Entropy

 The measure of the disorderly dispersal of energy or matter used in thermodynamics is called
the entropy, S.

The direction of spontaneous change

 To understand the processes occurring in organisms, we need to identify the factors that drive
any physical or chemical change.
 The apparent driving force of spontaneous change is the tendency of energy and matter to
disperse.
 For example, the molecules of a gas may all be in one region of a container initially, but their
ceaseless disorderly motion ensures that they spread rapidly throughout the entire volume of
the container. Example:

Figure 1
 One fundamental type of spontaneous process is the disorderly dispersal of matter. This
tendency accounts for the spontaneous tendency of a gas to spread into and fill the
container it occupies. It is extremely unlikely that all the particles will collect into one
small region of the container. (In practice, the number of particles is of the order of
1023.) As shown in figure 1.
 Another fundamental type of spontaneous process is the disorderly dispersal of energy
represented by the color: red is high temperature, blue is low temperature. As shown in figure2.

As shown in figure 2.
 A similar explanation accounts for spontaneous cooling, but now we need to consider the
dispersal of energy rather than of matter. In a block of hot metal in which there is a temperature
gradient, the atoms in the hot region are oscillating vigorously, and the hotter the region, the
more vigorous their motion. The cooler region also consists of oscillating atoms, but their

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 motion is less vigorous. The vigorously oscillating atoms jostle their neighbors in the cooler
region, and the energy of the atoms in the block is handed on to the atoms in the cooler region.
The process continues until the vigor with which the atoms in the system are oscillating is
uniform. The opposite flow of energy is very unlikely. It is highly improbable that there will be a
net accumulation of energy in one region as a result of the jostling of molecules within the
block. In this case, the natural direction of change corresponds to the disorderly dispersal of
energy. Similar remarks apply to the cooling of a hot block to the temperature of its
surroundings.

 We have identified two basic types of spontaneous physical process:

1 Matter tends to disperse in disorder.
2 Energy tends to disperse in disorder.

Entropy and the Second Law

 To make progress with our quantitative discussion of biological structure and reactivity, we need
to associate the dispersal of energy and matter with the change in a state function.
 The measure of the disorderly dispersal of energy or matter used in thermodynamics is called
the entropy, S.
 When matter and energy disperse in disorder entropy increases.
 We can combine the two remarks above into a single statement known as the Second Law of
thermodynamics: The entropy of an isolated system tends to increase (The Second Law).

 Definition of entropy change:

 The change in entropy of a system is equal to the energy transferred as heat to it reversibly
divided by the temperature at which the transfer takes place.
 In everyday life ‘reversible’ means a process that can be reversed; in thermodynamics - it means
that a process can be reversed by an infinitesimal modification in some variable (such as the
pressure).
 Mechanical reversibility refers to the equality of pressure acting on either side of a movable
wall.
 Thermal reversibility refers to the equality of temperature on either side of a thermally
conducting wall.
 Reversible transfer of heat is smooth, careful, restrained transfer between two bodies at the
same temperature. By making the transfer reversible, we ensure that there are no hot spots
generated in the object that later disperse spontaneously and hence add to the entropy.
 The change in entropy—the change in the degree of disorder of energy and matter—is
proportional to the energy transfer that takes place by making use of random motion rather
than orderly motion.

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 Example 1: An organism inhabits a pond. In the course of its life, the organism transfers 100 kJ of
heat to the pond water at 0°C (273 K). What is the resulting change in entropy of the water due to
this transfer?

Solution

The entropy change accompanying heating.

 The entropy of a sample of gas increases as it expands because the molecules are able
to move in a greater volume and so are more widely dispersed.
 The entropy of a sample increase as the temperature is raised because the thermal
motion is greater at the higher temperature.
 Change in entropy on heating:

 Where C is the heat capacity of the system; if the pressure is held constant during the
heating, we use the constant-pressure heat capacity, Cp, and if the volume is held
constant, we use the constant-volume heat capacity, CV.
 For an infinitesimal change in temperature and we introduce negligible error if we keep
the temperature in the denominator of equal to T during that transfer. As a result, the
entropy increases by an infinitesimal amount is given by :

Example 2: Calculate the change in molar entropy when water vapor is heated from 160°C to 170°C
at constant volume. (CV,m = 26.92 J K−1 mol−1 .) Answer: +0.615 J K−1 mol−1

 When we cannot assume that the heat capacity is constant over the temperature range of
interest, which is the case for all solids at low temperatures, we have to allow for the variation
of C with temperature.
 All we need to recognize is the standard result from calculus, that the integral of a function
between two limits is the area under the graph of the function between the two limits. In this
case, the function is C/T, the heat capacity at each temperature divided by that temperature.

 Experimental basis of determining an entropy change:

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Example 3: The molar heat capacity of chloroform between 20°C and 37°C was found to fit the following
expression: Cp,m(T) = 91.74 J K−1 mol−1 + 0.075T J K−2 mol−1 What is the change in entropy over this range?

Solution

ΔSm = Sm(310 K) − Sm(293 K)