Chapter 5: The First Law of

Thermodynamics

Thermodynamics
Joule’s Experiment
During 1843-1849, Joule conducted several
experiments that subsequently led to the
formulation of the first law of thermodynamics.

Thermodynamics – Chapter 5
 Joule's Paddle-Wheel Apparatus,
1849, London Science Museum
Thermodynamics – Chapter 5
 Experiment consists of two process cycle.
 In process 1-2, work W was done on the system
by means of a paddle wheel.
 Heat was transferred from the fluid to the
atmosphere in process 2-1 till the system returns
to the original temperature.

Thermodynamics – Chapter 5
 The amount of work was measured by the
change in potential energy of a weight mg
falling through a height Z.
 The amount of heat transfer Q from the fluid to
the atmosphere was measured.
 By repeating the experiments for different
systems, Joule found that net work input W was
always proportional to the net amount of heat
transfer Q from the system measured in their
conventional units.
J  δQ   δW
Thermodynamics – Chapter 5
 Joule found that in the English system of units,
in which historically heat is measured in British
thermal unit (Btu) and work in foot pound
force (ft lbf), the mechanical equivalent of heat
is
J = 778.17 ft lbf/Btu
 In SI units, both heat and work are expressed in
same unit.

Thermodynamics – Chapter 5
Mechanical Equivalent of Heat (J)

Joule experimented on the amount of

mechanical work needed to raise the
temperature of a pound of water by
one degree Fahrenheit and found a
consistent value of 778.17 foot
pound force (4.186 J/cal).
Thermodynamics – Chapter 5
Observations From Joule’s Experiment
 Net work input W is always proportional to the
net amount of heat transfer Q from the system.

 Since the system at the end is restored to its

original state, so, algebraic sum of heat and work
interactions during a thermodynamic cycle is
zero (when same units are used).

 This experiment led to the formulation of the first

law of thermodynamics.

Thermodynamics – Chapter 5
Statement of First Law of thermodynamics

For a system undergoing a thermodynamic cycle

the net heat transfer during the cycle (cyclic
integral of heat added) is equal to the net work
done during the cycle (cyclic integral of work
done).

 δQ   δW

Thermodynamics – Chapter 5
Important Points
 The symbol  is used to indicate that W and Q
are inexact differentials.

 The constraints of this law: This law applies to a

closed system and only to a thermodynamic
cycle.

 Both heat and work have same units.

 The first law of thermodynamics is also known as

the conservation of energy principle.

Thermodynamics – Chapter 5
 First Law of thermodynamics for a
Change in State of a Control mass
Path 1-A-2-B-1
P 2 1 2 1

  Q    Q   W   W
1
A
2
B
1
A
2
B

Path 1-C-2-B-1
2 1 2 1

  Q    Q   W   W
1
C
2
B
1
C
2
B

V Subtracting and rearranging

2 2 2 2

 Q   Q    WA    WC  2 2

  δQ  δW     δQ  δW C
A C
1 1 1 1
A
1 1

Thermodynamics – Chapter 5
 It is seen that for any process between states 1
and 2, the quantity (Q – W) is always the
same.
 It is independent of the path followed for this
change of state.
 So, it is a point or state function and hence a
property.
 This property is called energy (E) of the control
mass.
 Thus we can write,
dE   Q   W ------------ (1)

Thermodynamics – Chapter 5
Since E is a property, its derivative can be written as
dE. When Eq. (1) is integrated from an initial state 1
to a final state 2,
E2  E1  1Q2  1W2
where E1 and E2 are the initial and final values of
energy of the control mass.

 For a cycle, initial and final state is identical, so

energy increase is zero.
 For isolated system W and Q = 0. Hence E2 = E1

Thermodynamics – Chapter 5
Significance of the Property E
• It represents all the energy of the system
(macroscopic and microscopic forms) in the
given state.
• Macroscopic: Kinetic or Potential energy of the
system as a whole with respect to the chosen
coordinate frame.
• Microscopic: Energy associated with motion and
position of the molecules, and the structure of the
atom is called internal energy (U).

Thermodynamics – Chapter 5
• In absence of electrical, magnetic, surface tension
effects (for a simple compressible system)
E = U + KE + PE

dE  dU  d ( KE )  d ( PE ) ----- (2)

The first law of thermodynamics for a change of state

dE  dU  d ( KE )  d ( PE )   Q   W --- (3)
2
d (mV )
where d ( KE )  mVdV  and
2
d ( PE )  mg dZ  d (mg Z )

Thermodynamics – Chapter 5
 dE  dU  mVdV  mgdZ   Q   W --- (4)

Integrating for a change of state from state 1 to state

2 with constant g,
E2  E1  1 Q2  1W2
2 2
mV mV
U 2  U1  
2
 mgZ 2  mgZ1  1 Q2  1W2
1
2 2

Thermodynamics – Chapter 5
Three Observations
 The property E, the energy of the control mass,
was found to exist.
 The net change of the energy of the control mass
is always equal to the net transfer of energy across
the boundary as heat and work.
Ein  Eout  ESystem
Net Energy Transfer by heat and work Change in U, K.E and P.E energies

 This equation can give only changes in internal

energy, kinetic energy, and potential energy.
Thermodynamics – Chapter 5
Internal Energy – A Thermodynamic Property
• Internal energy is an extensive property.
• The symbol U designates the internal energy of a
given mass of a substance and u as the specific
internal energy.
• In the liquid – vapor saturation region,
U  U liq  U vap
mu  mlq u f  mvap u g
u  (1  x)u f  xu g  u f  x(u g  u f )
u  u f  xu fg

Thermodynamics – Chapter 5
Enthalpy -The Thermodynamic Property

• Consider a control mass

undergoing quasi-equilibrium
constant-pressure process.
• Assume there is no changes in
kinetic or potential energy .
• Work done during the process
is that associated with the
boundary movement.

Thermodynamics – Chapter 5
Taking the gas as our control mass and applying the
first law,
1
Q 2  U 2  U1  1W2

The work can be calculated from the relation,

2 2

1
W2   PdV  P  dV  P(V2  V1 )
1 1
Therefore,

1
Q2  U 2  U1  PV2 2
 PV
1 1
 (U 2  PV
2 2
)  (U1  PV1 1
)

Thermodynamics – Chapter 5
 Heat transfer during the process is given in terms
of the change in the quantity U + PV between
the initial and final states.
 Because all these quantities are thermodynamic
properties, that is, functions only of the state of
the system, their combination must have these
same characteristics.
 Therefore, it is convenient to define a new
extensive property, the enthalpy,
H = U + PV

Thermodynamics – Chapter 5
Many tables and charts of thermodynamics
properties give values for enthalpy but not for the
internal energy. Then use the following equation,
u = h – Pv
Students often become confused about the validity
of this calculation when analyzing system process
that do not occur at constant pressure, for which
enthalpy has no physical significance.

Thermodynamics – Chapter 5
The enthalpy of a substance in a saturation state and
with a given quality is found in the same way as the
specific volume and internal energy.

H  H liq  H vap
mh  mlq h f  mvap hg
h  (1  x)h f  xhg
h  h f  xh fg

For substances for which compressed-liquid tables

are not available, the enthalpy is taken as that
saturated liquid at the same temperature.
Thermodynamics – Chapter 5
The Concept of Specific Heat
 It takes different amounts of energy to raise the
temperature of identical masses of different
substances by 1 degree.

 This is because different substances have

different energy storing capabilities.
Thermodynamics – Chapter 5
 It is thus desirable to have a property that enables
us to compare the energy storage capabilities of
various substances. This property is the specific
heat.
 It is defined as the energy required to raise the
temperature of a unit mass of a substance by one
degree.

Thermodynamics – Chapter 5
Mathematical Model

 The SI unit of specific heat is kJ/kg.K.

 Denoting specific heat by C, we have by

definition

q 1  Q 
c   
 T m T 

Thermodynamics – Chapter 5
Specific Heat at Constant Volume and
Pressure

 It is viewed as the energy required to raise the

temperature of a unit mass of a substance by one
degree as the volume is maintained constant (cv).

 The energy required to do the same at constant

pressure is the specific heat at constant pressure
(cP).

Thermodynamics – Chapter 5
 The specific heat at constant pressure will always
be greater than that at constant volume because
at constant pressure the system can change
volume and energy for this expansion must be
supplied.

Thermodynamics – Chapter 5
Specific Heat at Constant Volume
From definition of specific heat
 q  1  Q 
cV      
  T V m   T V
Since for constant volume P dV  0
dU   Q   W (from First Law)

  q   u  1  U 
cV        
  T V  T V m  T V

Thermodynamics – Chapter 5
Specific Heat at Constant Pressure
From definition of specific heat
 q  1  Q 
cP      
  T P m   T P
Since for constant pressure process (first law)
Q  U 2  U1  PV
1 2 2 2
 PV
1 1

 (U 2  PV2 2
)  (U1  PV1 1
)  H 2  H1

  q   h  1  H 
Therefore, cP        
  T  P  T  P m  T  P
Thermodynamics – Chapter 5
Observations
 Both expressions for specific heats contain
thermodynamic properties and can be written as
cv = f (u, T, ) and cP = f (h, T, P )
 cv and cp are state functions and hence are
properties.
 cv is a measure of the variation of internal energy
of a substance with temperature. And cP is a
measure of the variation of enthalpy of a
substance with temperature

Thermodynamics – Chapter 5
 Note the equations for cP and cv are property
relations and as such independent of the type of
process. They are valid for any substance
undergoing any process.

Sketch showing two ways in which a given ΔU

may be achieved

Thermodynamics – Chapter 5
Specific Heat for Solids and Liquids
Since both of phases are nearly incompressible,
dh  du  d ( Pv)  du  v dP  Pdv  du  v dP
Also, for both of these phases, the specific volume
is very small, such that in many cases
dh  du  c dT
Where c is either the constant-volume or constant
pressure specific heat, as the two would be nearly
the same.
h2  h1 u2  u1 c (T2  T1 )
Engineering Thermodynamics
Internal Energy, Enthalpy and Specific
Heat Relations for Ideal Gases
For a low-density gas, however u depends
primarily on T and much less on the second term, P
or v.

Thermodynamics – Chapter 5
 For an ideal gas, Pv = RT and u = f (T )
 The relation between the internal energy and the
temperature can be given by
 u 
cv   
 T v
 Because the internal energy of an ideal gas is not
a function of specific volume, for an ideal gas
du
cv 0   du  cv 0 dT or dU  mcv 0 dT
dT
Where the subscript 0 denotes the specific heat of
an ideal gas
Thermodynamics – Chapter 5
 From definition of enthalpy, we have
h  u  pv  u  RT
 Since R is a constant and u = f (T), it follows that
h = f (T )
 The relation between the enthalpy and the
temperature can be given by
 h 
cp   
 T  p
dh
cp0   dh  c p 0 dT or dH  mc p 0 dT
dT
Thermodynamics – Chapter 5
 Pressure – volume diagram for an ideal gas

Since u and h are f (T ) for an ideal gas, cP and cv

will depend utmost on temperature only.

cv 0  f (T ), c p 0  f (T )

Thermodynamics – Chapter 5
 For an ideal gases,

du  cv 0 T  dT and dh  c p 0 T  dT

 The ideal gas specific heat for a given substance

is often called the zero-pressure specific heat.
 The zero-pressure, constant-volume specific heat
is given by Cvo.
 The zero-pressure, constant-pressure specific
heat is given by Cpo.

Thermodynamics – Chapter 5
Heat capacity for some gases as function of temperature.
These values are determined by the techniques of
statistical thermodynamics.

Thermodynamics – Chapter 5
 The principal factor causing specific heat to
vary with temperature is molecular vibration.
More complex molecules have multiple
vibrational modes and therefore show a greater
temperature tendency.

Thermodynamics – Chapter 5
Thermodynamics – Chapter 5
Thermodynamics – Chapter 5
Engineering Thermodynamics
The change in internal energy or enthalpy for an
ideal gas during a process from state 1 to 2,
h  h2  h1   C p 0 T  dT
To carry out the integrations relation for cP0 as
functions of T is required. There are three
possibilities to examine.

1) Assume constant specific heat, that is, no

temperature dependence.
h  h2  h1  C p 0 (T2  T1 )

Thermodynamics – Chapter 5
2) Use an analytical equation cP0 as a function of
temperature. Because the results of specific-heat
calculations from statistical thermodynamics don’t
lend themselves to convenient mathematical
forms, these results have been approximated
empirically. The equations for cP0 as a function of
temperature are listed in Table A.6 (Page 7) for a
number of gases.
C p 0  C0  C1  C2  C3
2 3
(KJ/kg)
Tavg T1  T2
where    Kelvin  and Tavg 
1000 2
h  h2  h1  C p 0 (T2  T1 )

Thermodynamics – Chapter 5
3) To integrate the results of the calculations of
statistical thermodynamics from an arbitrary
reference temperature to any other temperature
T and to define a function
T
hT   C p 0 dT
T0
T2 T1

h2  h1   C p 0 dT   C p 0 dT  hT2  hT1
T0 T0

and it is seen that the reference temperature

cancels out. This function hT is listed for air in
Table A.7 (Page 8).
Thermodynamics – Chapter 5
Specific Heat Relations for Ideal Gases
 It has been noted that for an ideal gas

h  u  pv  u  RT
Differentation and substituting for dh and du
dh  du  RdT
C p 0 dT  Cv 0 dT  RdT
C p 0  Cv 0  R

Thermodynamics – Chapter 5
 The ratio of two specific heats of a gas is called
the specific heat ratio and denoted by k or 
where
k =  = cP0 / cv0
 This ratio also is a function of temperature, but
the variation is mild.
 For monatomic gases, its value is essentially
constant at 1.667.
 Many diatomic gases, including air, have a
specific ratio of about 1.4 at room temperature.

Thermodynamics – Chapter 5
(5.83/5.82) We want to find the change in u for
carbon dioxide between 600 K and 1200 K.
a) Find it from a constant Cvo from table A.5
b) Find it from a Cvo evaluated from equation in
A.6 at the average T.
c) Find it from the values of u listed in table A.8

(a) u  u2  u1  Cv 0 (T2  T1 )
 0.653 kJ/kg.K  (1200  600) K
 391.8 kJ/kg

Engineering Thermodynamics
 T1  T2 1200  600
(b) Tavg    900
2 2
Tavg 900
   0.9
1000 1000
C p 0  C0  C1  C2  C3 (KJ/kg)
2 3

C p 0  0.45  1.67  0.9  1.27  0.9  0.39  0.9

2 3

 1.2086 kJ/kg.K
Cv 0  C p 0  R  1.2086  0.1889  1.0197 kJ/kg.K
u  u2  u1  Cv 0 (T2  T1 )
 1.0197 kJ.kg.K 1200  600  K  611.8 kJ/kg

Engineering Thermodynamics
(c) u  uT 2  uT 2
 u@1200 K  u@ 600 K
 996.64 kJ/kg  392.72 kJ/kg
 603.92 kJ/kg

Engineering Thermodynamics
The First Law as a Rate Equation
It is desirable to use the first law as a rate equation
that expresses either the instantaneous or average
rate at which energy crosses the control surface as
heat and work and the rate at which the energy of
the control mass changes. In so doing we are
departing from a strictly classical point of view,
because basically classical thermodynamics deals
with systems that are in equilibrium.
This form of the first law finds extensive
applications in thermodynamics, fluid mechanics,
and heat transfer.

Thermodynamics – Chapter 5
The First Law as a Rate Equation
Consider a time interval δt during which an amount
of heat δQ crosses the control surface, an amount of
work δW is done by the control mass, the internal
energy change is ∆U, the kinetic energy is ∆KE, and
the potential energy change is ∆PE.
From the first law we can write
U  KE  PE   Q   W
Dividing by δt we have average rate of energy
transfer as heat and work and increase of the energy
of the control mass
U /  t  KE /  t  PE /  t   Q /  t   W /  t

Thermodynamics – Chapter 5
The First Law as a Rate Equation
Taking the limit for each of these quantities as δt
approaches zero, we have
U dU KE d ( KE ) PE d ( PE )
lim  , lim  , lim 
 t 0  t dt  t 0  t dt  t 0  t dt
Q W
lim  Q, lim W
 t 0  t  t 0  t

Therefore, the rate equation form of the first law is

dU d  KE  d  PE 
   Q W
dt dt dt
dE
 Q W
dt

Thermodynamics – Chapter 5