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The First Law of Thermodynamics: Pre-Reading 19.1

1) The document discusses the first law of thermodynamics, which states that the total change in internal energy of a system is equal to the heat added to the system plus the work done on the system. 2) It defines important concepts like heat, work, internal energy, and explains that while heat and work depend on the path of a process, the change in internal energy depends only on the initial and final states. 3) For an ideal gas, the change in internal energy depends only on temperature change, allowing the definition of heat capacity. The molar heat capacities at constant volume (CV) and constant pressure (CP) are derived for an ideal gas.

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Umair Afzal Ch
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230 views25 pages

The First Law of Thermodynamics: Pre-Reading 19.1

1) The document discusses the first law of thermodynamics, which states that the total change in internal energy of a system is equal to the heat added to the system plus the work done on the system. 2) It defines important concepts like heat, work, internal energy, and explains that while heat and work depend on the path of a process, the change in internal energy depends only on the initial and final states. 3) For an ideal gas, the change in internal energy depends only on temperature change, allowing the definition of heat capacity. The molar heat capacities at constant volume (CV) and constant pressure (CP) are derived for an ideal gas.

Uploaded by

Umair Afzal Ch
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Lecture 6

The first law of


thermodynamics

Pre-reading: §19.1
1 st law of thermodynamics
A thermodynamic system is a collection of objects
we can regard as a unit, that can exchange energy
with its surroundings.

We can now think about energy transfers into and


out of these systems; through
– heat transfer Q and
– work W

YF §19.1
Sign convention
We need to be careful about signs:
Qin is positive W done by the system is positive
Qout is negative W done on the system is negative

YF §19.1
Work W
Let’s look at work done during volume changes.
Pressure exerts a force on the
piston, which moves from x1
to x2:
Z x2 Z x2
W = F · dx = (pA)dx
x1 x1
Z V2
= p dV
V1
W > 0 energy removed from system (work is done by the
system against its surroundings) (expansion)
W < 0 energy added to system (work is done on the system )
YF §19.2
(compression)
Work W
So the work done equals the
area under a pV curve.
Work W
There can be many different paths from one
thermodynamic state to another, so the work
done by a system during a transition between
two states depends on the path chosen

YF §19.3
Example: Isothermal expansion
An ideal gas undergoes a constant-temperature
expansion at temperature T, so its volume
changes from V1 to V2. How much work does the
gas do?

YF §19.2
Heat transfer Q
A system can interact with its surroundings by
doing work.
It can also interact with its surroundings by
means of heat transfer.

YF §19.3
Heat transfer Q
How much heat is transferred also depends on
the path taken.

YF §19.3
Heat and work
So both heat and work are only recognized as
they cross the boundary of a system.
•  They are associated with a process, not a state.
•  They are both path-dependent functions.
•  A system in general does not possess heat or
work.
[wrong description:　
‘work in a body;
‘heat in a body’]
YF §19.3
Internal energy U
We define the internal energy of a system to be the
sum of
– the kinetic energy of all its particles
– the potential energy of interactions between
particles
Kinetic energy: translation, vibration, rotation

YF §19.4
Internal energy U
U = ∑ KE + ∑ PE
interaction
Random chaotic between atoms
motion
& molecules

The kinetic and potential energies associated with


the random motion of molecules constitute the
internal energy U.
Value of U not important, ΔU during a thermal
process is what matters:
ΔU = U 2 − U1 = U final − U initial YF §19.4
The first law of thermodynamics
The first law of thermodynamics:
The total change in internal energy of a system
is the sum of the heat added to it and the work
done on it.
U =Q W
(conservation of energy)
Remember:
Qin is positive W done by the system is positive
Qout is negative W done on the system is negative
YF §19.4
The first law of thermodynamics
While Q and W depend on the path, ΔU = Q – W
does not.

The change in internal energy of a system during


any thermodynamic process depends only on the
initial and final states, not on the path leading
from one to the other.

i.e. U is an intrinsic property of the system.


YF §19.4
Equivalence of heat and work
The equivalence of heat and work was
demonstrated by Joule in the 1840s. His apparatus
converted the potential
energy of falling
weights into work done
on the water by a
rotating paddle.
U for an ideal gas
Recall that the internal energy is

U = ∑ KE + ∑ PE
interaction
Random chaotic between atoms
motion
& molecules
We showed that for an ideal gas
✓ ◆
1
KE = N f kT
2
where f is the number of degrees of freedom.
U for an ideal gas
For an ideal gas, there are no forces between
molecules, so PE = 0.

Hence for an ideal gas,


f
U = N kT
2
so the internal energy for an ideal gas depends
only on its temperature.
Heat capacity of an ideal gas
Consider adding heat to a fixed
volume of an ideal gas. Since
the volume is fixed, W = 0, so
ΔU = Q.
The temperature of the gas
changes when we add heat:
f f f
U = U2 U1 = N kT2 N kT1 = N k T
2 2 2
so f f
Q = Nk T = nR T
2 2
YF §18.4
Heat capacity of an ideal gas
But our definition of heat capacity was
Q = nC T
(where C is the molar heat capacity)
and so we must have
f
CV = R
2
So any ideal gas has the same heat capacity (with
the same number of degrees of freedom).

Change in internal energy: U = nCV T


YF §18.4
U for an ideal gas, again
We calculated U for a process at constant volume.
But since the internal energy of an ideal gas only
depends on temperature, the change in internal energy
during any process must be determined only by the
temperature change.

For an ideal gas, the internal energy change in any


process is give by
U = nCV T
whether the volume is constant or not.

YF §19.4
Heat capacity of an ideal gas
Now consider adding heat to an
ideal gas at constant pressure.
By definition, Q = nCp T
and W = p V = nR T
So from U =Q W
we get nCV T = nCp T nR T
or Cp = CV + R
It takes greater heat input to raise the temperature of a gas
a given amount at constant pressure than constant volume
YF §19.4
Ratio of heat capacities
Look at the ratio of these heat capacities: we have
f
CV = R
2
and f +2
C p = CV + R = R
2
so Cp
γ = >1
CV
3
For a monatomic gas, CV = R
3 5 2
so Cp = 2 R + R = 2 R
5
and C p 2R 5
= = 3 = = 1.67
CV 2R
3 YF §19.4
Problem
An ideal gas is enclosed in a cylinder which has a movable
piston. The gas is heated, resulting in an increase in
temperature of the gas, and work is done by the gas on the
piston so that the pressure remains constant.

a)  Is the work done by the gas positive, negative or zero?


Explain

b)  From a microscopic view, how is the internal energy of


the gas molecules affected?

c)  Is the heat less than, greater than or equal to the work?
Explain.
Next lecture

The first law of thermodynamics,


continued

Read: YF §18.1

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