Research: Science and Education
Particle Model for Work, Heat,
and the Energy of a Thermodynamic System
Howard DeVoe
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742; hdevoe@umd.edu
Classical thermodynamics makes a distinction between
heat and work, which are two different modes of energy trans-
fer between a thermodynamic system and its surroundings.
Heat can be generally described as an energy transfer owing
to a temperature difference or temperature gradient and work
as an energy transfer owing to displacement of macroscopic
matter on which a force is exerted. The distinction is impor-
tant in thermodynamic derivations because only the heat, and
not the work, is used to define the entropy changes of re-
versible processes needed to develop concepts of equilibrium.
This article shows how a simple particle model provides
insights into how heat and work are related to the behavior
of atoms and molecules. Classical thermodynamics ignores
the existence of these microscopic particles and instead treats
matter as a continuous material medium. The model de-
scribed here treats a thermodynamic system as a collection
of interacting material particles behaving according to the
principles of classical mechanics. There have been similar ear-
lier treatments (1–6).
The particle model allows details of several topics of in-
terest to chemists to be examined in a rigorous fashion: the
dependence of energy changes and work on a frame of refer-
ence; the effect of gravitational forces on the system’s energy
change; the quantitative difference between the energy change
and the internal energy change; problems associated with slid-
ing friction at the system boundary; and the issue of whether
the magnitudes of heat and work are the same from the view-
points of the system and the surroundings.
The particle model leads to an expression for the energy
of the system in an inertial lab frame as a function of the
speeds and elevations of the constituent particles and of in-
terparticle distances. The change of this energy during a pro-
cess is found to be given by a sum of integrals in which forces
exerted by the surroundings on particles in the system are
integrated over the displacements of these particles. The work
can be defined as a similar sum of integrals in which forces
exerted by the surroundings on macroscopic matter in the
system are integrated over displacements of this matter. A
comparison of the expressions for the energy change and the
work allows a new expression for heat to be derived, taking
the form of another sum of integrals involving displacements
of particles in the system relative to the system boundary. It
is found that for a given process heat, unlike work, has the
same value in any non-rotating reference frame. There is a
discussion of the special case of frictional work at the bound-
ary. The particle model is used to justify the need for a cen-
ter-of-mass reference frame for internal energy and to find
the difference in the values of an energy change and an in-
ternal energy change. Finally, the expression for work is ap-
plied to the example of a reversible or irreversible expansion
of a gas against a piston in a cylinder.
504 Journal of Chemical Education • Vol. 84 No. 3 March 2007
W
The Energy of the System
The mathematical formulation of the first law of ther-
modynamics equates the change ∆E of the energy of a ther-
modynamic system during a given process to the sum of heat
and work occurring during the process:
∆E = q + w (1)
The equation applies to a closed system. In the equation q
and w represent energy transferred as heat and as thermody-
namic work, respectively, between the system and its sur-
roundings. The value of q or w is positive if the energy transfer
is from the surroundings into the system and negative for
transfer from the system to the surroundings.
To apply eq 1 to a particular process, it is essential to
know what is being taken as the system. The system as a physi-
cal entity is defined by a boundary—that is, by an imaginary
three-dimensional closed surface that separates the system
from the surroundings. The size, shape, and position of the
boundary may change during the process, but only the mat-
ter within the boundary belongs to the system.
Once the boundary has been established, the question
arises: what is meant by the energy of the system at any given
instant? Certainly the energy represented by E should include
all contributions that can be assigned entirely to matter within
the boundary. These contributions include the translational,
rotational, vibrational, and electronic energies of the atoms
and molecules in the system, and the potential energy of in-
teractions among these particles.
We should also consider whether to include contribu-
tions to E from potential energies associated with forces act-
ing across the boundary. These forces are of two types: (i)
short-range contact forces between parts of the system and
surroundings that are in direct contact with one another at
the boundary and (ii) long-range field forces acting over a
distance, such as forces derivable from external electric, mag-
netic, and gravitational fields.
The potential energy Epcnt of contact forces acting across
the boundary is shared by the system and the surroundings
and logically should not be assigned to just the system. Thus
this potential energy is not a contribution to E. The magni-
tude of Epcnt is usually negligible compared to values of q or
w in typical laboratory experiments.1 According to Reid (7),
this energy is negligible because the interactions fall off dras-
tically within a few nanometers. A better explanation is that
the minima of noncovalent potential functions are shallow,
and also only a small fraction of the atoms and molecules
are next to the boundary in the usual systems. Although we
will be able to treat the potential energy of the contact forces
as negligible, the forces themselves will turn out to be the
crucial ones for evaluating thermodynamic work.
• www.JCE.DivCHED.org

It is less obvious how the assignment of the potential
energy of a field force should be assigned. The particle model
described in the next section assumes the earth creates a con-
servative time-independent gravitational field that acts on the
matter in the system, and in what follows we shall be con-
cerned with the gravitational potential energy of this inter-
action. Strictly speaking, the gravitational potential energy
is shared by the earth and the particles on which it acts (8,
9) and resides in the gravitational field (10, 11). We can con-
sider the earth to be part of either the system or the surround-
ings (8, 9, 12). If we consider the earth to be part of the
system, E will include the gravitational potential energy; how-
ever, the system’s center of mass is then practically at the cen-
ter of the earth and cannot be used to define a useful internal
energy by the method to be described presently. If however
the earth is part of the surroundings and we assign the gravi-
tational potential energy to the field, we lose the convenient
concept of a system gravitational potential energy. Instead of
either of these choices, this article will use a mixed approach:
the earth is part of the surroundings and the system consists
of the matter within the boundary plus the gravitational field,
so that the gravitational potential energy is included in E (11).
This leaves Epcnt as the only energy that is shared by the sys-
tem and surroundings.
The first law states that a change of E occurs by means
of either thermodynamic work or heat. The thermodynamic
work described by the particle model is confined to mechani-
cal work; that is, work that occurs when there is displace-
ment of a macroscopic portion of the system on which the
surroundings exert a force. Some examples of processes with
this kind of work are expansion or compression of a gas;
stretching or compression of a spring; the pulling of a string
under tension that passes through the boundary; and rota-
tion of a rod that passes through the boundary and on which
a torque is exerted.
To use eq 1 and understand its significance, we must
keep in mind that E is specified to be a state function—that
is, a function only of the macroscopic state of the system.
The chief significance of the first law is its assertion that when
the macroscopic state of a closed system undergoes a given
change, the sum of heat and thermodynamic work always
has the same value although the individual values of q and w
may vary depending on the path by which the change oc-
curs.
There is another consideration that is easily overlooked:
values of work and kinetic energy depend on a frame of refer-
ence, which is a system of coordinate axes used to define po-
sitions, displacements, and velocities. Values of w and ∆E are
in general different when measured in different reference
frames. The value of an energy change is meaningless unless
the reference frame is known. However, as will be shown in
a later section, the energy transferred as heat during a pro-
cess has the same value in all non-rotating reference frames.
When a thermodynamic derivation involving work or
energy does not explicitly specify a reference frame, it is natu-
ral to assume that a “lab frame” is intended, that is, one fixed
with respect to the earth’s surface. A lab frame may not al-
ways be the most appropriate choice. Consider for example
a sample of liquid water in a beaker resting on the lab bench,
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Research: Science and Education
and let the system be the water. Because E is supposed to be
a state function, its value for this system should depend only
on the variables needed to describe the macroscopic state of
the water. Usually the values of the temperature T and pres-
sure p suffice to specify the state of a fixed quantity of ho-
mogeneous fluid such as this. However, if we slide the beaker
along the bench the water’s kinetic energy increases; and if
we lift the beaker above the bench the water’s gravitational
potential energy increases. These energy changes, measured
in the lab frame, are positive even though T and p are un-
changed. Thus in the lab frame two additional variables, such
as the velocity and elevation of the system’s center of mass,
are needed to define the macroscopic state. In order for this
system to have only two independent state variables, we can
change to a center-of-mass reference frame, which is a non-
rotating frame whose origin moves with the system’s center
of mass. Measured in this frame, the water’s energy at con-
stant T and p remains constant as the beaker is slid or lifted.
The internal energy of the system, denoted by the sym-
bol U, refers to a function of only internal thermodynamic
variables such as temperature, pressure, volume, and the
amount of each substance; and not of external variables such
as the system’s overall velocity and position relative to a lab
frame. A later section will show these requirements are satis-
fied if the internal energy is defined as the energy of the sys-
tem relative to a center-of-mass frame (1–4).
In this article E will denote the energy of the system
measured in a lab frame, and w will be the thermodynamic
work in this frame. The internal energy U will be the energy
of the system measured in a center-of-mass (cm) frame, and
wcm will be the thermodynamic work in the cm frame. Thus
eq 1 expresses the first law with quantities measured in a lab
frame, and the equation
∆U = q + wcm (2)
expresses the first law with quantities measured in a cm frame.
If it happens that the system’s center of mass remains sta-
tionary in the laboratory during a process, then of course the
lab frame is also a cm frame and ∆U is the same as ∆E.
The Particle Model
In the model described in this section, the thermody-
namic system consists of uncharged point particles without
internal structure that interact with one another and the sur-
roundings through short-range central forces and with the
earth through gravitational forces. The particles represent at-
oms, and the short-range forces crudely represent bonding
forces between the atoms of molecules and van der Waals and
repulsion forces between atoms and molecules. The model
can be applied to systems of any degree of complexity and to
a variety of processes including gas expansions, phase changes,
and chemical reactions. There will be no need to stipulate
whether or not the process is carried out in a reversible limit
of infinite slowness, as the model is suitable for a process oc-
curring at any rate. Some aspects of real systems that the
model does not treat are quantum properties, interactions of
particles with radiation, electrical work, and changes of elec-
tronic energy. The model is the simplest that will allow us to
• Journal of Chemical Education 505
 Research: Science and Education
derive formulas for mechanical thermodynamic work and
heat in terms of microscopic behavior.
In this section the model is used to derive an expression
for the energy change ∆E of a system of particles in an earth-
fixed lab frame as a function of the interaction forces and
microscopic displacements of the particles. The derivation is
similar to others that have appeared in the physics education
literature (1–4, 6) but differs from them by including gravi-
tational potential energy as part of the energy of the system.
We assume the system has a well-defined boundary and
is closed: no particles cross the boundary. The indices i and j
will refer only to the particles belonging to the system and
not to any particles in the surroundings.
Classical mechanics is based on the idea that particles
act upon one another by means of forces that are indepen-
dent of the reference frame. The total force Fitot acting on
particle i (a system particle) is a vector quantity, as indicated
by the boldface symbol, and is equal to the vector sum of
three kinds of individual forces:
Fi tot = ∑ Fi j + Fi grav + Fi cnt
j ≠i
Here Fij is the force exerted on particle i by particle j (also a
system particle), Fi grav is the force exerted on particle i by
the earth’s gravitational field, and Ficnt is the net contact force
exerted on the particle by nearby particles in the surround-
ings. The value of Ficnt is nonnegligible only when particle i
is close to the boundary.
We assume the lab frame is inertial2 and the motion of
particle i obeys Newton’s second law of motion:
d vi
Fi tot = mi
dt
In this equation mi is the mass of the particle, vi is its veloc-
ity in the lab frame, and t is time. If Fitot is nonzero at a par-
ticular instant, the particle is accelerating and changing its
velocity. We will not attempt to trace the motion of the par-
ticle over time; that would be the goal of a molecular dy-
namics study.
In classical mechanics, the work done by the force Fitot
acting on particle i during a given period of time (the “inter-
action time period”) is evaluated by the line integral 兰Fitot⭈dri,
where ri is a position vector pointing from the origin of the
reference frame to particle i. That is, the work is the scalar
product of the total force exerted on the particle and the
particle’s displacement, integrated over the interaction time
period. For our purposes the interaction time period is the
duration of a process in which the system changes from an
initial state through intermediate states to a final state.
The total work Wtot done by the forces acting on all the
system particles during the interaction time period is the sum
of the work done on each particle:
W tot = ∑ Fi tot · dr i
i
(Note that Wtot is not the thermodynamic work appearing in
the first law.) Several other kinds of work equal to sums of
integrals as in eq 5 but involving different forces will appear
506 Journal of Chemical Education • Vol. 84 No. 3 March 2007
below, and they will be distinguished by appropriate sub-
scripts.
By substituting the expression for Fitot from eq 4 into
the integrand of eq 5 and replacing dri by vidt, we obtain
d vi
W tot = ∑ mi
dt
· vi dt = ∑ mi vi · d vi
i i
(6)
= ∑ d ( 12 mi vi2) = ∆ ∑ 12 mi vi2
i i
where vi is the magnitude of the velocity of particle i in the
lab frame. The sum Σi(1/2)mivi2 is the total kinetic energy of
the system particles in this frame. Thus, the total work dur-
ing the interaction time period is equal to the change in the
total kinetic energy. This result is known in classical mechan-
ics as the “work-energy relation” (3) or “work-energy prin-
ciple” (13).
By substituting the expression for Fitot given by eq 3 into
eq 5, we obtain a second expression for Wtot:
W tot = W int + W grav + W cnt (7)
(3)
The terms on the right side are defined by W int =
ΣiΣj≠i兰Fij⭈dri, the internal work from interactions between the
system particles; Wgrav = Σi兰Fi grav⭈dri, the work done by gravi-
tational forces acting on these particles; and W cnt =
Σi兰Ficnt⭈dri, the work done by contact forces from the sur-
roundings.
Next we look in detail at the internal work. We assume
the force Fij exerted on particle i by particle j is a central force
directed along the line between i and j; its magnitude de-
pends only on the interparticle separation rij, as is true of
(4) interatomic and intermolecular forces in general. We expect
the force to be repulsive when rij is small and to approach
zero as rij becomes large; however, the exact dependence of
Fij on rij does not concern us. We can define a potential func-
tion Φij for this force such that its change for an infinitesi-
mal change of rij is given by dΦij = ᎑(Fij⭈eij)drij, where eij is a
unit vector pointing from particle j to particle i. The value
of Φij at any separation distance rij is defined by this equa-
tion and the choice of a zero of energy.
The expression for the internal work, W int =
ΣiΣj≠i兰Fij⭈dri, is a double sum that can be written as a sum
over pairs of system particles, the term for the pair i and j
being
Fi j · dr i + F ji · dr j = Fi j · d ( r i − r j )
(8)
= ( Fi j · ei j )dri j = − dΦi j
Here we have used the relations Fij = ᎑Fji (from Newton’s third
law) and (ri − rj) = eijrij. The internal work is then given by
(5) W int = −∑ ∑ dΦi j = −∆ ∑ ∑ Φi j (9)
i j >i i j >i
The sum ΣiΣj>iΦij is the internal potential energy of the sys-
tem owing to interactions between the system particles. Un-
• www.JCE.DivCHED.org

Figure 1. Position vectors within the system: open circle–origin of
a lab frame; triangle–a point in the boundary at segment τ of the
interaction layer; and filled circle–particle i within segment τ.
like the kinetic energy, the internal potential energy is inde-
pendent of the reference frame since it is a function only of
interparticle distances.
The gravitational force acting on particle i is Fi grav =
᎑mi gez where g is the acceleration of free fall and ez is a unit
vector pointing in the vertical (upward) direction. The work
done by the gravitational forces acting on the system par-
ticles during the interaction time period is
grav
W grav = ∑ Fi · dr i = −∑ mi g ez · dr i
i i
= −∑ mi g d zi = −∆ ∑ mi g zi
i i
(The system’s vertical extent is assumed to be small compared
to the earth’s radius, so that we may approximate g by a single
value throughout the system.) The sum Σimi gzi is the gravi-
tational potential energy of the system, and is a function of
the elevations zi of the system particles in the lab frame.
By eliminating Wtot from eqs 6 and 7, making substitu-
tions from eqs 9 and 10, and rearranging, we obtain the im-
portant relation
W cnt = ∆ ∑ 12 mi vi2 + ∑ ∑ Φ i j + ∑ mi g zi
i i j >i
The expression within the parentheses on the right side of
this equation is the sum of the system’s total kinetic energy,
internal potential energy, and gravitational potential energy.
In accord with the discussion in the preceding section, we
shall use this expression to define E, the energy of the sys-
tem relative to the lab frame:
E = ∑ 12 mi vi2 + ∑ ∑ Φ i j + ∑ mi g zi
i i j >i i
Note that E is a function only of the speed and elevation of
each system particle and of the interparticle distances within
the system.
Equations 11 and 12 show that the system’s energy
change during the interaction time period equals the work
done by the short-range contact forces acting across the
boundary:
Fi cnt · d ri
∆E = Wcnt = ∑ (13)
i
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Research: Science and Education
It might seem that work done on the system particles
by gravitational forces should appear in the expression for
∆E. The reason this work does not appear in eq 13 is that we
have assumed the gravitational potential energy belongs only
to the system and is thus irrelevant to energy transfer from
or to the surroundings. It is instructive to look at some simple
examples of the role of the gravitational potential energy when
it is included like this as a contribution to E. Suppose the
system is a solid body. If the only force exerted on the body
is the downward force of gravity, the body is in free fall and
according to eq 13 ∆E is zero; the loss of gravitational po-
tential energy as the body falls equals the gain of kinetic en-
ergy. On the other hand, if we pull the body upwards at
constant speed with a string, work is being done on the sys-
tem by a contact force, and eq 13 shows ∆E is positive. In
this case the body’s gravitational potential energy increases
while its kinetic energy remains constant.
If we had omitted the gravitational potential energy from
our definition of E, then ∆E would have been the work done
on the system by both contact and gravitational forces. In
this case ∆E would have been positive for the body in free
fall and zero for the body pulled upwards at constant speed
with a string.
Equation 13 shows that ∆E is zero in a system without
external interactions—one for which Ficnt is zero for each i.
This can be interpreted as a statement of the conservation of
(10) the energy of the universe.
Macroscopic Work and Heat
In classical thermodynamics we are interested in work
involving displacements of macroscopic parts of the system
during a process; that is, the thermodynamic work w appear-
ing in eq 1.
We can define an “interaction layer” as a thin outer layer
of the system lying next to the boundary surface. This shell-
like layer must be sufficiently thick to include at each in-
stant all the system particles that are close enough to the
boundary to interact with the surroundings by short-range
(11) contact forces, that is, all the particles with nonnegligible val-
i ues of Ficnt. We imagine the interaction layer to be divided
into segments in such a way that all parts of each segment
are either stationary or move essentially in one direction dur-
ing the process. For example, the interaction layer of a fluid
next to a piston with linear motion needs only a single flat
segment, whereas the interaction layer of a system that ex-
pands in all directions must be divided into many segments
each moving in a different direction.
Let Rτ be a position vector from the origin of the lab
(12) frame to a point fixed in the outer face of segment τ at the
boundary, and let ri τ be a vector from this point to particle i
within segment τ, as shown in Figure 1. Then the position
vector for particle i can be written as the vector sum
r i = R τ + ri τ
The work done on the system particles by contact forces
exerted by the surroundings is given by the sum of integrals
in eq 13. Consider the work done on just the particles in a
particular segment τ. Since the particles may move in and
out of the segment during the interaction time period, the
• Vol. 84 No. 3 March 2007 • Journal of Chemical Education 507
 Research: Science and Education
work is found by limiting the integration for each particle to
the periods of time that the particle is located within this
segment. Define δi τ to be like a Kronecker delta: δi τ is equal
to 1 when particle i is in segment τ and is zero otherwise.
Then we can write the sum of integrals for segment τ as
∑ δi τ Ficnt · dr i
i is experiencing a repulsive contact force from the surround-
= ∑ δi τ Fi cnt · d R τ + ∑ δi τ Fi cnt · d ri τ (14)
i i
The delta function δi τ in the integrands of these integrals
ensures that the integrations are carried out only while par-
ticle i is in segment τ during the interaction time period.
The sum Σiδi τFicnt is the total contact force, Fτcnt, ex-
erted by the surroundings on segment τ at any instant, so
the first sum on the right side of eq 14 can be written
∑ δi τ Fi cnt · d R τ = Fτcnt · d R τ (15)
i surroundings show that an equal quantity of energy leaves
In the integral on the right side of this equation, the scalar
product of the contact force exerted on segment τ and the
displacement of the boundary at this segment is being inte-
grated over the displacement during the interaction time pe-
riod. We recognize this integral as the macroscopic work done
on segment τ.
Substituting from eq 15 into eq 14 and summing over
all segments of the interaction layer, we obtain the total work
done on the system particles by contact forces:
W cnt = ∑ Fτcnt · dR τ + ∑∑ δi τ Fi cnt · d ri τ (16)
τ τ i
The first sum on the right side is the total macroscopic work,
so this sum is the thermodynamic work for the whole sys-
tem:
w = ∑ Fτcnt · d R τ (17)
τ
Only the segments at moving portions of the boundary need
be included in this sum, because an integral with dRτ = 0 is
zero.
Since Wcnt is equal to ∆E (eq 13), which is the sum of q
and w (eq 1), the second sum of integrals on the right side
of eq 16 must be the heat:
δi τ Fi cnt · dr i τ
q = ∑∑ (18)
τ i
It is important to note that because the vector riτ gives the
position of particle i relative to a point at the nearby bound-
ary, rather than relative to the origin of the reference frame,
the integral 兰δiτFicnt⭈driτ has the same value in any non-ro-
tating reference frame. Thus q for a given process has the same
value in any lab frame and in a center-of-mass frame.3 In con-
trast, the value of w depends on the choice of reference frame.
In the integral 兰δiτFicnt⭈driτ in eq 18, the scalar product
of the contact force exerted on particle i and its displacement
relative to a point at the nearby boundary is being integrated
over the displacement during the period or periods the par-
508 Journal of Chemical Education • Vol. 84 No. 3 March 2007
ticle is in segment τ. At each instant the particles in this seg-
ment are moving in various directions relative to the point
at the boundary; even the atoms of a solid have vibrational
motion. The energy transferred as heat across the boundary,
as expressed by eq 18, is the net result of these contact forces
and chaotic motions. For example, during a period that par-
ticle i is moving away from the boundary at segment τ and
ings, the value of 兰Ficnt⭈driτ is positive and will make a posi-
tive contribution to q during this period.
An expression for heat similar to eq 18 was derived by
Besson (14). Instead of displacements of particles relative to
points at the boundary, his expression uses displacements rela-
tive to the centers of mass of “mesoscopic elements” that are
like the segments of the interaction layer described here.
Are work and heat transferred quantitatively across the
system boundary? That is, if a certain quantity of energy en-
ters the system in the form of work as defined by eq 17, does
the application of the equation to an interaction layer of the
the surroundings as work, and does a similar equality apply
to heat? Let wsys and qsys be the quantities of energy trans-
ferred into the system as work and heat during a given pro-
cess (the same as w and q above), and let wsurr and qsurr be
the energies transferred as work and heat into the surround-
ings during this process. A derivation in the Supplemental
MaterialW for this article shows that wsurr is equal to ᎑wsys and
that qsurr is equal to ᎑(qsys + ∆Epcnt), where Epcnt is the poten-
tial energy of the contact forces acting across the boundary.
As mentioned in an earlier section, Epcnt is usually negligible
so that qsurr is practically equal to ᎑qsys. We can therefore say
that both work and heat are transferred quantitatively.
The Problem of Friction at the Boundary
Difficulties arise if we attempt to use eq 17 to evaluate
energy transferred as work across a boundary where there is
a discontinuity of macroscopic motion. This situation occurs
in a system with sliding friction at the boundary.
Consider what happens when we slide a solid lead block
across a lab bench. The block exerts a frictional drag force (a
form of contact force) in the direction of its motion on the
bench, and the bench exerts a force of equal magnitude on
the block in the opposite direction. According to eq 17, if we
consider the block to be the system and the bench to be in
the surroundings then there is negative work at the interface;
but if we let the bench be the system then the work at the
interface is zero because the bench is stationary. This result
makes no sense, since we expect w to have the same magni-
tude and the opposite sign when the system and surround-
ings switch roles.
The source of the paradox is an incorrect assumption
that the surfaces at the sliding interface are completely rigid
as they move past one another. A more realistic picture of
dry (unlubricated) friction on a mesoscopic or nanometer
scale recognizes that when two solid surfaces touch, the only
places the two solids are in direct contact and can exert forces
on one another is at small areas where one or both of the
surfaces has a bump or “asperity” (15, 16). The tip of an as-
perity on one surface can temporarily adhere to the opposite
surface and become bent and distorted as the solids slide past
• www.JCE.DivCHED.org
 Research: Science and Education

system’s energy measured in a cm frame, ∆U, and in a lab

frame, ∆E.
In the lab frame, the system’s center of mass is defined
by the position vector

∑ mi r i
i
R cm = (19)
∑ mi
i

As shown in Figure 2, the vector ri from the origin of the lab

Figure 2. Position vectors in a lab frame (lower right) and a cm
frame (upper left): open circle–center of mass and filled circle–par-
ticle i.
frame to particle i is equal to the vector sum of the vector
Rcm from this origin to the center of mass and the vector r⬘i
from the center of mass to particle i:
r i = R cm + r ′i (20)

The particle’s velocity in the cm frame is

one another. An asperity on the surface of one solid may plow v ′i =

a furrow in the other solid. Heat may be transferred through
these direct contacts. At each small area of direct contact,
the forces the two solids exert on one another are equal in
magnitude and opposite in direction and the local displace-
ments are the same for both solids. Thus the work due to
friction is not simply equal to the product of the total fric-
tional force and the macroscopic displacement. If we could
use eq 17 to calculate the work on a small mesoscopic scale,
we would find that the magnitude of the work does not de-
pend on which solid we consider to be in the system, but its
sign does (12). Unfortunately, it is not practical to evaluate
this work because we have no way of knowing the forces and
displacements on this scale. Another difficulty with dry fric-
tion at the boundary is that if abrasion occurs here, we can-
not treat the system as a closed system whose parts remain
contiguous.
These problems were recognized by Bridgman, who of-
fered the sage advice that “we would do well not to attempt
to apply the conventional statement of the first law to a re-
gion whose bounding surface is a surface of mathematical
discontinuity where mechanical energy is converted at a fi-
nite rate into thermal energy” (17). Bridgman pointed out
that the difficulty of evaluating w for a system with dry fric-
tion can be avoided by redefining the boundary surface so
that it is displaced slightly away from the sliding interface,
leaving both surfaces of the sliding interface either entirely
in the system or entirely in the surroundings.
If two solid sliding surfaces are separated by a film of
liquid lubricant, there is no discontinuity of macroscopic
motion as there is with dry friction. With lubricated friction
present at the boundary, eq 17 can be used to evaluate the
energy transferred as macroscopic mechanical work. The work
depends on the exact location of the boundary surface rela-
tive to the solid surfaces (15).
Center-of-Mass Frame and Internal Energy
A center-of-mass frame (or cm frame) is a non-rotating
frame whose origin moves with the system’s center of mass.
This section derives the relation between the change of the
dr ′i
=
(
d r i − R cm ) = vi − v cm
dt dt
where vi is the velocity of particle i in the lab frame and vcm
is the velocity of the center of mass in this frame. From eq
19 we have the relation Σimiri = ΣimiRcm, and from eq 20 we
have Σimiri = ΣimiRcm + Σimir⬘i. Comparing these two rela-
tions, we deduce that the sum Σimir⬘i is zero. Taking the de-
rivative of this sum with respect to time, we find that the
sum Σimiv⬘i is also zero.
The internal energy U is the energy of the system mea-
sured in the cm frame. We find the contributions to U as
follows. The total kinetic energy of the particles measured in
the cm frame is Σi(1/2)mi(v⬘i )2. The internal potential energy
in this frame is the same as in the lab frame, because this
energy depends only on interparticle distances. The work
done by gravitational forces acting on the system particles,
measured in the cm frame, is given by
grav
∑ Fi · dr ′i = ∑ (−mi g ez ) · dr′i
i i
= −∑ mi g d z ′i = −∆ ∑ mi g z ′i
i i
where z⬘i is the vertical position of particle i in the cm frame.
Taking the vertical component of the relation Σimir⬘i = 0,
we obtain Σimiz⬘i = 0. Thus the gravitational work in the cm
frame is zero, and U does not include gravitational potential
energy. Accordingly, the only contributions to the internal
energy are the kinetic energy in the cm frame and the inter-
nal potential energy:
U = ∑ 12 mi (v′i )2 + ∑ ∑ Φ i j (21)
i i j >i
Note that the internal energy at any given instant de-
pends only on the speeds of the system particles in the cm
frame and on the interparticle distances. Since thermody-
namic variables such as temperature and pressure are the mac-
roscopic manifestations of these and other microscopic
variables, we can consider the function on the right side of

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 Research: Science and Education

eq 21 to be a state function.4 Equation 21 shows U does not

depend on the system’s overall velocity and position relative
to a lab frame, thus satisfying the requirement that the in-
ternal energy should be a function only of internal thermo-
dynamic variables.
In order to relate the kinetic energies of the system par-
ticles in the lab and cm frames, we expand the expression for Figure 3. Cylinder with gas confined by a piston.
the kinetic energy in the lab frame as follows:

∑ 12 mi vi2 = ∑ 12 mi ( vcm + v ′i ) · ( v cm + v ′i )
i i
2 Expansion Work
= 1
2
m vcm2 + vcm · ∑ mi v i′ + ∑ 12 mi ( v′i )
i i As an example of the use of eq 17 to evaluate thermo-
dynamic work, consider the cylinder-and-piston apparatus
Here m is the total system mass: m = Σimi. Since the sum shown in Figure 3. Let the system be the gas confined by the
Σimiv⬘i is zero, the expression becomes5 piston in the cylinder. The cylinder remains stationary in the
lab frame. By using the piston rod to apply a variable exter-
2
∑ 12 mi vi2 = 1
2
mv cm2 + ∑ 12 mi ( v′i ) (22) nal force to the piston, we can make the piston move in the
i i +x or ᎑x direction with an accompanying expansion or com-
pression of the gas.
This is a well-known result in classical mechanics, where it Because the only moving portion of the boundary in this
is described by saying that the kinetic energy of a system of apparatus is at the inner face of the piston, we can evaluate
particles in an inertial frame is equal to the sum of the ki- w using a thin disk-shaped segment of the interaction layer
netic energy that the system would have if all the mass were of the gas at the piston. We shall designate this segment at
concentrated at the center of mass, and the kinetic energy of the moving boundary by the subscript b. At each instant the
motion of the particles about the center of mass (18). The gas particles in this segment exert a force on the piston in
quantity 1/2mvcm2 is called the bulk kinetic energy. the +x direction of magnitude pb A, where pb is the average
The gravitational potential energy Σimi gzi, which is in- gas pressure at the piston and A is the cross-section area of
cluded in E but not in U, is related to the elevation zcm of the cylinder. We know from Newton’s third law that the pis-
the center of mass in the lab frame. By rearranging eq 19 to ton exerts a force Fbcnt on the segment in the ᎑x direction,
Σimiri = mRcm and taking the z component of both sides, we equal in magnitude to pb A. According to eq 17, the work
obtain the relation Σi mi zi = mzcm. From this we find the gravi- during this process is
tational potential energy is given by
w = F bcnt · d R b
∑ mi g zi = m g z cm (23)
i where Rb is a vector from the origin of the lab frame to a
By making substitutions from eqs 21–23 in eq 12, we point on the moving boundary (the inner face of the pis-
obtain E = U + 1/2mvcm2 + mgzcm, or ton). The change in Rb during the expansion or compres-
sion process is related to the piston displacement dx by dRb
= exdx, where ex is a unit vector in the +x direction. By set-
∆U = ∆E − 1 m ∆(vcm2 ) − m g ∆ z cm (24)
2 ting Fbcnt equal to ᎑pb Aex, we can express the work as an in-
tegration over the volume:
From eqs 1 and 2 we have the relation wcm = w + ∆U − ∆E,
which when combined with eq 24 yields w = − p b dV (26)

w cm = w − 1
2
m ∆(v cm2 ) − m g ∆ zcm
Equations 24 and 25 allow us to convert values of the sys-
tem energy change and the thermodynamic work measured
in a lab frame to the values in the cm frame. The correction
terms are the changes in the bulk kinetic energy and the gravi-
tational potential energy.
Suppose we had omitted the gravitational potential en-
ergy from our definition of E. Then instead of eqs 24 and
25 we would have the relations ∆U = ∆E − 1/2m∆(vcm2) and
wcm = w − 1/2m∆(vcm2).6 However, the values of ∆U and wcm
for a given process would not be affected by this change in
definition, because the values of ∆E and w would change so
as to keep ∆U and wcm the same.
(25) Equation 26 is similar to the familiar formula w = ᎑兰pdV
for reversible expansion work. The difference between the two
formulas is that pb is the pressure at the piston, whereas p is
the uniform pressure of the gas in the reversible limit of an
infinitely slow volume change. In the reversible limit pb is
the same as p and the two formulas are equivalent.
The initial and final states of a process are usually cho-
sen to be equilibrium states in which the center of mass is
stationary. In this case, the quantity ∆(vcm2) appearing in eqs
24 and 25 is zero. If in addition there is no change in the
elevation zcm of the system’s center of mass, as is the case for
the gas in the horizontal cylinder shown in Figure 3, then
according to eqs 24 and 25 w and wcm are equal and ∆E and
∆U are the same.

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For a process in which there is a change in the elevation
of the system’s center of mass, the values of w and wcm are no
longer equal. However, for most processes of interest to chem-
ists the difference between these two values is negligible. For
example, suppose we tilt up the cylinder of Figure 3 to a ver-
tical position with the piston situated above the gas and al-
low the gas to expand to twice its initial volume. If the gas is
ideal and the expansion is carried out reversibly and isother-
mally, the work measured in the lab frame is w = ᎑nRT ln 2
and the work measured in the cm frame is wcm = ᎑nRT ln 2
− mg∆l兾2 where l is the vertical length of the gas column.
For nitrogen gas at 300 K and an initial column length of
one meter, the difference between w and wcm is only 0.008
percent of w.
These considerations show that as a practical matter it
is usually unnecessary to make a distinction between the ther-
modynamic work measured in a lab frame and in a cm frame,
and between the energy change ∆E in the lab frame and the
internal energy change ∆U. In fact, most physical chemistry
textbooks ignore these distinctions.7 The only processes for
which it is important not to neglect the correction term
mg∆zcm are those in which relatively massive parts of the sys-
tem undergo substantial changes in elevation.
Discussion
In this article the energy E of the system relative to an
earth-fixed lab frame is defined to be the sum of the kinetic
energies of the individual system particles, the internal po-
tential energy from forces between these particles, and the
gravitational potential energy of the particles. The mathemati-
cal expression of the first law of thermodynamics for changes
measured in the lab frame is written ∆E = q + w, where q is
heat and w is thermodynamic work.
The general expressions for w and q obtained from the
particle model are given by eqs 17 and 18, respectively. The
expression for work was derived with the assumption that
mechanical thermodynamic work is an energy transfer across
the boundary surface owing to concerted motion of system
particles on which the surroundings exert contact forces; heat
is then found to be an energy transfer involving the same
contact forces and chaotic motions of the system particles.
By applying the expression for w to the particles in the sur-
roundings instead of the system, it is found that the energy
transfer is quantitative; that is, the work from the viewpoint
of the system corresponds to an equal quantity of work, with
sign reversed, from the viewpoint of the surroundings. A simi-
lar statement applies to the energy transferred as heat.
The model supports the concept of work and heat be-
ing quantities of energy transferred locally at the boundary.
This interpretation of w and q is entirely consistent with
Bridgman’s imagery of using imaginary “sentries” posted at
every infinitesimal element of the boundary surface to evalu-
ate the quantities of work and of heat that pass across the
boundary at these surface elements (19). As is well known,
work and heat are modes of energy transfer and not forms of
energy; once a quantity of energy is transferred across the
boundary, it can no longer be identified as work or heat.
The internal energy U of the system is a state function
that depends only on internal thermodynamic variables. By
subtracting the sum of changes in the bulk kinetic energy
www.JCE.DivCHED.org • Vol. 84 No. 3 March 2007
Research: Science and Education
and gravitational potential energy from ∆E, one obtains the
change ∆U (eq 24). In ordinary chemical processes in which
the initial and final states are equilibrium states, ∆U and ∆E
are usually nearly equal and in some situations are exactly
equal.
In the case of expansion or compression of a gas con-
fined by a piston in a stationary cylinder (Figure 3), the ther-
modynamic work according to eq 17 is w = ᎑兰pbdV where pb
is the pressure at the moving boundary (the inner face of the
piston). This expression is a general one for both reversible
and irreversible expansions and compressions. Equivalent ex-
pressions for expansion work have been given by other au-
thors (20–24). Kinetic-molecular theory shows that if the
piston has a finite velocity, pb is not the same as the pressure
p in the bulk of the gas; pb is less than p during expansion
and greater than p during compression (25). Gislason and
Craig have questioned the practicality of evaluating w from
the integral 兰pbdV because the value of pb for a finite piston
velocity is unknown (26). A possible way around this prob-
lem is the suggestion of Bauman and Cockerham (25) that
pb could be measured with transducers on the piston face.
Furthermore, formulas are available for estimates of pb when
the piston speed is small compared to the average speed of
the gas molecules (24, 25).
Some authors, including Planck (27), Zemansky (28),
and Castellan (29), state that thermodynamic work should
be defined by changes in the surroundings of the system rather
than by energy transfers at the boundary. Gislason and Craig
(26) give recipes for evaluating the work and heat during a
process from measurements in the surroundings and use the
term “surroundings-based” for these quantities (30). If the
process is carried out in the slow reversible limit, the sur-
roundings-based values are the same as the values of the w
and q defined in the present article (which they call “system-
based”). However, if the process is irreversible for the system
plus surroundings taken together the values can be different.
For example, the surroundings-based value of work for an
irreversible expansion is not necessarily equal to ᎑兰pbdV (30).
Regardless of whether or not the process is reversible, the value
of ∆E (the sum of the work and heat) is the same using ei-
ther set of definitions (30).
The particle model described in the present article sup-
ports the validity of definitions of mechanical work and heat
as quantitative transfers of energy at the boundary. If one takes
the view that mechanical work is a quantity of energy trans-
ferred across the boundary owing to displacements of mac-
roscopic portions of the system on which the surroundings
exert contact forces, then for a reversible or irreversible pro-
cess of a closed system one should use an expression for w
consistent with eq 17.
Acknowledgment
I wish to thank Eric A. Gislason for helpful comments
on a draft of this article.
W
Supplementary Material
A derivation showing that work and heat are transferred
quantitatively across the system boundary is available in this
issue of JCE Online.
• Journal of Chemical Education 511
 Research: Science and Education
Notes
1. Rough calculations based on heats of vaporization suggest
that the potential energy of contact forces between condensed
phases, per unit area of the interface, is typically between ᎑0.05 J兾m2
and ᎑0.2 J兾m2 (relative to infinite separation of the phases). The
value for a gas in contact with a solid wall is even smaller in mag-
nitude because of the lower frequency of collisions at the wall.
2. An inertial frame of reference is one in which Newton’s
first and second laws of motion are valid. An earth-fixed frame is
not absolutely inertial because the earth spins about its axis and
moves in an orbit around the sun, but Newton’s second law is
obeyed in this frame to a high degree of accuracy.
3. Since the change of the entropy S of a closed system dur-
ing a reversible process is defined by dS = dq兾T, we can conclude
that ∆S for a given process has the same value in all non-rotating
reference frames.
4. It would not be correct to say that a system with a given
macroscopic state has exactly the same value of U at each instant,
because the energy fluctuates slightly in time. For a system of par-
ticles whose macroscopic state is not changing, the internal energy
that is a state function is actually the time-averaged value of the
function given by eq 21.
5. Equation 22 is valid even if the center of mass accelerates
in the lab frame so that the cm frame is noninertial. Using a cm
frame for internal coordinates makes it possible to separate the ki-
netic energy in the lab frame into external and internal contribu-
tions as shown in this equation. It is this separability property that
makes a cm frame uniquely suitable for defining the internal en-
ergy of a thermodynamic system.
6. Erlichson (1) gives an equivalent expression for ∆U.
7. The text by Levine (31) is an exception.
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