First Law

First Law of Thermodynamics
Average Kinetic Energy of 1 particle
Internal Energy For ideal gas, we have only kinetic energy
Note: The internal energy depends only on the temperature and the number of particles.
Equipartition Theorem: The total internal energy of a gas is equally distributed

among all possible modes of energy. Each mode contributes the same part equal to .
The possible modes come from
- translational kinetic energy (all gases)
- rotational kinetic energy (diatomic or polyatomic gases)
- potential energy of a spring (at high T, the atoms of a molecule will vibrate
around their equilibrium position)
Degrees of Freedom:
The number of different modes which contributed to the total energy.
H
He O2
CH4
O O H
H
1. Monatomic Ideal Gas: Example He

the only possible type of energy is kinetic.
The x, y, and z components equally contribute to the energy.
2. Diatomic Ideal Gas: Example: O

degrees of freedom for the translational kinetic energy
2 degrees of freedom from the rotational kinetic energy
1
3. Triatomic Gas Example: CH
degrees of freedom for the translational kinetic energy
3 degrees of freedom from the rotational kinetic energy
6
3
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Question: How can the internal energy of a gas change?
1. Through exchange of energy with another system:

If the gas absorbs energy, , increases
2. Through work done by the gas or onto the gas:
If the gas performs work, decreases
Work done by a gas

P,V
dx
Heat exchanged:
" "#
Note: " is the molar specific heat, or the heat necessary to raise the temperature of 1 mol
by 1 degree.
First Law of Thermodynamics:
$ # $
For a closed system: The energy is conserved!
$
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2
Application to the First Law of Thermodynamics for various processes
1. Isothermal Process " %&
1. How can we achieve it?

$ heat reservoir
$ changes in the gas occur slowly
2. What can we calculate?
! ! !
! ! ! ! ! !
!
! ln !!
3. First Law:
" %&
ln !! ln !!
2. Isohoric Process: ! " %&
&How can we achieve it? Lock the gas in a container with fixed volume.

!
! !
3. First Law of Thermodynamics:
# "' ,
where c' is the molar specific heat at constant volume
Note: Since it can always be written in terms of the molar specific heat at
constant volume:
"'
3. Isobaric Process: " %&
3
&How can we achieve it? In a container with freely moving piston.
Pin Pout
2. What can we calculate:
When the pressure is constant, the Ideal Gas Law yields:
! !
! !
! ! ! ! #! #
3. First Law of Thermodynamics:
$ "( $ !
"( $ molar specific heat at constant pressure
"' "( $ ! "( $
"' "( $
The molar specific heat at constant pressure is:
"( "'
Adiabatic Process No exchange of heat
1. How can we achieve it?

$ insulator
$ the process occurs rapidly, no time for heat exchange
3. First Law:
$ $
4
"' $ !
4. The adiabatic law:
"' $ !
! !
Substituting in the First Law:
! !
"' $ !
! ! $ "' !
"' "(
"' ! "' ! "' ! $!
! "'
! $ "(
! ! "'
! !
$ "(
$ ""('
! "'
ln ! $ "( ln ln
$ ""('
!
!
"(
Definition: "'
! ! " %& Adiabatic Law!
PV Diagrams for the various processes:

include diagrams
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Example: An ideal gas is slowly compressed at a const. pressure of 2.0 atm from 10.0 L
to 2.0 L curve BD . Heat is then added, holding the volume constant until the
temperature reaches the initial temperature curve DA .
What is the work done by the gas in this process?
) How much total heat has flown?
5
P
A
P2
P1 B
D
V2 V1
Solution:
!
* % ) ! ! ! $!
) # "'
Applying the First Law:
# $ ! $!
Note: ! + ! thus, the gas has not done work. Instead, someone else did work on the
gas and gave it energy. That energy was released in the form of heat (Q<0)!
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Example: Free expansion
P=0
P
If the vessel is insulated:

The gas does not work - no effort is required to expand:
Thus: const.
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First Law

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First Law of Thermodynamics

Average Kinetic Energy of 1 particle

Internal Energy For ideal gas, we have only kinetic energy

Equipartition Theorem: The total internal energy of a gas is equally distributed

1. Monatomic Ideal Gas: Example He

2. Diatomic Ideal Gas: Example: O

Question: How can the internal energy of a gas change?

1. Through exchange of energy with another system:

Work done by a gas

First Law of Thermodynamics:

For a closed system: The energy is conserved!

1. Isothermal Process " %&

1. How can we achieve it?

2. What can we calculate?

2. Isohoric Process: ! " %&

2. What can we calculate?

3. First Law of Thermodynamics:

where c' is the molar specific heat at constant volume

3. Isobaric Process: " %&

2. What can we calculate:

When the pressure is constant, the Ideal Gas Law yields:

3. First Law of Thermodynamics:

"( $ molar specific heat at constant pressure

"' "( $ ! "( $

The molar specific heat at constant pressure is:

Adiabatic Process No exchange of heat

1. How can we achieve it?

2. What can we calculate?

4. The adiabatic law:

Substituting in the First Law:

! ! " %& Adiabatic Law!

PV Diagrams for the various processes:

Applying the First Law:

If the vessel is insulated:

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