1st law of Thermodynamics,

enthalpy, Second law of

Thermodynamics: Entropy & Gibbs
Energy
Biophysics
According: Daniel Goldfarb and Paul Davidovits
Thermodynamics is the study of the relationship between
heat, work, and the associated flow of energy. After many decades of
experience with heat phenomena, scientists formulated two fundamental laws as the
foundation of thermodynamics. The First Law of Thermodynamics states
that energy, which includes heat, is conserved(It has been shown
by the theory of relativity that the conservation law must include matter which is
convertible to energy); that is, one form of energy can be converted
into another, but energy can neither be created nor destroyed.
This implies that the total amount of energy in the universe is
a constant. The second law, more complex than the first, can be stated in a
number of ways which, although they appear different, can be shown to be
equivalent. Perhaps the simplest statement of the Second Law of
Thermodynamics is that spontaneous change in nature occurs
from a state of order to a state of disorder.
• A consequence of the law of conservation of energy is that
a perpetual motion machine of first kind cannot exist, that is to
say, no system without an external energy supply can deliver an
unlimited amount of energy to its surroundings.
• Numerous attempts were made to construct a perpetual
motion machine which would produce work for eternity
without any consumption of fuel.
• The first law as expressed above needs qualification. Einstein
has shown that, matter and energy are equivalent and the
interrelationship is given by the famous Einstein equation
E = mc2 where E is the energy, m is the mass and c is the
velocity of light.
 Prehistory of First Law of Thermodynamics
One of the first to state the law of energy conservation was the German
physician Robert Mayer (1814–1878). In 1840 Mayer was the physician on
the schooner Java, which sailed for the East Indies. While aboard ship, he
was reading a treatise by the French scientist Laurent Lavoisier in which
Lavoisier suggested that the heat produced by animals is due to the slow
combustion of food in their bodies. Lavoisier further noted that less food is
burned by the body in a hot environment than in a cold one.
When the ship reached the tropics, many of its crew became sick with
fever. Applying the usual remedy for fever, Mayer bled his patients. He
noticed that the venous blood, which is normally dark red, was nearly as red
as arterial blood. He considered this a verification of Lavoisier’s suggestion.
Because in the tropics less fuel is burned in the body, the oxygen content of
the venal blood is high, giving it the brighter color.
Mayer then went beyond Lavoisier’s theory and suggested that in the body there is an
exact balance of energy (which he called force). The energy released by the food is
balanced by the lost body heat and the work done by the body. Mayer wrote in an
article published in 1842, “Once in existence, force [energy] cannot be annihilated— it
can only change its form.” Considerably more evidence had to be presented before
conservation of energy was accepted as a law, but it is interesting that such a
fundamental physical law was first suggested from the observation of human
physiology. Conservation of energy is implicit in all our calculations of energy balance
in living systems. Consider, for example, the energetics for the functioning of an
animal. The body of an animal contains internal thermal energy Et, which is the
product of the mass and specific heat, and chemical energy Ec stored in the tissue of
the body. In terms of energy, the activities of an animal consist of simply eating,
working, and rejecting excess heat by means of various cooling mechanisms
(radiation, convection, etc.). Without going into detailed calculations, the first law
allows us to draw some conclusions about the energetics of the animal. For example,
if the internal temperature and the weight of the animal are to remain constant (i.e.,
Ec and Et constant), over a given period of time the energy intake must be exactly
equal to the sum of the work done and the heat lost by the body. An imbalance
between intake and output energy implies a change in the sum Ec +Et.
 The First Law of Thermodynamics
Thermodynamics is the study of energy and how it operates in the physical universe. The first
law of thermodynamics is simple and intuitive. It states that any change to the amount of
energy contained in a system is equal to the amount of energy put into the system minus the
amount of energy taken out of the system.
ΔEsys = Ein - Eout
This makes sense and is just another way of saying that energy cannot be created or
destroyed. As an analogy, imagine a bucket of marbles. The first law says that any change to
the number of marbles in the bucket is equal to the number of marbles we put into the
bucket minus the number of marbles we take out.
What is less intuitively obvious is the more conventional way to write In practice we don’t
usually break up the right side of the equation in terms of whether the energy is coming in or
going out. Instead we break it up in terms of the type of energy entering or leaving our
system and let the sign on each energy term (positive or negative) indicate the direction of
energy flow. By convention we write the first law of thermodynamics like this
ΔU = q – w (1)
where U is the symbol for the internal energy of a system (what we previously called E sys),
q represents heat put into the system, and w is work done by the system.
 What Is a System?

All of the above assumes we know what

we mean by system. In thermodynamics, a
system is simply that part of the universe
that we are interested in. The rest of the
universe is called the surroundings.

ΔU = q – w (1)
• Thermodynamic systems are further qualified in terms of their contact with
the surroundings. An open system can exchange both matter and energy
with its surroundings. A closed system can exchange energy, but not matter.
An adiabatic system is thermally isolated from its surroundings; there is no
exchange of heat or matter, but it is possible for the system to do work on
its surroundings (or to have work done on it).
 State of a system
A system is said to be in a particular state
when specific values of the properties of
the system called as variables of state are
known. These variables of state may are:
Temperature, Pressure, Volume,
composition and so on..
Hence these thermodynamic properties
completely define the state of system.
• Ein - Eout = ΔU = q – W (1)
The quantity E, the internal energy, is thus Although the heat absorbed or the
a characteristic of the state of the system work done by the system might vary
and is not dependent on the way in which with the path but E is not dependent
that state has been reached. on the way in which state has been
reached.
Although the heat
absorbed or the work
done by the system
might vary with the
path but E is not
dependent on the way
in which state has
been reached.
 In living body energy conversion is performed within these 4
types of energy.

Internal energy of the system is the sum of all forms of energy

of this system (mechanical, thermal, chemical and electrical).
Work is the measure of energy conversion from one form to
another.

The first law of thermodynamics is simply the law of

conservation of energy. This law has been stated in
various ways but the basic idea is that energy can
neither be created nor destroyed; the only change
which energy can undergo is a transformation from
one form to another.
The first law of thermodynamics was defined in the
following ways:
1. The total energy of an isolated system always remains constant, although
there may be a change from one form to another.
2. The energy of an isolated system remains constant and whenever a quantity
of some form of energy disappears, an exactly equivalent quantity of some
other form of energy must be produced.
3. Any gain or loss of energy by the system must be exactly equivalent to the
loss or gain, respectively, by the surroundings of the system.
4. That whenever a certain quantity of energy is produced, an equivalent
amount of other form of energy must be used up.
5. Energy can neither be created nor destroyed, the only change which energy
can undergo is a transformation from one form to another.
6. The total energy of a system, plus its surroundings remains constant.
• Equation (ΔU = q – w) presents the first law in terms of heat energy on the
one hand, and all other forms of energy on the other, which we lump
together into a single term called work. This is like saying that any change
in the number of marbles in our bucket is equal to specifically the number
of yellow marbles we put into the bucket minus the number of all other
marbles we take out of our bucket. This is not the most obvious way to
break things up. At least, not until you consider that maybe there’s
something special about yellow marbles.

• Indeed this is the case: there is something special about heat as a form of
energy. In fact there are three reasons why heat is special. It is primarily
the first of these three reasons that explains why, by convention, we
account for heat separately from other forms of energy. But the other
reasons also provide motivation for thinking of heat separately.
 Heat Is Special
The first reason we account for heat separately is historical. The laws and equations
of thermodynamics were originally developed through the study of heat engines. A
heat engine is a motor that converts heat energy into motion, for example, a steam
engine or an internal combustion engine. This is why the conventional way to write
the first law of thermodynamics is in terms of heat put into a system and work
(motion) done by the system. Historically, almost all of our early experiences with
thermodynamics involved lighting fires, boiling water, and trying to get some useful
work out if it. The second reason heat is special is that heat is the only type of energy
that is always readily available to measure and possibly use. This might not seem the
case on a very cold winter’s day, but it’s true. Heat is the kinetic energy and random
motion of molecules. Even on a cold winter’s day molecules are constantly vibrating
or moving about. Even in solid ice, the crystallized water molecules are continually
vibrating. Molecular kinetic energy (heat), as we will see, can contribute to
biochemical processes. Molecular motion is always present. Only at a temperature of
absolute zero ( - 273.15°C)—far colder than the coldest of winter days (and certainly
far colder than we ever expect to find any living things that we study in biophysics)—
does molecular motion stop. The third reason heat is special is that heat is, in a
sense, the lowest form of energy. Heat is the least organized form of energy. It is this
disorganized quality of heat that also makes it often the most inefficient form of
energy from which to extract useful work.
 Difference between Heat and Other Forms of Energy
We defined heat as energy being transferred from a hotter to a colder body. Yet
when we examined the details of this energy transfer, we saw that it could be
attributed to transfer of a specific type of energy such as kinetic, vibrational,
electromagnetic, or any combination of these. For this reason, it may not seem
obvious why the concept of heat is necessary. In many cases, energy is being
transferred to or from a body by different methods, and keeping track of each of
these is often not possible and usually not necessary. No matter how energy enters
the body, its effect is the same. It raises the internal energy of the body. The
concept of heat energy is, therefore, very useful. The main feature that
distinguishes heat from other forms of energy is the random nature of its
manifestations. For example, when heat flows via conduction from one part of the
material to another part, the flow occurs through the sequential increase in the
internal energy along the material. This internal energy is in the form of random
chaotic motion of atoms. Similarly, when heat is transferred by radiation, the
propagating waves travel in random directions.
The radiation is emitted over a wide wavelength (color) range, and the phases of the
wave along the wave front are random. By comparison, other forms of energy are
more ordered. Chemical energy, for example, is present by virtue of specific
arrangements of atoms in a molecule. Potential energy is due to the well-defined
position, or configuration, of an object. While one form of energy can be converted
to another, heat energy, because of its random nature, cannot be completely
converted to other forms of energy. We will use the behavior of a gas to illustrate our
discussion. First, let us examine how heat is converted to work in a heat engine (for
example, the steam engine). Consider a gas in a cylinder with a piston. Heat flows
into the gas; this increases the kinetic energy of the gas molecules and, therefore,
raises the internal energy of the gas. The molecules moving in the direction of the
piston collide with the piston and exert a force on it. Under the influence of this
force, the piston moves. In this way, heat is converted into work via internal energy.
The heat added to the gas causes the molecules in the cylinder to move in random
directions, but only the molecules that move in the direction of the piston can
exert a force on it. Therefore, the kinetic energy of only the molecules that move
toward the piston can be converted into work. For the added heat to be completely
converted into work, all the gas molecules would have to move in the direction of
the piston motion. In a large ensemble of molecules, this is very unlikely.
• The odds against the complete conversion of 1 cal of heat into work can be
expressed in terms of a group of monkeys who are hitting typewriter keys at
random and who by chance type out the complete works of Shakespeare
without error. The probability that 1 cal of heat would be completely
converted to work is about the same as the probability that the monkeys
would type Shakespeare’s works 15 quadrillion times in succession. The
distinction between work and heat is this: In work, the energy is in an ordered
motion; in heat, the energy is in random motion. Although some of the
random thermal motion can be ordered again, the ordering of all the motion is
very improbable. Because the probability of completely converting heat to
work is vanishingly small, the Second Law of Thermodynamics states
categorically that it is impossible. Heat can be partially converted to work as it
flows from a region of higher temperature T1 to a region of lower temperature
T2. A quantitative treatment of thermodynamics shows that the maximum
ratio of work to the input heat is:
Work/heat input = 1 - T2/T1
 Work/heat input = 1 - T2/T1
Here the temperature is measured on the absolute scale. From this equation, it
is evident that heat can be completely converted into work only if the heat is
rejected into a reservoir at absolute zero temperature. Although objects can be
cooled to within a very small fraction of absolute zero, absolute zero cannot be
attained. Therefore, heat cannot be completely converted into work.
In thermodynamics energy is typically measured in units of calories or joules.
One calorie is the amount of energy it takes to increase the temperature of 1 g
of water from 14.5°C to 15.5°C at 1 atmosphere of pressure.
One joule is the amount of energy it takes to lift an object weighing 1 N a
distance of 1 m. That is, 1 joule (J) = 1 newton meter (Nm).

One calorie is equal to 4.184 J.

PROBLEM : A 225-lb (225 lb (pound)= 102.058 kg) -athlete drinks a glass of orange juice (120 Calories) and walks up to the
top of the Empire State Building. What is the change in his internal energy, assuming the only heat transfer is the 120
calories from the orange juice, and the only work done by the athlete is lifting his own weight to the 102nd floor? Assume 3
m per floor.
We are going to use Eq. ΔU = q – w (1) to solve the problem. To begin with, however, we need to know that food calories
are actually kilocalories. So when the problem says a glass of orange juice has 120 Calories, then in terms of the scientific
unit of energy called calorie, this is 120,000 calories (cal), or 120 kilocalories (kcal). The amount of heat entering our athlete
is 120 kcal, or 502 kJ (120 kcal X 4.184 kJ/kcal).
Work is force times distance.
Therefore the amount of work done is the weight of the athlete (the force) times the distance he is lifted.
Converting to SI units, 225 lb is about 1000 N of force. So the amount of work to lift the athlete to the 102nd floor is
1000 N x (102 floors x 3 m/floor) = 306,000 Nm = 306 kJ of work.

The change in the athlete’s internal energy is

ΔU = q – w = 502 kJ - 306 kJ = 196 kJ

The athlete’s internal energy has increased (by 196 kJ) because the glass of orange
juice contained more energy than is necessary to lift 225 lb to the top of Empire State
Building. Our athlete used up less than 2/3 the calories in the glass of orange juice. If you have some concept as to what it
feels like to walk up almost 2000 steps, and how you might feel after such a workout, then it may seem odd that walking up
102 flights of stairs burns off fewer calories than are in 2/3 of a glass of orange juice.
 Simplifying Assumptions
In science, we often make simplifying assumptions. We purposely assume something to be the case,
even though we know it’s not true, in order to keep things simple. Keeping things simple can allow us
to make a calculation or discover something that we would otherwise not be able to do or discover.
Then, after we understand our system better, after we have calculated what we need to calculate, we
can (if we choose) refine our calculations and refine our understanding by gradually removing or
changing our simplifying assumptions. Of course, the most important aspect of this is to know what
our assumptions are and to make a judgment as to whether the assumptions are reasonable or at
least practically workable. By practically workable we mean that (1) even if our assumptions are
wrong, we understand that they are wrong and we have some idea where they are off (or where they
differ from the more correct solution) and (2) most importantly the simplifying assumptions allow us
to accomplish something that we would otherwise not be able to accomplish without their help. As an
example of accomplishing something practical even with assumptions that are incorrect, imagine if we
were to measure the energy content in food by drinking a glass of orange juice, doing some work, and
seeing how much work we can get done before we get hungry again. If the athlete in Prob.1. got
hungry when he reached the top of the Empire State Building, we would say that the orange juice had
306 kJ of energy. To say such a thing, we have to make some simplifying assumptions, not the least of
which is the idea that the athlete could tell by his hunger when he has burned off the glass of orange
juice. Even so, this method still gives us some clue as to how much energy is in the orange juice.
Assuming the athlete can achieve some accuracy in reporting his hunger, even if the resulting energy
content is way off, we can still compare various foods, and get an idea of their energy content relative
to one another.
Or, at the very least we have a measure of how well various foods (relative to
one another) stave off hunger during exercise, which is somewhat related to
energy content of the food. This example is perhaps a bit far fetched, but you
get the idea. Making simplifying assumptions is a useful tool. So what are the
simplifying assumptions that we made in Prob. 1? Here are a few of them. You
should try to think of others. The first and probably largest assumption is that
100% of the energy of the orange juice is converted into work done by our
athlete. As a general rule, animals are not the most efficient heat engines.
Humans, at best, convert only about 10% of their caloric intake into useful
work. The majority of the energy content of the food we eat is either
dissipated as heat or excreted as waste. Another assumption we made,
explicitly mentioned in the problem, is that the only work done by the athlete
is lifting his own weight to the 102nd floor. This is not entirely correct. There is
also work done to pump blood around the body and work to expand and
contract the lungs. And there is even some work overcoming friction of the
athlete’s shoes against the floor and of air resistance while walking up stairs.
 Energy Requirements of People
All living systems need energy to function. In animals, this energy is used
to circulate blood, obtain oxygen, repair cells, and so on. As a result, even
at complete rest in a comfortable environment, the body requires energy
to sustain its life functions. For example, a man weighing 70 kg lying
quietly awake consumes about 70 Cal/h (1 cal 4.18 J; 1,000 cal 1 Cal; 1
Cal/h). Of course, the energy expenditure increases with activity. The
amount of energy consumed by a person depends on the person’s weight
and build. It has been found, however, that the amount of energy
consumed by a person during a given activity divided by the surface area
of the person’s body is approximately the same for most people.
Therefore, the energy consumed for various activities is usually quoted in
Area (m2) = 0.202 x W 0.425 H 0.725
Cal/m2-hr. This rate is known as the metabolic rate. The metabolic rates
for some human activities are shown in Table. To obtain the total energy Here W is the weight of the person
consumption per hour, we multiply the metabolic rate by the surface area in kilograms, and H is the height of
of the person. The following empirical formula yields a good estimate for the person in meters.
the surface area. The surface area of a 70-kg man of height 1.55m is about
1.70 m2 . His metabolic rate at rest is therefore (40 Cal/m2 -hr)×1.70m2 68
Cal/hr, or about 70 Cal/hr as stated in our earlier example. This metabolic
rate at rest is called the basal metabolic rate.
Living organism belongs to the open thermodynamic system.

Energy is scalar measure of defined

type substance movement while
transforming from one form to
another. As a characteristic of
substance movement, energy always
defines the ability of the system to
perform work.
Enthalpy (heat Content)
(heat changes at constant pressure)

To evaluate the heat transferred

in a constant pressure process,
it is more convenient to make use
of a function known as
enthalpy or heat content denoted
by the symbol H.
Enthalpy: The “heat of reaction”
• Enthalpy is another thermodynamic property that we need to understand.
Enthalpy is denoted by the symbol H, and is a measure of the internal
energy of a system. In the course of a reaction, the change in internal
energy between reactants and products, or ΔH, can be measured by the
heat absorbed or released during the course of a reaction (One caveat: this
holds true as long as the reaction is performed under constant pressure,
which is generally the case in biological systems). Because the enthalpy can
be measured as heat, ΔH is often called the heat of reaction. Reactions that
consume enthalpy (have a positive ΔH) are said to be endothermic (heat
consuming), while reactions that release enthalpy (have a negative ΔH) are
said to be exothermic (heat releasing).
 Enthalpy
Enthalpy (H) is a classic thermodynamic property of a system, defined as
the sum of the internal energy (U) of a system plus its pressure(P) times
its volume(V).
H= U+ PV (2)
Although it may not be intuitively obvious how such a quantity can be
useful, we will see later that enthalpy can be easy to measure and it
plays a role in calculating whether a given biological process will occur
spontaneously. You can think of a system’s enthalpy in much the same
way you think of heat. A change in enthalpy Δ H is very similar to q, heat
flowing into the system (or flowing out if q is negative). The main
difference between heat and enthalpy is in the way we account for
changes in pressure.
The rest of this section provides experience with manipulating thermodynamic
quantities and can give you a deeper understanding into the nature of
enthalpy. By the definition of enthalpy (H= U+ PV),
the change in enthalpy is equal to the change in internal energy plus the
change in the product of pressure and volume.
ΔH = ΔU + Δ(PV) (3)
We can see the relationship between enthalpy and heat by rearranging Eq. (3).
First, we rewrite it in a form similar to Eq. (1), in which we expressed the first
law of thermodynamics with the internal energy on the left and all other terms
on the right.
ΔU= ΔH - Δ(PV) (4)
Next, we account for pressure and volume changes in separate terms. That is,
we can rewrite Δ(PV) as
Δ(PV) = PΔV + V ΔP (5)
This step may seem a bit like hand waving to you or may be familiar (if you are
familiar with calculus or differential equations). The general principle is that
the change of a product or two or more variables, Δ(PV) in our example, is
equal to a sum of two or more products, where each product contains the
change in only one variable multiplied by the value of each of the other
variables held constant. Thus Δ(ABC) for example, would be equal to (ΔA)BC +
A(ΔB)C + AB(ΔC).
If we take the right side of Eq. (5) and substitute it for Δ(PV) in Eq. (4),
we get
ΔU = ΔH – VΔP - PΔV (6)
The last term on the right PΔV is the work done by the system. We save the
proof for Prob. 3. In short, since work is defined as force times distance,
pressure times a change in volume is just the three-dimensional version of
force times distance. Therefore we can rewrite Eq. (6) as
ΔU= ΔH-V ΔP - w (7)
Comparing this with Eq. (1),
ΔU = q - w
we see that Eqs. (7) and (1) are equivalent if
q = ΔH - VΔP
This gives us some insight into what enthalpy is; it’s simply a way of dividing up heat into two different terms: one term is
the energy associated with a change in pressure (VΔP) and the other term is the change in enthalpy (ΔH).
Rearranging, we get
ΔH = q + V Δ P (8)
Enthalpy is just the heat flowing into the system plus the energy associated with a change in pressure.
Fortunately, almost all biological processes occur at constant pressure. At constant pressure, ΔP = 0. This means that for a
system at constant pressure, the enthalpy change is exactly equal to the heat flowing into the system: q = ΔH.

still struggling
What is pressure times volume (PV)? how is VΔP the energy associated with a change in pressure? often we can
understand a concept better by looking at the units of the quantities involved. The units of P are force per area (n/m2). if
we multiply these units by meters per meter (which does not change the value at all because meters per meter is always
equal to 1) we see that the units of P are nm/m3. But a Nm is a joule, so the units of P are actually J/m3 or energy per unit
volume. pressure is energy per unit volume, a kind of energy density. When we multiple the pressure (J/m3) by the
volume (m3), the units on PV are joules; PV is the potential energy associated with pressure, and VΔP is the change in this
energy due to a change in pressure.
 • A reaction which gives off heat to the
surroundings is said to be
“exothermic” and HB in such a case is
less than HA , so that ΔH has a
negative value.

• A reaction which absorbs heat from

the surroundings is said to be
“endothermic” and HB in such case is
greater than HA , so that H has a
positive value and there is increase in
enthalpy.