increase in entropy. This is about as

much as we need to know about entropy, except perhaps to stress

the inverse relationship between free energy and entropy. When

the free energy level of a molecule or system is high, the entropy

is low; when the free energy level is low, the entropy is high.

We can now state the second law of thermodynamics: the

entropy of the universe tends toward a maximum. The obvious