BULLETIN

February 2009, Volume 34, No. 2

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A Publication of the Materials Research Society
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Applying Old Lessons

A Mnemonic Scheme
for Thermodynamics
H

S P
U G
V T

F
H– ST = G

n-GaN
μCones on
Active
N-polar face
region

Hybrid Solar Cells Supercritical CO2

p-GaN

GaN-Based Lighting
 one corner of the potential (outer) square

A Mnemonic to a neighboring corner on the same

square, passing through the variable
(inner) square diagonally, for example, the
curved arrow from U, passing through V
and P diagonally, to H (Figure 2a). This

Scheme for reads as U + VP = H. The positive sign in

front of VP is dictated by the fact that the
direction of the arrow passing along the
diagonal of the inner square is upward

Thermodynamics Table I: List of Several Sets of

Fundamental Equations among the
J.-C. Zhao Four State Variables and the Four
Thermodynamic Potentials in
Classical Thermodynamics.
Abstract
A mnemonic scheme is presented to help recall the equations in classical Definitions of Variables and Potentials
thermodynamics that connect the four state variables (temperature, pressure, volume, T = temperature P = pressure
and entropy) to the four thermodynamic potentials (internal energy, Helmholtz free
V = volume S = entropy
energy, enthalpy, and Gibbs free energy). Max Born created a square to help recall the
thermodynamic equations. The new scheme here separates the Max Born square into U = internal energy H = enthalpy
two squares, resulting in easier recalling of several sets of equations, including the F = Helmholtz G = Gibbs free
Maxwell equations, without complicated rules to remember the positive or negative free energy energy
signs.
Definitions of F, H, and G from U
(Legendre Transforms)
F = U − TS
Thermodynamics is a phenomenologi- years;1–9 and they are all essentially based
cal science based on three fundamental on the famous Max Born square1 shown in H = U + PV
laws, generalized from a broad range of Figure 1a, but with different rules to G = H − TS = U + PV − TS = F + PV
scientific observations, that describes the remember the equations and the positive
energy and behavior of an arbitrary sys- or negative signs in front of the terms. Differential Equations for U, F, H, and G
tem as it reaches equilibrium with its sur- It is shown here that recalling these
dU = T dS − P dV dF = −S dT − P dV
roundings or exchanges heat, work, or equations can be significantly simplified
matter with its surroundings. The funda- by separating the Born square into two dH = T dS + V dP dG = −S dT + V dP
mental laws of thermodynamics govern sections, an inner square that contains
the universe and subsystems in the uni- only the variables T, P, S, and V (thus Equations to Compute Variables
verse (excluding nuclear reactions); thus, called the variable square) and an outer T, P, V, and S
thermodynamics is a pervasive science square that contains only the potentials G,
fundamental to physics, chemistry, bio- H, U, and F (thus called the potential æ ¶H ö æ ¶ U ö æ ¶U ö æ ¶F ö
T =ç ÷ =ç ÷ P = -ç ÷ = -ç ÷
logy, materials science, mechanical engi- square), as shown in Figure 1b. Such a è ¶S øP è ¶ S ø V è ¶V øS è ¶ V øT
neering, and other disciplines. The separation retains the advantage of the
principles of thermodynamics allow one Born square but makes recalling the equa- ⎛ ∂H ⎞ ⎛ ∂ G ⎞ ⎛ ∂G ⎞ ⎛ ∂F ⎞
V= ⎜ ⎟ =⎜ ⎟ S = −⎜ ⎟ = −⎜ ⎟
to derive relationships among the proper- tions much more straightforward. ⎝ ∂P ⎠ S ⎝ ∂P ⎠ T ⎝ ∂T ⎠ P ⎝ ∂T ⎠ V
ties of a system. These relationships dic- In the new scheme (Figure 1b), the four
tate the number of properties that have to fundamental thermodynamic potentials, G, Maxwell Equations
be determined in order to completely H, U, and F, are still on the same sides as the
specify all the properties of the system. respective natural variables upon which æ ¶T ö æ ¶P ö ⎛ ∂S ⎞ ⎛ ∂ P ⎞
ç ÷ = -ç ÷ ⎜ ⎟ =⎜ ⎟
The relationships among the four state they depend: G = G (T, P), H = H (S, P), è ¶V øS è ¶ S øV ⎝ ∂V ⎠ T ⎝ ∂ T ⎠ V
variables (temperature T, pressure P, U = U (S, V), and F = F (T, V). The various
volume V, and entropy S) and four ther- variables and potentials are also flipped ⎛ ∂T ⎞ ⎛ ∂ V ⎞ æ ¶S ö æ ¶ V ö
⎜ ⎟ =⎜ ⎟ -ç ÷ =ç ÷
modynamic potentials (internal energy U, upside down with respect to the Born ⎝ ∂P ⎠ S ⎝ ∂S ⎠ P è ¶P øT è ¶T øP
Helmholtz free energy F, enthalpy H, and square to make the plus and minus signs
Gibbs free energy G) are the core of classi- consistent with the equations (which will Differential Equations for U, F, H, and
cal thermodynamics (Table I). The chemi- become apparent soon). The conjugate vari- G with Variable Amounts of Matter
cal potential of species i is mi, and the ables (S and T, P and V) are arranged diag-
number of moles of species i is hi. The var- onally in the inner square. dU = T dS − P dV + Σµi dni
ious differential and partial differential The four thermodynamic potentials are dF = −S dT − P dV + Σµi dni
equations describing these relationships related by the Legendre transforms: H = U dH = T dS + V dP + Σµi dni
become difficult to remember. Several + PV, F = U − TS, and G = H − TS = U + PV
mnemonic schemes to help recall the rela- − TS = F + PV. These equations can be dG = −S dT + V dP + Σµi dni
tionships have been developed over the recalled by drawing a curved arrow from

92 MRS BULLETIN • VOLUME 34 • FEBRUARY 2009 • www.mrs.org/bulletin

 A Mnemonic Scheme for Thermodynamics

a b a b a b

+
c d c d

Figure 1. Comparison of the new

scheme based on (b) with the Max
Born square (a). The Born square (a)
was used in several textbooks to help +
recall thermodynamic equations that
relate four thermodynamic variables
(temperature T, pressure P, volume V, Figure 2. Scheme to recall the Figure 3. Scheme to obtain the
and entropy S) and four thermodynamic Legendre transforms that define the differential equations of the
potentials (internal energy U, Helmholtz Helmholtz free energy F, enthalpy H, thermodynamic potentials (U, F, H,
free energy F, enthalpy H, and Gibbs and Gibbs free energy G from the and G) that are the core of
free energy G). The new double-square internal energy U. thermodynamic relations.
scheme (b) significantly simplifies the
procedures to recall several sets of
thermodynamic equations.
a b

(Figure 2a). Similarly, the curve in Figure

2b gives U − ST = F. The minus sign in
front of ST is due to the fact the arrow
points downward from S to T. Figures 2c
and 2d give H − ST = G and F + VP = G. In
fact, all of the arrows can be drawn back-
ward, and the equations still work—just
remember to use a minus sign when the
arrow passing along the diagonal of the
inner square is pointing downward.
To obtain the differential of a potential,
for example dU, draw two curved arrows
c d
toward the potential U from the two far
ends of the inner square, that is, P and T,
crossing the inner square diagonally,
as shown in Figure 3a. These two curved
arrows give +T dS and −P dV, thus
dU = T dS − P dV. [The variables (S and V)
close to the potential (U) are with differen-
tials.] The positive or negative sign in
front of each term is simply determined
by the upward or downward direction of
the arrow crossing along the diagonal
of the inner square. In the same fashion,
Figures 3b–3d provide dG = −S dT + V dP,
dF = −S dT − P dV, and dH = T dS + V dP.
One can also find the quantity for each Figure 4. Scheme to obtain the quantity of one variable from the partial differential of a
of the variables from the partial differen- thermodynamic potential with respect to the conjugate variable.
tial of a potential with respect to the con-
jugate variable. This is schematically
shown in Figure 4. To obtain T, draw a end of it (somewhat backward). However, The Maxwell relations involve only the
curved arrow from T, and cross the inner this curved arrow still points toward a variables, not the thermodynamic poten-
square diagonally (thus passing S) toward thermodynamic potential term (a corner tials; thus, they can be obtained using the
one of the nearby potentials (e.g., H). The of the outer square) as do all of the other inner (variable) square only without both-
curved arrow gives T = ∂H/∂S⎪P. This arrows in Figures 2 and 3. In this regard, ering with the outer (potential) square, as
term has a positive sign because the arrow the scheme is consistent. Similarly, the shown in Figure 5. In this case, one can
points upward (Figure 4a). The constant P arrow can go toward U, thus giving T = start at any corner of the square, going
is shown by the nearby variable with the ∂U/∂S⎪V. Similar equations can be around the square either clockwise or
dotted circle. Note that the T is at the obtained for V, S, and P, as shown in counterclockwise for half a square
beginning of the curved arrow, not the Figures 4b–4d. (including three variables each time). For

MRS BULLETIN • VOLUME 34 • FEBRUARY 2009 • www.mrs.org/bulletin 93

 A Mnemonic Scheme for Thermodynamics

4. Y.V.C. Rao, Postulational and Statistical

Thermodynamics (Allied Publishers, Mumbai,
India, 1994), p. 107.
5. F.O. Koenig, J. Chem. Phys. 56, 4556 (1972).
6. R.F. Fox, J. Chem. Educ. 53, 441 (1976).
7. M. Isihara, Bull. Chem. Soc. Jpn. 59, 2932 (1986).
8. G. Mitchell, Phys. Educ. 26, 145 (1991).
9. S.F. Pate, Am. J. Phys. 67, 1111 (1999).

Prof. Ji-Cheng Zhao

joined the Department of
Figure 5. Scheme to obtain the Maxwell equations. Materials Science and
Engineering at the Ohio
State University in
instance, from T to V to S, it yields the from this sentence reflect the arrange- January 2008 after 12 year
partial derivative of T with respect to V at ments of G–P–H–S–U–V–F–T counter- as a materials scientist and
constant S (left-hand side of Figure 5). The clockwise starting from the three o’clock project/team leader at GE
positive or negative sign of the term is position. Global Research in
again dictated by the upward or down- All of the above equations are among Niskayuna, NY. He has worked at GE since
ward direction of the arrow connecting the hardest to remember in classical 1995 when he obtained his PhD degree in
the first letter (T) to the third letter (S) thermodynamics without a mnemonic materials science and engineering from Lehigh
(thus crossing the square diagonally). For scheme. When the composition or amount University. His research focuses are on high-
the case of T to V to S, the arrow is of a chemical species changes, one can throughput materials science methodologies,
upward, so the term has a positive sign. To simply add a term Σ µi dni to each of the hydrogen storage materials, phase diagrams,
find the other part of the Maxwell pair, four differential equations (dU, dH, dG, thermodynamics, diffusion, and design of
perform the same procedure starting with and dF in Figure 3 and Table I) and derive advanced alloys and coatings. In addition to
the fourth variable (the only one that is not the rest of the equations using Maxwell many materials innovations, he developed a
included before) and going in the opposite relations. The µi and ni are the chemical diffusion-multiple approach and co-developed
direction with respect to the first term; potential and the number of moles of several associated micro-scale measurement
which would give the partial derivative of the species i, respectively. Fortunately, tools for accelerated materials discovery and
P with respect to S at constant V (or sim- the term Σµi dni remains the same, and development. Zhao has received several hon-
ply read as partial P, partial S at constant the sign in front of it is always positive ors, including the Geisler Award from ASM
V). This term has a negative sign because for the four differential equations, for International and the Hull Award from GE
the arrow from P to V points downward. example, dG = −S dT + V dP + Σµi dni. Global Research, and was elected a Fellow of
The other three Maxwell equations can be Alternatively, one can use a “thermody- ASM International in 2003. He has published
obtained in the same way as shown in namic cube” or a “thermodynamic cuboc- approximately 70 papers and edited/co-edited
Figure 5. This scheme is basically the same tahedron” to help remember the three books and two theme issues of MRS
as the Born square.8,9 The only differences relationships;5–9 but this capability is lost Bulletin. He also holds 38 U.S. patents with
are that the locations of the variables are when the three-dimensional devices are 27 more pending. Zhao serves as an associate
flipped upside down and the way to not readily available. editor for the Journal of Phase Equilibria
remember the positive and negative signs and Diffusion and on the Editorial Board of
is slightly modified. Acknowledgments Advanced Engineering Materials. He was
To help remember the arrangements/ The author thanks Prof. Ju Li for shar- one of the 2006 volume organizers of MRS
positions of the variables and potentials in ing his lecture notes, which contain a Bulletin and is serving as one of the meeting
Figure 1b, one can invoke Gilverry’s sen- scheme similar to Figure 5 that prompted chairs for the MRS Fall Meeting in 2009. His
tence:3 “Good Professors Have Studied the author to develop the overall scheme innovations were featured in news, covers, and
Under Very Fine Teachers.” (I took the described in this article. a cover story in Nature, C&E News, MRS
liberty to switch the original word Bulletin, and Advanced Engineering
“Physicists” to “Professors” to “glorify” Materials. Zhao can be reached at the
my own profession and to reflect the fact
References
1. H.B. Callen, Thermodynamics (Wiley, Department of Materials Science and
that thermodynamics is fundamental not New York, 1960), p. 117. Engineering, The Ohio State University, 286
only to physics, but to chemistry, biology, 2. D.E. Christie, Am. J. Phys. 25, 486 (1957). Watts Hall, 2041 College Road, Columbus,
materials science, mechanical engineer- 3. M.V. Zemansky, Heat and Thermodynamics OH 43210, USA; e-mail zhao.199@osu.edu,
ing, and other disciplines.) The first letters (McGraw-Hill, New York, 1968). http://www.mse.osu.edu/faculty/zhao/.

94 MRS BULLETIN • VOLUME 34 • FEBRUARY 2009 • www.mrs.org/bulletin