First Law for Controlled Mass (closed) Systems

Work

Work done at a moving boundary (simple compressible systems)

Constant Volume Process (Isochoric)
Constant Pressure Process (Isobaric)
Constant Temperature (Isothermal)
Polytropic Processes
Heat Transfer Revisited (Conduction, Convection, Radiation)
Internal Energy and Enthalpy
Specific Heats
Internal Energy, Enthalpy and Specific Heat (for gases, solids and liquids)
Conservation of energy principle (1st law) for a closed system Revisited
Problem Solving technique
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Work
Consider the two systems
labeled A and B.
In system A, a gas is stirred
by a paddle wheel: the paddle
wheel does work on the gas.
In principle, the work could
be evaluated in terms of the
forces and the motions at the
boundary between the paddle
wheel and the gas.
By contrast, consider system B, which includes only the battery.
At the boundary of system B, forces and motions are not evident. Rather, there is
an electric current i driven by an electrical potential difference existing across the
terminals a and b. That this type of interaction at the boundary can be classified
as work follows from the thermodynamic definition of work given previously:
We can imagine the current is supplied to a hypothetical electric motor that lifts a
weight in the surroundings.
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Work Revisited
A thermodynamic definition
of work states:
Work is done by a system on
its surroundings if the sole
effect on everything external
to the system could have
been the raising of a weight.
In other words, work is the
energy transfer (across a
boundary) associated with a
force acting through a
distance resulting (usually)
in a movement of the
boundary.
Mathematically:

Forms of Work
Expansion/Compression Work
(Moving Boundary Work)

V2

p dV

V1

Elongation of a solid bar

Stretching of a Liquid Film

Rotating Shaft

Electric
Others:
Polarization
Magnetization
Surface tension
Spring work

Moving Boundary Work

This is the work associated with the expansion or
compression of a gas in a pistoncylinder device. During
this process, part of the boundary (the inner face of the
piston) moves back and forth. Therefore, the expansion
and compression work is often called moving boundary
work, or simply boundary work. Some call it the P dV
work.
Moving boundary work is the primary form of work
involved in automobile engines. During their expansion,
the combustion gases force the piston to move, which in
turn forces the crankshaft to rotate.
The moving boundary work associated with real engines
or compressors cannot be determined exactly from a
thermodynamic analysis alone because the piston
usually moves at very high speeds, making it difficult for
the gas inside to maintain equilibrium.
Then the states through which the system passes during
the process cannot be specified, and no process path can
be drawn. Work, being a path function, cannot be
determined analytically without a knowledge of the path.
Therefore, the boundary work in real engines or
compressors is determined by direct measurements.
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Moving Boundary Work

We analyze the moving boundary work for a quasiequilibrium process, a process during which the system
remains nearly in equilibrium at all times. A quasiequilibrium process, also called a quasi-static process, is
closely approximated by real engines, especially when
the piston moves at low velocities.
Consider the gas enclosed in the pistoncylinder device
shown. The initial pressure of the gas is P, the total
volume is V, and the cross-sectional area of the piston is
A. If the piston is allowed to move a distance ds in a
quasi-equilibrium manner, the differential work done
during this process is

The total boundary work done during the entire process as the piston moves is
obtained by adding all the differential works from the initial state to the final state:

Strictly speaking, the pressure P in the above equation is the pressure at the inner
surface of the piston. It becomes equal to the pressure of the gas in the cylinder only
if the process is quasi-equilibrium and thus the entire gas in the cylinder is at the
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same pressure at any given time.

Moving Boundary Work

An idealized type of process is called a quasi-equilibrium

process; this a process in which all states through which
the system passes may be considered equilibrium states.
The intensive properties of the system are assumed
uniform throughout the system.
To consider how a gas (or liquid) might be expanded or
compressed in a quasi-equilibrium fashion, refer to the
figure on the right which shows a system consisting of a
gas initially at an equilibrium state. The gas pressure is
maintained uniform throughout by a number of small
masses resting on the freely moving piston.
Imagine that one of the masses is removed, allowing the
piston to move upward as the gas expands slightly.
During such an expansion the state of the gas would depart
only slightly from equilibrium. The system would
eventually come to a new equilibrium state, where the
pressure and all other intensive properties would again be
uniform in value.
Moreover, were the mass replaced, the gas would be
restored to its initial state, while again the departure from
equilibrium would be slight.
If several of the masses were removed one after another,
the gas would pass through a sequence of equilibrium
states without ever being far from equilibrium. In the limit
as the increments of mass are made vanishingly small, the
gas would undergo a quasi-equilibrium expansion process.

Moving Boundary Work

Remember that the limits on the integral
mean from state 1 to state 2 and cannot
be interpreted as the values of work at
these states. The notion of work at a state
has no meaning as the differential of
work, W, is inexact because, in general,
the integral cannot be evaluated without
specifying the details of the process; i.e.
the integral can be evaluated only if we
know the functional relationship
between P and V during the process.
That is, P = f (V) should be available
either as a mathematical relationship or
from experimental data. Note that
P = f (V) is simply the equation of the
process path on a P-V diagram.
The quasi-equilibrium expansion process
described is shown on a P-V diagram
opposite. The differential area dA is
equal to P dV, which is the differential
work. The total area A under the process
curve 12 is obtained by adding these
differential areas:

Moving Boundary Work

A gas can follow several different paths as it
expands from state 1 to state 2. In general,
each path will have a different area
underneath it, and since this area represents
the magnitude of the work; the work done
will be different for each process (as shown).
This is expected, since work is a path
function (i.e., it depends on the path
followed as well as the end states).
If work were not a path function, no cyclic
devices (car engines, power plants) could
operate as work-producing devices. The work
produced by these devices during one part of
the cycle would have to be consumed during
another part, and there would be no net work
output.
The cycle shown on the right produces a net
work output because the work done by the
system during the expansion process (area
under path A) is greater than the work done
on the system during the compression part of
the cycle (area under path B), and the
difference between these two is the net work
done during the cycle (the colored area).

Moving Boundary Work

Remember that work is a mechanism for energy interaction between a system and
its surroundings, and Wb represents the amount of energy transferred from the
system during an expansion process (or to the system during a compression
process). Therefore, it has to appear somewhere else and we must be able to
account for it since energy is conserved.
In a car engine, for example, the boundary work done by the expanding hot gases
is used to overcome friction between the piston and the cylinder, to push
atmospheric air out of the way, and to rotate the crankshaft. Mathematically:

Of course the work used to overcome friction appears as frictional heat and the
energy transmitted through the crankshaft is transmitted to other components
(such as the wheels) to perform certain functions. But note that the energy
transferred by the system as work must equal the energy received by the
crankshaft, the atmosphere, and the energy used to overcome friction.
The use of the boundary work relation is not limited to the quasi-equilibrium
processes of gases only. It can also be used for solids and liquids.
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Moving Boundary Work

As mentioned earlier, to perform the integral
requires a relationship between the gas pressure at the moving boundary and the system
volume.
This relationship may be difficult, or even impossible, to obtain for actual compressions
and expansions.
In the cylinder of an automobile engine, for example, combustion and other nonequilibrium effects give rise to non-uniformities throughout the cylinder. Scatter might
exist in the pressurevolume data, as illustrated below. Still, performing the integral of
the above equation based on a curve fitted to the data could give a plausible estimate of
the work.

Note that the relationship between

pressure and volume during an expansion
or compression process is often described
analytically (coming up).
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Moving Boundary Work

(Isochoric process) Constant Volume Process

Consider a rigid tank containing air at 500 kPa and 150C. As a result of heat transfer
to the surroundings, the temperature and pressure inside the tank drop to 65C and 400
kPa, respectively. Let us determine the boundary work done during this process.
Is there a change in volume?
Since a rigid tank has a constant volume,
i.e. dV = 0. Therefore:

i.e. there is no boundary work done

during this process. The boundary
work done during a constantvolume process is always zero. This
is also evident from the P-V
diagram of the process (the area
under the process curve is zero).
Note that in an isochoric process, heat is added (or removed) to change the temperature
without changing the volume.
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Moving Boundary Work

Constant Pressure Process (Isobaric process)

Consider a frictionless pistoncylinder device which contains 10 lbm of steam at 60

psia and 320oF. Heat is now transferred to the steam until the temperature reaches
400oF. If the piston is not attached to a shaft and its mass is constant, determine the
work done by the steam during this process.
The expansion process is quasiequilibrium. Even though it is not
explicitly stated, the pressure of
the steam within the cylinder
remains constant during this
process since both the
atmospheric pressure and the
weight of the piston remain
constant. Therefore, this is a
constant-pressure process, and,
from

Usually the isobaric expansion is accomplished by adding heat to a system. A consequence

of the process is that a total quantity of heat Q is added and the temperature increases.
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Moving Boundary Work

Constant Temperature Process (Isothermal process)
Consider a pistoncylinder device which initially contains 0.4 m3 of air at 100 kPa and
80C. The air is now compressed to 0.1 m3 in such a way that the temperature inside
the cylinder remains constant. Determine the work done during this process.

The compression process is quasiequilibrium. At the specified

conditions, air can be considered to
be an ideal gas since it is at a high
temperature and low pressure relative
to its critical-point values. For an
ideal gas the relationship is given by:
PV = NRT = C

Substituting this into

or

we have:

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Moving Boundary Work

As mentioned earlier, the relationship between pressure and volume during an
expansion or compression process can also be described analytically. Pressure
and volume are often related by PVn = C, where n and C are constants. A
process of this kind is called a Polytropic process. The pressure for a
polytropic process can be expressed as:
Substituting this into

We have:

Since
.

Note the following:

The equation for work, Wb, above can be written in terms of temperatures, n and R
For the case of n=1 the above equation cannot be used!
For the case when n=1 and for an ideal gas equations of state assumption, the
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equations used in the previous slide for an isothermal process can be used