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Equipartition

First Law of Thermodynamics

Ideal gases

Isothermal and adiabatic processes

Lecture 3, p 1

William Thomson (1824 – 1907)

of Thermodynamics (1852)

of Glasgow at age 22!

(not age 1.1 x 1021)

Ideal Gas p-V, p-T Diagrams

NkT

p=

p vs V at various constant T’s V p vs T at constant V

increasing T

Isotherms

Pressure

Pressure

0

0 Temperature

Volume

Pressure → zero as

For an ideal gas at constant T,

T → absolute zero, because

p is inversely proportional

the thermal kinetic energy of

to the volume.

the molecules vanishes.

Lecture 3, p 3

Last time: The First Law of

Thermodynamics

Energy is conserved !!!

∆U = Q + Won

total internal energy to system on the system

alternatively:

∆U = Q - Wby

Note: For the rest of the course, unless explicitly stated, we will

ignore KECM, and only consider internal energy that does not

contribute to the motion of the system as a whole.

Lecture 3, p 4

Heat Capacity

Look at Q = ∆U + Wby

for the energy:

• It will “heat up” the system (i.e., raise T).

• It can make the system do work on the surroundings.

temperature of a system by 1K (=1º C). Its SI units are J/K.

Q

C≡ (for small ∆T)

∆T

The heat capacity will depend on whether energy goes into work,

instead of only increasing U. Therefore, we distinguish between:

• Heat capacity at constant pressure (Cp), for which W > 0

(most systems expand when heated).

Lecture 3, p 5

Constant-Volume Heat Capacity

of an α-ideal Gas

Add heat to an ideal gas at constant volume:

W = 0 so ∆U = Q = Cv ∆T

U = αNkT = αnRT

# available modes

⇒ CV = ∆U/∆T = αNk = αnR per atom (or molecule)

Diatomic gas → CV = (5/2)Nk = (5/2)nR

Non-linear gas → CV = (6/2)Nk = (6/2)nR

High-T, non-metallic solid → CV = (6/2)Nk = (6/2)nR

For an α-ideal gas, CV is independent of T. This results from the fact that the

number of available modes is constant.

• this fails at low temperature, because there are fewer available modes.

• this fails at high temperature, because there are more available modes.

Lecture 3, p 6

CV ~ α Substances with more internal

degrees of freedom require more energy to

produce the same temperature increase:

into “heating up” those other degrees of

freedom!

“equipartition”

Lecture 3, p 7

ACT 1

Consider the two systems shown to the right.

In Case I, the gas is heated at constant

volume; in Case II, the gas is heated at

constant pressure.

heat QI heat QII

Compare QI , the amount of heat needed to

raise the temperature 1ºC in system I to QII, the

amount of heat needed to raise the

temperature 1ºC in system II.

Lecture 3, p 8

ACT 1: Solution

Consider the two systems shown to the right.

In Case I, the gas is heated at constant

volume; in Case II, the gas is heated at

constant pressure.

heat QI heat QII

Compare QI , the amount of heat needed to

raise the temperature 1ºC in system I to QII, the

amount of heat needed to raise the

temperature 1ºC in system II.

In Case II, Wby > 0, because the gas is expanding.

Both cases have the same ∆U, because the temperature rise is the same.

→ more heat is required in Case II

→ Cp > Cv Lecture 3, p 9

Work Done by a Gas

When a gas expands, it does work on its environment.

Consider a cylinder filled with gas. A

For a small displacement dx, the work done by the gas is

dWby = F dx = pA dx = p (Adx)= p dV dx

Vf

This is just the area under the p-V curve: Wby = ∫ p dV

Vi

Examples:

because T varies

p Wby p p differently along

Wby Wby the paths. (Heat

is added at

V different times.)

V V

The amount of work performed while going from one state

to another is not unique! It depends on the path taken,

i.e., at what stages heat is added or removed.

That’s why W is called a process variable.

Lecture 3, p 10

Act 2: Work along different paths

f

1) Consider the two paths, ia, and af connecting a

points i and f on the pV diagram. Compare the

i

work done by the system in going from i to a p

(Wia ) to that done by the system in going from

a to f (Waf):

A) Wia > Waf B) Wia = Waf C) Wia < Waf V

points i and f on the pV diagram. Compare the

work W2, done by the system along path 2, with 2

the work W1, along path 1. 1 i

p

A) W2 > W1 B) W2 = W1 C) W2 < W1

Lecture 3, p 11

Solution

f

1) Consider the two paths, ia, and af connecting a Wiaf is the area

of the triangle

points i and f on the pV diagram. Compare the

i

work done by the system in going from i to a p Wia and W af

(Wia ) to that done by the system in going from cancel here.

a to f (Waf):

A) Wia > Waf B) Wia = Waf C) Wia < Waf V

Not only is the area under ia less than the area under af, but

Wia is negative, because the volume is decreasing.

The net work, Wia+Waf, is the (positive) area of the triangle.

points i and f on the pV diagram. Compare the

work W2, done by the system along path 2, with 2

the work W1, along path 1. 1 i

p

A) W2 > W1 B) W2 = W1 C) W2 < W1

Lecture 3, p 12

Solution

f

1) Consider the two paths, ia, and af connecting a

points i and f on the pV diagram. Compare the

i

work done by the system in going from i to a p

(Wia ) to that done by the system in going from

a to f (Waf):

A) Wia > Waf B) Wia = Waf C) Wia < Waf V

Not only is the area under ia less than the area under ab, but

Wia is negative, because the volume is decreasing.

The net work, Wia+Wab, is the area of the triangle.

points i and f on the pV diagram. Compare the

work W2, done by the system along path 2, with 2

the work W1, along path 1. 1 i

p

A) W2 > W1 B) W2 = W1 C) W2 < W1

area of the triangle.

Lecture 3, p 13

Constant-Pressure Heat Capacity

of an Ideal Gas

Add heat to an ideal gas at constant pressure, work Wby

allowing it to expand. We saw in the Act that more

heat is required than in the constant volume case,

because some of the energy goes into work:

Q = ∆U + Wby = ∆U + p ∆V

For an ideal gas at constant pressure, p ∆V = Nk ∆T

Q ∆U p ∆V

CP = = + heat Q

∆T ∆T ∆T

= CV + Nk = ( α + 1) Nk

that at constant volume will be useful:

Cp

=

( α + 1)

≡γ

definition

CV α

Lecture 3, p 14

Work Done by an Expanding Gas (1)

Suppose that 10 moles of O2 gas are allowed to expand

isothermally (T = 300 K) from an initial volume of 10 liters

to a final volume of 30 liters.

How much work does the gas do on the piston?

Lecture 3, p 15

Solution

Suppose that 10 moles of O2 gas are allowed to expand

isothermally (T = 300 K) from an initial volume of 10 liters

to a final volume of 30 liters.

How much work does the gas do on the piston?

Vf Vf

dV V

Wby = ∫ p dV = nRT ∫ = nRT ln f

Vi Vi

V Vi

= 10 × 8.314 × 300 × ln ( 3 ) = 2.7 × 10 4 J

p

nRT

Note: pi =

Vi

10 × 8.314 × 300

=

0.01

= 2.49 × 106 Pa = 24.6 atm

V

Lecture 3, p 16

Adiabatic (Q = 0) Process

of an α-ideal Gas

How are p and V related when Q = 0? In this case, ∆U = -Wby.

∆U = −Wby

NkT

α Nk ∆T = − p ∆V = − ∆V

V

∆T ∆V dT dV

α

T

=−

V

→ α ∫T ∫V

= −

α ln (T ) = − ln (V ) + constant

( ) ( )

ln T α + ln (V ) = ln T αV = constant

T αV = constant

pV γ = constant

Note that pV is not constant. The temperature is changing.

Lecture 3, p 17

Compare Adiabats and Isotherms

Adiabat:

γ

pV = constant

γ = (α+1)/α

p

Isotherms.

pV = constant

V

The adiabat is steeper, because γ > 1. The temperature drops if the

gas expands during an adiabatic process, because U is decreasing.

because there is no heat flow from hot to cold.

This is always true, not just for ideal gases.

“Quasi-static” means slow enough that the system is always near

thermal equilibrium. We’ll discuss this more later. Lecture 3, p 18

Work Done by an Expanding Gas (2)

Suppose, instead, that the gas expands adiabatically from

10 to 30 liters.

How much work does the gas do?

Lecture 3, p 19

Solution

Suppose, instead, that the gas expands adiabatically from

10 to 30 liters.

How much work does the gas do?

Vf

We still have: Wby = ∫ p dV

Vi

constant

But now: p=

Vγ

Vf

cons tan t 1−γ Vf

So, Wby = cons tan t ∫ V −γ dV = V

Vi

1− γ Vi

But, what’s the constant? It’s constant, so just use pi and Vi:

γ

constant = pV

i i = (2.49 × 10 )(0.01)

6 7/5

= 3946 SI units

Therefore, Wby = 2.2×104 J. It’s smaller than the isothermal result. (why?)

Lecture 3, p 20

Four Thermodynamic Processes

of Particular Interest to Us

• Isochoric (constant volume) • Isobaric (constant pressure)

2 1 2

p p

1

V V

• Isothermal (constant temperature) • Adiabatic (Q = 0)

1

1

steeper

p 2

line 2

p

V V

These processes will illustrate most of Remember the FLT

the physics we’re interested in. ∆U = Q - Wby

Lecture 3, p 21

Isochoric and Isobaric

2

Wby = ∫ pdV = 0

p

Q = ∆U = CV ∆T 1

= α Nk ∆T *= αV ∆p* Q

V Temperature

Make sure changes

you understand

these equations!

Isobaric (constant pressure) Don’t just memorize!

Wby = ∫ pdV = p∆V p

∆U = α Nk ∆T *= α p∆V * 1 2

Q = Cp ∆T p

= ∆U + Wby = (α + 1) p∆V * Q

V Temperature and

volume change

Beware!!! Many of these equations (marked with *) rely on the ideal gas law.

Lecture 3, p 22

Isothermal and Adiabatic

1

p∝

Isothermal (constant temperature) V

1

∆U = 0* 2

p

Q = Wby*

dV * V2 *

Q

Thermal Reservoir

Wby = ∫ pdV = NkT ∫ = NkT ln V T

V V1

Volume and

pressure change

1

1 p∝

Vγ

Q=0 p

2

V

Volume, pressure and

temperature change

Beware!!! Many of these equations (marked with *) rely on the ideal gas law.

Lecture 3, p 23

Example: Isothermal Compression

Suppose we have 3 moles of an ideal polyatomic gas initially with a volume

of 2 m3, and a temperature of 273 K. This gas is compressed isothermally

to 1/2 its initial volume. How much heat must be added to the system

during this compression?

Lecture 3, p 24

Solution

Suppose we have 3 moles of an ideal polyatomic gas initially with a volume

of 2 m3, and a temperature of 273 K. This gas is compressed isothermally

to 1/2 its initial volume. How much heat must be added to the system

during this compression?

Q = −Won FLT

Vf Vf

dV

= + ∫ pdV = nRT ∫ Definition of work then use ideal gas

Vi Vi

V law

Vf

= nRT ln Integral of dV/V

Vi

= −nRT ln 2 Note that the heat added is negative -

= −4.7 kJ heat actually must be removed from

the system during the compression to

keep the temperature constant.

Lecture 3, p 25

Example: Escape Velocity

How much kinetic energy must a nitrogen molecule have in order to escape

from the Earth’s gravity, starting at the surface? Ignore collisions with other

air molecules. How about a helium atom? At what temperatures will the

average molecule of each kind have enough energy to escape?

Lecture 3, p 26

Solution

How much kinetic energy must a nitrogen molecule have in order to escape

from the Earth’s gravity, starting at the surface? Ignore collisions with other

air molecules. How about a helium atom? At what temperatures will the

average molecule of each kind have enough energy to escape?

= 2.9×10-18 J negative potential energy. Simplify using

GMEm/rE2 = g = 9.8 m/s2. Use rE = 6.4×106 m

(4000 mi), and mN2 = 4.7×10-26 kg.

= 1.4×105 K That’s hot!

THe = 2×104 K. The mass of a helium atom is smaller by a

factor of 4/28. KE and T needed for escape

are reduced by the same factor.

T is still too low to let much He escape, but it does get high enough to get

ionized by the Sun’s UV, and then other processes sweep it away.

Lecture 3, p 27

Next Week

• Thermal conductivity

• Irreversibility

Lecture 3, p 28

A Quick Probability Problem

We’ll spend a lot of time calculating probabilities. Here’s a quick

introduction.

Calculate the probability that all the air molecules will be found in the

left half of the room.

Each molecule is equally likely to be found in either half, so the

probability that they are all in the same half is (1/2)1029 ~ 10-3×1028.

It is hard to conceive how small this number is. All the molecules will

be in the left half of the room once every 10+3×1028 years (i.e., never).

You can divide this time by any conceivable number you want (a billion,

a trillion, a google) without affecting this result significantly.

Lecture 3, p 29

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