Chapter Two

The first law and other basic

concepts
Joules experiments
h
T
1
T
2

mg
VI. Internal Energy and the First
Law
6.1 Joules experiments (textbook, p18)
The really important feature of Joules
work was that the peddle-wheel
experiments gave the same
proportionality as was obtained in
several other quite different methods of
transforming work into temperature
rise of a quantity of water.
Joules experiments
the paddle-wheel experiments
experiments in which mechanical work
was expanded in the compression of a
gas in a cylinder which was immersed in
the water
experiments in which mechanical work
was expanded on two pieces of iron
which rubbed each other beneath the
surface of water.
Joules experiments
The significant conclusion is that each of the
above method of transforming mechanical
work into temperature rise gives essentially the
same result.
Therefore the conclusion to be drawn is that
the performance of a given amount of
mechanical work, on a quantity of adiabatically
enclosed water, causes the same temperature
rise (ie the same change of state by whatever
method the process is carried out).
Joules experiments
This important empirical result has been
confirmed by many later workers and
using several different substances other
than water. Hence, without discussing
the great mass of evidences, we shall
make a preliminary formulation of the
first law of thermodynamics as follows:
first law of thermodynamics
The change of a body inside an
adiabatic enclosure from a give initial
state to a given final state involves the
same amount of work by whatever
means the process was carried out.
first law of thermodynamics
The student should convince
himself/herself that if this law is
erroneous it would be possible to
contract a perpetual motion machine.
Total energy change
AU + AE
R
+ AE
P


where AU: internal energy,
AE
R
: Kinetic energy (1/2 mu
2
)
AE
P
: Potential energy (mgh)
Closed system often undergoes processes that
cause no change in external energy, therefore,
the first law can be expressed as

AU = Q +W involving finite change

Q and W are positive when transferred from
surrounding to the system.
The change of internal energy of the system
that does not undergo the change of external
energy is equal to the heat transferred into the
system plus the work done by the system on its
surroundings.
The differential form : dU = dQ + dW
For an adiabatic system: AU = W
6.2 Internal Energy: (textbook, p18)
In Joules experiments
Energy
Water
extracted
In the form of heat
In the form of work
Logic suggests that the energy that is
contained in the water in another form, a form
which we define as internal energy U.
Explain internal energy:
Potential energy in gravitational field and/or electric
fields, only depends on position.
Joules experiments allow us to think a kind of
energy which depends on the change of temperature,
pressure, and composition of the body.
For this purpose, we construct a new function U, the
internal energy, which depends on the internal state
of a body, as determined by its temperature, pressure
and composition.
Internal energy
Internal energy of a substance does not include
any energy that it may possess as a result of its
macroscopic position or movement.
Rather it refers to the energy of the molecules
making up the substances, which are in
ceaseless motion and possesses kinetic energy
of translation.
Internal energy
The designation of this form of energy as
internal energy distinguishes it from kinetic
and potential energy which the substance may
possess as a result of its macroscopic position
and motion, and which can be thought of as
external forms of energy.
The scheme of Joules experiments
Mechanical Work
(same amount)
Turbulent motion
of water
Temp. rise of
Water (773)
Compression of
gas
Friction of iron
blocks
Temp. rise of
Water (838)
Temp. rise of
Water (775)
The figure in brackets show the number of foot-
pounds of work needed to rise the temperature of
1lb of water by 1F.
6.3 Heat:
In examining Joules experiments of the
change of the states of a body in an adiabatic
enclosure.
It would have been wrong to have spoken of
the temperature rise of water as having been
due to heat.
Another statement of the first law of
thermodynamics
Although energy assumes many forms, the
total quantity of energy is constant, and when
energy disappears in one form often it
simultaneously appears in other forms.

the mathematical form of the First
Law
It must apply to both system and its
surroundings.
In its basic form, the first law may be written:
A(energy of the system) + A(energy of
surroundings) = 0,
Q and W
In the thermodynamic sense, heat and work
refer to the energy in transit across the
boundary between the system and its
surroundings. This form of energy cannot be
stored.
Q and W
To speak of work or heat as being contained
in a body or system is wrong
Q and W
Energy is stored in its potential, kinetic, and
internal forms. The transformation of energy
often occurs through the mechanism of work
and heat.
First Law
If the system is a closed system, all energy
passing across the boundary between the
system and the surroundings is transferred in
the form of heat and work. Therefore, the
second mathematical form of the first law of
thermodynamics is
A(energy of the system) = W + Q
Q and W
Q from surroundings to the system (+)
positive
W from surroundings to the system (+)
positive
Q and W
What we were clearly concerned with was the
changes of the state due only to work.
However, it is also known from experience
that the same amount changes of state can be
produced by contacting the system to a hot
source through a non-adiabatic wall, without
the expenditure of work.
What is Heat (HQ?)
Our sense and instruments provide us with no
direct knowledge of heat which is quite
distinct from hotness.
Heat has been very obscure to people since
the ancient civilization.
The amount of heat transfer to a body can thus
be determined in mechanical units, only by
measuring the amount of work which causes
the same changes of state.
What is Heat (HQ?)
It was found that at 1 atm, for 1g of water
To change, T
1
= 14.5 C T
2
= 15.5 C
requires 4.184 Joules (work). Then the certain
amount of heat that has been transferred to the
system is then arbitrarily defined as 1 cal
(calorie).
The work equivalent to this heat unit is 4.184
Joules (no matter how the work is performed).
6.4 Expression of the first law for
an infinitesimal process
dU = dQ + dW
dU: increment of the already existing internal
energy of a body
whereas dQ and dW do not have the
corresponding interpretation.
For this reason some authors use oQ and oW
instead.
The essential point is that dU is the differential
function of state and its integral is always U
B
-
U
A





A B
B
A
U U dU =
}
}
= Q dQ
}
=W dW
As an example, consider the change of state of
a substance
(1 atm, 5 m
3
) (2 atm, 10 m
3
)
initial state A final state B
It has infinite variety of ways to make the
process occur.
(p
A
, v
A
)
(p
B
, v
B
)
(a)
(b)
(c)
For each of the above processes, if it is carried
out slowly without friction, the work is equal
to the area under the curve


The work obviously varies from one path to
another
}
pdv
However, we always have

A B
B
A
U U dU =
}
if the system undergoes A B C

A C B C A B
C
B
B
A
C
A
U U U U U U dU dU dU = + = + =
} } }
State Function
for a loop path


}
= 0 dU
State Functions
Another difference is:
State function represents a property of a
system and always has a value.
Work and heat appear only when changes are
caused in a system by a process, which
requires time.
6.5 Total Internal energy

E
T
= E
P
+ E
R
+ U


6.6 Enthalpy (textbook, p 35)


U = Q + W (positive when surrounding
does work to the system)
U = Q - W (negative when system does
work to surrounding)
PV U H +
6.8 Steady flow process (textbook, p44)

U
1

V
1
,

P
1

Q
U
2

V
2
,

P
2

W
s
to generate electricity
or does mechanical work
Coal
burning
Nuclear
power
Water
High pressure steam
Low pressure
steam (exhaust)
Flow process
The first law for an open system
The first law for a closed system



The first law for an open system

W Q z g
u
U + = A +
A
+ A
2
) (
2
s
W Q z g
u
H + = A +
A
+ A
2
) (
2
6.6 Enthalpy (textbook, p 35)


U = Q + W (positive when surrounding
does work to the system)
U = Q - W (negative when system does
work to surrounding)
PV U H +
3.3 The Ideal Gas, Page 66:
1st Law of thermodynamics: dU = dQ + dw
PV=RT
H=U + PV=U + RT
(Eqn 2.16 and eqn 3.15)


V
V
T
U
C
|
.
|

\
|
c
c

dT
dH
T
H
C
P
P
=
|
.
|

\
|
c
c

Ideal Gas
H=U + PV=U + RT

C
p
= C
v
+ R

We also define
V
P
C
C

Ideal Gas
Again from the 1
st
law
dQ = dU dW
since dW = - PdV
dQ = C
v
dT + PdV
Since
V
RT
P =
Ideal Gas
we have


now take
V
dV
RT dT C dQ
V
+ =
P
RT
V =
P
dP
RT dT R C dp
p
RT
dT
P
R
P dT C dQ
V V
+ = + = ) ( ) (
2
Ideal Gas
Eqn: 3.23 (p 69)
P
dP
RT dT C dQ
P
=
Ideal Gas
also


Now, let


We have
P
dP
RT RdT dW + =
R
PV
T =
PdV dV
R
P
dP
R
V
C dQ
V
+ + = ) (
PdV
R
C
VdP
R
C
dQ
P V
+ =
Ideal Gas
Isothermal Process (p-70)
AU = AH = 0



1
2
1
2
ln ln
P
P
RT
V
V
RT Q = =
1
2
1
2
ln ln
P
P
RT
V
V
RT W = =
Ideal Gas
Adiabatic Process:
0 = + = PdV
R
C
VdP
R
C
dQ
P V

|
|
.
|

\
|
=
2
1
1
2
V
V
P
P
A Rocket Problem
An Example of the 1st Law
A
n

P
atm

.
.
.
.
.
.
. . .
.
.
H
2
O
P(t) High
Pressure gas
A wonderful toy rocket consists of a hollow rocket
casing which is filled approximately one half full
with water. Air is pumped into the rocket casing with
the rocket point upward so that the compressed air is
in the upper half and water is in the lower half. When
the air pump is disconnected, the compressed air
pushes out the water and the rocket rises. The
objective of todays lecture is to show the
thermodynamics can be used to determine the highest
distance that a rocket like that described can fly and
the trade-offs in the design of such a rocket.
the thrust of the rocket
The thrust or net force on the rocket is caused
by a force imbalance within the rocket body.
If the water is expelled relatively slowly, i.e.
over a few seconds, the pressure on all inner
surfaces of the rocket casing may be
considered equal as the compressed air and
water will rapidly flow to eliminate any
pressure imbalance.
the thrust of the rocket
The water at the nozzle, however,
expands ever so slightly and very rapidly
goes to atmospheric pressure as it
escapes.
The pressure at the nozzle will nearly
equal atmospheric pressure.
the thrust of the rocket
The pressure difference between the top of the
rocket which opposes the nozzle area and
atmospheric pressure at the nozzle causes a
pressure imbalance which acts on an area
equal to the nozzle cross section.
the thrust of the rocket
The thrust is given as

(P P
m
) A
n
= thrust
A force imbalance on the rocket
determines the flight
n atm r r
A P t P g t m
dt
dv
t m ) ) ( ( ) ( ) ( =
To integrate the force imbalance, we must
determine the internal rocket pressure as a
function of the time and the mass of the rocket
as a function of time (the mass changes as the
water is expelled).
The internal rocket pressure is then
given by






where P
i
= initial pressure and = initial
air volume

|
|
.
|

\
|
=
) (
) (
t V
V
P
t P
t
t
i
i
t
i
V

The sum of the rocket volume must equal
the volume of the water and the
compressed air.
t t
w
t
r
V V V + =
The mass of the rocket is given by the
sum of the rocket casing mass and that of
the water. The mass of the compressed air
is considered small.


)) ( (
2
t V V m m
t t
r O H rc r
+ =
Choose the system
We now have determined the rocket mass and internal
pressure as a function of compressed air or water
volume and can integrate the rocket force balance
equation if we can determine the volumetric flow rate of
water from the rocket.
To determine the time dependence of the water flow
from the rocket, we must consider a system about the
water as it passes through the nozzle. We can do this
with an open or closed system. The closed system would
follow a packet of water as it flows out of the rocket and
thus the system boundaries would move in time so as to
contain the same portion of water.
time
The first law for a closed system

W Q z g
u
U + = A +
A
+ A
2
) (
2
The first law for an open system

s
W Q z g
u
H + = A +
A
+ A
2
) (
2
First consider what the change in internal
energy will be as water flows through the
nozzle. The internal energy is given
mathematically by
V
V
U
T
T
U
U
T V
A
|
.
|

\
|
c
c
+ A
|
.
|

\
|
c
c
= A
The change in the internal energy caused by water
expansion with the pressure drop as it flows through the
nozzle is very small, as the change in volume is virtually
zero; water is quite incompressible. Assuming that the
water is inviscid (i.e. has a viscosity of zero and
therefore does not resist flow and dissipate energy as it
flows), the internal energy is not increased by the flow
through the nozzle. To a very reasonable approximation,
we can assume that the internal energy of the water
does not change as it flows from the rocket. The change
in potential energy is small as the height difference in the
rocket is small. Little heat transfer to the water can occur
in a few seconds so the process can be considered
adiabatic. The first laws for the open and closed system
reduces to
Closed system



Open system
W
u
+ =
A
2
) (
2
0
2
) (
2
=
A
+ A
u
H
The work done on the closed system is
equal to the PV work since no shaft work
or other work is performed. The work per
unit mass flow PV on the internal surface
of the closed system. The work per unit
mass flow is P
atm
V on the external surface
of the closed system. The net work is thus
W = -(P
atm
P)V
and the first law for the closed system
gives


V P P
u
atm
) (
2
) (
2
=
A
For the open system, the change in enthalpy is
given by
) (PV U H A + A = A
=
(as = 0)

where AP = (P
atm
P)
0 = AU V P P V H A + A = A
P VA
V PA
the first law for the open system gives the
same result as the closed system which must
be the case
0
2
) (
2
=
A
+ A
u
P V
The velocity of the water expulsion is
determined by its inertia as it is accelerated
V P P
u
atm
) (
2
2
=
V P P u
atm
) ( 2 =
The velocity of water exiting the rocket is
determined by nozzle area and the volumetric
flowrate
dt
dV
A
u
t
n
1
=

m
V
P
V
V
P
dt
dV
A
t
w
atm
t
t
i
i
t
n (
(

|
|
.
|

\
|
=

2
1
integrating
) (
1 t
V f t

=
) (t f V
t
=
Now the mass of the rocket and the pressure as
a function of time can be determined
)) ( ( ) (
2
t f V m t m
t
r O H rc r
+ =

|
|
.
|

\
|
=
|
|
.
|

\
|
=
t
i
i
t
i
t
i
V
t f
P
V
V
P t P
) (
) (
The height that the rocket can fly
n atm r r
A P t P g t m
dt
du
t m ) ) ( ( ) ( ) ( =
20m
5cm
2m
2m
20m
1
3
2
In city pack
20m
5cm
2m
2m
20m
1
3
2
In city pack
City park
Estimate the power requirement
(ignoring frictional losses)
p k s
H E E W Q A + A + A = +
Between planes 1and 2

2
2
, 0
0
(20 2) 0
2
2(20 2) 10
360 /
s
H W and Q
V
g
V
m s
A

+ =
=
=
Between planes
3and 2


0
p k s
H E E W Q
H and Q
A + A + A = +
A

s
m v A
Power W m
=
=