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Thermodynamics, science of the relationship between heat, work, temperature, and energy.

In broad
terms, thermodynamics deals with the transfer of energy from one place to another and from one form to
another. The key concept is that heat is a form of energy corresponding to a definite amount of
mechanical work.
Heat was not formally recognized as a form of energy until about 1798, when Count Rumford (Sir
Benjamin Thompson), a British military engineer, noticed that limitless amounts of heat could be
generated in the boring of cannon barrels and that the amount of heat generated is proportional to the
work done in turning a blunt boring tool. Rumfords observation of the proportionality between heat
generated and work done lies at the foundation of thermodynamics. Another pioneer was the French
military engineer Sadi Carnot, who introduced the concept of the heat-engine cycle and the principle of
reversibility in 1824. Carnots work concerned the limitations on the maximum amount of work that can be
obtained from a steam engine operating with a high-temperature heat transfer as its driving force. Later
that century, these ideas were developed by Rudolf Clausius, a German mathematician and physicist,
into the first and second laws of thermodynamics, respectively.

The most important laws of thermodynamics are:

The zeroth law of thermodynamics. When two systems are each in thermal equilibrium with a third
system, the first two systems are in thermal equilibrium with each other. This property makes it
meaningful to use thermometers as the third system and to define a temperature scale.
The first law of thermodynamics, or the law of conservation of energy. The change in a systems internal
energy is equal to the difference between heat added to the system from its surroundings and work done
by the system on its surroundings.
The second law of thermodynamics. Heat does not flow spontaneously from a colder region to a hotter
region, or, equivalently, heat at a given temperature cannot be converted entirely into work.
Consequently, the entropy of a closed system, or heat energy per unit temperature, increases over time
toward some maximum value. Thus, all closed systems tend toward an equilibrium state in
which entropy is at a maximum and no energy is available to do useful work. This asymmetry between
forward and backward processes gives rise to what is known as the arrow of time.
The third law of thermodynamics. The entropy of a perfect crystal of an element in its most stable form
tends to zero as the temperature approaches absolute zero. This allows an absolute scale for entropy to
be established that, from a statistical point of view, determines the degree of randomness or disorder in a

Although thermodynamics developed rapidly during the 19th century in response to the need to optimize
the performance of steam engines, the sweeping generality of the laws of thermodynamics makes them
applicable to all physical and biological systems. In particular, the laws of thermodynamics give a
complete description of all changes in the energy state of any system and its ability to perform useful
work on its surroundings.

This article covers classical thermodynamics, which does not involve the consideration of
individual atoms or molecules. Such concerns are the focus of the branch of thermodynamics known as
statistical thermodynamics, or statistical mechanics, which expresses macroscopic thermodynamic
properties in terms of the behaviour of individual particles and their interactions. It has its roots in the
latter part of the 19th century, when atomic and molecular theories of matter began to be generally

Thermodynamics is the field of physicsthat deals with the relationship between heat and other properties
(such as pressure, density, temperature, etc.) in a substance.

Specifically, thermodynamics focuses largely on how a heat transfer is related to various energy changes
within a physical system undergoing a thermodynamic process. Such processes usually result
in work being done by the system and are guided by the laws of thermodynamics.

Broadly speaking, the heat of a material is understood as a representation of the energy contained within
the particles of that material. This is known as the kinetic theory of gases, though the concept applies in
varying degrees to solids and liquids as well. The heat from the motion of these particles can transfer into
nearby particles, and therefore into other parts of the material or other materials, through a variety of

Thermal Contact is when two substances can affect each other's temperature.
Thermal Equilibrium is when two substances in thermal contact no longer transfer heat.
Thermal Expansion takes place when a substance expands in volume as it gains heat. Thermal
contraction also exists.
Conduction is when heat flows through a heated solid.
Convection is when heated particles transfer heat to another substance, such as cooking
something in boiling water.

Radiation is when heat is transferred through electromagnetic waves, such as from the sun.
Insulation is when a low-conducting material is used to prevent heat transfer.


A system undergoes a thermodynamic process when there is some sort of energetic change within the
system, generally associated with changes in pressure, volume, internal energy (i.e. temperature), or any
sort of heat transfer.

There are several specific types of thermodynamic processes that have special properties:

Adiabatic process - a process with no heat transfer into or out of the system.
Isochoric process - a process with no change in volume, in which case the system does no work.
Isobaric process - a process with no change in pressure.
Isothermal process - a process with no change in temperature.


A state of matter is a description of the type of physical structure that a material substance manifests, with
properties that describe how the material holds together (or doesn't). There are five states of matter,
though only the first three of them are usually included in the way we think about states of matter:

superfluid (such as a Bose-Einstein Condensate)

Many substances can transition between the gas, liquid, and solid phases of matter, while only a few rare
substances are known to be able to enter a superfluid state. Plasma is a distinct state of matter, such as

condensation - gas to liquid

freezing - liquid to solid
melting - solid to liquid
sublimation - solid to gas
vaporization - liquid or solid to gas


The heat capacity, C, of an object is the ratio of change in heat (energy change, Q, where the Greek
symbol Delta, , denotes a change in the quantity) to change in temperature (T).

C = Q / T

The heat capacity of a substance indicates the ease with which a substance heats up. A good thermal
conductor would have a low heat capacity, indicating that a small amount of energy causes a large
temperature change. A good thermal insulator would have a large heat capacity, indicating that much
energy transfer is needed for a temperature change.


There are various ideal gas equations which relate temperature (T1), pressure (P1), and volume (V1). These
values after a thermodynamic change is indicated by (T2), (P2), and (V2). For a given amount of a
substance, n (measured in moles), the following relationships hold:

Boyle's Law (T is constant):

P1V1 = P2V2

Charles/Gay-Lussac Law (P is constant):

V1/T1 = V2/T2

Ideal Gas Law:

P1V1/T1 = P2V2/T2 = nR

R is the ideal gas constant, R = 8.3145 J/mol*K.

For a given amount of matter, therefore, nR is constant, which gives the Ideal Gas Law.


Zeroeth Law of Thermodynamics - Two systems each in thermal equilibrium with a third system
are in thermal equilibrium to each other.
First Law of Thermodynamics - The change in the energy of a system is the amount of energy
added to the system minus the energy spent doing work.
Second Law of Thermodynamics - It is impossible for a process to have as its sole result the
transfer of heat from a cooler body to a hotter one.
Third Law of Thermodynamics - It is impossible to reduce any system to absolute zero in a finite
series of operations. This means that a perfectly efficient heat engine cannot be created.


The Second Law of Thermodynamics can be restated to talk about entropy, which is a quantitative
measurement of the disorder in a system. The change in heat divided by the absolute temperature is
the entropy change of the process. Defined this way, the Second Law can be restated as:

In any closed system, the entropy of the system will either remain constant or increase.
By "closed system" it means that every part of the process is included when calculating the entropy of the


In some ways, treating thermodynamics as a distinct discipline of physics is misleading. Thermodynamics

touches on virtually every field of physics, from astrophysics to biophysics, because they all deal in some
fashion with the change of energy in a system. Without the ability of a system to use energy within the
system to do work the heart of thermodynamics there would be nothing for physicists to study.

That having been said, there are some fields use thermodynamics in passing as they go about studying
other phenomena, while there are a wide range of fields which focus heavily on the thermodynamics
situations involved. Here are some of the sub-fields of thermodynamics:

Cryophysics / Cryogenics / Low Temperature Physics - the study of physical properties in

low temperature situations, far below temperatures experienced on even the coldest regions of the
Earth. An example of this is the study of superfluids.

Fluid Dynamics / Fluid Mechanics - the study of the physical properties of "fluids,"
specifically defined in this case to be liquids and gases.
High Pressure Physics - the study of physics in extremely high pressure systems, generally
related to fluid dynamics.
Meteorology / Weather Physics - the physics of the weather, pressure systems in the
atmosphere, etc.
Plasma Physics - the study of matter in the plasma state.

Transitions between solid, liquid, and gaseous phases typically involve large amounts of energy compared to the specific heat. If heat w
plateaus in the temperature vs time graph. The graph below presumes that the pressure is one standard atmosphere.
HyperPhysics***** Thermodynamics R Nave
The data for the vaporization phase change presumes that the pressure is one standard atmosphere.

HyperPhysics***** Thermodynamics R Nave

Why is the Potential Energy Negative?

In discussing the energy of the phase changes in water, we found that the potential energy is treated as a negative
quantity. An analogy with a mechanical system with gravitational potential energy and kinetic energy might be
helpful in understanding the logic of a negative energy quantity. You are always free to choose the zero of
potential energy, and it seems logical to choose the zero of potential energy such that a free molecule at rest has
zero energy. A bound particle at rest then has negative potential energy.



Water phase changes

Go Back
HyperPhysics***** Thermodynamics R Nave
It is known that 100 calories of energy must be added to raise the temperature of one gram of water from 0 to 100C. Part of that energ

The sizes of the blocks which represent the kinetic energy of the molecules at 0C and 100C provide a visual illustration of the meanin
temperatures. But the kinetic temperature is inherently the absolute temperature, so that the ratio of the heights of the blocks is 373K/27

HyperPhysics***** Thermodynamics R Nave

Some energy details related to heating water

In the process of heating water from from 0 to 100 C, 100 calories of energy must be added. Part of that energy increases the
kinetic energy of the molecules, and some adds to the potential energy. To assess the amount added to kinetic energy, the
molecular speeds at the two temperatures may be evaluated with the Boltzmann speed distribution.

The net gain in kinetic energy is then 16.7 calories/gram when the water is heated from 0 to 100 C. The remainder of the
energy goes into weakening the attractive forces between the water molecules. This weakening of the intermolecular forces
manifests itself in the reduction of the surface tension of water as it is heated.

In the process of vaporization of water, a large amount of energy must be added to overcome the remaining cohesive forces
between the molecules and an additional amount of energy goes into PdV work to expand the gas from its very small liquid
volume to the volume occupied by the resulting vapor.

If the heat of vaporization of water at 100C is 539 calories, then subtracting the 41 calorie work component suggests that the
actual binding energy of the water molecules at 100C is 539-41=498 calories.

Why is the heat of vaporization more at body temperature?

An interesting feature of the process of cooling the human body by evaporation is that the heat extracted by the evaporation
of a gram of perspiration from the human skin at body temperature (37C) is quoted in physiology books as 580 calories/gm
rather than the nominal 540 calories/gm at the normal boiling point. The question is, why is it larger at body temperature?

The main part of the answer is that the binding energy of the water molecules is greater at that lower temperature, and it
therefore takes more energy to break them apart into the gaseous state. The change in the heat of vaporization can be roughly
calculated using what we know from the specific heat of water, 1 calorie/gm C. It takes 37 calories to heat a gram of water
from 0C to 37C, but the change in the kinetic energy is much less than that:

It was shown above that the kinetic energy of the water molecules only increases by 61.7 - 45 = 16.7 calories/gm when the
water is heated from zero to 100C but we know it takes 100 calories to do that heating. Therefore the contribution to
weakening the water bonds is 83.3 calories/gm. Using the result for water at 37C it is evident that 52.4 calories of additional
energy must be supplied at 37C to vaporize the water.

There is one additional element in modeling the heat of vaporization at body temperature - the PdV work required to expand
the water into its gaseous form is slightly less at 37C. By analogy with the work calculation above, that work is found to be
34.2 calories/gm, 6.8 calories/gm less than at 100C.

This model then suggests a heat of vaporization at 37C:

Body temperature heat of vaporization = 539 cal/gm + 52.4 cal/gm - 6.8 cal/gm = 585 cal/gm.

So this simple model agrees fairly well with the quoted 580 cal/gm.

Changes of Phase (or State)

The term 'change of phase' means the
same thing as the term 'change of state'.
There are four states, or phases, of matter:
We will not be discussing the plasma state here.

When a substance changes from one state, or phase,

of matter to another we say that it has undergone a change of state, or we say that it has
undergone a change of phase. For example, ice melts and becomes water; water evaporates and
becomes water vapor.

These changes of phase always occur with a change of heat. Heat, which is energy, either comes
into the material during a change of phase or heat comes out of the material during this change.
However, although the heat content of the material changes, the temperature does not.
Here are the five changes of phase. They are diagrammed
in the opening animation and listed below.

Heat Movement
Description of Temperature Change
Term for Phase Change During Phase
Phase Change During Phase Change

Heat goes into the

Solid to liquid Melting None
solid as it melts.

Heat leaves the

Liquid to solid Freezing None
liquid as it freezes.

Vaporization, which Heat goes into the

Liquid to gas includes boiling and liquid as it None
evaporation vaporizes.

Heat leaves the gas

Gas to liquid Condensation None
as it condenses.

Heat goes into the

Solid to gas Sublimation solid as it None

So, how could there be a change in heat

during a state change without a change in
temperature? During a change in state the heat energy is used to change
the bonding between the molecules. In the case of melting, added energy is used to break the
bonds between the molecules. In the case of freezing, energy is subtracted as the molecules bond
to one another. These energy exchanges are not changes in kinetic energy. They are changes in
bonding energy between the molecules.

If heat is coming into a substance during a phase change, then this energy is used to break the
bonds between the molecules of the substance. The example we will use here is ice melting into
water. Immediately after the molecular bonds in the ice are broken the molecules are moving
(vibrating) at the same average speed as before, so their average kinetic energy remains the
same, and, thus, their Kelvin temperature remains the same.
Below is a picture of solid ice melting into
liquid water. The molecule of ice and the molecule of water (the black balls) are
moving with the same rate of vibration in this diagram. This is meant to show that they have the
same average speed and thus the same average kinetic energy (since they have the same mass)
and thus the same Kelvin temperature. The motions are, though, greatly exaggerated. Actually,
the motions of the molecules should be considered tiny vibrations.

At the moment of melting the average kinetic energy o

molecules does not change.

The heat is used to break the bonds between the ice

molecules as they turn into a liquid phase.

Since the average kinetic energy of the molecules does

change at the moment of melting, the temperature of th
molecules does not change.

Since both the ice and the water molecules have the sa
average kinetic energy at the time of melting, the
temperatures of both are the same.

Click this button to see the computer code for this animation.

In the ice the molecules are strongly bonded to

one another, thus forming a rigid solid.When heat is
added to the ice these bonds are broken and the ice melts. The molecules afterward bond to one
another with less strength and a different geometry, and water is formed.

Now, before the melting, the molecules were actually moving when in the solid state. They were
vibrating back and forth. They had an average kinetic energy. So they had a Kelvin temperature
proportional to this average kinetic energy.
After the melting the water molecules are still vibrating. And they have the same average kinetic
energy as they had before the melting. So, the water is at the same temperature at the moment
after the melting that the ice was at the moment before the melting.

Heat came into the situation, but it was not

used to change the kinetic energy of the
molecules. It was used to change the bonding between the molecules. Breaking the
bonds between the molecules of the ice requires energy, and this energy is the added heat.

In a similar way heat enters a liquid to change the molecular bonding when the liquid boils or
evaporates into a gas, and heat enters a solid to change the molecular bonding when it sublimates
into a gas.

In an inverse way heat leaves a gas to change the molecular bonding when the gas condenses
into a liquid, and heat leaves a liquid to change the molecular bonding when it freezes into a

In none of these changes of state is the heat

(energy) that is input or output used to change
the speed of the molecules. The average speed of the molecules is the
same before and after a phase change, and so is the average kinetic energy.

Since the bonds

among the ice
The heat is used Since the ice and
molecules have
to break the water molecules
been broken, water
Heat bonds between both have the
is formed. The
(energy) is molecules, not same average
water molecules, at
transferred to increase the kinetic energy,
this moment, have
into the ice. average kinetic they are at the
the same average
energy of the same Kelvin
kinetic energy as
molecules. temperature.
they did when they
were ice.

What kind of system are you: open or closed? As it turns out, this is a physics
question, not a philosophical one. You, like all living things, are an open
system, meaning that you exchange both matter and energy with your
environment. For instance, you take in chemical energy in the form of food,
and do work on your surroundings in the form of moving, talking, walking,
and breathing.

All of the exchanges of energy that take place inside of you (such as your
many metabolic reactions), and between you and your surroundings, can be
described by the same laws of physics as energy exchanges between hot and
cold objects, or gas molecules, or anything else you might find in a physics
textbook. Here, well look at two physical laws the First and Second Laws
of Thermodynamics and see how they apply to biological systems like you.

Systems and surroundings

Thermodynamics in biology refers to the study of energy transfers that occur
in molecules or collections of molecules. When we are discussing
thermodynamics, the particular item or collection of items that were
interested in (which could be something as small as a cell, or as large as an
ecosystem) is called the system, while everything that's not included in the
system weve defined is called the surroundings.
Generalized depiction of the system (a circle), the surroundings (a square
surrounding the circle), and the universe (system + surroundings).

For instance, if you were heating a pot of water on the stove, the system
might include the stove, pot, and water, while the surroundings would be
everything else: the rest of the kitchen, house, neighborhood, country, planet,
galaxy, and universe. The decision of what to define as the system is arbitrary
(up to the observer), and depending on what you wanted to study, you could
equally well make just the water, or the entire house, part of the system. The
system and the surroundings together make up the universe.

There are three types of systems in thermodynamics: open, closed, and


An open system can exchange both energy and matter with its surroundings.
The stovetop example would be an open system, because heat and water
vapor can be lost to the air.
A closed system, on the other hand, can exchange only energy with its
surroundings, not matter. If we put a very tightly fitting lid on the pot from
the previous example, it would approximate a closed system.
An isolated system is one that cannot exchange either matter or energy with
its surroundings. A perfect isolated system is hard to come by, but an
insulated drink cooler with a lid is conceptually similar to a true isolated
system. The items inside can exchange energy with each other, which is why
the drinks get cold and the ice melts a little, but they exchange very little
energy (heat) with the outside environment.
[Why is a cooler sometimes called a "closed" system?]

You, like other organisms, are an open system. Whether you think about it or
not, you are constantly exchanging energy and matter with your
surroundings. For instance, suppose that you eat a carrot, or lift a bag of
laundry onto a table, or simply breathe out and release carbon dioxide into
the atmosphere. In each case, you are exchanging energy and matter with
your environment.
Exchanges of energy that take place in living creatures must follow the laws
of physics. In this regard, they are no different from energy transfers in, say,
an electrical circuit. Let's take a closer look at how the laws of
thermodynamics(physical rules of energy transfer) apply to living beings
like yourself.

The First Law of Thermodynamics

The first law of thermodynamics thinks big: it deals with the total amount of
energy in the universe, and in particular, it states that this total amount does
not change. Put another way, the First Law of Thermodynamics states that
energy cannot be created or destroyed. It can only change form or be
transferred from one object to another.
Image of ice cream cone (chemical energy) being converted to motion of kids
riding bikes (kinetic energy).
Image of sun (light energy) being converted to sugars in a leaf (chemical
Image credit: OpenStax Biology. Credit Ice cream," modification of work by D. Sharon Pruitt; credit "Kids
on bikes," modification of work by Michelle Riggen-Ransom, and credit Leaf: modification of work by Cory

This law may seem kind of abstract, but if we start to look at examples, well
find that transfers and transformations of energy take place around us all the
time. For example:

Light bulbs transform electrical energy into light energy (radiant energy).
One pool ball hits another, transferring kinetic energy and making the second
ball move.
Plants convert the energy of sunlight (radiant energy) into chemical energy
stored in organic molecules.
You are transforming chemical energy from your last snack into kinetic
energy as you walk, breathe, and move your finger to scroll up and down this
Importantly, none of these transfers is completely efficient. Instead, in each
scenario, some of the starting energy is released as thermal energy. When it's
moving from one object to another, thermal energy is called by the more
familiar name of heat. It's obvious that glowing light bulbs generate heat in
addition to light, but moving pool balls do too (thanks to friction), as do the
inefficient chemical energy transfers of plant and animal metabolism. To see
why this heat generation is important, stay tuned for the Second Law of

The Second Law of Thermodynamics

At first glance, the first law of thermodynamics may seem like great news. If
energy is never created or destroyed, that means that energy can just be
recycled over and over again, right?

Wellyes and no. Energy cannot be created or destroyed, but it can change
from more-useful forms into less-useful forms. As it turns out, in every real-
world energy transfer or transformation, some amount of energy is converted
to a form thats unusable (unavailable to do work). In most cases, this
unusable energy takes the form of heat.

Although heat can in fact do work under the right circumstances, it can never
be turned into other (work-performing) types of energy with 100% efficiency.
So, every time an energy transfer happens, some amount of useful energy
will move from the useful to the useless category.

Heat increases the randomness of the universe

If heat is not doing work, then what exactly does it do? Heat that doesnt do
work goes towards increasing the randomness (disorder) of the universe. That
may seem like a big logic jump, so lets take a step back and see how it can
be the case.

When you have two objects (say, two blocks of the same metal) at different
temperatures, your system is relatively organized: the molecules are
partitioned by speed, with those in the cooler object moving slowly and those
in the hotter object moving quickly. If heat flows from the hotter object into
the cooler object (as it will spontaneously), the molecules of the hot object
slow down, and the molecules of the cool object speed up, until all the
molecules are moving at the same average speed. Now, rather than having a
partition of between fast and slow molecules, we simply have one big pool of
molecules going about the same speed a less ordered situation than our
starting point.

The system will tend to move towards this more disordered configuration
simply because its statistically much more likely than the temperature-
separated configuration (i.e., there are many more possible states
corresponding to the disordered configuration). You can explore this concept
further in the videos in this tutorial, or in this straightforward physics video.

Entropy and the Second Law of Thermodynamics

The degree of randomness or disorder in a system is called its entropy. Since
we know that every energy transfer results in the conversion of some energy
to an unusable form (such as heat), and since heat that does not do work goes
to increase the randomness of the universe, we can state a biology-relevant
version of the Second Law of Thermodynamics: every energy transfer that
takes place will increase the entropy of the universe and reduce the amount of
usable energy available to do work (or, in the most extreme case, leave the
overall entropy unchanged). In other words, any process, such as a chemical
reaction or set of connected reactions, will proceed in a direction that
increases the overall entropy of the universe.
[Click here for some mind-bending implications of the Second Law!]

10^{10^{56}}10, start superscript, 10, start superscript, 56, end superscript,

end superscript

To sum up, the First Law of Thermodynamics tells us about conservation of

energy among processes, while the Second Law of Thermodynamics talks
about the directionality of the processes, that is, from lower to higher entropy
(in the universe overall).
Entropy in biological systems
One implication of the second law of thermodynamics is that in order for a
process to happen, it must somehow increase the entropy of the universe.
This may immediately raise some questions for you when you think about
living organisms such as yourself. After all, arent you a pretty ordered
collection of matter? Every cell in your body has its own internal
organization; the cells are organized into tissues, and the tissues into organs;
and your entire body maintains a careful system of transport, exchange, and
commerce that keeps you alive. Thus, at first glance, it may not be clear how
you, or even a simple bacterium, can represent an increase in the entropy of
the universe.

To clarify this, lets look at the energy exchanges that take place in your body
say, when you are going for a walk. As you contract the muscles of your
legs to move your body forward, you are using chemical energy from
complex molecules such as glucose and converting it into kinetic energy
(and, if youre walking uphill, potential energy). However, youre doing this
with pretty low efficiency: a large fraction of the energy from your fuel
sources is simply transformed into heat. Some of the heat keeps your body
warm, but much of it dissipates into the surrounding environment.
Cartoon of person walking, with a hamburger in his hand. The person is
taking in complex macromolecules in the hamburger, and releasing them as
carbon dioxide and water molecules, increasing entropy. He is also walking
forward (converting chemical energy from macromolecules into kinetic
energy), but much of the energy released is lost as heat (also increasing

This transfer of heat increases the entropy of the surroundings, as does the
fact that youre taking large, complex biomolecules and converting them into
a lot of small, simple molecules, such as carbon dioxide and water, as you
metabolize fuel to power your walk. This example uses a person in motion,
but the same would be true for a person, or any other organism, at rest. The
person or organism will maintain some basal rate of metabolic activity,
causing the breakdown of complex molecules to smaller and more numerous
ones and the release of heat, thus increasing the entropy of the surroundings.

Stated more generally, processes that locally decrease entropy, such as those
that build and maintain the highly organized bodies of living things, can
indeed take place. However, these local decreases in entropy can occur only
with an expenditure of energy, where some of that energy is converted into
heat or other non-usable forms. The net effect of the original process (local
decrease in entropy) and the energy transfer (increase in entropy of
surroundings) is an overall increase in the entropy of the universe.

To sum up, the high degree of organization of living things is maintained by a

constant input of energy, and is offset by an increase in the entropy of the

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