Lecture 2 The First Law of Thermodynamics (Ch.

1)
Lecture 1 - we introduced macroscopic parameters that describe
the state of a thermodynamic system (including temperature), the
equation of state f (P,V,T) = 0, and linked the internal energy of
the ideal gas to its temperature.

Outline:
1. Internal Energy, Work, Heating
2. Energy Conservation the First Law
3. Enthalpy
4. Heat Capacity
Internal Energy
system
U = kinetic + potential
system
boundary
environment
The internal energy of a system of particles, U, is the sum of the kinetic
energy in the reference frame in which the center of mass is at rest and the
potential energy arising from the forces of the particles on each other.
Difference between the total energy and the internal energy?
The internal energy is a state function it depends only on
the values of macroparameters (the state of a system), not
on the method of preparation of this state (the path in the
macroparameter space is irrelevant).
U = U (V, T)
In equilibrium [ f (P,V,T)=0 ] :
U depends on the kinetic energy of particles in a system and an average
inter-particle distance (~ V
-1/3
) interactions.
P
V
T
A
B
For an ideal gas (no interactions) : U = U (T) - pure kinetic
Internal Energy of an Ideal Gas
The internal energy of an ideal gas
with f degrees of freedom:
T Nk
f
U
B
2
=
f 3 (monatomic), 5 (diatomic), 6 (polyatomic)
How does the internal energy of air in this (not-air-tight) room change
with T if the external P = const?
PV
f
T k
PV
N T k N
f
U
B
room in B room in
2 2
=
(

= = =
(here we consider only trans.+rotat. degrees of freedom, and neglect
the vibrational ones that can be excited at very high temperatures)
- does not change at all, an increase of the kinetic energy of individual
molecules with T is compensated by a decrease of their number.
Work and Heating (Heat)
We are often interested in AU , not U. AU is due to:
Q - energy flow between a system and its
environment due to AT across a boundary and a finite
thermal conductivity of the boundary
heating (Q > 0) /cooling (Q < 0)
(there is no such physical quantity as heat; to
emphasize this fact, it is better to use the term
heating rather than heat)
W - any other kind of energy transfer across
boundary - work
Heating/cooling processes:
conduction: the energy transfer by molecular contact fast-moving
molecules transfer energy to slow-moving molecules by collisions;
convection: by macroscopic motion of gas or liquid
radiation: by emission/absorption of electromagnetic radiation.
HEATING
WORK
Work and Heating are both defined to describe energy transfer
across a system boundary.
The First Law
For a cyclic process (U
i
= U
f
) Q = - W.
If, in addition, Q = 0 then W = 0
Perpetual motion machines come in two types: type 1 violates
the 1
st
Law (energy would be created from nothing), type 2 violates
the 2
nd
Law (the energy is extracted from a reservoir in a way that
causes the net entropy of the machine+reservoir to decrease).
The first law of thermodynamics: the internal energy of a system can be
changed by doing work on it or by heating/cooling it.
AU = Q + W
From the microscopic point of view, this statement is equivalent to
a statement of conservation of energy.
P
V
T
An equivalent formulation:
Perpetual motion machines of the first type do not exist.
Sign convention: we consider Q and W to be positive if energy flows
into the system.
Quasi-Static Processes
Quasi-static (quasi-equilibrium) processes sufficiently
slow processes, any intermediate state can be considered
as an equilibrium state (the macroparamers are well-
defined for all intermediate states).
Examples of quasi-
equilibrium processes:
isochoric: V = const
isobaric: P = const
isothermal: T = const
adiabatic: Q = 0
For quasi-equilibrium processes, P, V, T are
well-defined the path between two states
is a continuous lines in the P, V, T space.
P
V
T
1
2
Advantage: the state of a system that participates in a quasi-equilibrium
process can be described with the same (small) number of macro
parameters as for a system in equilibrium (e.g., for an ideal gas in quasi-
equilibrium processes, this could be T and P). By contrast, for non-
equilibrium processes (e.g. turbulent flow of gas), we need a huge number
of macro parameters.
Work
The sign: if the volume is decreased, W is positive (by
compressing gas, we increase its internal energy); if the
volume is increased, W is negative (the gas decreases
its internal energy by doing some work on the
environment).
}
=

2
1
) , (
2 1
V
V
dV V T P W
The work done by an external force on a gas
enclosed within a cylinder fitted with a piston:
W = (PA) dx = P (Adx) = - PdV
Ax
P
W =- PdV - applies to any
shape of system boundary
The work is not necessarily associated with the volume changes e.g.,
in the Joules experiments on determining the mechanical equivalent of
heat, the system (water) was heated by stirring.
dU = Q PdV
A the
piston
area
force
W and Q are not State Functions
P
V
P
2

P
1

V
1
V
2

A B
C D
- the work is negative for the clockwise cycle; if
the cyclic process were carried out in the reverse
order (counterclockwise), the net work done on
the gas would be positive.
( ) ( )
( )( ) 0
1 2 1 2
2 1 1 1 2 2
< =
= + =
V V P P
V V P V V P W W W
CD AB net
}
=

2
1
) , (
2 1
V
V
dV V T P W
- we can bring the system from state 1 to
state 2 along infinite # of paths, and for each
path P(T,V) will be different.
U is a state function, W - is not
thus, Q is not a state function either.
AU = Q + W
Since the work done on a system depends not
only on the initial and final states, but also on the
intermediate states, it is not a state function.
PV diagram
P
V
T
1
2
Comment on State Functions
U, P, T, and V are the state functions, Q and W are not. Specifying an initial and final
states of a system does not fix the values of Q and W, we need to know the whole
process (the intermediate states). Analogy: in classical mechanics, if a force is not
conservative (e.g., friction), the initial and final positions do not determine the work, the
entire path must be specified.
x
y
z(x
1
,y
1
)
z(x
2
,y
2
)
dy
y
z
dx
x
z
z d
x
y
|
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
( ) ( )dy y x A dx y x A a d
y x
, , + =
- it is an exact differential if it is
( )
( )
x
y x A
y
y x A
y
x
c
c
=
c
c
,
,
( ) ( ) y x z dy y dx x z a d , , + + =
the difference between the values of some (state) function
z(x,y) at these points:
A necessary and sufficient condition for this:
If this condition
holds:
( )
( )
( )
( )
y
y x z
y x A
x
y x z
y x A
y x
c
c
=
c
c
=
,
,
,
,
e.g., for an ideal gas: |
.
|

\
|
+ = + = dV
V
T
dT
f
Nk PdV dU Q
B
2
o
- cross derivatives
are not equal
dV P S d T U d =
U
V
S - an exact differential
In math terms, Q and W are not exact differentials of some functions
of macroparameters. To emphasize that W and Q are NOT the state
functions, we will use sometimes the curled symbols o (instead of d)
for their increments (oQ and oW).
Problem
Imagine that an ideal monatomic gas is taken from its initial state A to state
B by an isothermal process, from B to C by an isobaric process, and from
C back to its initial state A by an isochoric process. Fill in the signs of Q,
W, and AU for each step.
V, m
3

P,
10
5
Pa
A
B
C
Step Q W AU

A B





B C

C A
2
1
1 2
+ -- 0
-- + --
+ 0 +
T=const
Another Problem
During the ascent of a meteorological helium-gas filled balloon,
its volume increases from V
i
= 1 m
3
to V
f
= 1.8 m
3
, and the
pressure inside the balloon decreases from 1 bar (=10
5
N/m
2
) to
0.5 bar. Assume that the pressure changes linearly with volume
between V
i
and V
f
.
(a) If the initial T is 300K, what is the final T?
(b) How much work is done by the gas in the balloon?
(c) How much heat does the gas absorb, if any?
P
V
P
f

P
i

V
i
V
f

K 270
1m bar 1
1.8m bar 5 . 0
K 300
3
3
=

= = = =
i i
f f
i f
B
B
V P
V P
T T
Nk
PV
T T Nk PV
(a)
(b)
}
=
f
i
V
V
ON
dV V P W ) ( o
( ) bar 625 . 1 bar/m 625 . 0
3
+ = V V P
(c)
ON
W Q U o o + = A
( ) J m bar m bar m bar
3 3 3 4
10 6 6 . 0 4 . 0 5 . 0 8 . 0 5 . 0 ) ( = = + = =
}
f
i
V
V
BY
dV V P W o
- work done on a system
}
=
f
i
V
V
BY
dV V P W ) ( o
- work done by a system
BY ON
W W o o =
( ) ( ) J J J
4 4 5
10 5 . 4 10 6 1 . 0 10 5 . 1 1
2
3
2
3
= + = +
|
|
.
|

\
|
= = A =
BY
i
f
i i ON i f B ON
W
T
T
V P W T T Nk W U Q o o o
Quasistatic Processes in an Ideal Gas
isochoric ( V = const )
isobaric ( P = const )
0
2 1
=

W
( ) ( ) T C T T Nk Q
V B
A = > =

0
2
3
1 2 2 1
( ) 0 ) , (
1 2
2
1
2 1
< = =
}

V V P dV T V P W
( ) ( ) T C T T Nk Q
P B
A = > =

0
2
5
1 2 2 1
2 1
= Q dU
2 1 2 1
+ = Q W dU
V
P
V
1,2

PV= Nk
B
T
1

PV= Nk
B
T
2

1
2
V
P
V
1

PV= Nk
B
T
1

PV= Nk
B
T
2
1
2
V
2

(see the last slide)
Isothermal Process in an Ideal Gas
1
2
2 1
ln ) , (
2
1
2
1
V
V
T Nk
V
dV
T Nk dV T V P W
B
V
V
B
V
V
= = =
} }

f
i
B f i
V
V
T Nk W ln =

W
i-f
> 0 if V
i
>V
f
(compression)
W
i-f
< 0 if V
i
<V
f
(expansion)

isothermal ( T = const ) :
V
P
PV= Nk
B
T

V
1
V
2

W
2 1 2 1
= W Q
0 = dU
Adiabatic Process in an Ideal Gas
adiabatic (thermally isolated system)
PdV dT Nk
f
dU T Nk
f
U
B B
= = =
2 2
( f the # of unfrozen degrees of freedom )
dT Nk VdP PdV T Nk PV
B B
= + =
PV PdV
f
VdP PdV = +
2
f P
dP
f V
dV 2
1 , 0
2
1 + = = +
|
|
.
|

\
|
+
}

const V P PV
P
P
V
V
= =
|
.
|

\
|
=
|
|
.
|

\
|

1 1
1
1
ln ln
The amount of work needed to change the state of a thermally isolated system
depends only on the initial and final states and not on the intermediate states.
0
2 1
=

Q
2 1
=W dU
to calculate W
1-2
, we need to know P (V,T)
for an adiabatic process
}
=

2
1
) , (
2 1
V
V
dV T V P W
0
1 1
= +
} }
P
P
V
V
P
dP
V
dV

V
P
V
1

PV= Nk
B
T
1

PV= Nk
B
T
2

1
2
V
2

Adiabatic Process in an Ideal Gas (cont.)
V
P
V
1

PV= Nk
B
T
1

PV= Nk
B
T
2

1
2
|
|
.
|

\
|

=
= =

} }
1
1
1
2
1 1
1 1
2 1
1 1
1
1
) , (
2
1
2
1

V V
V P
dV
V
V P
dV T V P W
V
V
V
V
1+2/3~1.67 (monatomic), 1+2/5 =1.4 (diatomic), 1+2/6 ~1.33 (polyatomic)
(again, neglecting the vibrational degrees of freedom)
const V P PV = =

1 1
An adiabata is steeper than an isotherma:
in an adiabatic process, the work flowing
out of the gas comes at the expense of its
thermal energy its temperature will
decrease.
V
2

Problem
Imagine that we rapidly compress a sample of air whose initial pressure is
10
5
Pa and temperature is 22
0
C (= 295 K) to a volume that is a quarter of
its original volume (e.g., pumping bikes tire). What is its final temperature?

2 2 1 1
2 2 2
1 1 1
V P V P
T Nk V P
T Nk V P
B
B
=
=
=
1
2
1
2
1
2
1
1 1
2
1
2
1 1
2
1 1
2
T
T
V
V
T
T
V P
T Nk
V
V P
V
V P
P
B
=
|
|
.
|

\
|
= = =

const V T V T = =
1
2 2
1
1 1

K K K
V
V
T T 514 74 . 1 295 4 295
4 . 0
1
2
1
1 2
~ ~ =
|
|
.
|

\
|
=

For adiabatic processes:
Rapid compression approx. adiabatic, no time for the energy
exchange with the environment due to thermal conductivity
const T P =

/
1
also
- poor approx. for a bike pump, works better for diesel engines
Non-equilibrium Adiabatic Processes
- applies only to quasi-
equilibrium processes !!!
const TV =
1
2. On the other hand, AU = Q + W = 0
U ~ T T unchanged
(agrees with experimental finding)
Contradiction because approach
#1 cannot be justified violent
expansion of gas is not a quasi-
static process. T must remain the
same.
(Joules Free-Expansion Experiment)
const TV =
1
1. V increases
T decreases (cooling)
The Enthalpy
Isobaric processes (P = const):
dU = Q - PAV =Q -A(PV) Q =A U +A(PV)
The enthalpy is a state function, because U, P,
and V are state functions. In isobaric processes,
the energy received by a system by heating equals
to the change in enthalpy.
Q = A H
isochoric:
isobaric:
in both cases, Q
does not
depend on the
path from 1 to 2.
Consequence: the energy released (absorbed) in chemical reactions at constant
volume (pressure) depends only on the initial and final states of a system.
H U + PV - the enthalpy
The enthalpy of an ideal gas:
(depends on T only)
T Nk
f
T Nk T Nk
f
PV U H
B B B
|
.
|

\
|
+ = + = + = 1
2 2
Q = A U
Heat Capacity
T
Q
C
A

o
The heat capacity of a system - the amount of energy
transfer due to heating required to produce a unit
temperature rise in that system
C is NOT a state function (since Q is not a
state function) it depends on the path
between two states of a system
T
V
T
1

T
1
+dT
i
f
1
f
2
f
3

The specific heat capacity
m
C
c
( isothermic C = , adiabatic C = 0 )
C
V
and C
P
dT
PdV dU
dT
Q
C
+
= =
o
V
V
T
U
C
|
.
|

\
|
c
c
=
the heat capacity at
constant volume
the heat capacity at
constant pressure
P
P
T
H
C
|
.
|

\
|
c
c
=
To find C
P
and C
V
, we need f (P,V,T) = 0 and U = U (V,T)
dT
dV
P
V
U
T
U
dV
V
U
dT
T
U
dU
dT
PdV dU
C
T V
T V
(

+
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
(

|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
= =
+
=
P T
V P
dT
dV
P
V
U
C C
|
.
|

\
|
(

+
|
.
|

\
|
c
c
=
C
V
and C
P
for an Ideal Gas
nR
f
Nk
f
C
B V
2 2
= =
C
V
=dU/dT
3/2Nk
B
5/2Nk
B
7/2Nk
B
10

100

1000

T, K
Translation
Rotation
Vibration
C
V
of one mole of H
2
R
Nk
P
Nk
P
dT
dV
P
V
U
C C
B
B
P T
V P
=
= =
|
.
|

\
|
(

+
|
.
|

\
|
c
c
=
( for one mole )
0
nR
f
Nk
f
Nk C C
B B V P
|
.
|

\
|
+ =
|
.
|

\
|
+ = + =
1
2
1
2
For an ideal gas
T Nk
f
U
B
2
=
# of moles
For one mole of a monatomic ideal gas: R C R C
P V
2
5
2
3
= =