First Law of

Thermodynamics
PC1431 Lecture 13

System
Change in
Heat Q Internal Work W
energy U
Surroundings
Thermodynamic Processes & Variables
Quasi-static process: Processes that are carried out slowly
enough so that the system passes through a continuous
sequence of thermal equilibrium states.
State variables: Temperature, volume, pressure, internal
energy.
Describe the state - can assign values to these variables.
Can be specified only if the system is in thermal
equilibrium internally, namely the thermodynamic
properties of every part of the system are the same.
Transfer variables: Heat, Work - present only in process.
Characteristics of the process - could be different even if
the initial and final states are the same.
Work and its Sign Convention
When an object is heated and its volume is allowed to expand, it
forces back the surroundings. Work is done by the object and the
amount of work done depends generally on the pressure (p) and
change of volume (V).
Different textbooks used different conventions. We will adopt the
convention used in Young and Freedman which defines W as the
work done by the gas (a more common convention) but Serway and
Jewett takes W as work done on the gas in Chapters 20 21 and
Weng as work done by the engine in Chapter 22.

W is the work done by the thermodynamic system and is

positive when the gas expands. When the work is done on the
system such that its volume decreases, W is negative.
Work Done by Gas
System exerts a force = pA on piston.
When piston moves infinitesimal
distance dx, work done by gas is:

Total work by the gas as its

volume changes from V1 to V2.
Work done is Path Dependent
The work done in bringing the gas from
an initial state 1 to a final state 2 depends
on the path taken between the two states
since the work done is area under curve:

W1
W2 W3

It is obvious that the work done also depends on the initial and
final states.
Work & Kinetic Energy of Molecules
It is easy to see that the kinetic energies of the molecules are
decreased when the gas expands and increased when the gas
contracts:

KEmolecules
when work is
done by gas.

Recall that for elastic collision,

speed of approach = speed of separation

KEmolecules
when work is
done on gas.
 Heat Transfer is Process-Dependent
Energy transferred by heat is also process-dependent / path-dependent.
E.g.

Isothermal Process: (Adiabatic) free expansion:

Pressure is reduced slowly, Partition is broken. Gas rapidly
T kept constant by supplying expands into upper half.
heat. Q > 0 Well insulated: Q = 0
Q W and Cyclic Processes
Q and W are individually path-dependent.
However, experimental evidence shows that (Q W) depends
only on the initial and final states of the system!
In particularly, for a cyclic process (originates and terminates at
the same state),

Work done by gas =

Area enclosed by path

Note: if cycle goes in a clockwise

direction, positive work is done by
gas, and vice versa.
First Law of Thermodynamics
When a system undergoes a change from one state to another, the
change in its internal energy U is given by:

1st Law of Thermodynamics

where Q is the energy transferred into the system and W is the

work done by the system. (Note: we will use U for internal energy
as used in Y&F. S&J used Eint for internal energy.)

System
Change in
Heat Q Internal Work W
energy U
Surroundings
Differential Form of the First Law
When a system undergoes only an infinitesimal change in state,
only small amount of heat is absorbed and only an small amount
of work is done, so that the internal energy change is also
infinitesimal. In such a case, the first law is written in differential
form as:

In systems where the work is given by pdV, the first law in

differential form becomes:
Remarks on the First Law
The first law of thermodynamic is essentially the law of
energy conservation that includes the change in internal
energy. In other words, the net energy gained (Q W) by the
system during a process is converted into internal energy.
U is path-independent and the internal energy U is a state
property.
In general, the internal energy of most real gases is a function
of p, V and T. However, for ideal gas, the assumptions we
took in our studies of kinetic theory that there are no attractive
forces between the molecules except during collisions made U
a simple function of T alone.
Internal Energy of an Ideal Gas
Consider the free expansion case.
When the partition is broken, and
the gas expands into the whole
container, no work and heat was
exchange with the surrounding and
thus by the First Law:

Experiments conducted with low-pressure gas (approximately

ideal gas) shows also that the temperature does not change from
its original value when it reaches its final equilibrium state.
U is constant when T is constant, indep. of changes in V and P
U is a function of T only for an ideal gas.
In fact, from Kinetic Theory, we have shown that U = 3/2 nRT
for a monatomic gas!!
Thermodynamic Processes
1. Isothermal

2. Isobaric

3. Isochoric

4. Adiabatic
Thermodynamic Processes
Obviously, there is no limit to the types of thermodynamic
processes that are possible. Any path joining two states
represents a possible thermodynamic process to bring it from
the initial to the final state.
These are the
more common
processes we will
deal with and used
as approximation
for real processes
conditions
making some
quantities
relatively easy to
calculate.
Isochoric (Isovolumetric) process
In an isochoric process, the volume
of the system remains unchanged.

This means that the heat that flows into the system has served
to increase its internal energy or if heat flow out, U decreases.
(For our purpose, we will assume that isochoric means W = 0. Note
that even if V = 0, mechanical work is still possible, eg, by stirring!)
Isobaric Process
In an isobaric process, the pressure of the system is constant.

All the three quantities (U, Q and W) are non-zero.

Isothermal Process
In an isothermal process, the
temperature of the system remains
constant all the time.
For ideal gas, U is a function of T only.
Adiabatic Process
In an adiabatic process, there is
no heat transfer between the
system and its surroundings.

The internal energy decreases as work is done by the system on

the surroundings, and this usually leads to a decrease in
temperature of gas. If work is done on the system, the internal
energy increases and this is usually accompanied by a
temperature rise.
(Adiabatic) Free Expansion Process
In the free expansion, there is no heat
entering the system - thermally isolated.
There is also no work done on or by the
system - expands into vacuum.
Initial and final energies are equal!
T = 0 (for ideal gas).

No line here
Can only represent it by
2 points but not a line
intermediate states are
not in equilibrium.
Heat Capacities of an Ideal Gas
From the first law, we can derive a very simple relationship
between the molar heat capacities for an ideal gas at constant
volume and at constant pressure CV and CP:
Consider a constant volume process
where the gas is heated from T1 to T2.

For the isobar process:

Heat Capacities of an Ideal Gas
But since the internal energy of an ideal gas is a function of its
temperature only, the change in internal energy when a gas
goes from T1 to T2 is independent of the path even if final V
and P are different. So the U for the isobaric case is the same
as the isochoric case. In fact for an ideal gas, in all processes:

So that:
Ratio of Heat Capacities
The ratio of the heat capacities is an
important quantity, especially for adiabatic
processes.
For the different types of gas discussed in kinetic theory of gases,
we can predict their respective value of . For monatomic gases

For diatomic gases:

For polyatomic gases:

Molar specific heat C P & C V
CP CV CP-CV = CP/CV
Gas
Meas. Theory Meas. Theory Meas. Theory Meas. Theory
He 20.78 12.47 8.31 1.67
20.78 12.47 8.31 1.67
Ar 20.78 12.47 8.31 1.67
H2 28.74 20.42 8.32 1.41
N2 29.07 20.76 8.31 1.40
29.10 20.79 8.31 1.40
O2 29.17 20.85 8.31 1.40
CO 29.16 20.85 8.31 1.40
CO2 36.94 28.46 8.48 1.30
SO2 40.37 33.26 31.39 24.94 8.98 8.31 1.29 1.33
H2S 34.60 25.95 8.65 1.33
Adiabatic Process for an Ideal Gas
To derive a relationship similar
to pV = const (if isothermal) for
an adiabatic process, we use the
first law again.
Since Q = 0, we have
Adiabatic Process for an Ideal Gas
But

Or:
Adiabatic Process for an Ideal Gas

At a particular (p, V)
coordinate, adiabatic
curves are always steeper
than isothermal curves.
During expansion, work
done by gas is at expanse
of internal energy. T
decreases.
 Work Done in Adiabatic Process
If the initial and final
temperatures of the gas during
an adiabatic process are known,
then, work done by the gas is:

Or use the ideal gas equation to

express W in terms of p and V,

(Used R/CV = -1 again. Can also get this directly from W =pdV too.)
Example: First Law
A sample of an ideal gas is in a vertical cylinder fitted with a piston.
As 5.79 kJ of energy is transferred to the gas by heat to raise its
temperature, the weight of the piston is adjusted so that the state of
the gas changes from point A to point B along the semicircle as
shown. Find the change in internal energy of the gas.
Example: Cyclic Process I
A diatomic ideal gas ( = 1.40) confined to a cylinder is put through
a closed cycle. Initially the gas is at Pi, Vi, and Ti. First, its pressure
is tripled under constant volume. It then expands adiabatically to its
original pressure and finally is compressed isobarically to its original
volume.
(a) Draw a P-V diagram for this cycle.
(b) Determine the volume at the end
of the adiabatic expansion.
(c) Find the temperature of the gas at
the start of the adiabatic expansion.
(d) Find the temperature at the end of
the cycle.
(e) What was the net work done by
the gas for this cycle?
Example: Cyclic Process II
An ideal gas is carried through a thermodynamic cycle ABCD
consisting of two isobaric and two isothermal processes as shown in
the figure below. Show that the net work done by the gas in the
entire cycle is given by

T2
T1