Intensive and extensive properties

Physical properties of materials and systems can often be categorized as being either intensive or
extensive, according to how the property changes when the size (or extent) of the system changes.
According to IUPAC, an intensive quantity is one whose magnitude is independent of the size of the
system[1] whereas an extensive quantity is one whose magnitude is additive for subsystems.[2] This
reflects the corresponding mathematical ideas of mean and measure, respectively.

An intensive property is a bulk property, meaning that it is a local physical property of a system
that does not depend on the system size or the amount of material in the system. Examples of intensive
properties include temperature, T; refractive index, n; density, ρ; and hardness of an object, η.

By contrast, extensive properties such as the mass, volume and entropy of systems are additive for
subsystems because they increase and decrease as they grow larger and smaller, respectively.[3]

These two categories are not exhaustive since some physical properties are neither exclusively intensive
nor extensive.[4] For example, the electrical impedance of two subsystems is additive when — and only
when — they are combined in series; whilst if they are combined in parallel, the resulting impedance is
less than that of either subsystem.

The terms intensive and extensive quantities were introduced by Richard C. Tolman in 1917.[5]

Contents
Intensive properties
Examples
Extensive properties
Examples
Composite properties
Specific properties
Potential sources of confusion
Limitations
Complex systems and entropy production
References

Intensive properties
An intensive property is a physical quantity whose value does not depend on the amount of the
substance for which it is measured. For example, the temperature of a system in thermal equilibrium is
the same as the temperature of any part of it. If the system is divided by a wall that is permeable to heat
or to matter, the temperature of each subsystem is identical; if a system divided by a wall that is
impermeable to heat and to matter, then the subsystems can have different temperatures. Likewise for
the density of a homogeneous system; if the system is divided in half, the extensive properties, such as
the mass and the volume, are each divided in half, and the intensive property, the density, remains the
same in each subsystem. Additionally, the boiling point of a substance is another example of an intensive
property. For example, the boiling point of water is 100 °C at a pressure of one atmosphere, which
remains true regardless of quantity.

The distinction between intensive and extensive properties has some theoretical uses. For example, in
thermodynamics, the state of a simple compressible system is completely specified by two independent,
intensive properties, along with one extensive property, such as mass. Other intensive properties are
derived from those two intensive variables.

Examples

Examples of intensive properties include:[3][5][4]

chemical potential, μ specific heat capacity, cp

color[6] specific internal energy, u
concentration, c specific rotation, [α]
density, ρ (or specific gravity) specific volume, v
magnetic permeability, μ standard reduction potential,[7] E°
melting point and boiling point[7] surface tension
molality, m or b temperature, T
pressure, p thermal conductivity
refractive index viscosity
Specific conductance (or electrical conductivity)

See List of materials properties for a more exhaustive list specifically pertaining to materials.

Extensive properties
An extensive property is a physical quantity whose value is proportional to the size of the system it
describes, or to the quantity of matter in the system. For example, the mass of a sample is an extensive
quantity; it depends on the amount of substance. The related intensive quantity is the density which is
independent of the amount. The density of water is approximately 1g/mL whether you consider a drop of
water or a swimming pool, but the mass is different in the two cases.

Dividing one extensive property by another extensive property generally gives an intensive value—for
example: mass (extensive) divided by volume (extensive) gives density (intensive).

Examples

Examples of extensive properties include:[3][5][4]

amount of substance, n heat capacity, Cp

energy, E Helmholtz energy, A or F
enthalpy, H internal energy, U
entropy, S mass, m
Gibbs energy, G volume, V
Composite properties
The ratio of two extensive properties of the same object or system is an intensive property. For example,
the ratio of an object's mass and volume, which are two extensive properties, is density, which is an
intensive property.[8]

More generally properties can be combined to give new properties, which may be called derived or
composite properties. For example, the base quantities[9] mass and volume can be combined to give the
derived quantity[10] density. These composite properties can also be classified as intensive or extensive.
Suppose a composite property is a function of a set of intensive properties and a set of extensive
properties , which can be shown as . If the size of the system is changed by some
scaling factor, , only the extensive properties will change, since intensive properties are independent of
the size of the system. The scaled system, then, can be represented as .

Intensive properties are independent of the size of the system, so the property F is an intensive property
if for all values of the scaling factor, ,

(This is equivalent to saying that intensive composite properties are homogeneous functions of degree 0
with respect to .)

It follows, for example, that the ratio of two extensive properties is an intensive property. To illustrate,
consider a system having a certain mass, , and volume, . The density, is equal to mass (extensive)
divided by volume (extensive): . If the system is scaled by the factor , then the mass and volume

become and , and the density becomes ; the two s cancel, so this could be written
mathematically as , which is analogous to the equation for above.

The property is an extensive property if for all ,

(This is equivalent to saying that extensive composite properties are homogeneous functions of degree 1
with respect to .) It follows from Euler's homogeneous function theorem that

where the partial derivative is taken with all parameters constant except .[11] This last equation can be
used to derive thermodynamic relations.

Specific properties

A specific property is the intensive property obtained by dividing an extensive property of a system by its
mass. For example, heat capacity is an extensive property of a system. Dividing heat capacity, Cp, by the
mass of the system gives the specific heat capacity, cp, which is an intensive property. When the
extensive property is represented by an upper-case letter, the symbol for the corresponding intensive
property is usually represented by a lower-case letter. Common examples are given in the table below.[3]

Specific properties derived from extensive properties

Intensive Intensive
Extensive SI
Symbol (specific) Symbol SI units (molar) Symbol SI units
property units
property property

Volume V m3 or Specific volume* v m3/kg or Molar volume Vm m3/mol

L L/kg or L/mol

Specific internal Molar internal

Internal energy U J u J/kg Um J/mol
energy energy
Enthalpy H J Specific enthalpy h J/kg Molar enthalpy Hm J/mol

Gibbs free Specific Gibbs free Chemical

G J g J/kg Gm or µ J/mol
energy energy potential
Entropy S J/K Specific entropy s J/(kg·K) Molar entropy Sm J/(mol·K)

Molar heat
Heat capacity Specific heat
capacity
at constant CV J/K capacity cV J/(kg·K) CV,m J/(mol·K)
at constant
volume at constant volume
volume
Specific heat Molar heat
Heat capacity
capacity capacity
at constant CP J/K cP J/(kg·K) CP,m J/(mol·K)
at constant at constant
pressure
pressure pressure

*Specific volume is the reciprocal of density.

If the amount of substance in moles can be determined, then each of these thermodynamic properties
may be expressed on a molar basis, and their name may be qualified with the adjective molar, yielding
terms such as molar volume, molar internal energy, molar enthalpy, and molar entropy. The symbol for
molar quantities may be indicated by adding a subscript "m" to the corresponding extensive property.
For example, molar enthalpy is Hm.[3] Molar Gibbs free energy is commonly referred to as chemical
potential, symbolized by μ, particularly when discussing a partial molar Gibbs free energy μi for a
component i in a mixture.

For the characterization of substances or reactions, tables usually report the molar properties referred to
a standard state. In that case an additional superscript ° is added to the symbol. Examples:

Vm° = 22.41 L/mol is the molar volume of an ideal gas at standard conditions for temperature and
pressure.
CP,m° is the standard molar heat capacity of a substance at constant pressure.
ΔrHm° is the standard enthalpy variation of a reaction (with subcases: formation enthalpy,
combustion enthalpy...).
E° is the standard reduction potential of a redox couple, i.e. Gibbs energy over charge, which is
measured in volt = J/C.

Potential sources of confusion

The use of the term intensive is potentially confusing. The meaning here is "something within the area,
length, or size of something", and often constrained by it, as opposed to "extensive", "something without
the area, more than that".

Limitations
The general validity of the division of physical properties into extensive and intensive kinds has been
addressed in the course of science.[12] Redlich noted that, although physical properties and especially
thermodynamic properties are most conveniently defined as either intensive or extensive, these two
categories are not all-inclusive and some well-defined physical properties conform to neither
definition.[4] Redlich also provides examples of mathematical functions that alter the strict additivity
relationship for extensive systems, such as the square or square root of volume, which may occur in
some contexts, albeit rarely used.[4]

Other systems, for which standard definitions do not provide a simple answer, are systems in which the
subsystems interact when combined. Redlich pointed out that the assignment of some properties as
intensive or extensive may depend on the way subsystems are arranged. For example, if two identical
galvanic cells are connected in parallel, the voltage of the system is equal to the voltage of each cell, while
the electric charge transferred (or the electric current) is extensive. However, if the same cells are
connected in series, the charge becomes intensive and the voltage extensive.[4] The IUPAC definitions do
not consider such cases.[3]

Some intensive properties do not apply at very small sizes. For example, viscosity is a macroscopic
quantity and is not relevant for extremely small systems. Likewise, at a very small scale color is not
independent of size, as shown by quantum dots, whose color depends on the size of the "dot".

Complex systems and entropy production

Ilya Prigogine’s [13] groundbreaking work shows that every form of energy is made up of an intensive
variable and an extensive variable. Measuring these two factors and taking the product of these two
variables gives us an amount for that particular form of energy. If we take the energy of expansion the
intensive variable is pressure (P) and the extensive variable is the volume (V) we get PxV this is then the
energy of expansion. Likewise one can do this for density/mass movement where density and velocity
(intensive) and volume (extensive) essentially describe the energy of the movement of mass.

Other energy forms can be derived from this relationship also such as electrical, thermal, sound, springs.
Within the quantum realm, it appears that energy is made up of intensive factors mainly. For example,
the frequency is intensive. It appears that as one passes to the subatomic realms the intensive factor is
more dominant. The example is the quantum dot where color (intensive variable) is dictated by size, size
is normally an extensive variable. There appears to be the integration of these variables. This then
appears as the basis of the quantum effect.

The key insight to all this is that the difference in the intensive variable gives us the entropic force and
the change in the extensive variable gives us the entropic flux for a particular form of energy. A series of
entropy production formulas can be derived.

∆S heat= [(1/T)a-(1/T)b] x ∆ thermal energy

∆S expansion= [(pressure/T)a-(pressure/T)b] x ∆ volume

 ∆S electric = [(voltage/T)a-(voltage/T)b] x ∆ current

These equations have the form

∆Ss = [(intensive)a -(intensive)b] x ∆ extensive

where the a and b are two different regions.

This is the long version of Prigogine’s equation

∆Ss = XsJs
where Xs is the entropic force and Js is the entropic flux.

It is possible to derive a number of different energy forms from Prigogine’s equation.

Note that in thermal energy in the entropy production equation the intensive factor’s numerator is 1.
Whilst the other equations we have a numerator of pressure and voltage and the denominator is still
temperature. This means lower than the level of molecules there are no definite stable units.

References
1. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected
version: (2006–) "Intensive quantity (https://goldbook.iupac.org/I03074.html)".
doi:10.1351/goldbook.I03074 (https://doi.org/10.1351%2Fgoldbook.I03074)
2. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected
version: (2006–) "Extensive quantity (https://goldbook.iupac.org/E02281.html)".
doi:10.1351/goldbook.E02281 (https://doi.org/10.1351%2Fgoldbook.E02281)
3. Cohen, E. R.; et al. (2007). IUPAC Green Book (http://media.iupac.org/publications/books/gbook/IUP
AC-GB3-2ndPrinting-Online-22apr2011.pdf) (PDF) (3rd ed.). Cambridge: IUPAC and RSC
Publishing. pp. 6 (20 of 250 in PDF file). ISBN 978 0 85404 433 7.
4. Redlich, O. (1970). "Intensive and Extensive Properties" (https://escholarship.org/content/qt5mp6r34
r/qt5mp6r34r.pdf?t=p0fu3t) (PDF). J. Chem. Educ. 47 (2): 154–156. Bibcode:1970JChEd..47..154R
(https://ui.adsabs.harvard.edu/abs/1970JChEd..47..154R). doi:10.1021/ed047p154.2 (https://doi.org/
10.1021%2Fed047p154.2).
5. Tolman, Richard C. (1917). "The Measurable Quantities of Physics" (https://books.google.com/?id=K
vMKAAAAYAAJ&pg=PA237&lpg=PA237&dq=The+Measurable+Quantities+of+Physics#v=onepage&
q=The%20Measurable%20Quantities%20of%20Physics&f=false). Phys. Rev. 9 (3): 237–253.
6. Chang, R.; Goldsby, K. (2015). Chemistry (12 ed.). McGraw-Hill Education. p. 312. ISBN 978-
0078021510.
7. Brown, T. E.; LeMay, H. E.; Bursten, B. E.; Murphy, C.; Woodward; P.; Stoltzfus, M. E. (2014).
Chemistry: The Central Science (13th ed.). Prentice Hall. ISBN 978-0321910417.
8. Canagaratna, Sebastian G. (1992). "Intensive and Extensive: Underused Concepts". J. Chem. Educ.
69 (12): 957–963. Bibcode:1992JChEd..69..957C (https://ui.adsabs.harvard.edu/abs/1992JChEd..6
9..957C). doi:10.1021/ed069p957 (https://doi.org/10.1021%2Fed069p957).
9. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected
version: (2006–) "Base quantity (https://goldbook.iupac.org/B00609.html)".
doi:10.1351/goldbook.B00609 (https://doi.org/10.1351%2Fgoldbook.B00609)
10. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected
version: (2006–) "Derived quantity (https://goldbook.iupac.org/D01614.html)".
doi:10.1351/goldbook.D01614 (https://doi.org/10.1351%2Fgoldbook.D01614)
11. Alberty, R. A. (2001). "Use of Legendre transforms in chemical thermodynamics" (http://www.iupac.or
g/publications/pac/2001/pdf/7308x1349.pdf) (PDF). Pure Appl. Chem. 73 (8): 1349–1380.
doi:10.1351/pac200173081349 (https://doi.org/10.1351%2Fpac200173081349).
12. George N. Hatsopoulos, G. N.; Keenan, J. H. (1965). Principles of General Thermodynamics. John
Wiley and Sons. pp. 19–20. ISBN 9780471359999.
13. Ilya Prigogine, Isabelle Stengers (2018). Order Out of Chaos, MAN’S NEW DIALOGUE WITH
NATURE. Verso. ISBN 9781786631008.

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