Chapter 4 First Law of Thermodynamics for a System

Although heat and work interactions were known independently for a long time,
a detailed understanding of their inter-relationship was not known until the mid-19th
century. Also, it was not realized that heat is a form of energy interaction. The prevailing
theory for heat in the early times was the calorific theory, which likened heat to an
invisible fluid. It was thought that just as water flows from a higher level to lower level,
heat flows from a higher temperature to a lower temperature. It was James Prescott
Joule, who between the years 1840 to 1849, clearly showed the equivalence of heat and
work through his experiments. He computed mechanical work W as the product of force
into distance, and heat in terms of the temperature rise using the expression Q =
m.c.T. He demonstrated that the magnitudes of work input and heat input required
for achieving the same temperature rise in a substance always had a fixed ratio, W/Q =
4.186 N.m/Calorie, which is known as the “Mechanical equivalent of heat”. The set up
used by Joule for arriving at this conclusion is shown in Fig. 4.1. It consists of a known
mass of water whose temperature is raised by the operation of a paddle wheel. The
work input for paddle wheel is calculated as torque x angular displacement; the torque
in turn, is given as the force due to the mass hung from the rope x radius of the shaft
which drives the paddle wheel. Equivalent heat is calculated as Q = mass of water x
specific heat of water x T for water.

Fig. 4.1 Joule’s experiment for finding mechanical equivalent of heat

 The above- mentioned experiment of Joule conclusively proves that both heat
and work are energy interactions. It also provides another interesting insight about
cyclic processes. Let us denote the work needed to raise the temperature of water by T
as W. Now the heat (in Calories) which has to be removed from water to bring it back to
the initial temperature is equal to W/J where J is the mechanical equivalent of heat (=
4.186 N.m/Calorie). Thus, irrespective of how long the paddle wheel is operated or what
is the T achieved, the heat to be removed for restoring the water back to its initial
temperature Q = W/J. This result can be generalized further for any cycle with many
work and heat interactions as:

W  J  Q
cycle cycle
(4.1)

In other words, for a cyclic process, the net heat and net work interactions during the
cycle are always related through Eq. (4.1). This form of equation is preferable when
there is a finite number of sub-processes in the cycle (see, Fig. 4.2 a). In the case of
continuous changes without any identifiable sub-processes for the cycle (see Fig. 4.2 b),
the more appropriate form is:

W  J  Q (4.2)

In both equations (4.1) and (4.2), the constant J performs the job of converting from
the heat unit to work unit. In other words, if the same units are employed for heat and
work (say kJ), then the conversion constant J = 1. In such a case, equations (4.1) and
(4.2) can be rewritten as:

W   Q
cycle cycle
(4.3)

and, (4.4)
W   Q
The above equations (4.1) to (4.4), are said to be the forms of I Law of
Thermodynamics, which are applicable to a system (of fixed mass) undergoing a cyclic
process.
 2

Fig. 4.2 (a) Cycle with sub-processes (b) cycle without any sub-processes

For the cycle shown in Fig. 4.2(a) with four sub-processes 1-2, 2-3, 3-4 and 4-1, Eq.
(4.3) can be written as:

W12  W23  W34  W41  Q12  Q23  Q34  Q41

The first law for a cyclic process can be understood as follows: Since the system returns
to its initial state at the end of the cycle, there is no net storage of energy in the system.
Therefore, the net heat and work interactions between the system and surroundings
should balance (i.e. input = output) for the whole cycle, irrespective of whether their
values are positive or negative (Fig. 4.3).

Q
Q W W

(a) (b)

Fig. 4.3 Energy Interactions

For a non- cyclic process, the heat and work interactions need not be equal. In that
case, the difference between the two will be the stored energy during the process.
Considering positive heat input to the system and positive work output by the system
(Fig. 4.3a), the I law can be expressed as
 Q - W = E. (4.5)

For instance, if heat input is 10 kJ and work output is 6 kJ, the change in total stored
energy E is 4 kJ. Now, it is easy to see that Eq. (4.5) is valid even if Q and W are
negative. Referring to Fig. (4.3b), if W = - 10kJ and Q = - 6 kJ, the stored energy is still
E = 4 kJ as per Eq. (4.5). In the cases where input energy interaction is less than the
output, E of the process can be negative.

In Eq. (4.5), Q and W are path dependent quantities, while the total stored energy E is a
property. Change in E depends only on the end states and not on the path followed in
the process. This can be illustrated using the first law for a cyclic process. In order to
prove that E is a property, consider the two cycles 1-A-2-C-1 and 1-B-2-C-1 as shown in
Fig. 4.4.

Fig. 4.4 Proof for E as a property

For the cycle 1-A-2-C-1, application of I law gives:

Q1 A2  Q2C 1  W1 A2  W2C 1 (4.6)

Similarly, for the cycle 1-B-2-C-1, we get:

Q1 B2  Q2C 1  W1 B2  W2C 1 (4.7)

Subtracting Eq. (4.7) from Eq. (4.6) gives:

Q1 A2  Q1 B2  W1 A2  W1 B2 (4.8)

The above equation can be rearranged as:

Q1 A2  W1 A2  Q1 B2  W1 B2 (4.9)

Since no assumptions have been made about the processes 1-A-2 and 1-B-2, it is
evident that for two given end states 1 and 2, the difference between Q1-2 and W1-2 is
path independent.

Having shown that the total stored energy E is a state function (property), let us
now understand its intrinsic characteristics. The total energy E may be the sum total of
different forms of energy, namely: kinetic energy, potential energy, electrical energy,
magnetic energy, internal energy, etc. Each of these energy forms, in turn, may be
linked with a particular property such as the velocity, elevation etc., for a system of
given mass m. Thus, change in the total stored energy E may be expressed as:

E  KE  PE  EE  ME  U  ...... (4.10)

The properties associated with the individual energy forms (at fixed mass) are: KE-
velocity; PE- elevation; EE- charge; ME- magnetization; U – Temperature. For a system
which does not have energy storage in the form of kinetic energy, potential energy,
electrical energy, etc. the first law (Eq. 4.5) can be simplified to the form:

Q – W = U (4.11)

Consider for example, a gas undergoing expansion in a piston- cylinder device as a

consequence of heat addition (Fig. 4.5). If the heat added is Q = 10 kJ and the work
done by the gas is W = 6 kJ, then the increase in the internal energy of the gas will be
U = 4 kJ. The increase in the internal energy of the gas will reflect as an increase in
the temperature of the gas.
 W

Gas

Q
Fig. 4.5 Expansion of a gas due to heat addition

For an infinitesimal change, equation (4.11) can be rewritten as:

Q  W  dU

Substituting for the expansion work of the gas as p.dV, we get:

Q  pdV  dU (4.12)

Note that in the above expressions, heat and work are represented as Q and W, while
the internal energy change is written as dU, in order to differentiate the exact and
inexact differentials.

Internal energy is the energy associated with the random motion of molecules
(and bond energies between the atoms which form the molecules). The molecular
motion, in turn, can involve the translation of molecules in 3-D space and therefore, at
any instant, one can describe the motion in terms of the x-,y- and z- velocity
components of each molecule. The velocity components keep changing with respect to
time because of collisions between molecules. For substances having more than one
atom per molecule (eg. N2, H2, O2, CO2, H2O), apart from translational motion, there
could also be rotation or vibration. Detailed analysis based on kinetic theory shows that
the energy associated with each mode of random molecular motion (under equilibrium
conditions) is equal to ½ T, where  is known as the Boltzmann‟s constant and T is the
temperature in Kelvin. Thus, if one considers the nitrogen molecule which could exhibit
three modes of translation, two modes of rotation and one mode of vibration under
certain conditions (see Fig. 4.5), the associated kinetic energy per molecule will be 6 x
½ T. Adding up the energy of random motion (and the bond energies which are
essentially constants) associated with all the molecules in a system, gives rise to the
internal energy of the system. It is evident from the above discussion that the internal
energy U of a system, primarily depends on its temperature.

(a) Translation (b) Rotation (c) Vibration

Fig. 4.6 Molecular motion

The internal energy of a system can be expressed in a form U = U(T). Since the internal
energy of the whole system is an extensive property which depends on the mass of the
system, it is often convenient to deal with internal energy per unit mass of the system.
This is known as the specific internal energy and is denoted by the symbol „u‟.
Considering the I law form of Eq. (4.12), it is clear that for a constant volume process
(dV = 0), the heat transfer Q = U. Now, the specific heat at constant volume which is
defined as the amount of heat required to raise the temperature of unit mass of the
substance by 1oC while maintaining the volume constant, can be expressed as:

 U   u 
Cv      (4.13)
 m  T  v const  T  v

As can be seen from equation (4.12), the units for internal energy and specific internal
energy are J (Joule) and J/kg respectively. The unit of Cv is J/(kg K).
Now let us define another property called Enthalpy (H), which is useful in constant
pressure processes of a system or the flow processes of a control volume, as given
below:

H = U + pV (4.14)

The second term on the right hand side of equation (4.14) is known as flow work. It is
associated with the work done by a fluid element on the fluid ahead of it, during a flow
process. The change in enthalpy can written as

dH = dU + pdV + Vdp (4.15)

For a constant pressure process, dp = 0 and hence,

dH = dU + pdV = Q (4.16)

as per Eq. (4.12). It is evident from Eq. (4.16) that for a constant pressure process, the
heat transfer is given by

Q1-2 = H = H2 – H1 (4.17)

Now the specific heat at constant pressure which is defined as the amount of heat
required to raise the temperature of unit mass of the substance by 1oC while
maintaining the pressure constant, can be expressed as:

 H   h 
Cp      (4.18)
 m  T  pconst  T  p

In the above expression, „h‟ is the specific enthalpy which is enthalpy per unit mass. The
units for enthalpy, specific enthalpy and specific heat at constant pressure are given by
J, J/kg and J/(kg K) respectively. The specific heats can be viewed as the slopes of the
internal energy variation or enthalpy variation curves with respect to temperature along
V = constant or p = constant paths respectively, as shown in Fig. 4.7. In this sense, the
specific heats are also properties, which are point (state) functions.
 p = const

V = const Cp
h
u
Cv

T T

Fig. 4.7 Specific heats at constant volume and constant pressure