ME 201 Thermodynamics

THE FIRST LAW OF THERMODYNAMICS AND

ENERGY BALANCE FOR CLOSED SYSTEMS
The First Law of Thermodynamics: is a statement of the conservation of energy
principle for closed (fixed mass) and open/flow systems.
The first law cannot be proven mathematically, but no process in nature is known
to have violated the first law, and this should be taken as sufficient proof.
In this chapter, we will apply the First Law of Thermodynamics to develop the
general energy balance applied to Closed Systems.
We will solve energy balance problems for closed (fixed mass) systems that
involve heat and work interactions for general pure substances, ideal gases, and
incompressible substances
As we use the First Law of Thermodynamics we need to define the specific heat at
constant volume and the specific heat at constant pressure.
We will use the specific heats for the calculation of changes in internal energy and
enthalpy of ideal gases.

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ME 201 Thermodynamics
Various forms of the first-law relation for closed systems.

For a closed system undergoing a cycle, the initial and final states are identical,
and thus Esystem = E2 - E1 = 0. Then the energy balance for a cycle simplifies to
Ein - Eout = 0 or Ein = Eout. Noting that a closed system does not involve any
mass flow across its boundaries, the energy balance for a cycle can be expressed in
terms of heat and work interactions as:

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EXAMPLES OF CLOSED SYSTEMS

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THERMODYNAMIC SYSTEM MODELLING

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MOVING BOUNDARY WORK
Quasi-equilibrium Process: is a process during which the system remains
nearly in equilibrium at all times. A quasi-equilibrium process, also
called a quasi-static process, is closely approximated by real engines,
especially when the piston moves at low velocities.

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The area under the process curve on a P-V diagram is equal, in magnitude, to the
work done during a quasi-equilibrium expansion or compression process of a
closed system. On the P-v diagram, it represents the boundary work done per unit
mass.

The boundary work done during a process depends on the path followed as well as
the end states.
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ME 201 Thermodynamics
Real boundary work must overcome:

Boundary Work for a Constant-Volume Process

Boundary Work for a Constant-Pressure Process

Boundary Work for an Isothermal Compression of an Ideal Gas

Polytropic Process: During an actual expansion and compression

processes of gases, pressure and volume are often related by PVn =C,
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ME 201 Thermodynamics
where n and C are constants. A process of this kind is called a polytropic
process.

&

For the special case of n = 1 the boundary work becomes

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ME 201 Thermodynamics
Specific Heats
SPECIFIC HEATS: The specific heat is defined as the energy required to raise
the temperature of a unit mass of a substance by one degree. In general, this energy
depends on how the process is executed. In thermodynamics, we are interested in
two kinds of specific heats: specific heat at constant volume cv and specific heat
at constant pressure cp.

Helium Gas as an Example

The specific heat at constant volume cv can be viewed as the energy required to
raise the temperature of the unit mass of a substance by one degree as the volume
is maintained constant. Similarly the energy required to do the same as the
pressure is maintained constant is the specific heat at constant pressure cp.
The specific heat at constant pressure cp is always greater than cv because at
constant pressure the system is allowed to expand and the energy for this
expansion work must also be supplied to the system. To express the specific heats
in terms of other thermodynamic properties:

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ME 201 Thermodynamics
The left-hand side of this equation represents the net amount of energy transferred
to the system. From the definition of cv, this energy must be equal to cv dT, where
dT is the differential change in temperature.

at constant volume

Similarly, an expression for the specific heat at constant pressure cp can be

obtained by considering a constant-pressure expansion or compression process.

INTERNAL ENERGY, ENTHALPY,

AND SPECIFIC HEATS OF IDEAL GASES
Note that cv and cp are expressed in terms of other properties; thus, they must be
properties themselves. Like any other property, the specific heats of a substance
depend on the state that, in general, is specified by two independent, intensive
properties.
We defined an ideal gas as a gas whose temperature, pressure, and specific volume
are related by
It has been demonstrated mathematically (later chapter) and experimentally (Joule,
1843) that for an ideal gas the internal energy is a function of the temperature only.
Using the definition of enthalpy and the ideal gas equation:

Since R is constant and u = u(T), it follows that the enthalpy of an ideal gas is also
a function of temperature only:
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ME 201 Thermodynamics
Since u and h depend only on temperature for an ideal gas, the specific heats cv
and cp also depend on temperature only. Therefore, at a given temperature, u, h, cv,
and cp of an ideal gas have fixed values regardless of the specific volume or
pressure.
Thus, for ideal gases, the partial derivatives equations:

and
can be replaced by ordinary derivatives. Then the differential changes in the
internal energy and enthalpy of an ideal gas can be expressed as

To carry out these integrations, we need to have relations for cv and cp as functions
of temperature.
At low pressures, all real gases approach ideal-gas behavior, and therefore their
specific heats depend on temperature only. The specific heats of real gases at low
pressures are called ideal-gas specific heats, or zero-pressure specific heats, and
are often denoted cp0 and cv 0.
Accurate analytical expressions for ideal-gas specific heats, based on direct
measurements or calculations from statistical behavior of molecules, are available
and are given as third-degree polynomials in tables for several gases.

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ME 201 Thermodynamics
Ideal-gas constant-pressure specific heats for some gases are shown below

A special relationship between cp and cv for ideal gases can be obtained by

differentiating the relation h = u + RT, which yields
dh = du + R dT
Replacing dh by cp dT and du by cv dT and dividing the resulting expression by dT
gives

Defining another ideal-gas property called the specific heat ratio k, defined as

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Three ways of calculating u and h
1. By using the tabulated u and h data. This is the easiest and most accurate way
when tables are readily available.
2. By using the cv or cp relations (Table A-2c) as a function of temperature and
performing the integrations. This is very inconvenient for hand calculations but
quite desirable for computerized calculations. The results obtained are very
accurate.
3. By using average specific heats. This is very simple and certainly very convenient
when property tables are not available. The results obtained are reasonably
accurate if the temperature interval is not very large.

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SUMMARY OF EQUATION

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q =du + w =du + pdv

@ dv = 0 =>
q = du
h u + pv =
>
dh =
du + pdv + vdp =
>
du =dh pdv vdp

q =du + w =[ dh pdv vdp ] + pdv

@ dp = 0 =>

q = dh

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ME 201 Thermodynamics
Moving boundary work
Wb for an isothermal process
Wb for a constant-pressure process
Wb for a polytropic process
Energy balance for closed systems
Energy balance for a constant-pressure expansion or compression process
Specific heats
Constant-pressure specific heat, cp
Constant-volume specific heat, cv
Internal energy, enthalpy, and specific heats of ideal gases
Specific heat relations of ideal gases
Internal energy, enthalpy, and specific heats of incompressible substances (solids
and liquids)

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EXAMPLES ON SPECIFIC HEATS cp & cv
EXAMPLE #1
Determine the enthalpy change h of nitrogen, in kJ/kg, as it is heated from 600 to 1000
K, using (a) the empirical specific heat equation as a function of temperature (Table A
2c), (b) the cp value at the average temperature (Table A2b), and (c) the cp value at
room temperature (Table A2a).
Using the empirical relation for

c p (T )

from Table A-2c,

c p = a + bT + cT 2 + dT 3
where a = 28.90, b = -0.157110-2, c = 0.808110-5, and d = -2.87310-9. Then,

h =

c p (T ) dT =

[a + bT + cT
2

+ dT 3 dT

= a (T2 T1 ) + 12 b(T22 T12 ) + 13 c(T23 T13 ) + 14 d (T24 T14 )

= 28.90(1000 600) 12 (0.1571 10 2 )(10002 6002 )
+ 13 (0.8081 105 )(10003 6003 ) 14 (2.873 109 )(10004 6004 )
= 12,544 kJ/kmol
h 12,544 kJ/kmol
=
= 447.8 kJ/kg
M
28.013 kg/kmol
(b) Using the constant cp value from Table A-2b at the average temperature of 800 K,
h =

c p ,avg = c p @800 K = 1.121 kJ/kg K

h = c p ,avg (T2 T1 ) = (1.121 kJ/kg K)(1000 600)K = 448.4 kJ/kg
(c) Using the constant cp value from Table A-2a at room temperature,

c p ,avg = c p @ 300 K = 1.039 kJ/kg K

h = c p ,avg (T2 T1 ) = (1.039 kJ/kg K)(1000 600)K = 415.6 kJ/kg

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EXAMPLE #2
Determine the internal energy change _u of hydrogen, in kJ/kg, as it is heated from 200
to 800 K, using (a) the empirical specific heat equation as a function of temperature
(Table A2c), (b) the cv value at the average temperature (Table A2b), and (c) the cv
value at room temperature (TableA2a).
Using the empirical relation for

c p (T )

from Table A-2c and relating it to

cv (T )

cv (T ) = c p Ru = (a Ru ) + bT + cT 2 + dT 3
where a = 29.11, b = -0.191610-2, c = 0.400310-5, and d = -0.870410-9. Then,

u =

cv (T ) dT =

[(a R ) + bT + cT
2

+ dT 3 dT

= (a Ru )(T2 T1 ) + 12 b(T22 + T12 ) + 13 c(T23 T13 ) + 14 d (T24 T14 )

= (29.11 8.314)(800 200) 12 (0.1961 10 2 )(800 2 200 2 )
+ 13 (0.4003 10 5 )(8003 2003 ) 14 (0.8704 10 9 )(800 4 2004 )
= 12,487 kJ/kmol
u 12,487 kJ/kmol
=
= 6194 kJ/kg
M
2.016 kg/kmol
(b) Using a constant cp value from Table A-2b at the average temperature of 500 K,
u =

cv ,avg = cv @ 500 K = 10.389 kJ/kg K

u = cv ,avg (T2 T1 ) = (10.389 kJ/kg K)(800 200)K = 6233 kJ/kg

(c) Using a constant cp value from Table A-2a at room temperature,

cv ,avg = cv @ 300 K = 10.183 kJ/kg K

u = cv ,avg (T2 T1 ) = (10.183 kJ/kg K)(800 200)K = 6110 kJ/kg

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EXAMPLE #3
Consider a well-insulated horizontal rigid cylinder that is divided into two
compartments by a piston that is free to move but does not allow either gas to leak into
the other side. Initially, one side of the piston contains 1 m3 of N2 gas at 500 kPa and
80C while the other side contains 1 m3 of He gas at 500 kPa and 25C. Now thermal
equilibrium is established in the cylinder as a result of heat transfer through the piston.
Using constant specific heats at room temperature, determine the final equilibrium
temperature in the cylinder. What would your answer be if the piston were not free to
move?

Both N2 and He are ideal gases with constant specific heats. The energy stored in
the container itself is negligible. The cylinder is well-insulated and thus heat
transfer is negligible.
The gas constants and the constant volume specific heats are
R = 0.2968 kPa.m3/kg.K & cv = 0.743 kJ/kgC for N2
R = 2.0769 kPa.m3/kg.K & cv = 3.1156 kJ/kgC for He (Tables A-1 and A-2)
The mass of each gas in the cylinder is

( )
(
)
(500 kPa )(1 m )
=
(2.0769 kPa m /kg K )(298 K ) = 0.808 kg

mN 2

P1V1
(
500 kPa ) 1 m3
=
= 4.77 kg
=
3

RT
(
)
0.2968
kPa
m
/kg
K
353
K

1 N2

mHe

PV
= 1 1
RT1 He

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ME 201 Thermodynamics
Taking the entire contents of the cylinder as our system, the 1st law relation can be
written as
E Eout
=
Esystem
in

Net energy transfer

by heat, work, and mass

Change in internal, kinetic,

potential, etc. energies

0 = U = (U )N 2 + (U )He

0 = [mcv (T2 T1 )]N 2 + [mcv (T2 T1 )]He

Substituting,

(4.77 kg )(0.743 kJ/kg C)(T f

gives

80 C + (0.808 kg )(3.1156 kJ/kg C ) T f 25 C = 0

Tf = 57.2C

where Tf is the final equilibrium temperature in the cylinder.

The answer would be the same if the piston were not free to move since it would
effect only pressure, and not the specific heats.

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ME 201 Thermodynamics
EXAMPLE #4
A vertical 12-cm diameter pistoncylinder device contains an ideal gas at the ambient
conditons of 1 bar and 24C. Initially, the inner face of the piston is 20 cm from the base
of the cylinder. Now an external shaft connected to the piston exerts a force
corresponding to a boundary work input of 0.1 kJ. The temperature of the gas remains
constant during the process. Determine (a) the amount of heat transfer, (b) the final
pressure in the cylinder, and (c) the distance that the piston is displaced.

The kinetic and potential energy changes are negligible,

friction between the piston and the cylinder is negligible.

ke pe 0 . The

(a)We take the ideal gas in the cylinder to be the system. This is a closed system
since no mass crosses the system boundary. The energy balance for this stationary
closed system can be expressed as
E Eout
in

Net energy transfer

by heat, work, and mass

Esystem

Change in internal, kinetic,

potential, etc. energies

Wb,in Qout = U ideal gas mcv (T2 T1 )ideal gas ) = 0 (since T2 = T1 and KE = PE = 0)
Wb,in = Qout

Thus, the amount of heat transfer is equal to the boundary work input

Qout = Wb,in = 0.1 kJ

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ME 201 Thermodynamics
(b) The relation for the isothermal work of an ideal gas may be used to determine
the final volume in the cylinder. But we first calculate initial volume

V1 =

D 2
4

L1 =

(0.12 m) 2
4

(0.2 m) = 0.002262 m 3

Then,
V
Wb,in = P1V1 ln 2
V1

V2

3
V
0.1 kJ = (100 kPa)(0.002262 m3 )ln

=
0
.
001454
m

2
3
0.002262 m
The final pressure can be determined from ideal gas relation applied for an
isothermal process
(100 kPa)(0.002262 m 3 ) = P2 (0.001454 m 3 )
P2 = 155.6 kPa
P1V 1 = P2V 2

(c) The final position of the piston and the distance that the piston is displaced are

V2 =

D 2

(0.12 m) 2

L2
L2
0.001454 m =
L2 = 0.1285 m
4
4
L = L1 L2 = 0.20 0.1285 = 0.07146 m = 7.1 cm
3

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EXAMPLE #5
A pistoncylinder device initially contains 0.15-kg steam at 3.5 MPa, superheated by
5C. Now the steam loses heat to the surroundings and the piston moves down, hitting a
set of stops at which point the cylinder contains saturated liquid water. The cooling
continues until the cylinder contains water at 200C. Determine (a) the final pressure
and the quality (if mixture), (b) the boundary work, (c) the amount of heat transfer
when the piston first hits the stops, (d) and the total heat transfer.

The kinetic and potential energy changes are negligible, ke pe 0 .

The friction between the piston and the cylinder is negligible.
We take the steam in the cylinder to be the system. This is a closed system since
no mass crosses the system boundary. The energy balance for this stationary
closed system can be expressed as
E Eout
=
Esystem
in

Net energy transfer

by heat, work, and mass

Change in internal, kinetic,

potential, etc. energies

Wb,in Qout = U

(since KE = PE = 0)

Denoting when piston first hits the stops as state (2) and the final state as (3), the
energy balance relations may be written as
Wb,in Qout,1-2 = m(u 2 - u 1 )

Wb,in Qout,1-3 = m(u 3 - u 1 )

The properties of steam at various states are (Tables A-4 through A-6)

Tsat@3.5 MPa = 242.56C

T1 = T1 + Tsat = 242.56 + 5 = 247.56C
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P1 = 3.5 MPa v 1 = 0.05821 m 3 /kg

T1 = 247.56Cu1 = 2617.3 kJ/kg

P2 = P1 = 3.5 MPa v 2 = 0.001235 m3 /kg

x2 = 0
u2 = 1045.4 kJ/kg
x = 0.00062

v 3 = v 2 = 0.001235 m 3 /kg P3 = 1555 kPa

3
T3 = 200C

u = 851.55 kJ/kg
3

Wb,in Qout,1-2 = m(u 2 - u 1 )

Wb,in Qout,1-3 = m(u 3 - u 1 )

(b) Noting that the pressure is constant until the piston hits the stops during which
the boundary work is done, it can be determined from its definition as
Wb,in = mP1 (v1 v 2 ) = (0.15 kg)(3500 kPa)(0.05821 0.001235)m3 = 29.91 kJ

(c) Substituting into energy balance relations,

Qout,1- 2 = 29.91 kJ (0.15 kg)(1045.4 2617.3)kJ/kg = 265.7 kJ

(d)

Qout,1-3 = 29.91 kJ (0.15 kg)(851.55 2617.3)kJ/kg = 294.8 kJ

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