First Law of Thermodynamics

The first law of thermodynamics is the application of the conservation of

energy principle to heat and thermodynamic processes:

Index

Heat
engine
The first law makes use of the key concepts of internal energy, heat, and concepts
system work. It is used extensively in the discussion of heat engines.

It is typical for chemistry texts to write the first law as U=Q+W. It is the
same law, of course - the thermodynamic expression of the conservation of
energy principle. It is just that W is defined as the work done on the system
instead of work done by the system. In the context of physics, the common
scenario is one of adding heat to a volume of gas and using the expansion of
that gas to do work, as in the pushing down of a piston in an internal
combustion engine. In the context of chemical reactions and process, it may be
more common to deal with situations where work is done on the system rather
than by it.

Internal Energy in the Thermodynamic Identity

Go Back
HyperPhysics***** Thermodynamics R Nave
 Second Law of Thermodynamics
Second Law
The second law of thermodynamics is a general principle which statements
places constraints upon the direction of heat transfer and the Heat engine
attainable efficiencies of heat engines. In so doing, it goes
Refrigerator
beyond the limitations imposed by the first law of
thermodynamics. It's implications may be visualized in terms of Entropy
the waterfall analogy. Heat transfer Index

Second
law
concepts

Heat
engine
concepts

The maximum efficiency which can be achieved is the Carnot efficiency.

Qualitative statements of the Second Law of Thermodynamics

Go Back
HyperPhysics***** Thermodynamics R Nave
 Second Law: Heat Engines
Second Law of Thermodynamics: It is impossible to extract an amount of heat
QH from a hot reservoir and use it all to do work W . Some amount of heat QC
must be exhausted to a cold reservoir. This precludes a perfect heat engine.
Index
This is sometimes called the "first form" of the second law, and is referred to
as the Kelvin-Planck statement of the second law. Second
law
concepts

Heat
engine
concepts

Alternative statements: Second Law of Thermodynamics

Go Back
HyperPhysics***** Thermodynamics R Nave

Index
Second Law: Refrigerator
Second
Second Law of Thermodynamics: It is not possible for heat to flow from a law
colder body to a warmer body without any work having been done to concepts
accomplish this flow. Energy will not flow spontaneously from a low
temperature object to a higher temperature object. This precludes a perfect Heat
refrigerator. The statements about refrigerators apply to air conditioners and engine
heat pumps, which embody the same principles. concepts

This is the "second form" or Clausius statement of the second law.

 Alternative statements: Second Law of Thermodynamics

Go Back
HyperPhysics***** Thermodynamics R Nave

Second Law: Entropy

Second Law of Thermodynamics: In any cyclic process the entropy will either
increase or remain the same.
Index

a state variable whose change is defined for a Second

Entropy: reversible process at T where Q is the heat law
absorbed. concepts
a measure of the amount of energy which is
Entropy: Heat
unavailable to do work.
engine
Entropy: a measure of the disorder of a system. concepts
Entropy: a measure of the multiplicity of a system.
Entropy
concepts
Since entropy gives information about the evolution of an isolated system with
time, it is said to give us the direction of "time's arrow" . If snapshots of a
system at two different times shows one state which is more disordered, then it
could be implied that this state came later in time. For an isolated system, the
natural course of events takes the system to a more disordered (higher entropy)
state.

Alternative statements: Second Law of Thermodynamics

Biological systems are highly ordered; how does that square with entropy?

Go Back
HyperPhysics***** Thermodynamics R Nave

Qualitative Statements: Second Law

of Thermodynamics
The second law of thermodynamics is a profound principle of nature which
affects the way energy can be used. There are several approaches to stating this
principle qualitatively. Here are some approaches to giving the basic sense of Index
the principle.
Second
1. Heat will not flow spontaneously from a cold object to a hot Further law
object. discussion concepts

2. Any system which is free of external influences becomes more Heat

Further
disordered with time. This disorder can be expressed in terms of engine
discussion
the quantity called entropy. concepts
3. You cannot create a heat engine which extracts heat and Further
converts it all to useful work. discussion
4. There is a thermal bottleneck which contrains devices which Further
convert stored energy to heat and then use the heat to accomplish discussion
work. For a given mechanical efficiency of the devices, a
machine which includes the conversion to heat as one of the steps
will be inherently less efficient than one which is purely
mechanical.
Alternative statements: Second Law of Thermodynamics

HyperPhysics***** Thermodynamics Go Back

 Internal Energy
Internal energy is defined as the energy associated with the random, disordered
motion of molecules. It is separated in scale from the macroscopic ordered
energy associated with moving objects; it refers to the invisible microscopic
energy on the atomic and molecular scale. For example, a room temperature
glass of water sitting on a table has no apparent energy, either potential or
kinetic . But on the microscopic scale it is a seething mass of high speed
molecules traveling at hundreds of meters per second. If the water were tossed
across the room, this microscopic energy would not necessarily be changed
when we superimpose an ordered large scale motion on the water as a whole.

Index

Internal
energy
concepts

U is the most common symbol used for internal energy.

Related energy quantities which are particularly useful in chemical

thermodynamics are enthalpy, Helmholtz free energy, and Gibbs free energy.

Temperature and kinetic energy Equipartition of energy Thermal energy

Can a molecule's trajectory be predicted like that of a baseball?

Go Back
HyperPhysics***** Thermodynamics R Nave