Lecture 4

Chapter 5: First Law of

Thermodynamics for a Control Mass
 THE 1ST LAW FOR A CONTROL
MASS UNDERGOING A CYCLE
• During any cycle a system undergoes, the
cyclic integral of the heat is proportional to
the cyclic integral of work.

where
J   Q    W
 Q = net heat transfer for the cycle

 W = net heat work for the cycle

•The proportionality constant J is due to the difference in energy units for heat (Btu or
calorie) and work (ft-lbf) in the English system; J=1 in SI
•Formulated from measurements of work and heat during a cycle for a wide variety of
systems
THE 1ST LAW FOR A CONTROL
MASS UNDERGOING A CHANGE
OF STATE
The 1st law for a change in state of a control mass or closed system can be
established using the first law applied to a cycle.
• Consider two arbitrary cycles, Cycle AB and Cycle AC , that go through
states 1 and 2 as shown in Fig. 5.2
THE 1ST LAW FOR A CONTROL
MASS UNDERGOING A CHANGE
OF STATE
• For Cycle AB:
 AB  Q   AB  W    Q    Q
2 1 2 1

1
A
2
B   1
 WA   2
 WB (1)

• For Cycle CB:

CB  Q  CB W    Q    Q 1
2
C
1

2 B  
2

1
 WC  
1

2
 WB (2)

• Subtracting (2) from (1),

2 2 2 2
 1
 QA   1
 QC   1
 WA   1
 WC
or

  Q   W    Q   W 
2 2
A
 C
1 1
THE 1ST LAW FOR A CONTROL
MASS UNDERGOING A CHANGE
OF STATE
  Q   W    Q   W 
2 2
A
 C
1 1
•Since processes A and C are arbitrary between states 1 and 2,
the quantity ( Q - W ) is the same for all processes between 1
and 2
•( Q - W ) depends only on the initial and final states,
therefore a point function, and a differential of a property
•This leads to a definition of a new property called total energy
The Property TOTAL ENERGY, E
The property called total energy is defined as,
dE  Q  W
•It represents all the energy of the system or control mass in any given state
•This energy may be present in a variety of forms as system kinetic energy,
potential energy, chemical energy, energy associated with molecular motion and
position, etc.
•Having identified and defined the property E, the 1st Law for a control mass
or closed system undergoing a change of state is written as

 Q  dE   W
Q12   E2  E1   W12
For a control mass (closed system) undergoing a change of state, the net
change in total energy of the system is equal to the net energy that crosses the
system boundary in the form of heat and/or work.
THE PROPERTY Internal Energy, U

• The property internal energy U is defined as a result

of segregating the total energy E into three
components as
• E = Internal Energy + Kinetic Energy + Potential Energy
The reason for this segregation being
Both Kinetic Energy (KE) and Potential Energy (PE) are associated with the
coordinate frame selected for the system; can be specified by mass m, velocity v,
and elevation z.

1
KE  m v 2 PE  m g z
2
U represents all other forms of energy which the system contains and is
associated with the thermodynamic state of the system
 Example
• A Car of mass 1100 kg drives a velocity such
that it has a kinetic energy of 400 kJ.Find the
velocity of the car. If the car is raised with a
crane how high should it be lifted in the
standard gravitational field to have a potential
energy that equals the kinetic energy?
THE PROPERTY Internal Energy, U
• Because the internal energy U or u ( = U/m ) is associated only with the
thermodynamic state of a substance, it is a property.
• It can be used therefore to specify the state of a substance together with
the other properties P, V, T, and x.
• In the saturated region:
• U = Uliq + Uvap
• mu = mliquliq + mvapuvap = mliquf + mvapug
In terms of the quality x,
• u = (1-x) uf + x ug = uf + x ufg
• In the compressed liquid region:
• In the absence of tables, the compressed liquid internal energy is
approximated by the saturated liquid internal energy at the same
temperature,
uCL)T,P ≈ uf)T
 Determine the missing Property
(P,T or x) and also v
• Water at
• A) T=300 °C, u=2780 kJ/kg
• B) P=2000kPa, u=2000 kJ/kg
 1st Law of Thermodynamics
• Having identified the components of the total
energy E, the 1st Law for a control mass
undergoing a change of state is now written as
• Q = dU + d(KE) + d(PE) + W = dU + ½d(mv2) + d(mgz) + W
• or in integrated form as
• Q12 = (U2 - U1) + ½m (v22 – v12) + mg (z2 – z1) + W12
 1st Law of Thermodynamics
• Q12 = (U2 - U1) + ½m (v22 – v12) + mg (z2 – z1) + W12
• Note that the 1st law gives only the changes in internal,
kinetic, and potential energies.
• To assign values to U, KE, and PE, reference states must be
assumed and values assigned to U, KE, and PE at these
reference states.
• The 1st law tells us that as a control mass or closed system
changes state:
– energy may cross the boundary as heat and work
– the total energy of the system may change due to changes in
internal energy, kinetic energy, and potential energy
– the net change in total energy of the system is equal to the net
energy that crosses its boundaries
Q12 = (U2 - U1) + ½m (v22 – v12) + mg (z2 – z1) + W12
(Q12)A + (Q12)B + (Q12)C = (U2 - U1)A + (U2 - U1)B + (U2 - U1)C
+ ½m (v22 – v12)A + ½m (v22 – v12)B + ½m (v22 – v12)C
+ mg (z2 – z1)A + mg (z2 – z1)B + mg (z2 – z1)C
+ (W12)A + (W12)B + (W12)C
 Example
• A tank containing a fluid is stirred by a paddle
wheel. The work input to the paddle wheel is
5090 kJ. The heat transfer from the tank is
1500 kJ. Consider the tank and the fluid inside
a control surface and determine the change in
internal energy of this control mass.
 Example
• A vessel having a volume of 5 m³ contains 0.05
m³ of saturated liquid water and 4.95 m³ of
saturated water vapor at 0.1 MPa. Heat is
transferred until the vessel is filled with
saturated vapor. Determine the heat transfer
for this process.
 Enthalpy
• Let us introduce and define another property called enthalpy :
• H  U + PV
• h  u + Pv
• Units: H, (Joule) h, Joule/kg
• The reasons for so doing include
• The combination u + Pv appears often in thermodynamic problems that it
becomes convenient to define a property to represent it
• Some thermodynamic tables only have entry for h so that u has to be
calculated from this definition (e.g., Tables B.4.2, B.5.2, B.6.2, etc.)
• When dealing with open systems or control volumes, h is not only a
property of the substances involved but also represents what is known as
flow wor
• Being a property, it can be used to specify the state of a substance
together with the other properties P, v, T, x, & u.
 Enthalpy
• In the saturated region, the enthalpy of a substance is
given by
• h = (1-x) hf + hg = hf + x hfg
• In the compressed liquid region:

• In the absence of tables, the compressed-liquid

enthalpy is approximated by the following:
• hCL)T  hf)T + ( PCL – Psat ) vf )T
• For small pressure differences, the pressure correction
is usually quite small so that
• hCL)T  hf)T
 Example
• A cylinder fitted with a piston has a volume of
0.1 m³ and contains 0.5 kg of steam at 0.4
Mpa.Heat is transferred to the steam until the
temperature is 300°C, while the pressure
remains constant.
Determine the heat transfer and the
work for this process.
 Specific Heat of a Simple
Compressible Substance
• The specific heat of a simple compressible substance with a
homogeneous phase is
– the amount of heat required per unit mass to raise the
temperature by one degree.
• It is a measurable thermodynamic property typically used
to calculate internal energy or enthalpy (e.g., for property
tables)
• The relationships among specific heat, internal energy, and
enthalpy can be derived from
• the specific heat definition
• the 1st Law for a simple compressible system undergoing a
quasiequilibrium process neglecting changes in KE and PE
– Q = dU + W = dU + P dV
 Specific Heat of a Simple
Compressible Substance
Constant-Volume Specific Heat, Cv
• The relationship between specific heat and internal
energy is determined by considering a constant-
volume process for a closed system in which
• V = const.,  dV = 0  Q = dU
• thus,
• Note that the resulting expression for the constant-
volume specific heat contains only thermodynamic
properties  Cv is also a thermodynamic property
 Specific Heat of a Simple
Compressible Substance
Constant-Pressure Specific Heat, Cp
• The relationship between specific heat and
enthalpy is determined by considering a
constant-pressure process for a closed system in
which
• P = const.,  Q = dH
• thus,
• Note that the resulting expression for the
constant-pressure specific heat contains only
thermodynamic properties  Cp is also a
thermodynamic property
 Specific Heat of a Simple
Compressible Substance
Change in Enthalpy and Internal Energy of Solids or Liquids
• When solids or liquids undergo a change of state without a change
of phase, a common approximation to the change in internal
energy and enthalpy is determined by considering that
• h = u + Pv
• dh = du + d(Pv) = du + P dv + v dP
since
• a) these phases are nearly incompressible, dv  0
• b) their specific volume is very small, v dP  0
• so that
dh  du  C dT where C = Cv or C = Cp
• For cases where the specific may be assumed constant, then
h2 – h1  u2 – u1  C (T2 - T1)
 The Internal Energy, Enthalpy,
and Specific Heats of IDEAL GASES
Internal Energy
• It can be shown analytically and experimentally that for an
ideal gas, the internal energy is a function of temperature
only, i.e.,
u = f(T)
• The internal energy of an ideal gas can be determined from its
specific heat as follows:
since u = f(T) only
Then
du = Cvo dT
dU = m Cvo dT
 The Internal Energy, Enthalpy,
and Specific Heats of IDEAL GASES
Enthalpy
• For an ideal gas, the enthalpy is also a function of
temperature only

• h = u + Pv = u + RT = h(T)
• The enthalpy of an ideal gas can be determined from its
specific heat as follows:
since h = f(T) only
Then
dh = Cpo dT
dH = m Cpo dT
 The Internal Energy, Enthalpy,
and Specific Heats of IDEAL GASES
• Specific Heats
Cvo and Cpo are functions of temperature only since u = f(T)
and h = f(T)
 The Internal Energy, Enthalpy,
and Specific Heats of IDEAL GASES
• Specific Heats
Cvo and Cpo are functions of temperature only since u = f(T) and
h = f(T)

• The translational and rotational energies of molecules increase linearly with temperature  contributions to the
specific heat are not temperature-dependent
• Contributions from vibrational and electronic modes are temperature-dependent  more vibrational modes
causes higher increase in specific heat with temperature
 The Internal Energy, Enthalpy,
and Specific Heats of IDEAL GASES
• The difference of Cvo(T) and Cpo(T) is always equal to the gas
constant

h = u + Pv = u + RT  dh = du + R dT
Cpo dT = Cvo dT + R dT  Cvo - Cpo = R
• The specific heat ratio  is defined as

•   Cpo / Cvo  R = (  - 1 ) Cvo

 Using Specific Heat to Evaluate
Ideal Gas Enthalpy
• In evaluating the enthalpy of gases using the specific heat,
the accuracy depends upon the assumption used regarding
the specific heat.
• I Constant Specific Heat
• The specific heat is not a function of temperature but a
constant (see e.g. Table A.5)

• Reasonable assumption for monatomic gases, small

temperature range, or an average specific heat for the
temperature range is used.

• h2 – h1 = Cpo(T2 – T1)
Using Specific Heat to Evaluate
Ideal Gas Enthalpy
• II Specific Heat as a Function of Temperature
• The specific heat is expressed as an analytical
function of temperature which is an empirical
approximation to results of statistical
thermodynamic calculations (see e.g. Table A.6)
• The change in enthalpy is a close empirical
approximation and is given by:
T2
h2  h1   T1
C po (T ) dT
Using Specific Heat to Evaluate
Ideal Gas Enthalpy
• III Specific Heat as Function of Temperature and
Integrated Directly from a Reference Temperature
• The enthalpy of the gas at any temperature T
relative to a reference temp. To is defined using the
function
T
hT   T0
C po (T ) dT
where Cpo is calculated using statistical thermodynamics

•Values of hT vs. T for some gases and air are tabulated in

• Table A.7 and Table A.8
The enthalpy change is most accurate and is given by
h2 – h1 = h T2 – h T1
The 1st Law as a Rate Equation
• The 1st Law can be written in rate form to
express the instantaneous or average rates of
energy transfer through and energy change
within the system boundary.
• This departs from a strict classical point of
view but is useful in many applications.

dU d  KE  d  PE 
Q     W
dt dt dt
 Conservation of Mass
• The relationship between mass and energy
from relativistic considerations,
E = m c2
• will be disregarded in the present analysis of
thermodynamic problems due to its negligible
effects.
• Thus, the conservation of mass and
conservation of energy equations are
considered as independent equations.
Key Concepts and Formulas
1st Law of Thermodynamics:
Q12   E2  E1   W12
Total Energy:
1
E  U  KE  PE  mu  mV 2  mgZ
2
Enthalpy :
h  u  Pv
Two  phase mass average:
u  u f  xu fg  (1  x)u f  xu g
h  h f  xh fg  (1  x )h f  xhg
Specific Heat:
 u   u 
Cv    ;C   
  T  p
p
 T v
 Key Concepts and Formulas

Solid and Liquids(Incompressible v=constant  v f and v are very small)

C  Cv  C p [Tables A.3 and A.4]
h 2 -h1  u 2  u1  C (T2  T1 )
Ideal Gas
h  u  Pv  u  RT (only functions of T)
du dh
Cv  ;Cp   Cv  R
dT dT
u2  u1   Cv dT  Cv (T2  T1 )

h2  h1   C p dT  C p (T2  T1 )