Chapter 5

The First Law of

Thermodynamics
 Introduction
 THE FIRST LAW OF THERMODYNAMICS
– FOR A CONTROL MASS UNDERGOING A CYCLE
– FOR A CHANGE IN STATE OF A CONTROL MASS
 INTERNAL ENERGY
– A THERMODYNAMIC PROPERTY
 ENTHALPY
– THE THERMODYNAMIC PROPERTY
 SPECIFIC HEATS
– CONSTANT-VOLUME
– CONSTANT-PRESSURE
 INTERNAL ENERGY,ENTHALPY, AND
SPECIFIC HEAT OF IDEAL GASES
 THE FIRST LAW AS A RATE EQUATION
CONSERVATION OF MASS
THE FIRST LAW OF THERMODYNAMICS
FOR A CONTROL MASS UNDERGOING
A CYCLE

– The First Law is often called the

conservation of energy law.

– The first law of thermodynamics states

that during any cycle a system (control
mass) undergoes, the cyclic integral of
the heat is proportional to the cyclic
integral of the work.
THE FIRST LAW OF THERMODYNAMICS FOR
A CHANGE IN STATE OF A CONTROL MASS
Three observations should be made
regarding this equation
 The first is that the property E, the energy of
the control mass, was found to exist.
– However, rather than deal with this property
E, we find it more convenient to consider the
internal energy and the kinetic and potential
energies of the mass.
 The second is that Eqs. 5.10 and 5.11 are
in effect a statement of the conservation
of energy.

– The net change of the energy of the control mass is a

lways equal to
the net transfer of energy across the boundary as he
at and work.

– There are two ways in which energy can cross the bo

undary of a control mass—either as heat or as work.
 The third is that Eqs. 5.10 and 5.11 c
an give only changes in energy.
 We can learn nothing about absolute values of these
quantities from these equations.
– If we wish to assign values to internal energy, kinetic energy,
and potential energy, we must assume reference states and
assign a value to the quantity in this reference state.
• The kinetic energy of a body with zero velocity relative to the
earth is assumed to be zero.
• Similarly, the value of the potential energy is assumed to be
zero when the body is at some reference elevation.
• With internal energy, therefore, we must also have a
reference state if we wish to assign values of this property.
5.3 INTERNAL ENERGY
 Internal energy, kinetic and potential en
ergies are extensive properties, becaus
e they depends on the mass of the syst
em.
 U designates the internal energy of a gi
ven mass of a substance, and u as the
specific internal energy.
 The values are given in relation to an ar
bitrarily assumed reference state, whic
h, for water in the steam tables, uf is tak
en as zero for saturated liquid at the tri
ple-point temperature, 0.010C.
 u = ( 1 –x ) uf + x ug
 u = uf + x ufg
Example 5.3
5.4 PROBLEM ANALYSIS AND SOLUTION
TECHNIQUE

 What is the control mass or control

volume?
 What do we know about the initial state
(i.e., which properties are known)?
 What do we know about the final state?
 What do we know about the process that
takes place? Is anything constant or
zero? Is there some known functional
relation between two properties?
 Is it helpful to draw a diagram of the
information in steps 2 to 4 (for example, a T
.or P–v diagram)?
 What is our thermodynamic model for the
behavior of the substance (for example,
steam tables, ideal gas, and so on)?
 What is our analysis of the problem (i.e., do
we examine control surfaces for various
work modes, use the first law or
conservation of mass)?
 What is our solution technique? In other
words, from what we have done so far in
steps 1–7, how do we proceed to find
whatever it is that is desired? Is a trial-and-
error solution necessary?
Example 5.4
5.5 ENTHALPY
Let us consider a control mass undergoing a quasi-equilibrium
constant-pressure process, as shown in Fig. 5.6.
 [ specific enthalpy, h, and total enthalpy, H. ]

(The significance and use of enthalpy is not restricted to

the special process just described. Other cases in which th
is same combination of properties u +Pv appear will be deve
loped later, notably in Chapter 6 in which we discuss contr
ol volume analyses.)
Students often become confused about the validity of this calculation
when analyzing system processes that do not occur at constant
pressure, for which enthalpy has no physical significance.
We must keep in mind that enthalpy, being a property, is a state
or point function, and its use in calculating internal energy at the
same state is not related to, or dependent on, any process that
may be taking place.
Example 5.5

(Table at page 398, P2=400kPa,T 2=300oC)

5.6 THE CONSTANT-VOLUME AND CONSTANT-PRESSURE
SPECIFIC HEATS
5.7 THE INTERNAL ENERGY, ENTHALPY,
and SPECIFIC HEAT of IDEAL GASES
For a low-density gas, however, u depends primarily on T and
much less on the second property, P or v.
For example,
 As gas density becomes so low that the ideal-gas
model is appropriate, internal energy does not
depend on pressure at all, but is a function only of
temperature.
That is, for an ideal gas,
P v = R T and u =f (T ) only

where the subscript 0 denotes the specific heat of an

ideal gas.
Calculate the change of enthalpy
------ as 1 kg of ideal gas is heated from T1 to T2 K

(1)
(2)

Empirical
Equation
(3
)

Ideal-gas Entropy
(to integrate at constant
pressure of 0.1 MPa)
Example 5.6
Calculate the change of enthalpy as 1 kg of oxygen is heated
from 300 to 1500 K. Assume ideal-gas behavior.

Let us solve this problem in these ways and compare

the answers.
(3)
Our most accurate answer for the ideal-gas enthalpy
change for oxygen between 300 and 1500 K would be fr
om the ideal-gas tables, Table A.8. This result is,
using Eq. 5.29,
h2 - h1 = 1540.2 – 273.2 = 1267.0 kJ/ kg
Example
5.7
5.8 The First Law as a Rate Equation
( Dividing the first law equation by δt )
5.9 Conservation of Mass

E = mc2

Ex.
2900 KJ = m x ( 2.9979x10-8 )2

m = 3.23 x 10 –11Kg