Adiabatic Work Interactions

Adiabatic Work Interaction

• An interaction involving two closed systems for which the events
occurring in both systems can be repeated in such a way that the
sole effect external to one system could be duplicated by the rise
(or fall) of weights in a standard gravitational field and the sole
effect external to the other system can be duplicated by an
equivalent fall (or rise) of weights of equal magnitude
Adiabatic Work Interactions
 Adiabatic Work Interactions
Consider the following example …

Compare system A+B with system C

• This is an adiabatic work interaction – system A+B can be replaced
by a drum that has a weight attached to it
Compare system A with system B+C
• External to A – sole effect is lowering a weight (final temperature
of water in system B will be 0 oC)
• External to B+C – our experience tells us that it is impossible to
devise an experiment for which the sole effect is the rise of a weight
 Adiabatic Work Interactions
Take Home Message
• An adiabatic work interaction requires that all common boundaries
be adiabatic walls
• Systems and boundaries must be carefully delineated

Example 3.1
Consider the situation illustrated below, in which an electric
generator is operated by a falling weight and in which the power
generated is dissipated in a resistor. Neglect any dissipative
processes such as i2R line losses, friction in bearings, etc. Is this an
adiabatic work interaction?
 Energy
Postulate III
For any states (1) and (2), in which a closed system is at
equilibrium, the change of state represented by (1)  (2) and/or
the reverse change (2)  (1) can occur by at least one adiabatic
process and the adiabatic work interaction between this system
and its surroundings is determined uniquely by specifying the
end states (1) and (2)

• From Postulate III it follows that all stable states can be bridged by
adiabatic processes originating from a given initial state
• The adiabatic work for a process is a function of the end states only
• This indicates that the adiabatic work is a derived property, which
we give the name total energy, E
• The adiabatic work for a given process is given by the total energy
change
E 2  E 1  W1
a
2
 Energy
Internal Energy
• For simple systems (no external force fields or inertial forces) the
total energy is reduced to the internal energy, denoted by U
• The internal energy is related to molecular motions, intramolecular
effects, and intermolecular interactions
• Postulate I tells us that the internal energy is a function of two
independently variable properties (say  and P) plus the masses Mi

U  f   , P , M 1 , M 2 , , M n 

• The internal energy is also first order in the total mass of the system

aU   , P, M 1 , M 2 , , M n   U   , P, aM 1 , aM 2 , , aM n 
 Heat Interactions
Heat
• The “missing work” for any process (adiabatic or non-adiabatic)
• The difference of the total energy change and the actual work
performed

Q   E final  E initial   W

Sign Convention
• Work (W) – positive if work is done on the system by the
surroundings
• Heat (Q) – positive if heat is “added” to the system
• This is the “modern” sign convention
• A positive heat or work interaction leads to an increase in the total
energy of the system
 The First Law for Closed Systems
Energy Balance
• Based on our previous findings, we can write

E  Q W

• The left hand side represents the total energy change of the system
• The terms on the right hand side (Q and W) represent mechanisms
for energy transfer
• Q and W are defined only in terms of the interactions at boundaries
for a prescribed process – “boundary phenomena”

• In first law for closed systems in differential form is

d E  Q  W

• Differential operators: d for state functions,  for path functions

 Heat Interactions
Heat Interactions
• Consider the following system

• The only type of interaction that can occur between system A and B
is a pure heat interaction (W = 0  EA = – EB or QA = – QB)
• If an interaction occurs, the primitive properties of A and B will
change
• No interaction: composite system is at equilibrium (Postulate II)
• Interaction: the system must tend toward equilibrium and the
interaction must eventually cease (Postulate II)
• When the interaction ceases, the systems are said to be in thermal
equilibrium
 Heat Interactions
Postulate IV
If the sets of systems A-B and A-C each have no heat interactions
when connected across nonadiabatic walls, there will be no heat
interaction if systems B and C are also connected
(Zeroth Law of Thermodynamics)

Thermometric Temperature
• This postulate is used to rank thermometric temperature
• We say that if EA = – EB < 0 or equivalently if QA = – QB < 0,
then A > B
• In words – if energy is transferred from system A to B as a result of
a pure heat interaction, then the thermometric temperature of
system A is greater than that of system B
• For a pure heat interaction to occur, there must be a temperature
difference between system A and B
 The Ideal Gas
Ideal Gas Review
• Ideal gas temperature …

measure the volume of a

piston-cylinder device
containing helium when
placed in both an ice water
and boiling water bath

• Equation of state: PV = NRT

• The internal energy and enthalpy of an ideal gas are functions of
temperature only
U = g (T) and H = f (T)
The Ideal Gas
 Example 3.3
Two well-insulated cylinders are placed as shown below. The pistons in both
cylinders are of identical construction. The clearances between piston and wall are
also made identical in both cylinders. The pistons and the connecting rod are
metallic.
Cylinder A is filled with gaseous helium at 2 bar and cylinder B is filled with gaseous
helium at 1 bar. The temperature is 300 K and the length L is 10 cm. Both pistons
are only slightly lubricated.
The stops are removed. After all oscillations have ceased and the system is at rest,
the pressures in both cylinders are, for all practical purposes, identical.
Assuming the gases are ideal with a constant Cv and, for simplicity, assuming that the
masses of cylinders and pistons are negligible, what are the final temperatures?
 The First Law for Open Systems
Open Systems
• Consider the system bounded by
the -surface to the right
• Over a short time interval a small
quantity of mass nin enters the system
• Now consider the composite system
+ nin as a closed system and
apply the first law
E 2   E 1  Einnin   Q  W  PinVinnin

• Rearranging and differentiating gives

d E  Q  W   Ein  PinVin  nin

• Generalization to multiple streams and integration gives

 E  Q  W     Ein  PinVin  nin     Eout  PoutVout  nout
in out
 The First Law for Open Systems
First Law for Open Simple Systems
• For simple systems, the total energy E becomes the internal energy U
• By defining the enthalpy, H ≡ U + PV, we can write the first law for
open simple systems in differential form as
d U  Q  W   H innin   H outnout
in out

First Law for Open Non-Simple Systems

• If we assume that the total energy can be split into three major parts:
kinetic energy (mv2/2), potential energy (mgz), and internal energy,
a generalized first law for open systems can be expressed as
 vin2   2
vout 
d E  Q  W    H in  gzin  nin    H out  gzout  nout
in  2 out  2 
 m v 
2

with d E  d U  mg z  
 2 
 Example 3.5
A 4-m3 storage tank containing 2 m3 of liquid is about to be pressurized with air from
a large, high-pressure reservoir through a valve at the top of the tank to permit rapid
ejection of the liquid. The air in the reservoir is maintained at 100 bar and 300 K.
The gas space above the liquid contains initially air at 1 bar and 280 K. When the
pressure in the tank reaches 5 bar, the liquid transfer valve is opened and the liquid is
ejected at the rate of 0.2 m3/min while the tank pressure is maintained at 5 bar.
What is the air temperature when the pressure reaches 5 bar and when the liquid has
been drained completely?
Neglect heat interactions at the gas-liquid and gas-tank boundaries. It may be
assumed that the gas above the liquid is well mixed and that air is an ideal gas with a
constant Cv = 20.9 J/mol-K
Problem 3.6
Problem 3.6