CHAPTER THREE

FIRST LAW OF THERMODYNAMICS

The First Law of Thermodynamics is essentially the law of conservation of energy formulated in a unified
manner to include all energy forms. The first law relates work and heat interactions that occur at the
boundary of a system, to the energy possessed or stored by a system which is called the internal energy of
the system.

First Law for a Cyclic Process

The first law states that when a closed system undergoes a cyclic process, the net heat interaction is equal
to the net work interaction. This statement of the law can be further elaborated by referring to the cyclic
process consisting of ‘n’ individual processes shown graphically in Fig. 3-11. In the figure, the arrows
indicate the heat flow into the system and the work flow out of the system for the different processes that
constitute the cycle.

Fig. 3-1 Cyclic process

The first law for a cyclic process now translates to the following mathematical form
Q1 + Q2 +....+ Qi +.....+ Qn = W1 +W2 +......+W i+.....+Wn (3-1)
Expressed in the compact form Eq. (3-1) reads
i =n i=n

∑ Q = ∑W
i =1
i
i =1
i (3-2)

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In the cyclic-integral notation Eq. (3-2) can be written in the form

∫ δQ = ∫ δW (3-3)

Where dQ and dW are the heat input and work output during an infinitesimal change of state of
the system. Recall that both heat and work are path-dependent quantities and are therefore not
properties of the system. The symbol ‘d’, instead of the more common ‘d’, is used to
differentiate the changes of path-dependent quantities from those of properties.

First Law for a Change of State

Not all processes of importance in engineering thermodynamics are cyclic processes. There are
numerous situations where there is need to apply the first law to a single process which results in
a change of state of the system. We shall now derive the form of the first law for a change of
state using the cyclic-form of the law that we have already stated above.

Fig. 3-2 Change of state

Consider the cyclic process that consists of two processes depicted in Fig. 3-2. The system
undergoes a process A resulting in a change of state from 1 to 2, both of which are equilibrium
states. The process B returns the system back to state 1 to complete a cycle. Therefore 1A2B1
constitutes a cyclic process to which we apply the first law to obtain the equation
Q12 A + Q21B = W12 A + W21B (3-4)
Consider an alternative process C to return the state of the system from 2 to 1. Since 1A2C1 is a
cyclic process we can apply the first law to obtain the equation

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 Q12 A + Q21C = W12 A + W21C (3-5)
Subtracting Eq. (3-5) from Eq. (3-4) and rearranging we have
Q21B − W21B = Q21C − W21C (3-6)
Equation (3-5) shows that the difference between the heat interaction and the work interaction
for processes B and C is the same. Since the process C was chosen arbitrarily, note that the
quantity (Q-W) is independent of the process path. Recalling the definition of a property, it can
be concluded that (Q-W) is a property of the system. This new property is called the internal
energy of the system and denoted by the symbol E.
In summary, the first law for a single process states that although Q and W are path-dependent
quantities, the difference (Q-W) is path independent and therefore a property of the system. It
depends only on the state of the system. However, as for the physical nature of this new property
the first law has little to add.
Equation (3-6) can be expressed in terms of the end-states 1 and 2 of a single process in the form
Q1-2 – W1-2 = Increase in internal energy
Q1-2 = (E2 – E1) + W1-2 (3-7)
where E2 and E1 are the internal energy of the system in states 2 and 1 respectively. Q1-2 is the
heat input and W1-2 is the work output or done by the system during the process.
The differential form of Eq. (3-7) for an infinitesimal change of state is
δQ = dE +δW (3-8)
where dE is the increase in the internal energy.
The rate-form of Eq. (3-8) is
δQ dE δW
= + (3-9)
dt dt dt
where dt is the infinitesimal increment of time.
The internal energy of a system could, in general, include a number of different energy forms.
These include kinetic energy, potential energy, thermal internal energy, chemical binding energy,
surface energy, nuclear binding energy and others. However, in most of the systems and
applications of interest at this level we would be dealing mainly with only three forms of internal
energy. These are the kinetic energy, the gravitational potential energy and the thermal internal
energy. Expressed mathematically
E = MC2/2 +Mgz +U (3-10)

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where M is the mass of the system, C is the velocity, g is the acceleration due to gravity and z is
the vertical height above a datum level where the potential energy is taken as zero. U is the
thermal internal energy associated with microscopic-level motion of the molecules that constitute
the system.
Most systems encountered in practice are stationary, that is, they do not involve any changes in
their velocity or elevation during a process. Thus, for stationary systems, the changes in kinetic
and potential energies are zero, and the total energy change in relation is reduces to
∆E = ∆U (3-11)
for such systems. Also, the energy of a system during a process will change even if only one
form of its energy changes while the other forms of energy remain unchanged.

Worked Example
1. Water is being heated in a closed pan on top of a range while being stirred by a paddle
wheel. During the process, 30 kJ of heat is transferred to the water, and 5 kJ of heat is lost
to the surrounding air. The paddle-wheel work amounts to 500 N · m. Determine the final
energy of the system if its initial energy is 10 kJ.
Solution

Water is heated in a pan on top of a range while being stirred. The energy of the water at the end
of the process is to be determined.

Assumptions The pan is stationary and thus the changes in kinetic and potential energies are
negligible.

Analysis We take the water in the pan as our system. This is a closed system since no mass
enters or leaves. Applying the energy balance on this system gives

Qin + Wpw,in − Qout = ∆U = U 2 − U 1

30 kJ + 0.5 kJ − 5 kJ = U 2 − 10 kJ
U 2 = 35.5 kJ

Therefore, the final internal energy of the system is 35.5 kJ.

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 2. The radiator of a steam heating system has a volume of 20 L and is filled with
superheated vapor at 300 kPa and 250°C. At this moment both the inlet and exit valves to
the radiator are closed. Determine the amount of heat that will be transferred to the room
when the steam pressure drops to 100 kPa. Also, show the process on a P-υ diagram with
respect to saturation lines.

STEAM

Solution
The radiator of a steam heating system is initially filled with superheated steam. The valves are
closed, and steam is allowed to cool until the pressure drops to a specified value by transferring
heat to the room. The amount of heat transfer is to be determined, and the process is to be shown
on a P-v diagram.

Assumptions 1 The tank is stationary and thus the kinetic and potential energy changes are zero.
2 There are no work interactions.

Analysis We take the radiator as the system. This is a closed system since no mass enters or
leaves. Noting that the volume of the system is constant and thus there is no boundary work, the
energy balance for this stationary closed system can be expressed as

− Qout = ∆U = m(u 2 − u1 ) (since W = KE = PE = 0)

STEAM
Qout = m(u1 − u 2 )
Q
Using data from the steam tables some properties are determined to be
P1 = 300kPa  v1 = 0.7964m 3 /kg

T1 = 250 ο C  u1 = 2728.7kJ/kg
v f = 0.001043, v g = 1.6940m 3 /kg
P2 = 100kPa →
u f = 417.36, u fg = 2088.7kJ/kg

Noting that v1 = v2 and vf < v2 < vg , the mass and the final internal energy becomes

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 V1 0.020 m 3
m= = = 0.0251 kg P 1
v1 0.7964 m 3 /kg
v2 − v f 0.7964 − 0.001043
x2 = = = 0.470
v fg 1.6940 − 0.001043
u 2 = u f + x 2 u fg = 417.36 + (0.470 × 2088.7) = 1399.0 kJ/kg 2

v
Substituting,

Qout = m(u1 − u 2 )
= (0.0251 kg)(2728.7 − 1399.0) kJ/kg
= 33.4 kJ
3. A0.5-m3 rigid tank contains refrigerant-134a initially at 200 kPa and 40 percent quality.
Heat is now transferred to the refrigerant until the pressure reaches 800 kPa. Determine
(a) the mass of the refrigerant in the tank and (b) the amount of heat transferred. Also,
show the process on a P-υ diagram with respect to saturation lines.
Solution

A rigid tank is initially filled with superheated R-134a. Heat is transferred to the tank until the
pressure inside rises to a specified value. The mass of the refrigerant and the amount of heat
transfer are to be determined, and the process is to be shown on a P-v diagram. √
Assumptions 1 The tank is stationary and thus the kinetic and potential energy changes are zero.
2 There are no work interactions.
Analysis (a) We take the tank as the system. This is a closed system since no mass enters or
leaves. Noting that the volume of the system is constant and thus there is no boundary work, the
energy balance for this stationary closed system can be expressed as
R-134a
Qin = ∆U = m(u 2 − u1 ) (since W = KE = PE = 0)
200 kPa

Using data from the refrigerant tables, the properties of R-134a are determined to be

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 P1 = 200kPa  v f = 0.0007532, v g = 0.0993m 3 /kg

x1 = 0.4  u f = 36.69, u g = 221.43kJ/kg

v1 = v f + x1 v fg = 0.0007532 + [0.4 × (0.0993 − 0.0007532)] = 0.04017m 3 /kg

u1 = u f + x1u fg = 36.69 + [0.4 × (221.43 − 36.69)] = 110.59kJ/kg

P2 = 800kPa 
 u 2 = 349.82kJ/kg (Superheated vapor)
(v 2 = v1 ) 

Then the mass of the refrigerant is determined to be

P 2
3
V1 0.5m
m= = = 12.45kg
v1 0.04017m 3 /kg

(b) Then the heat transfer to the tank becomes 1

Qin = m(u 2 − u1 ) v
= (12.45 kg)(349.82 − 110.59) kJ/kg
= 2978 kJ

4. A 3-m3 rigid tank contains hydrogen at 250 kPa and 500 K. The gas is now cooled until
its temperature drops to 300 K. Determine (a) the final pressure in the tank and (b) the
amount of heat transfer.
Solution
The hydrogen gas in a rigid tank is cooled until its temperature drops to 300 K. The final
pressure in the tank and the amount of heat transfer are to be determined.

Assumptions 1 Hydrogen is an ideal gas since it is at a high temperature and low pressure
relative to its critical point values of -240°C and 1.30 MPa. 2 The tank is stationary, and thus the
kinetic and potential energy changes are negligible, ∆ke ≅ ∆pe ≅ 0 .

Properties The gas constant of hydrogen is R = 4.124 kPa.m3/kg.K (from table of property). The
constant volume specific heat of hydrogen at the average temperature of 400 K is, Cv,ave = 10.352
kJ/kg.K (from table).

Analysis (a) The final pressure of hydrogen can be determined from the ideal gas relation,

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(b) We take the hydrogen in the tank as the system. This is a closed system since no mass enters
or leaves. The energy balance for this stationary closed system can be expressed as

− Qout = ∆U H2
Qout = − ∆U = − m(u 2 − u1 ) ≅ mC v (T1 − T2 )
250 kPa
where

P1V (250 kPa)(3.0 m 3 )

m= = = 0.3637 kg
RT1 (4.124 kPa ⋅ m 3 /kg ⋅ K)(500 K)

Substituting into the energy balance,

Qout = (0.3637 kg)(10.352 kJ/kg·K)(500 - 300)K = 753.0 kJ

5. A piston-cylinder device contains 0.8 kg of nitrogen initially at 100 kPa and 27°C. The
nitrogen is now compressed slowly in a polytropic process during which PV1.3= constant
until the volume is reduced by one-half. Determine the work done and the heat transfer
for this process.
Solution
A cylinder initially contains nitrogen gas at a specified state. The gas is compressed
polytropically until the volume is reduced by one-half. The work done and the heat transfer are
to be determined.

Assumptions 1 The cylinder is stationary and thus the kinetic and potential energy changes are
zero. 2 The N2 is an ideal gas with constant specific heats. 3 The thermal energy stored in the
cylinder itself is negligible. 4 The compression or expansion process is quasi-equilibrium.

Properties The gas constant of N2 are R = 0.2968 kPa.m3/kg.K (from property of table). The Cv
value of N2 at the average temperature (369+300)/2 = 335 K is 0.744 kJ/kg.K (from table).

Analysis We take the contents of the cylinder as the system. This is a closed system since no
mass crosses the system boundary. The energy balance for this closed system can be expressed
as

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 E − Eout = ∆Esystem
1 in
4 2 43 14 2 43
Net energy transfer Change in internal, kinetic,
by heat, work, and mass potential, etc. energies

Wb,in − Qout = ∆U = m(u2 − u1 ) N2

Wb,in − Qout = mCv (T2 − T1 )
100 kPa

The final pressure and temperature of nitrogen are 27°C

1.3
V 
P2V21.3 = P1V11.3 → P2 =  1  P1 = 21.3 (100kPa) = 246.2kPa
 V2 
P1V1 P2V2 P V 246.2kPa
= 
→ T2 = 2 2 T1 = × 0.5 × (300K) = 369.3K
T1 T2 P1 V1 100kPa

Then the boundary work for this polytropic process can be determined from

2 P2V2 − P1V1 mR(T2 − T1 )

1 ∫
Wb,in = − P dV = −
1− n
=−
1− n
(0.8 kg)(0.2968 kJ/kg ⋅ K)(369.3 − 300)K
=− = 54.8 kJ
1 − 1.3

Substituting into the energy balance gives

Qout = Wb,in − mCv (T2 − T1 )

= 54.8 kJ − (0.8 kg)(0.744 kJ / kg.K)(369.3 − 360)K
= 13.6 kJ

STEADY FLOW ENERGY EQUATION

Flow processes may be classified into steady and non-steady flow processes.

For a flow process to be regarded as steady, the rate of mass flow must be constant and the same
at the inlet and outlet and the properties of the fluid at any point in the open system must not vary
with time.

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