Department of Chemical Engineering

College of Engineering
KNUST

CHE 253
CHEMICAL ENGINEERING
THERMODYNAMICS I

Compiled by: Mr. Jim K. M. Mensah

2014
 UNIT 1
Objectives
 Understand the general scope of thermodynamics.
 Explain the basic concepts of thermodynamics such as system, state, state postulate,
equilibrium, process, and cycle.
 Review concepts of temperature, temperature scales, pressure, and absolute and gauge
pressure.
 Discuss these terms in brief; work, heat and energy with respect to its thermodynamic
applications.

1.0 INTRODUCTION
1.1 Definition and Scope
What is thermodynamics?

Thermodynamics can simply be defined as the science of energy. It is the branch of science that
embodies the principles of energy transformation in macroscopic systems. The general restrictions
which experience has shown to apply to all such transformations are known as the laws of
thermodynamics. These laws are primitive; they cannot be derived from anything more basic and
comprises of a network of equations which find application in all branches of science and
engineering. Presently it is broadly interpreted to include all aspects of energy and energy
transformations, including power generation, refrigeration, and relationships among the properties
of matter. The chemical engineer copes with a particularly wide variety of problems. Among them
are calculation of heat and work requirements for physical and chemical processes, and the
determination of equilibrium conditions for chemical reactions and for the transfer of chemical
species between phases. The application of thermodynamics to any real problem starts with the
identification of a particular body of matter as the focus of attention. This body of matter is called
the system, and its thermodynamic state is defined by a few measurable macroscopic properties.
These depend on the fundamental dimensions of science such as length, time, mass, temperature,
and amount of substance.
1.2 Basic Concepts
Systems and Control volume
A system is defined as a quantity of matter or a region in space chosen for study. The mass or
region outside the system is called the surroundings. The real or imaginary surface that separates
the system from its surroundings is called the boundary. The boundary serves either to isolate the
system from its surroundings or to provide for interaction in specific ways between system and
surroundings.

Systems may be considered to be closed or open, depending on whether a fixed mass or a fixed
volume in space is chosen for study.

1.2.1 Closed System

A closed system (also known as a control mass) consists of a fixed amount of mass, and no mass
can cross its boundary. That is, no mass can enter or leave a closed system. But energy, in the
form of heat or work, can cross the boundary; and the volume of a closed system does not have
to be fixed. See figure 1.2

Fig. 1.2 A closed system

1.2.2 Open System
An open system, or a control volume, as it is often called, is a properly selected region in space. It
usually encloses a device that involves mass flow such as a compressor, turbine, or nozzle. Flow
through these devices is best studied by selecting the region within the device as the control
volume. Both mass and energy can cross the boundary of a control volume.

Figure 1.3 An open system (a control volume) with one inlet and one exit.

1.2.3 Isolated system

An isolated system can exchange neither matter nor energy with its surroundings.

1.3 Dimensions and Units

Primary units have been set by international agreement, and are codified as the International
System of Units (abbreviated SI, for Systѐme International).
The second, symbol s, the SI unit of time, is the duration of 9 192 631 770 cycles of radiation
associated with a specified transition of the cesium atom.
The meter, symbol m, is the fundamental unit of length, defined as the distance light travels in a
vacuum during 11299 792 458 of a second.
The kilogram, symbol kg, is the mass of a platinum/iridium cylinder kept at the International
Bureau of Weights and Measures at Sѐvres, France.
The unit of temperature is the kelvin, symbol K, equal to 11273.16 of the thermodynamic
temperature of the triple point of water.

Other systems of units, such as the English engineering system, use units that are related to SI units
by fixed conversion factors eg. Foot (ft) is defined as 0.3048 m.
(Ask students to read on the conversion factors from EES to SI units)
Any physical quantity can be characterized by dimensions. The magnitudes assigned to the
dimensions are called units. Some basic dimensions such as mass m, length L, time t, and
temperature T are selected as primary or fundamental dimensions, while others such as velocity
V, energy E, and volume V are expressed in terms of the primary dimensions and are called
secondary dimensions, or derived dimensions.
1.4 Properties of a System
Any characteristic of a system is called a property. Examples of some familiar properties are
pressure P, temperature T, volume V, and mass m. The list can be extended to include less familiar
ones such as viscosity, thermal conductivity, modulus of elasticity, thermal expansion coefficient,
electric resistivity, and even velocity and elevation.

1.4.1 Intensive Properties

Intensive properties are those that are independent of the mass of a system, such as temperature,
pressure, and density.

1.4.2 Extensive Properties

Extensive properties are those whose values depend on the size or extent of the system. Total
mass, total volume, and total momentum are some examples of extensive properties.

1.4.3 Specific Properties

Extensive properties per unit mass are called specific properties. Some examples of specific
properties are specific volume (v = V/m) and specific total energy (e = E/m).

1.5 Measures of amount or size

Three measures of amount or size are in common use:

 Mass, m
 Number of moles, n
 Total volume, Vt

These measures for a specific system are in direct proportion to one another. Mass, a primitive
without definition, may be divided by the molar mass M, commonly called the molecular weight,
to yield number of moles:
m
n (1.1)
M
Total volume, representing the size of a system, is a defined quantity given as the product of three
lengths. It may be divided by the mass or number of moles of the system to yield specific or molar
volume:
 Vt
 Specific volume: V (1.2)
m
Vt
 Molar volume: V (1.3)
n
1
Specific or molar density is defined as the reciprocal of specific or molar volume: p  V

These quantities (V and p) are independent of the size of a system, and are examples of intensive
thermodynamic variables. They are functions of the temperature, pressure, and composition of a
system, additional quantities that are independent of system size.

In performing evaluations of systems and cycles with steam, a convenient variable is the quality
of steam, x. It is defined as the ratio of the mass of steam to total mass of steam and water in a
mv
mixture, i.e., x (1.4)
mt
where mt = mv + ml.
It is frequently used to compute thermodynamic properties of two-phase mixtures of steam and
water:

mix  v x  l (1  x) (1.5)

In this equation,  can be specific volume, internal energy, enthalpy, or entropy.

1.6 Force
The SI unit of force is the newton, symbol N, derived from Newton's second law, which expresses
force F as the product of mass m and acceleration a:
= (1.6)
Thus force is measured in the composite unit kg.m.s-2 also referred to as the newton (N).
In the metric engineering system of units, force is treated as an additional independent dimension
along with length, time, and mass. The kilogram force (kgf) is defined as that force which
accelerates 1 kilogram mass 9.806 65 meters per second per second.
= (1.7)
 1
1 = ×1 × 9.80665 .

gc = 9.80665kgm.kgf-1s-2

1.7 Temperature
Temperature is commonly measured with liquid-in-glass thermometers, wherein the liquid
expands when heated.
Kelvin temperatures are given the symbol T; Celsius temperatures, given the symbol t, are defined
in relation to Kelvin temperatures:
= − 273.15 (1.8)
The unit of Celsius temperature is the degree Celsius, oC, equal in size to the kelvin. However,
temperatures on the Celsius scale are 273.15 degrees lower than on the Kelvin scale. Thus the
lower limit of temperature, called absolute zero on the Kelvin scale, occurs at -273.15oC.
The Rankine scale is an absolute scale directly related to the Kelvin scale by:
( ) = 1.8 (1.9)
The Fahrenheit scale is related to the Rankine scale by an equation analogous to the relation
between the Celsius and Kelvin scales:
( ) = ( ) − 459.67 (1.10)
Thus the lower limit of temperature on the Fahrenheit scale is -459.67(oF). The relation between
the Fahrenheit and Celsius scales is:
( ) = 1.8 + 32 (1.11)
The ice point is therefore 32(oF) and the normal boiling point of water is 212(oF).
The Celsius degree and the kelvin represent the same temperature interval, as do the Fahrenheit
degree and the rankine.

1.8 Pressure
In the ideal gas law, Eq. (1), absolute pressure, P, is required. Absolute pressure is defined as the
normal component of force exerted by the fluid per unit area acting on a surface in the system, and
it has SI units of Newtons per square meter (N/m2) or Pascals (Pa). Most instruments measure
pressure relative to local atmospheric pressure, i.e., they give readings in gauge pressure.
Consequently, the local atmospheric pressure or barometric pressure must be added to the gauge
pressure to convert it to absolute pressure for use in Eq. (1).

absolute pressure = gauge pressure + barometric pressure

F mg Ah g
gauge pressure =    h g
A A A

The pressure to which a fluid height corresponds is determined by the density of the fluid (which
depends on its identity and temperature) and the local acceleration of gravity. Thus the (torr) is the
pressure equivalent of 1 millimeter of mercury at 273.15 K (0°C) in a standard gravitational field,
and is equal to 133.322 Pa. Another unit of pressure is the standard atmosphere (atm), the
approximate average pressure exerted by the earth's atmosphere at sea level, defined as 101 325
Pa, 101.325 kPa, or 0.101 325 MPa. The bar, an SI unit defined as l05 Pa, is equal to 0.986 923
atm.

1.9 Work

Work, W, is done when a force acts through a distance, and the amount of work is the product of
the distance and the force acting through this distance. In thermodynamics an important type of
work occurs when a change in the volume of a fluid causes the movement of a piston. A force, F,
exerted on a piston by the fluid is equal to the product of the fluid pressure, P, and the cross-
sectional area, A, of the piston. The distance through which the force acts is the displacement of
the piston, and this is equal to the volume change of the fluid divided by the cross-sectional area
of the piston, d (V/A). The pressure and the volume of the fluid vary according to an equation of
state, so the work must be written in a differential form as:
dW  Fdx  PAd (V A) (1.12)
For a piston with a constant cross-sectional area A, Eq. (1) becomes:
dW  PdV (1.13)
This equation can be integrated over the volume change from point 1 to point 2 to obtain the
work for the process, i.e.,
v2
W   PdV (1.14)
v1
The pressure must be known as a function of this change in volume to evaluate the integral and
determine the work. The SI units of work are the Newton-meter or joule, and in English units foot-
pounds of force are frequently used.

Work can be related to kinetic and potential energy using concepts from particle mechanics. For
example, the work done on a body to accelerate it from velocity u1 to velocity u2 is the change in
kinetic energy. To show this relation, the definition of work dW = Fdl is used, where F is the force
on the body of mass, m.
u 2 u 2 
W  m 2  1  (1.15)
 2 2 

Thus, the work required to accelerate mass from u1 to u2 is the change in kinetic energy of this
body.

The work required to raise a mass from an initial elevation z1 to a final higher elevation z2 is the
change in potential energy of the body. Using the definition of work for this case,
dW  Fdl  madl  mgdl , and integrating dl from z1 to z2 gives:

W  m  z2  z1  (1.16)

Thus, work is equal to the change in potential energy for this case.
Changes in kinetic energy and potential energy will appear in the first law of thermodynamics
along with the work done by the system. The ideas presented above are to show that work is a
quantitative and unambiguous physical entity. Also, work is energy in transit. When work is done
it does not appear simultaneously as work elsewhere. It is converted into a form of energy. As
described above, work done on a mass increases it’s kinetic and potential energy.
Work is done by a system, and the system can be many useful devices, from an elevator to an
automobile engine. When work is performed, it is either done by the system on the surroundings
or vice versa. Also, energy is transferred to the system from the surroundings or in the reverse
direction. Work is done only when there is a change in energy, as described by the first law of
thermodynamics.
There is a sign convention associated with work being performed. If work is being performed on,
or transferred to, the system by the surroundings, it is considered negative, i.e., work consumed by
compressors, pumps, and mixers is negative. If work is being performed by or transferred from the
system to the surroundings, it is considered positive, i.e., work produced by turbines and engines
is positive. Using this sign convention, the first law of thermodynamics is written as:

E  Q  W (1.17)

where  E is the change in total energy of the system, Q is heat transferred to the system, and W
is work done by the system on the surroundings.

There are several forms of work as implied above. One is shaft work, which means work done on
or by a fluid flowing through a piece of equipment like a pump, compressor, or turbine which
causes the shaft to rotate or reciprocate. This shaft is connected to another machine which uses the
motion for another purpose, e.g., a generator to produce electricity. Another form of work is called
PV work, and this was described earlier in terms of the action of a fluid volume change on a piston.
Also, work is required when a wire is stretched in the elastic region, when a magnetic field is
charged on a ferromagnet, and when an electrical conductor passes through a magnetic field.
The concept of a reversible process for a closed system is used to represent the upper limit for the
performance of an actual process. It is convenient to use the work of compression or expansion
from a frictionless piston to describe a reversible process for a closed system. In a reversible
process there is only infinitesimal displacement from equilibrium, and work and heat effects are
sufficient to restore the system to its original state, i.e., there is no lost work to friction or
turbulence. The first law of thermodynamics is written in terms of differential changes to describe
the infinitesimal displacement from equilibrium for a closed system:

dU  dQ  dW (1.18)
For a closed system, the change in total energy, dE , is equal to the change in internal energy, .

1.9.1 Adiabatic Process

In an adiabatic process, no heat is transferred between the system and the surroundings, and
compressors, pumps, and turbines operate essentially adiabatically. The upper limit of
performance of these systems is described by an adiabatic, reversible process.
To evaluate the work, W, for an adiabatic, reversible, closed system, the first law of
thermodynamics, Eq. (7), has dQ  0 . Also, dW  PdV from Eq. (2), and Eq. (7) becomes:
 dU   PdV (1.19)

Next, to obtain equations that relate the pressure, volume, and temperature changes of an ideal gas
in an adiabatic, reversible, closed system, the equation for internal energy is used: dU  Cv dT .

This can be combined with Eq. (8) and the ideal gas law, PV  nRT to give the following relations
for changes in temperature, pressure, and volume between points 1 and 2:

k 1  k 1 / k
T2  V1  P 
   2  (1.20)
T1  V2   P1 

Another form of this equation is:

k k k
PV
1 1  PV
2 2  PV  constant (1.21)

where k  C p Cv the ratio of heat capacities at constant pressure and volume which has
approximate values of 1.67 for monatomic gases, 1.4 for diatomic gases, and 1.3 for simple
polyatomic gases.

The above results can be used to evaluate the work for an adiabatic, reversible, closed system. Two
equivalent, frequently used equations are given below. One is in terms of initial and final pressures
and volumes, and the other is in terms of the initial temperature and pressure and final pressure to
compute the work for this case:

W   PV 2 2  /  k  1
1 1  PV (1.22)

 k 1 / k 
RT1   P2 
W 1  (1.23)
 k  1   P1  

In an isothermal process, heat is transferred between the system and its surroundings, and boilers
and condensers essentially operate isothermally (at constant temperature). The upper limit of
performance of these systems is described by an isothermal, reversible process.
To evaluate the work for an isothermal, reversible, closed system, the first law of thermodynamics,
Eq. (7), has dU = 0 because dT = 0. Thus, the heat transferred to the system Q is equal to the work
done by the system W. Using Eq. (1.13) to evaluate the work for an ideal gas gives:

V2 V2
dV V 
W   PdV   RT  RT In  2  (1.24)
V1 V1
V  V1 

Using P1 / P2  V2 / V1 from the ideal gas law gives another frequently used form of Eqn. (13) to
compute work for this case:

P
W  RT In  1  (1.25)
 P2 

For work associated with a steady state flow system, the first law of thermodynamics has the
following form:

u 2
H   g z  Q  Ws (1.26)
2

where Ws is the shaft work. This equation is used to compute the shaft work for reversible and
irreversible processes.

For a reversible process, Eq. (15) is written in terms of differential changes. Using the fundamental
relation dH  TdS  VdP with dQ  TdS  VdP for a reversible change, Eq. (15) can be written
as:

P2
u 2
Ws   VdP   g z (1.27)
P1
2

For an incompressible fluid (constant density  or specific volume V), the integral can be replaced
by  P  , and the shaft work is given by:

P u 2
Ws    g z (1.28)
 2
For an irreversible process, an additional lost work term can be added to Eq. (17). This lost work
term for pipe flow is 2 f  L / D  u 2 , where f , is the Fanning friction factor and u is the average
fluid velocity in the pipe of length L and diameter D. The equation for pipeline calculations is:
 Pu 2 L
Ws    g z  2 f   u 2 (1.29)
 2 D

This equation is used to compute the shaft work to pump the fluid from point 1 to point 2 where
the pressure, velocities, and elevations are known at these points.
In turbines and expanders, shaft work is obtained from a high velocity gas stream impinging on
blades attached to a rotating shaft. The first law of thermodynamics for this system, Eq. (15),
simplifies to the following equation because they are operated adiabatically and kinetic and
potential energy, changes are small compared to the enthalpy change:

Ws  H  H1  H2 (1.30)

Here the shaft work is equal to the change in enthalpy of the entering and exiting streams. If the
expansion is isentropic and the entrance conditions are known, then the maximum shaft work can
be computed as a function of exit conditions. Turbines and expanders have efficiencies which are
in the range of 70 to 80 percent of the isentropic approximation.
Work computed by Eq. (19) is also applicable to compressors, and the isentropic approximation
gives the minimum shaft work to compress a fluid from an initial state to a final state. Compressor
efficiencies also range from 70 to 80 percent of the isentropic approximation.
For work done by pumps moving liquids, a convenient design equation is given below. This is a
simplification of Eq. (18), neglecting kinetic and potential energy changes:

Ws  V  P1  P2  (1.31)

where V is the liquid specific volume. Pump efficiencies are in the range of 70 to 80 percent.

1.9.2 Lost work

Lost work is energy that is unavailable for work due to irreversibilities in a process. It is defined
as the difference between the ideal and actual work of the process. The amount of lost work is
given by the following equation, which is obtained from the definition of lost work and the first
and second laws of thermodynamics:
Wlost  To Stotal (1.32)
where Wlost is the lost work per unit mass of fluid flowing in the system, To is the temperature of
the heat reservoir, and Stotal is the total change in entropy for the actual process.
1.10 Energy
Energy is simply defined as the capacity to do work. Energy is expended in agriculture for land
clearing, planting, plant protection, harvesting and processing of produce; energy in the form of
petrol and diesel oil is required for automobiles and farm tractors; energy in the form of sunshine
is required to dry agricultural produce; nuclear energy is used to generate electricity. In whatever
form of application, the essential practical characteristic of energy is that it can be transformed
from one form to another and transferred between systems by work and heat transfer. Note that
the total amount of energy is conserved in all transformations and transfers. The purpose of this
chapter is to organize the above ideas into suitable forms for engineering analysis.

1.10.1 Kinetic Energy

The curved line in Fig. 1.4 represents the path of a body of mass m (closed system) moving relative
to the x-y coordinate frame shown. Let us consider the body as it moves from s = s1, where the
magnitude of its velocity is V1, to s = s2, where its velocity is V2. If we assume that the only
interaction between the body and its surroundings involves the force F, then by Newtons 2nd Law,
the magnitude of the component Fs is related to the change in the magnitude of V by

Fig.1.4 Forces acting on a moving system

(1.33)
where, V = ds/dt. Rearranging Eq. 1.33 and integrating from s1and s2 gives

(1.34)
The integral on the left of Eq. 1.33 is evaluated as follows:

(1.35)
The quantity 1/2mV2 is the kinetic energy, KE, of the body. Kinetic energy is a scalar quantity.
The change in kinetic energy, of the body is

The integral on the right side of Eq. 2.2 is the work of the force Fs as the body moves from s1 to s2
along the path. Work is also a scalar quantity. Combining Eqs. 1.34 and 1.35 we have

(1.36)
Equation 2.4 states that the work of the resultant force on the body equals the change in its kinetic
energy. When the resultant force accelerates the body, the work done on the body can be
considered a transfer of energy to the body, where it is stored as the kinetic energy.

Kinetic energy can be assigned a value knowing only the mass of the body and the magnitude of
its instantaneous velocity relative to a specified coordinate frame, without regard for how this
velocity was attained. Hence, kinetic energy is a property of the body. Since kinetic energy is
associated with the body as a whole, it is an extensive property of the body. The units of kinetic
energy are the same as that of work. The SI unit of work is the Newtonmetre, N m, called the joule,
J.

1.10.2 Potential Energy

Consider a body of mass m that moves vertically from an elevation z1to an elevation z2 relative to
the surface of the earth, as shown in Fig. 1.4. Two forces are shown acting on the system: a
downward force due to gravity with magnitude mg and a vertical force with magnitude R
representing the resultant of all other forces acting on the system.
In accordance with Eq. 1.36, the total work equals the change in kinetic energy. That is,
 (1.37)
Assuming acceleration due to gravity to be constant we obtain

(1.38)
The quantity mgz is called the gravitational potential energy. Like kinetic energy, potential energy
is an extensive property.
Equation 1.38 states that when a resultant force causes the elevation of a body to be increased, the
body to be accelerated, or both, the work done by the force can be considered a transfer of energy
to the body, where it is stored as gravitational potential energy and/or kinetic energy. If we consider
a body on which the only force acting is that due to gravity, the right side of equation (1.38)
vanishes
and it reduces to

(1.39)
or

(1.40)

Equation 1.40 also illustrates that energy can be transformed from one form to another: For the
object falling under the influence of gravity only, the potential energy would decrease as the kinetic
energy increases by an equal amount.

1.11 Energy Conservation

In any examination of physical processes, an attempt is made to find or to define quantities which
remain constant regardless of the changes which occur. One such quantity, early recognized in the
development of mechanics, is mass. The great utility of the law of conservation of mass suggests
that further conservation principles could be of comparable value. Thus the development of the
concept of energy logically led to the principle of its conservation in mechanical processes. If a
body is given energy when it is elevated, then the body conserves or retains this energy until it
performs the work of which it is capable. An elevated body, allowed to fall freely, gains in kinetic
energy what it loses in potential energy so that its capacity for doing work remains unchanged. For
a freely falling body this means that:
∆ +∆ =0 (1.41)

Or
− + − =0 (1.42)
Other forms of mechanical energy besides kinetic and gravitational potential energy are possible.
The most obvious is potential energy of configuration. When a spring is compressed, work is done
by an external force. Since the spring can later perform this work against a resisting force, the
spring possesses capacity for doing work. This is potential energy of configuration. Energy of the
same form exists in a stretched rubber band or in a bar of metal deformed in the elastic region.

1.11 Heat
Heat is energy in transit from one body to another, and it flows from a higher to a lower
temperature. The rate of heat transfer is proportional to the local temperature gradient, and the
proportionality constant is the thermal conductivity. Like work, it only exists in transit between a
system and its surroundings, and a body does not store heat but stores internal, kinetic, and
potential energy. Joule's experiment demonstrated that work was quantitatively converted to heat,
and this heat increased the internal energy of water in the experimental apparatus. This experiment
provided a basis for the first law of thermodynamics.

The first law of thermodynamics for a closed system (nonflow process) is given by:
U  Q  W (1.43)
There are three cases that can be considered for heat being added to a closed system. They are a
constant volume process, a constant pressure process, and a constant temperature process.
For a nonflow constant volume process, heat added to the system is given by the change in internal
energy of the system. No work is performed (W = 0), and Eq. (1.43) becomes:

T2

Q  U   Cv dT  Cv ,avg T2  T1  (1.44)

T1

where the change in internal energy ΔU is given in terms of Cv, the heat capacity at constant
volume.
For a nonflow constant pressure (isobaric) process, heat added to the system is given by the change
in enthalpy of the system from the first law of thermodynamics, i.e., in Eq. (1.43) W  PV , and
H  U  PV to have H  Q

T2

Q  H   CP dT  C p ,avg T2  T1  (1.45)

T1

where the change in enthalpy,  H is given in terms of CP , the heat capacity at constant pressure.
This equation is used to analyze calorimetry data to measure heats of reaction.
For a nonflow constant temperature (isothermal) process, heat added to the system Q is equal to
the work done by the system W from the first law of thermodynamics, i.e., U  0 in Eq. (1.43).
For an ideal gas, the amount of heat transferred was given by;

V  P
Q  RTIn  2   RTIn  1  (1.46)
 V1   P2 

Sensible heat is heat causing the temperature change in a system given by either Eq. (1.44) or
(1.45), and does not include heat from phase changes, chemical reactions, or concentration
changes.
Latent heat is the heat transferred at constant temperature to a substance undergoing a phase
transition, such as being vaporized or liquefied.
WORKED EXAMPLES

1. Calculate the absolute pressure for a system, given a gauge pressure of 1.5 MPa and a barometric
pressure (atmospheric pressure) of 104 kPa.

Solution

Pabs  Patm  Pgauge

Pgauge  1.5 MPa
= 1.5 1000 kPa
= 1500 kPa
Pabs  1500  104
= 1604 kPa

2. An open end mercurial manometer shown below in the figure is connected to a gas tank. The
mercury meniscus in the left leg of the manometer is opposite 33.8 cm on the meter stick; in the
right leg it is opposite 16.2 cm. Atmospheric pressure is 747 mm Hg. Find the pressure of the gas.

Solution

Always equate pressures at the lower liquid surface, that is, Pg = Pa + PHg. The gas pressure is
greater than atmospheric pressure as shown in the figure.
PHg  33.8  16.2  17.6 cm = 176 mm Hg
Pa  747 mm Hg
Pg  747  176
= 923 mm Hg.

3. A 0.2 m3 container holds oxygen at 70°C and 25 bars. Calculate the amount of oxygen in the
container if the atmospheric pressure is 1 bar.
Solution

mRT
For ideal gas, PV 
M
PVM
 m
RT
where
P  25  1  26 bars
= 26  105 N/m 2

V  0.2 m3, R  8314.3 J/kg.mol-oK, T  273 70  343o K, M  32 kg/kg.mol

26  10 5 N/m 2  0.2 m 3  32 kg/kg.mol
m
8314.3 J/kg.mol- o K  343 o K
= 5.8354 kg

4. A container having a volume of 2.5 ft3 initially contains oxygen gas at a pressure of 125 psia
and a temperature of 75°F. Oxygen then leaks from the container until the pressure drops to 100
psia, while the temperature remains the same. Assuming ideal gas behavior, determine how many
pounds of oxygen leaked out of the container.

Solution
For ideal gas
PV
1 1M
m1 
RT1
PV
2 2M
m2 
RT2
For oxygen, R 1545.3 ft-lb/lbm.mol-oR and M  32 lbm/lbm.mol
P1  125 psia
T1  75  460  535 o R
V1  2.5 ft 3
125 lb/in 2 122 in 2 / ft 2  2.5 ft 3  32 lbm/lbm.mol
m1 
1545.3 ft-lb/lbm.mol-o R  535o R
= 1.74 lbm
 P2  100 psia
T2  T1  535 o R
V2  V1  2.5 ft 3
100 lb/in 2 122 in 2 / ft 2  2.5 ft 3  32 lbm/lbm.mol
m2 
1545.3 ft-lb/lbm.mol-o R  535o R
= 1.393 lbm
 m1  m 2  1.74  1.393
= 0.347 lbm
SAMPLE QUESTIONS
1. A cylinder contains 3 kg if water and water vapour mixture in equilibrium at a pressure of 500
kN/m2. The volume of the cylinder is 1 m3. Calculate:
a. The temperature of the mixture,
2 o
[ANS: Tsat at P = 500 kN/m is 434.95 K ]
b. The volume and mass of water
the volume of the liquid = m f v f
the mass of liquid = 3(1-x) = 0.333  0.0011
[ANS: , ]
= 0.333 kg = 0.000366 m 3
= 0.366 liter
and

c. The volume and mass of vapor.

[ANS:
the mass of vapor = mx = 0.889  3
= 2.667 kg
the volume of vapor = m g vg ]
= 2.667(0.3737 + 0.0011)
= 0.9995 m 3

2. A cylinder which contains 3 pounds of saturated liquid water at a constant pressure of 30 psia
is heated until the quality of the mixture is 70%. Calculate:
a. The initial temperature
b. The final pressure and temperature
c. The volume change of the mixture
(Answer: a. 250.34 F, b. 30 psia and 250.34oF (because fluid is not completely vapourised) read
o

from steam tables, 28.8 ft3)

3. A nonconducting container filled with 25 kg of water at 293.15 K (20°C) is fitted with a stirrer,
which is made to turn by gravity acting on a weight of mass 35 kg. The weight falls slowly through
a distance of 5 m in driving the stirrer. Assuming that all work done on the weight is transferred
to the water and that the local acceleration of gravity is 9.8 ms-2, determine:
(a) The amount of work done on the water.
(b) The internal-energy change of the water.
(c) The final temperature of the water, for which Cp = 4.18 kJ kg-1 oC-1.
(d) The amount of heat that must be removed from the water to return it to its initial temperature.
(e) The total energy change of the universe because of (1) the process of lowering the weight, (2)
the process of cooling the water back to its initial temperature, and (3) both processes together.
Solution
TRY
 TUTORIAL SET 1
1. Determine the weight, in newtons, of an object whose mass is 10 kg at a location where the
acceleration due to gravity is 9.81 m/s2
2. An object occupies a volume of 25 ft3 and weighs 20 lbf at a location where the acceleration of
gravity is 31.0 ft/s2. Determine its weight, in lbf, and its average density, in lbf/ft3, on the moon,
where g = 5.57 ft/s2.

3. A spring stretches 0.2 cm per Newton of applied force. An object is suspended from the
spring and a deflection of 3 cm is observed. If g = 9.81 m/s2, what is the mass of the object, in
kg?

4. Determine the absolute pressure exerted on an object submerged 1000 m below the surface of
the sea, in bars. The density of seawater is 1020 kg/m3 and the acceleration of gravity is 9.7 m/s2.
The local atmospheric pressure is 0.98 bar.

5. The following table lists temperatures and specific volumes of water at two pressures.

P = 0.1 MPa P = 0.12 MPa

T/(oC) V/m3kg T/(oC) V/m3kg
200 2.172 200 1.808
240 2.359 240 1.965
280 2.546 280 2.120

Data encountered in solving problems often do not exactly on the grid values provided by property
tables and linear interpolation between adjacent table entries becomes necessary. Using the data
provided, estimate
(a) The specific volume at T = 200 0C, p = 0.113Mpa.
(b) The temperature at p = 0.12 MPa, v = 1.85 m3/kg in 0C
(c) The temperature at p = 0.11 MPa, v = 2.20 m3/kg, in K