HARARE INSTITUTE OF TECHNOLOGY

Chemical & Process Systems Engineering

Chemical Engineering Thermodynamics
ECP 216 Lecture Notes
BY F.M. Saziya
 Property, State, and Process
• To describe a system and predict its behaviour requires
knowledge of its properties and how those properties are
related.
• A Property is a macroscopic characteristic of a system such
as mass, volume, energy, pressure, and temperature to
which a numerical value can be assigned at a given time
without knowledge of the previous behaviour (history) of
the system.
• State refers to the condition of a system as described by its
properties
• When any of the properties of a system change, the state
changes and the system is said to have undergone a
Process.
• A Thermodynamic Cycle is a sequence of processes that
begins and ends at the same state. At the conclusion of a
cycle all properties have the same values they had at the
beginning.
 Extensive and Intensive Properties

• A property is called extensive if its value for an overall

system is the sum of its values for the parts into which
the system is divided. E.g. Mass, volume, energy
• Intensive properties are not additive. Their values are
independent of the size or extent of a system and may
vary from place to place within the system at any
moment.
• Thus, intensive properties may be functions of both
position and time, whereas extensive properties vary at
most with time.
• Intensive Property examples: Specific volume, pressure,
and temperature
 Equilibrium
• In mechanics, equilibrium means a condition of balance
maintained by an equality of opposing forces.
• In thermodynamics, several types of equilibrium must exist
individually to fulfill the condition of complete equilibrium;
among these are mechanical, thermal, phase, and chemical
equilibrium
• The system can be said to be at an equilibrium state, if
observable properties p, T, are uniform throughout the
system.
• Processes are sometimes modelled as an idealized type of
process called a quasiequilibrium (or quasistatic) process. A
quasiequilibrium process is one in which the departure from
thermodynamic equilibrium is at most infinitesimal.
 Lecture 3
Work and Heat
It is essential for the student of thermodynamics to
understand clearly the definitions of both work and
heat, because the correct analysis of many
thermodynamic problems depends on distinguishing
between them.
Work and heat are energy in transfer from one system
to another and thus play a crucial role in most
thermodynamic systems or devices.
To analyze such systems, we need to model heat and
work as functions of properties and parameters
characteristic of the system or the way it functions.
 WORK
From Newtonian mechanics, we know going from state
1 to state 2, that the work W12 is done by a force moving
through a distance.
.
dx
We take the following sign convention:
• (positive work) + work done by the system,
• (negative work) − work done on the system
This sign convention is not universal. Many physicists use
precisely the opposite convention. Probably the reason for this
convention is that thermodynamics is a science that was invented
by engineers in the nineteenth century. And those engineers
wanted to produce work from steam engines. Systems doing
work were viewed favourably and endowed with a positive sign.
 WORK Cont’d

• In differential form, we have δW = F · dx.

• We associate energy with the ability to do
work. We define
• Power: the time rate of doing work = δW/dt.
• Specific work: the work per unit mass w =
W/m.
• Because work is path-dependent, the
intensive quantity w is not a thermodynamic
state variable.
 Work for a simple compressible substance
• Sketch of piston-cylinder arrangement as work is done as the
material expands when weights are removed

Figure 3.1: Sketch of piston-cylinder arrangement as work is done

as the material expands when weights are removed.
• Consider the scenario sketched above
• In state 1, we have a material at pressure P confined in a
cylinder of cross-sectional area A.
• The height of the piston in the cylinder is x. The pressure force
of the material on the piston is just balanced by weights on
top of the piston.
• Now, remove one of the weights. We notice a motion of the
piston to a new height x+dx.
• We let a long time elapse so the system comes to rest at its
new equilibrium. We notice there is a new pressure in the
chamber, P + dP sufficient to balance the new weight force
 Work Done.
• δW = Fdx.
• Now, F varies during the process. At state 1, we have F = pA.
At state 2, we have F = (p + dp)A.
• The differential of work, W, is said to be inexact because, in
general, the following integral cannot be evaluated without
specifying the details of the process
• The work done by the system as the piston is displaced a
distance dx is δW = pAdx.
• Now, since Adx = dV , the differential volume, we get the
important formula: δW = pdV.
• We can integrate this and get the equally important
FIG Use of a P–V diagram to show work done at the moving
boundary of a system in a quasi-equilibrium process.

FIG 3.2:Use of a P–V diagram to show work done at the

moving boundary of a system in a quasi-equilibrium process .
• P is the pressure of the gas and A is the area of the piston.
Therefore, the work δW is
• δW = PA dL
• But A dL = dV, the change in volume of the gas. Therefore,
• δW = P dV (3.17)
• The work done at the moving boundary during a given quasi-
equilibrium process can be found by integrating Eq. 3.17.
• However, this integration can be performed only if we know
the relationship between P and V during this process. This
relationship may be expressed as an equation or it may be
shown as a graph.
 • The work done on the air during this compression process can
be found by integrating Eq. 3.17:

The symbol 1W2 is to be interpreted as the work done during the

process from state 1 to state 2. It is clear from the P–V diagram that
the work done during this process,

is represented by the area under curve 1–2, area a–1–2–b–a. In this

example the volume decreased, and area a–1–2–b–a represents
work done on the system. If the process had proceeded from state 2
to state 1 along the same path, the same area would represent work
done by the system.
FIGURE 3.3 Various quasi-equilibrium processes between two
given states, indicating that work is a path function.
• Further consideration of a P–V diagram, such as Fig.
3.3, leads to another important conclusion. It is
possible to go from state 1 to state 2 along many
different quasi-equilibrium paths, such as A, B, or C.
• Since the area under each curve represents the
work for each process, the amount of work done
during each process not only is a function of the
end states of the process but also depends on the
path followed in going from one state to another.
• For this reason, work is called a path function or, in
mathematical parlance, δW is an inexact
differential.
 OTHER SYSTEMS THAT INVOLVE WORK
• In general, work can be expressed by the integral of the product of an
intensive property and the change of an extensive property.
• The following is a summary list of these processes and their work
expressions:
 Polytropic process:

• Polytropic process: a process which is described well by an equation of the

form
• PVn = constant = C.
• Here, n is known as the polytropic exponent.
• Example 3.1
• Find the work for a gas undergoing a polytropic process with n≠1.
• A polytropic process has

• So the work is
• Note this formula is singular if n = 1.
• Now, if n = 1, we have PV = C, which corresponds to an isothermal process
if the material is also an ideal gas. Note that non-ideal gases can also have
PV = C; they just are not isothermal. We need to be able to analyze
polytropic processes with n = 1.
• Example 3.2
• Find the work for a gas undergoing a polytropic process with n = 1.
• For this process, we have

• Therefore the work is

• Since P1V1 = C, we can say

 Example 3.4 Find the work for an isochoric process.

• An isochoric process has dV = 0. Thus

• There is no work for an isochoric process. This also corresponds to a

polytropic process with n → ∞.

• Figure 3.4: P − V diagram for various polytropic processes.

 Example 3.5 Find the work for an isobaric process.

• An isobaric process is a polytropic process

with n = 0. Thus

• We also have P2 = P1. The work is

Example 3.6 An ideal gas undergoes a two-step process.
Beginning at state 1, it is isothermally compressed
to state 2. Then it is isobarically compressed to state 3.
Find the work. The process is sketched inFig. 4.7.
• We have
• Note that 1W3 < 0, since V2 < V1 and V3 < V2. So work is done
on the system in compressing it.
• Note also that even though we do not know T, we can solve
the problem. This is because work only requires information
about the P-V state of the system and the nature of the
process.

Figure 4.7: Sketch of two-step, isothermal-isobaric,

compression of an ideal gas.
 Example 3.7
• Consider the piston-cylinder arrangement sketched in Fig. 3.7.
Here, m = 2 kg of water is initially at V1 = 0.02 m3, T1 = 50 ◦C.
When P = 100 kPa, the piston leaves the stops. The water is
heated from its initial state to a final state of 200 ◦C. Find
diagrams for the process in the P −T, T −v, and P − v planes and
the work done by the water.

Figure 3.7: Sketch of piston-cylinder arrangement for water heating example.

• At state 1, we have

• Go to the saturated water tables, temperature entry. At

T1 = 50 ◦C, we find vf = 0.001012 m3/kg
• and vg = 12.0318 m3/kg. This gives vfg = 12.0308 m3/kg.
Since vf < v1 < vg, we have a two-phase
• mixture at the initial state. This fixes P1 = 12.350 kPa.
• Now, we have
Next, heat at constant volume until
• the piston leaves the stops at P = 100 kPa, or
• the fluid becomes saturated.
We search the saturated water tables and examine the state at P =
100 kPa. We see at that pressure that vf = 0.001043 m3/kg and vg =
1.69296 m3/kg. So when P reaches 100 kPa, we still have vf < v < vg,
so the water is still a two-phase mixture.
• We define then state 2 as the state where P2 = 100 kPa with v2 =
v1 = 0.01 m3/kg.
• From here on the process is isobaric. It is useful at this stage to
consider a sketch of the processes given in Fig. 4.9.
• Now, at P2 = 100 kPa, we find that T2 = 99.62 oC. And we have v2 =
v1 = 0.01 m3/kg. Using vf and
• vg at P = 100 kPa, we find
Now, we heat isobarically until T3 = 200 ◦C, with P3 = P2 = 100 kPa. This gives us two
properties, so we know the state. The superheat tables give us v 3 = 2.17226 m3/kg.
Now, the final volume is

Let us get the work.

But 1W2 = 0 since this is an isochoric process. So

Substituting numbers, we find

 A summary table is given in Table

• Numerical values for water heating example

 Example 3.8
A gas is compressed from state (P1, V1) to (P2, V2)
via two different paths, A and B:
• Path A: a polytropic process in which PVn = C.
• Path B: an isobaric compression to (P1, V2)
followed by an isochoric compression to (P2,
V2).
• Determine the work along both paths.
 Example 3.8 cont’

• First consider Path A. On Path A, we have

• So

• Now, the work is

• Now, using C = P1V1n = P2V2n , we get

 Example 3.8 cont’

• Now, for Path B, we denote the intermediate state as ∗ and

quickly calculate

• Now, the ∗ state has V∗ = V2, so

• Now, since the first part of the process is isobaric with P = P1,
the first integral is easy. And the second integral is zero, since
the integral has no width. So we get

• Note the work for the different paths is different!

The two different paths are sketched in the P − V diagrams. In
both processes, A and B, the work is negative. The gas is worked
upon; it is thus doing negative work.
 HEAT
• Heat: a form of energy transferred across the boundary
of a system at a given temperature to another system
(or the surroundings) at a different temperature by
virtue of the temperature difference between the two.
• We adopt the notion that bodies do not contain heat,
but that heat only has relevance as a type of energy that
crosses system boundaries.
• Note that work is in a similar class; it is not contained
within a system, but can be identified when it crosses
system boundaries.
 HEAT

• We adopt the traditional engineering sign convention for

heat:
• +ve heat enters the system,
• -ve heat leaves the system.
• The sign convention again is motivated by nineteenth
century steam engines. Heat had to be added into a system
to get work out of the system. Since engineers were and are
concerned with this problem, this convention is taken
• We define a special kind of process in which Q = 0 as
• Adiabatic: a type of process for which there is no heat
transfer.
• As is work, heat transfer is a path function characterized by
inexact differentials. We take

• Here, q is the specific thermal energy transfer. It has units

J/kg. Note q ≠ q, where q is the heat flux with units W/m2.
• In this thermodynamics course, we will mainly be
concerned with q. In a heat transfer course, q is more
important
 HEAT TRANSFER MODES

• Heat transfer is the transport of energy due to a temperature difference

between different amounts of matter. We know that an ice cube taken out of
the freezer will melt when it is placed in a warmer environment such as a glass
of liquid water or on a plate with room air around it.
• From the discussion about energy, we realize that molecules of matter have
translational (kinetic), rotational, and vibrational energy. Energy in these modes
can be transmitted to the nearby molecules by interactions (collisions) or by
exchange of molecules such that energy is emitted by molecules that have more
on average (higher temperature) to those that have less on average (lower
temperature).
• This energy exchange between molecules is heat transfer by conduction, and it
increases with the temperature difference and the ability of the substance to
make the transfer.
• This is expressed in Fourier’s law of conduction,

• giving the rate of heat transfer as proportional to the conductivity, k, the total
area, A, and the temperature gradient. The minus sign indicates the direction of
the heat transfer from a higher-temperature to a lower-temperature region.
• A different mode of heat transfer takes place when a medium is flowing,
called convective heat transfer. In this mode the bulk motion of a
substance moves matter with a certain energy level over or near a surface
with a different temperature.
• Now the heat transfer by convection is dominated by the manner in which
the bulk motion brings the two substances in contact or close proximity.
Examples are the wind blowing over a building or flow through heat
exchangers, which can be air flowing over/through a radiator with water
flowing inside the radiator piping.
• The overall heat transfer is typically correlated with Newton’s law of
cooling as

• where the transfer properties are lumped into the heat transfer
coefficient, h, which then becomes a function of the media properties, the
flow and geometry
• The final mode of heat transfer is radiation, which transmits energy as
electromagnetic waves in space.
• The transfer can happen in empty space and does not require any matter,
but the emission (generation) of the radiation and the absorption do
require a substance to be present.
• Surface emission is usually written as a fraction, emissivity ε, of a perfect
black body emission as

• with the surface temperature, Ts, and the Stefan-Boltzmann constant, σ.

 HEAT & WORK

• Now, . We will see in future lectures that

there is an equivalent for heat in that
where S is the entropy, to be defined later.
• We finish with some notes of comparison:
– Q and W as well as q and w are affiliated with
transient phenomena; both cross boundaries when
the system changes state.
– Q and W as well as q and w only exist at system
boundaries.
– Q and W as well as q and w are both path-
dependent, have inexact differentials, and are not
properties of the system.
 COMPARISON OF HEAT AND WORK
Similarities between heat and work.
1. Heat and work are both transient phenomena. Systems never
possess heat or work, but either or both cross the system
boundary when a system undergoes a change of state.
2. Both heat and work are boundary phenomena. Both are
observed only at the boundary of the system, and both
represent energy crossing the boundary.
3. Both heat and work are path functions and inexact differentials.
• It should also be noted that in our sign convention, +Q
represents heat transferred to the system and thus is energy
added to the system,
• and +W represents work done by the system and thus is energy
leaving the system.
 Path versus State Functions
• In the above treatment two different differential operators d
and δ have been used to indicate exact and path–dependent
functional behavior, respectively.
• δ refers to the path dependent transfer of a differential
amount of work or heat (and mass as well).
• d refers to a differential change in a state function such as E or
U. When these functional differentials are integrated important
differences appear. For example,
• (total amount of work or heat as a path dependent line
integral)
• (total change of the system energy E from state 1 to state 2 as
indicated by the difference operator D)
• (total change of E around a closed cycle is zero)
• (in general, these line integrals are not necessarily zero)
• (total change of E around a closed cycle is zero)
 ENGINEERING APPLICATIONS
• When work needs to be transferred from one body to another, a moving
part is required, which can be a piston/cylinder combination.
• If the substance that generates the motion is a gas, it is a pneumatic
system, and if the substance is a liquid, it is a hydraulic system.
• The gas or vapour is typically used when the motion has to be fast or the
volume change large and the pressures moderate.
• For high-pressure (large-force) displacements a hydraulic cylinder is used
(examples include a bulldozer, forklift, front-loader, and backhoe.
• We also consider cases where the substance inside the piston/cylinder
undergoes a combustion process, as in gasoline and diesel engines.
• Heat transfer occurs between domains at different temperatures, as in a
building with different inside and outside temperatures. The double set of
window panes are used to reduce the rate of heat transfer through
windows.
• In situations where an increased rate of heat transfer is desirable, fins are
often used to increase the surface area for heat transfer to occur.
 KEY CONCEPTS AND FORMULAS

• Work: Energy in transfer: mechanical, electrical, and chemical

• Heat: Energy in transfer caused by 𝝙 T
• Displacement work

• Specific work:
• Power, rate of work: