Chemistry 223: Work, Heat, and Energy: 1. Zeroth Law of Thermodynamics

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Chemistry 223: Work, Heat, and Energy

David Ronis
McGill University

1. Zeroth Law of Thermodynamics


If two bodies at equilibrium are brought into thermal contact (i.e., no mechanical,
electrical, magnetic, gravitational, etc., work is performed) and nothing happens,
then they are at the same temperature.
Given this, we can always measure the temperature of any system by bringing it into thermal contact with some standard thermometer. As we shall see, a very convenient choice is the
ideal-gas thermometer. Here a manometer is used to measure the pressure of a fixed amount of
gas in a fixed volume and the relation
NRT
V
is used to calculate the temperature. Needless to say, other temperature standards can (and are)
used.
P=

2. Some Definitions
Intensive

Doesnt depend on the size of the system; e.g., P, T, partial molar quantities.

Extensive

The opposite of intensive; e.g., mass, volume, energy (but not energy per unit
volume or mass), heat capacities (but not specific heats).

System

The part of the universe under investigation. Systems can be:


a)

Isolated: no interaction of any kind with surroundings. Note that real


systems cannot be truly isolated, but can be approximately so on the
time-scale of relevance.

b)

Closed: energy can be exchanged with surroundings, but matter cannot.

c)

Open: matter and energy can be exchanged.

Surroundings

The part of the universe not under investigation.

Boundary

What divides the system from the surroundings (and controls whether the system is open, closed, or isolated).

State

A systems state is specified when all measurable properties have definite values to the accuracy of the experiment.

State Variables

A set of measurable quantities, which when known, completely specify the


state of the system. In classical or quantum mechanics there are on the order
of 1023 state variables; however, in thermodynamics, experience tells us that
the macroscopic state of the system is specified after a small set of measurements are made (e.g., T, P, V, x 1 , . . . , x r ).

Process

Something whereby the state of a system is changed. A process has two parts:
a)

Initial and final states (i.e., where the system starts and ends).

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Work, Heat, and Energy

A Path. The path describes how the change was effected. In order to
specify the path, intermediate changes in the system, surroundings and
boundary must be specified. This is clearly something which we would
like to avoid in many cases.

Reversible

A process is said to be reversible if it is possible to return both the system and


the surroundings to their original state. If not, it is irreversible (even if the
system can be returned to the original state).

State Function

A property of the system which only depends on the current state of the system. Hence, changes in state functions do not depend on the path taken. State
functions play a key role in thermodynamics and allow macroscopic properties
of matter to be studied in a rigorous, systematic manner. Examples of state
functions are: energy, entropy (to be introduced later), P, V, T, etc. A onecomponent ideal gas has a pressure, P(T,N,V), given by PV=NRT no matter
what--how the T, V, or N attained their current values is irrelevant.

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3. Eulers Theorem, Partial Molar Quantities, and the Gibbs-Duhem Relations


Next consider any extensive quantity in a mixture containing r components; i.e.,
A(T , P, N 1 , . . . , N r ). Real examples could be the energy, volume, mass, heat capacity, etc.. Consider the small change in A associated with changes in its arguments, namely*
dA =

A
A
A
A
dT +
dP +
dN 1 +. . . +
dN .
P T ,N 1 ,...,N r
N 1 T ,P,N 2 ,...,N r
N r T ,P,N 1 ,...,N r1 r
T P,N 1 ,...,N r
(1)

Now, by assumption, A is extensive; hence,


A(T , P, N 1 , . . . , N r ) = A(T , P, N 1 , . . . , N r ).

(2)

If we differentiate both sides of this equation with respect to and evaluate the result at = 1 it
follows that
A(T , P, N 1 , . . . , N r ) =

A
A
N 1 +. . . +
N
N r T ,P,N 1 ,...,N r1 r
N 1 T ,P,N 2 ,...,N r

(3)

Ai N i ,
i=1

(4)

where
Ai

A
N i T ,P,N ji

(5)

is called a partial molar quantity. Note that the partial molar quantities are intensive. In obtaining Eq. (3) you may use Eq. (1) for dT = dP = dN i = 0 and d( N i ) = N i d for i = 1, . . . , r).
Also note that Eq. (3) is a special case of Eulers theorem for homogeneous functions in calculus.
Equations (3) or (4) allow us to explicitly express the nontrivial features of an extensive
quantity in terms of intensive ones, thereby reducing the number of dependencies we must worry
about. It also turns out that the partial molar quantities (or more specifically, changes in them)
are not all independent. To see this, we calculate dA from Eq. (4):
dA =

Ai dN i + N i d Ai ,

(6)

i=1

where we have used the calculus result d(xy) = xdy + ydx. Of course, dA could have been computed from Eq. (1); i.e.,
*

Note that we may use Eq. (1) to work out what is known as a total derivative. Consider the case where
r = 1, i.e., N 1 = N (T , P). Well keep P constant and consider the remaining N be a function of T and P.
By dividing Eq. (1) by dT it follows that
A
A N
dA
=
+
.
dT P T P,N N T ,P T P
Note that the first term on the right hand side is just the usual derivative while the second is an example of
the chain rule.

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Work, Heat, and Energy

r
A
A
dT +
dP + Ai dN i ,
P T ,N 1 ,...,N r
T P,N 1 ,...,N r
i=1

(7)

where we have rewritten the derivatives with respect to the numbers of moles in terms of the partial molar quantities, cf. Eq. (5). By equating the right hand sides of Eqs. (6) and (7) it follows
that
r
A
A
dT +
dP N i d Ai = 0,
T P,N 1 ,...,N r
P T ,N 1 ,...,N r
i=1

(8)

and hence, the changes in the partial molar quantities and other derivatives are not all independent. Equation (8) is known as a Gibbs-Duhem relation and can be used to relate seemingly disparate thermodynamic derivatives.
As an exercise, what are the partial molar volumes for an ideal gas mixture obeying Daltons law of partial pressures? Do they obey the Gibbs-Duhem relation?
4. Work and Heat in Thermodynamics
Two central concepts in thermodynamics are work and heat. You probably have seen examples of the former in your freshman physics class, and the latter is something you experience in
daily life. In thermodynamics, both have very precise definitions.
Work: Anything which crosses the boundary of the system and is completely convertible into
the lifting of a weight in the surroundings.
Note that work only appears at the boundary of a system, during a change of state, is extensive, and is manifested by an effect in the surroundings. From mechanics, we know that
dW = Fdx = mgdx,

(9)

where dW is the incremental work done, F is the force being exerted on the system, and dx is the
distance traversed. The second equality is for moving a mass m a distance dx in a gravitational
field (g is the gravitational acceleration constant). Note that there are two sign conventions for
work in thermodynamics. In the older, the force is that exerted by the system on the surroundings, and the corresponding work is the work done by the system on the surroundings. In the
newer convention, things are reversed; the force is the force the surroundings exert on the system
and the work is that done by the surroundings on the system. Since Newtons law states that
these two forces must be equal and opposite, the two conventions differ by a sign. The text, and
we, will use the latter convention here although note that Castellan uses the older convention.
Consider the following apparatus:

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The inside of the piston is filled with some gas at pressure P


and is maintained at constant temperature T. Instead of
characterizing the work done in terms of the mass, it is
more convenient to introduce the pressure exerted on the
top of the piston (i.e., force per unit area, A)

M (mass)

F mg
=
,
A
A
and acts downward. Note that P op need not equal P.
P op

dx

A (area)

Thus
d W = P op Adx = P op dV ,

(10)

(11)

where dV is the incremental change in the volume of the system. The work involved in these
sorts of processes is known as pressure-volume work.
Note that the work done is not a state function--it depends on the pressure exerted on the
piston (the path) and is not simply a function of the state of the gas in the piston. To stress this
fact, the notation d will be used for infinitesimal changes in quantities which depend on the path.
For an process whereby the gas is expanded against some pressure, dV > 0, and hence,
d W < 0. Conversely, in a compression process, d W > 0, i.e., negative work is done by the system. The surroundings do positive work on the system.
This diagram shows a process for the isothermal
expansion of a gas (in this case an ideal gas). The solid
curve gives the pressure of the gas (i.e., its equation of
state). The dotted curve gives the opposing pressure actually used in the expansion. Note that the latter lies completely below the former. If at any point this were not the
case, then the expansion would not proceed spontaneously
(i.e., the opposing pressure would be too large and the gas
would contract).
The total work done by the surroundings on the system (- the total work done by the system on surroundings)
is just the negative of the area under the dotted curve:
W =

V final

P op (V )dV

initial

V final

P(V )dV W rev .

(12)

initial

If the gas inside the piston is ideal, then the ideal-gas equation of state is valid and
W rev =

V final

initial

NRT
dV = NRT ln(V final /V initial ).
V

(13)

Note that the maximum work you can get out of a spontaneous expansion is obtained when
the opposing pressure is infinitesimally less than the pressure being exerted by the gas in the piston. In this case, W = W R . Unfortunately, the rate of such an expansion would be zero, as would
be the power delivered by the system. On the other hand, it is easy to show that the path given
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Work, Heat, and Energy

by P op = P is the only reversible one for the isothermal expansion of an ideal gas.
Consider the following apparatus (from L. K. Nash, Elements of Chemical Thermodynamics, Addison-Wesley, 1970):

The spring is assumed to obey Hookes law (i.e, the force is proportional to the elongation). A
series of experiments are performed whereby weights are moved to pan from platforms at various
heights in the surroundings. In doing so, the system (the spring and pan) move from state I to II.
How much work is performed in each of the cases (a)(c) (assume that there is a total 1cm elongation of the spring and ignore the mass of the pan and spring)?
In order to reverse the process (i.e., the expansion of the spring) the weights are moved back
to the adjacent platforms. However, it is easy to see that while the spring will be fully compressed at the end of the experiment, the surroundings will not be restored to their initial state;
specifically, in the best case, the topmost weight will be transferred to the lowest platform, no
matter how many platforms are used. Clearly the biggest change in the surroundings will happen
in case (a) and the smallest in (c). Moreover, the smaller the individual weights we use, the more
reversible the process becomes (i.e., the change to the surroundings decreases). The process is
reversible in the limit where the applied force (the weight) is only infinitesimally more than the
force exerted by the spring.
This argument can easily be extended to our discussion of pressure-volume work or to other
kinds of work. Hence, the maximum work in a P-V expansion is obtained for a reversible path.
Another key quantity in thermodynamics is heat.
Heat:

Anything which flows across the boundary of a system by virtue of a temperature difference between the system and the surroundings.

Heat is quantified by measuring the temperature rise (or fall) in a standard material (e.g., a
calorie corresponds to the amount of heat required to raise the temperature of 1 g of water 1 oC).
Like work, heat appears only at the boundary of a system, during a change of state, is extensive,
and is manifested by an effect in the surroundings. It is also not a state function since it depends
on the nature of the thermal contact allowed at the boundary of the system.

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In a classic set of experiments in the 19th century, J. P. Joule showed that the same changes
in the state of a system could be achieved by either adding work or heat to the system. One of
his devices is shown below.
As the weight falls, the paddles turn and
heat up the liquid in the container by friction
(viscous heating). The same temperature
rise can be achieved by directly heating the
container using a known amount of heat.
The amounts of heat and work were
definite and Joule concluded that work and
heat were simply two different ways in
which energy could be added to a system.
Specifically, Joule showed that
1 calorie = 4. 184 kg m 2 /sec 2 .
We are now ready to state the first law of thermodynamics.
5. The First Law of Thermodynamics:
In any cyclic process (i.e., one where the system returns to its initial state) the
net heat absorbed by the system is equal to the work produced by the system.
Suppose this were not the case. Then you could presumably find a process which produced
more work than it absorbed heat. This extra work could be used to run a generator, which in turn
could be used to produce more heat, which could run more of the process, producing even more
excess work, and so on. The energy crisis, electric bills, etc. would be things of the past. Unfortunately, no such device has ever been built and the first law still stands.
In mathematical terms, the first law implies that there is a state function, called the internal
energy of the system, defined up to an arbitrary additive constant through its differential
dE d Q + d W ,
(14)
where d W is the work done by the surroundings on the system (the negative of the work done
by the system on the surroundings). For a finite change of state, the change in the internal
energy, E, is given by
E =

final state

initial state d Q + d W .

(15)

The first law states that

odE = od Q + od W = 0.

(16)

The first law implies that the energy change computed along different paths must give the
same answer. If not, two such paths could be used to to build the energy-creating device discussed above (i.e., by reversing one of the paths). The appendix contains a detailed discussion of
the conservation of energy in (classical) mechanics; as expected there the discussion revolves
around forces, which while similar to the discussion of d W in special cases, leaves the
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Work, Heat, and Energy

connection to heat and d Q somewhat obscure.


6. Some Properties of the Energy
In order to calculate or measure energies, we note that d W = 0 for constant volume systems, assuming that only pressure-volume work can be done. Hence, dE = dQV , where we have
dropped the d in favor of d and have put a "V" subscript on the Q to emphasize that we are
working at constant volume. (Why is this valid?). In the absence of phase changes (e.g., vaporization), the increments of heat absorbed by the system are proportional to the incremental temperature change of the system; i.e.,
dE = dQV = CV dT ,

(17)

E
is known as the constant volume heat capacity and in general is an extensive
T V ,N
property of the system that depends on T, P, composition and phase, and is positive in general.
3
3
Since E = NRT for an ideal gas of point particles, it follows that CV = NR. By integrating

were CV

both sides of the equation we find that


E T i T f = QV =

Tf

CV (T , V , N )dT .

(18)

Note that E is positive for an endothermic constant volume process and is negative for an
exothermic one. If there is a phase change during the experiment, we have to add the latent
energy change of the phase transition (i.e., the heat we would have to add at the transition temperature to convert all the material from one phase to another) to the right hand side of our
expression.
Thus, we have found a simple situation in which the energy change is related to heat.
Unfortunately, the requirement of constant volume, while realizable to high accuracy in the lab,
is inconvenient. Is there another quantity that becomes the heat absorbed by the system under
other conditions, and in particular for constant pressure? In fact there is and a simply trick
allows us to find it.
Consider the quantity H E + PV , known as the Enthalpy. Since E and PV are state functions, so too is H. Next, by taking the differential of each side of the definition and using the
First Law, we find that
dH = dE + PdV + VdP = d Q + (P P op )dV + VdP,
(19)
where only pressure-volume work has been allowed; i.e., d W = P op dV . As we discussed
above, for reversible changes, P op = P and
dH = dQ + VdP

(20)

For processes where the pressure is constant, P op = P and dP = 0, which gives


dH = dQ P = C P dT

(21)

H
is the constant pressure heat capacity. For the ideal gas,
T P,N
5
5
H = E + PV = NRT , and thus, C P = NR. Note that C P > CV , something that is true more
2
2
generally. Finally, by repeating the discussion we had for the energy, it follows that
where, C P

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Tf

Work, Heat, and Energy

C P (T , P, N )dT ,

(22)

again with extra terms to account for the latent enthalpy (heat) of transition(s) should phase
changes occur. This procedure is known as a Legendre transformation, and we will see other
applications of it later.
7. Appendix: Energy in Classical Mechanics
You probably have heard the statement "energy is conserved." What does this mean
exactly? Consider a system comprised of N point particles of mass m, at positions r1 , . . . , r N ,
and moving with velocities v1 , . . . , v N . The system is subjected to external forces described by a
time dependent potential ext (r, t), e.g., as might arise from the interaction of the molecules in
the system with a moving piston, or with the atoms in the bottom of a container being heated
from below. In addition, assume that Newtons laws of motion are valid and that the particles
interact via pairwise additive forces which are derivable from a potential; i.e., the force particle j
exerts on i, Fi, j is given by
Fi, j

ui, j
,
ri

(23)

where ui, j is the potential energy of interaction between molecules i and j and depends on the
molecular positions through ri r j (i.e., only through the separation between the molecules).
Consider the mechanical energy, E, defined as
E

i=1

N
m 2 1 N N
vi + ui, j + ext (ri , t).
2 i=1 j=1
2
i=1

(24)

i j

Note that the last term describes the interaction between the system and its surroundings, and the
internal energy would drop this term in its definition. How does E change as the particles move
around under the action of Newtons Laws?
N
N (r , t)

dE
1 N N
ext i
= vi Fi Fi, j (vi v j ) +
vi Fext (ri , t)
ri
dt i=1
t
2 i=1 j=1
i=1

(25)

i j

where Fext (r,t) ( ext (r, t)/r)t , is the external force, and Fi

Fi, j + Fext (ri , t), is the total

ji

force acting on the ith particle. By using this expression for Fi in the rate of change of E we
find that
N (r , t)
N (r , t)
dE 1 N N
1 N N
ext i
ext i
= Fi, j (vi + v j ) +
= (Fi, j + F j,i ) vi +
, (26)
ri 2 i=1 j=1
ri
dt
2 i=1 j=1
t
t
i=1
i=1
i j

i j

where the dummy summation indices, i and j, were exchanged for the terms in v j in obtaining
the last equality. Newtons third law states that Fi, j = F j,i ; i.e., the force i exerts on j is equal in
magnitude and opposite in direction to that j exerts on i. Using this in our last expression immediately shows that

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Work, Heat, and Energy

N (r , t)
dE
ext i
=
.
ri
t
dt i=1

(27)

In other words, in the absence of explicitly time-dependent external forces, the energy of our
classical system of particles doesnt change in time i.e., it is conserved. The same is true under
the laws of quantum mechanics.
Finally, note that our result is dependent on our definition of the energy. For example, if we
consider the so-called internal energy, i.e.,
E int

i=1

m 2 1 N N
v + ui, j ,
2 i 2 i=1
j=1

(28)

i j

cf. Eq. (24), and repeat the steps leading to Eq. (27), it follows that
N
dE int
= vi Fext (ri , t),
dt
i=1
which is essentially the result we obtain by starting with d W = F dr.

(29)

The first law of thermodynamics also has something to say about changes in energy, although not
in precisely the same way as in classical or quantum mechanics. Specifically, where are work
and heat, and is our expression for the energy (or internal energy) a state function? Indeed, all
that appears the rate of change of the internal energy, cf. Eq. (29), are forces acting on the full
many-body system; no distinction is made between heat, mechanical work, etc., and which while
certainly correct, leaves one wondering where to find the practical simplifications the thermodynamic approach gives.

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