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Lecture 3

Lecture 3 First Law of Thermodynamics

Observation leads to the following two assertions:

1. There exists for every system a property called energy, E. The system energy can be
considered as a sum of internal energy, kinetic energy, potential energy and chemical
energy.

a. Zeroth Law, defined a useful property, temperature, the First Law defines a
useful property called energy.
b. The two new terms the internal energy and the chemical energy. We will generally
use the internal energy, u. It arises from the random or disorganized motion of
molecules in the system, as shown in Figure 3.1. Since this molecular motion is
primarily a function of temperature, the internal energy is sometimes called
thermal energy.

Figure 3.1: Random motion is the physical basis for internal energy

The internal energy , is a function of the state of the system. Thus , or

, or . Recall that for pure substances the entire state of the
system is specified if any two properties are specified.

2. The change in energy of a system is equal to the difference between the heat added to the
system and the work done by the system,

where E is the energy of the system, Q is the heat input to the system, and W is the
work done by the system.

a. Like the Zeroth Law, First Law describes the behaviour of the new property
b. The equation can also be written on a per unit mass basis i.e
c. In many situations the potential energy, kinetic energy, and chemical energy
of the system are constant or not important. Then
; and
d. Note that Q and W are not functions of state, but U , which arises from
molecular motion (see above), depends only on the state of the system; U does
not depend on how the system got to that state. We therefore have the striking
result that:

U is independent of path even though Q and W are not!

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Lecture 3

Sometimes this difference is emphasized by writing the First Law in differential form,

where the symbol is used to denote inexact differentials and dependent on path.

e. Note that the signs are important:

Q is defined to be positive if it is transferred to the system;

W is defined to be positive if it is done by the system; W = psdV

f. For quasi-static processes we can substitute ,

To give an example of where the first law is

applied, consider the device shown in
Figure 3.2. We heat a gas, it expands against a
weight, some force (pressure x area) is applied
over a distance, and work is done. The change
in energy of the system supplies the
connection between the heat added and work
done. Thermodynamics deals with various
applications of the first law -- in one form or
Figure 3.2: The change in energy of a system
another.
relates the heat added to the work done

The form of the first law we have given here is sometimes called the control mass form,
because it is well suited to dealing with systems of a fixed mass. This form can be written for
a control volume with mass flow in and mass flow out (like a jet engine for example). We
will call this the control volume form of the first law [VW, S & B: 5.8-5.12].

Corollaries of the First Law

1. Work done in any adiabatic (Q = 0) process is a function of state. We can
write the first law, setting the heat transfer term equal to zero, as
2. Since depends only on the state change, now can be found as a
function of the state change.
3. For a cyclic process heat and work transfers are numerically equal
4. Since energy is a function of state only, any process that returns a
system to its original state leaves its energy unchanged. Ufinal = Uinitial

Therefore ; and
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Lecture 3

Applications of the First Law to motivate the use of

a property called ``enthalpy''
Adiabatic, steady, throttling of a gas (flow through a valve or other
restriction)

Figure 3.3 shows the configuration of interest. We wish to know the relation between
properties upstream of the valve, denoted by ``1'' and those downstream, denoted by ``2''.

Figure 3.3: Adiabatic flow through a valve, a generic throttling process

Figure 3.4: Equivalence of actual system and piston model

To analyze this situation, we can define the system (choosing the appropriate system is often
a critical element in effective problem solving) as a unit mass of gas in the following two
states. Initially the gas is upstream of the valve and just through the valve. In the final state
the gas is downstream of the valve plus just before the valve. The figures on the left of
Figure 3.4 show the actual configuration just described. In terms of the system behaviour,
however, we could replace the fluid external to the system by pistons which exert the same
pressure that the external fluid exerts, as indicated schematically on the right side of
Figure 3.4.

The process is adiabatic, with changes in potential energy and kinetic energy assumed to be
negligible. The first law for the system is therefore:

The work done by the system is:

Use of the first law leads to:

In words, the initial and final states of the system have the same value of the quantity U +
PV. For the case examined, since we are dealing with a unit mass, the initial and final states
of the system have the same value of u + Pv.
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We define this quantity as the ``enthalpy,'' usually denoted by H, H = U + PV

In terms of the specific quantities, the enthalpy per unit mass is:

It is a function of the state of the system. H has units of Joules, and h has units of
Joules/kilogram.

Evaluating the energy of an object of volume V, you have to remember that the object had to
push the surroundings out of the way to make room for it. With pressure p on the object, the
work required to make a place for itself is pV. This is so with any object or system, and this
work may not be negligible. (The force of one atmosphere pressure on one square meter is
equivalent to the force of a mass of about 10 tons) Thus the total energy of a body is its
internal energy plus the extra energy it is credited with by having a volume V at pressure p.
We call this total energy the enthalpy, H.

Quasi-Static Expansion of a Gas

Consider a quasi-static process of constant pressure expansion. We can write the first law in
terms of the states before and after the expansion as

, since

By grouping terms we can write the heat input in terms of the enthalpy change of the system:

Because the combination appears so frequently, it is not only defined but also tabulated as a
function of temperature and pressure for a number of working fluids.

The First Law in Terms of Enthalpy

We start with the first law in differential form and substitute for by assuming a
quasi-static or reversible process:

(true for any process, neglecting and )

(true for any quasi-static process, no and )

The definition of enthalpy, , can be differentiated (applying the chain rule to the
term) to produce

Substituting the above for the in the First Law, we obtain

(valid for any process)

(valid for any quasi-static process)

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Lecture 3

Specific Heats: the relation between temperature

change and heat [VW, S& B: 5.6]

How much does a given amount of heat transfer change the temperature of a substance? It
depends on the substance. In general

where C is a constant that depends on the substance. We can determine the constant for any
substance if we know how much heat is transferred. Since heat is path dependent, however,
we must specify the process, i.e., the path, to find C.

Two useful processes are constant pressure and constant volume, so we will consider these
each in turn. We will call the specific heat at constant pressure , and that at constant
volume , or and per unit mass.

The Specific Heat at Constant Volume

Remember that if we specify any two properties of the system, then the state of the system is
fully specified. In other words we can write , or

Consider the form , and use the chain rule to write how u changes with respect to T
and v:

For a constant volume process, the second term is zero since there is no change in volume,
. Now if we write the First Law for a quasi-static process, with ,

we see that again the second term is zero if the process is also constant volume. Equating
above equations with dv cancelled in each,

By definition of specific heat; the specific heat for a constant volume process,
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The Specific Heat at Constant Pressure

If we write , and consider a constant pressure process, we can perform a similar
derivation to the one above and show that

In the derivation of , we considered only a constant volume process, hence the

name, specific heat at constant volume.'' It is more useful, however, to think of in
terms of its definition as a certain partial derivative, which is a thermodynamic
property, rather than as a quantity related to heat transfer in a special process.
In fact, the derivatives above are defined at any point in any quasi-static process
whether that process is constant volume, constant pressure, or neither. The names
specific heat at constant volume'' and ``specific heat at constant pressure'' are
therefore unfortunate misnomers;
and are thermodynamic properties of a substance, and depend only the state.

Over small temperature changes , it is often assumed that and are

constant. Furthermore, there are wide ranges over which specific heats do not vary greatly
with respect to temperature. It is thus often useful to treat them as constant. If so

and

Therefore; and

A very important relation between the constant-pressure and constant-volume specific heats
of an ideal gas may be developed from the definition of enthalpy

Differentiating and substituting, we have

Therefore,

An expression that will appear often is the ratio of specific heats, which we will define as

The simple relations between changes in energy (or enthalpy) and temperature are a
consequence of the behaviour of an ideal gas, specifically the dependence of the energy and
enthalpy on temperature only, and are not true for more complex substances.