phys 241

Thermodynamics

CH3
1 Law of
st

Thermodynamics
Balance of Energy
 Joules Experiments
• At the 1800 it was thought the nature of heat as an indestructible and invisible fluid (caloric) which flowed from a hot
body (rich in caloric) to a cold body (which had less caloric)
• Heat was quantified by the temperature rise it produced in a unit mass of water (water was the reference substance)
• when two bodies were put in thermal contact, the heat lost by one was equal to the heat gained by the other (confirm
heat was a conserved entity)

Benjamin Thompson
• Noticed the rise in water T when cannons were being bored
• found water could even be boiled, and the supply of heat appears unlimited
• concluded that heat could not be a finite substance such as caloric and that
there was a direct relation between the work done and the heat produced

James Joule
• Did a careful series of experiments (1840-1849) as shown in next figure
• constructed a tub containing a paddle wheel which could be rotated by the
action of weights falling outside the tub a height h
• A work is done by the falling weights = mgh on the system (water in tub)
rotating the water (by the paddle) and after some turbulence the system
reached equilibrium, the T of water increased
• The walls of the tub were insulating  adiabatic work
 Joules Experiments
James Joule
• Found the following:
1. mechanical equivalent of heat
4.186 kJ of work is needed to raise T of 1 kg of water by 1 K
2. This result is independent of the adiabatic work nature
Joule changed the weights and the number of drops and
performed the same amount of adiabatic work electrically

If a thermally isolated system is brought from one equilibrium state to another,

the work necessary to achieve this change is independent of the process used

𝑊𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 = 𝑈2 − 𝑈1 (for both reversible and irreversible)

• In mechanics , W done on a system increases K.E. (and/or) P.E.

• However, In our discussion we have excluded any change in these bulk energies ( Joule's tub was neither lifted up nor was
it set in motion across the floor of the laboratory)
• So where is the energy (which transferred by work to the system) stored? Stored as Internal Energy
 the physical meaning of internal energy (molecular viewpoint)

• the external work does in fact go into increasing kinetic and potential energies of the individual molecules which have
K.E. because of their random motion and P.E. because of their mutual attraction
• There are many microscopic forms of energy  their sum is the internal energy U

microscopic forms of energy

K.E. latent energy Chemical Energy Nuclear Energy

Translational Energy required or Energy associated the energy that holds
Rotational released for phase with the chemical the nucleus of an
change bonds in a molecule atom together
Vibrational
e.g. change from liquid (create new
Electron translation
and spin to gas phase requires substance)
Nuclear spin of heat of vaporization
molecules
(same substance)
 Important concepts
Grand equation and conservation of energy (remember Phys-110?)
Heat is a way to transfer
energy to the system but
this energy is not stored as
heat
the amount of energy transferred to the system by: the total energy of the system:
• W: work • TMT : matter transfer • Kinetic
• Q: heat • TET : electrical transmission • Potential
• TMW: mechanical waves • TER : electromagnetic radiation • internal

In almost all cases, the system as a whole wont move (no change in macro kinetic), we assume there is no gravitational or
electromagnetic field (no change in macro potential)
However, the earth’s gravitational field on a system can be important to be considered as we will see in the special topic
at the end of this chapter
 Heat
If a process is not adiabatic, W is a path dependent. However, for a system change
from initial equilibrium point (1) to another equilibrium point (2)
Δ𝐔 = 𝑼𝟐 − 𝑼𝟏 non-adiabatic
there is a difference between adiabatic and non-adiabatic work required to bring path
this change (from 12) with the latter having an infinite number of possible values
adiabatic
path

ΔU = 𝑊𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 (for both reversible and irreversible)

non-adiabatic
path
ΔU = 𝑊 + 𝑄 (for both reversible and irreversible)

Heat is a non-mechanical exchange of energy between the system and the surroundings because of their
temperature difference
Convention sign of heat: Q is positive when it enters the system, and negative if it leaves the system

For an infinitesimal process ҧ (only reversible)

dU = −𝑃𝑑𝑉 + 𝑑𝑄
 Heat vs Work example
gas in a container with rigid diathermal walls which are wrapped heating coils (resistance R) and current I flows through coils

𝑊 = 𝐼 2 𝑅𝑡 𝑄 = 𝐼 2 𝑅𝑡
energy crossing the system boundary energy crossing the system boundary
is in the form of work is in the form of heat
 Work vs Heat (molecular viewpoint)
• when we add energy to the system in the form of heat , we increase the random motion of the constituent molecules
• when we increase the energy by performing work, we displace the molecules in an ordered way

Energy transfer by heat (random collision) Thermal equilibrium

Q W

Energy transfer by work (initially ordered collision) mechanical equilibrium

 gas molecule K.E. and thermal energy
CH1:
ideal gas law 𝑉𝑃 = 𝑅𝑛𝑇 𝑉𝑃 = 𝑘𝑁𝑇

𝟑 𝑣𝑥
𝑲𝒕𝒓𝒂𝒏𝒔 = 𝒌𝑻
𝟐 𝑣

For ideal gas U is only the gas particles K.E. U(T)

i

f
 Heat Capacity
Heat capacity C : is the limiting ratio of the heat introduced reversibly into the system divided by the temperature rise
𝑑𝑄ҧ
𝐶=
𝑑𝑇
Specific Heat c : is the heat capacity per a unit mass 𝑸 = න 𝑪 𝒅𝑻
1 𝑑𝑄ҧ 𝒑𝒂𝒕𝒉
𝑐=
𝑚 𝑑𝑇
Now a process is not completely defined simply by the temperature difference ΔT between the end points. There are a
large number of possible reversible paths between these end points, each with a different Q. It follows that there are a
large number of possible heat capacities. We will consider only two:

1. heat capacity at constant volume Cv ഥ 𝑽

𝒅𝑸 𝝏𝑼
ҧ 𝑪𝑽 = =
dU = −𝑃𝑑𝑉 + 𝑑𝑄 𝒅𝑻 𝝏𝑻 𝑽
ҧ 𝑉
dU = 𝑑𝑄 𝛥U = න 𝐶𝑉 𝑑𝑇 = 𝑄𝑉
𝑟𝑒𝑣−𝑐𝑜𝑛𝑠𝑡(𝑉)

2. heat capacity at constant pressure CP ഥ 𝑷

𝒅𝑸 𝝏𝑯
𝑪𝑽
dH = dU + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 𝑪𝑷 = = 𝑪𝑷
H = U + 𝑃𝑉
dH = −𝑃𝑑𝑉 + 𝑑𝑄ҧ + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 𝒅𝑻 𝝏𝑻 𝑷
ҧ
dH = 𝑉𝑑𝑃 + 𝑑𝑄 𝛥H = න 𝐶𝑃 𝑑𝑇 = 𝑄𝑃
ҧ 𝑃
dH = 𝑑𝑄 𝑟𝑒𝑣−𝑐𝑜𝑛𝑠𝑡(𝑃)
 Heat Capacity

Reversibility and Reality

• Calculation of heat capacity requires the heat to be introduced reversibly
• As the heat is introduced , the system must pass through a series of equilibrium states, with the
pressure and temperature always being uniform throughout the system
• In reality, a measurement is done by putting in a small burst of heat at some point in the system
(gas system) from a source at a finite temperature above that of the system.
• This will cause local heating , with pressure and temperature gradients being set up in the gas
system (no equilibrium and there does appear to be an inconsistency)
• However, If the relaxation time for the attainment of an equilibrium state in the system is much
shorter than the time scale of the heating, the system is always so close to an equilibrium state
that there are no significant internal pressure and temperature gradients. The irreversible nature of
the heating is then of no significant consequence
• This is the usual situation in the lab when determining the heat capacity and so there is no
inconsistency between our definition of heat capacity and its experimental determination
 Method of Mixtures
Two systems A and B are put in thermal contact with an adiabatic wall surrounding both systems. If each system evolves form
an initial to a final state, the first law for each system is

UfA − UiA = 𝑄 𝐴 + 𝑊 𝐴
UfB − UiB = 𝑄𝐵 + 𝑊 𝐵
Add the two eq

UfA + UfB − (UiA +UiB ) = (𝑄 𝐴 + 𝑄𝐵 ) + (𝑊 𝐴 + 𝑊 𝐵 )

2 systems 2 systems
Uf − Ui = 𝑄 2 systems + 𝑊 2 systems

𝑄 of the two systems must be zero as this composite system is surrounded by an adiabatic wall

𝑄 𝐴 + 𝑄𝐵 = 0

𝑄 𝐴 = −𝑄𝐵 Heat lost = Heat gained

 water has the highest specific heat  moderate
climates found near large bodies of water

Calorimetry calorimeter
for measuring specific heat; heat a sample to some
known temperature Tx , place it in a vessel containing
water of known mass and temperature Tw < Tx , and
measure the temperature of the water after
equilibrium has been reached
 Ideal Gases U(T) 𝐶𝑉 =
𝜕𝑈
𝜕𝑇 𝑉

𝜕𝑈 𝜕𝑇 𝜕𝑉
= −1
𝜕𝑉 𝑇
𝜕𝑈 𝑉
𝜕𝑇 𝑈

• In general 𝜕𝑈 𝜕𝑈 𝜕𝑈 𝜕𝑈 𝜕𝑇
=− = −𝐶𝑉 μJ
𝑈 𝑇, 𝑉 → 𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉 𝜕𝑉 𝑇
𝜕𝑇 𝑉
𝜕𝑉 𝑈
𝜕𝑇 𝑉
𝜕𝑉 𝑇

• In section 7.3, it will be found that the internal energy of ideal gas is only a function of temperature U(T)
• This is consistent with the result from kinetic theory that the kinetic energy per mole is 3/2 NAkBT

Free exppansion
• no W done by or on the system
• no Q added or removed from the system
• the 1st law  no change in U
ΔU = 𝑊 + 𝑄 (for both reversible and irreversible)

ΔU = 0
• Since U is only a function of T for an ideal gas  there is no change in the ideal gas temperature before and
after expansion Ti =Tf
 Real gas free expansion and T decreases
• In 1843 , Joule attempted to measure the temperature change in a free expansion for air. He was
unable to detect, within the experimental error, any temperature change
• By modern sensitive equipment, scientists were able to measure a very small change in temperature
• Thus air approximates at normal temperatures to an ideal gas
• It is found that all known gases cool slightly on undergoing a free expansion
• This is consistent with the kinetic theory idea that temperature is associated with the K.E. of the
molecules
• If the gas expands, then the intermolecular attraction potential energy goes up as the molecules
get further apart
• As the total internal energy U is constant for the free expansion, this means that the kinetic
energy, and therefore the temperature , goes down
• The quantity (𝜕T/𝜕V)U is a measure of the cooling effect occurring in a free expansion and is known as
the Joule coefficient μJ . Later, we shall see how thermodynamics helps us to derive an expression for μJ
from the equation of state, even though a free expansion is an irreversible process
 Ideal Gases U(T)
• In section 7.3, it will be found that the internal energy of ideal gas is only a function of temperature U(T)
• This is consistent with the result from kinetic theory that the kinetic energy per mole is 3/2 NAkBT

CP - CV
• consider n moles of an ideal gas
• for an infinitesimal reversible process
ҧ = dU + 𝑃𝑑𝑉 (reversible)
𝑑𝑄
𝜕𝑈 𝑑𝑈
• CV = , since U is only a function of T for an ideal gas  CV =
𝜕𝑇 𝑉 𝑑𝑇
dU = CV 𝑑𝑇
ҧ = CV 𝑑𝑇 + 𝑃𝑑𝑉
𝑑𝑄
𝜕
• For an isobaric process, apply 𝜕𝑇 𝑃

ҧ 𝑃 Ideal gas
𝑑𝑄 𝜕𝑉 𝑛𝑅
= 𝐶𝑃 = CV + 𝑃 = CV + 𝑃 → 𝑪𝑷 = 𝑪𝑽 + 𝒏𝑹
𝑑𝑇 𝜕𝑇 𝑃
𝑃
we shall derive a relation for CP— Cv for a general
system in section 7.1
CP CV and kinetic theory of gas

HW
CV and Equipartition of Energy (Gas)

𝐇𝟐 (𝐠𝐚𝐬)

Monoatomic diatomic
Degree of freedom 3 5
𝑐𝑉 3 5
𝑅 𝑅
(molar value) 2 2
𝑐𝑃 5 7
𝑅 𝑅
(molar value) 2 2
CV and Equipartition of Energy (solid)

Solid as bed-spring model

• Each atom is a ball connected to its neighbors by springs
• For each atom there are 6 degrees of freedom

for 1 mole
• 3 K.E.
• 3 P.E.
• According to equipartition theory, total U energy
6*1/2*NkT=3 nRT

ഥ 𝑽
𝒅𝑸 𝝏𝑼
𝑪𝑽 = = = 𝟑𝒏𝑹
𝒅𝑻 𝝏𝑻 𝑽

For one mole of the solid material CV =3R

 Ideal Gases U(T)
• In section 7.3, it will be found that the internal energy of ideal gas is only a function of temperature U(T)
• This is consistent with the result from kinetic theory that the kinetic energy per mole is 3/2 NAkBT

equation of an Adiabatic
• There is a very simple relation between P and V if the expansion is
performed both adiabatically and reversibly

ҧ = dU + 𝑃𝑑𝑉 (reversible)
𝑑𝑄 𝑐𝑜𝑛𝑠𝑡 ∗∗ = 𝑇 𝑉 (γ−1)
𝑉γ 𝑉γ 𝑉γ
0 = dU + 𝑃𝑑𝑉 (reversible and adiabatic) 𝑐𝑜𝑛𝑠𝑡 ∗∗ =𝑇 = 𝑇𝑃 =𝑃
𝑉 𝑛𝑅𝑇 𝑛𝑅
0 = CV 𝑑𝑇 + 𝑃𝑑𝑉 𝑐𝑜𝑛𝑠𝑡 ∗∗∗ = 𝑃𝑉 γ
𝑛𝑅𝑇
0 = CV 𝑑𝑇 + 𝑑𝑉
𝑉
𝑑𝑇 𝑑𝑉
0 = CV + 𝑛𝑅
𝑇 𝑉
integration Ideal gas adiabatic
𝑐𝑜𝑛𝑠𝑡 = CV ln 𝑇 + 𝑛𝑅 𝑙𝑛(𝑉) 𝑪𝑷 = 𝑪𝑽 + 𝒏𝑹
𝑛𝑅
𝑃𝑉 γ = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑐𝑜𝑛𝑠𝑡 ∗ = ln 𝑇 + 𝑙𝑛(𝑉)
𝐶𝑉
CP
∗ γ=
𝑐𝑜𝑛𝑠𝑡 = ln 𝑇 + (γ − 1) 𝑙𝑛(𝑉)
𝐶𝑉
 Ideal Gases Ideal gas adiabatic
A reversible Adiabatic W 𝑃𝑉 γ = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
Notice that in an adiabatic process, all variables for an ideal gas change P,V,T
between two equilibrium points on an adiabatic curve 𝐂𝐏
𝑉
𝑊 = − ‫ 𝑉׬‬2 𝑃𝑑𝑉
𝜸=
1
(only for reversible) 𝑪𝑽
𝑉2
𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑊 = −න 𝑑𝑉
𝑉1 𝑉γ
1 1−γ 1−γ
𝑊=− (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑉2 − 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑉1 )
1−γ
γ γ
𝑃1 𝑉1 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 = 𝑃2 𝑉2

1
𝑊=− (𝑃 𝑉 − 𝑃1 𝑉1 )
1−γ 2 2

𝑷𝟏 𝑽𝟏 − 𝑷𝟐 𝑽𝟐 Vf Vi
𝑻𝟏 − 𝑻𝟐 𝟑
𝑾= 𝑾 = 𝒏𝑹
𝟓 𝟐
= − 𝒏𝑹(𝑻𝟏 − 𝑻𝟐 )
𝟐
𝟏−𝜸 𝟏− ∗
𝟐 𝟑 𝑾 = 𝜟𝑼(𝑻) = 𝑪𝑽 𝜟𝑻
 Ideal Gases U(T)
Ideal gas
𝑃𝑉 = 𝑛𝑅𝑇 𝐧𝐑 = 𝑵𝒌𝑩

Ideal gas adiabatic

𝐂𝐏
𝑃𝑉 γ = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝜸=
𝑪𝑽
Ideal Gases
process isothermal Isobaric Isochoric Adiabatic
W Yes Yes No Yes (reversible and irreversible)

reversible
𝑉2
W = −𝑛𝑅𝑇 ln( )
𝑉1
W = −P (𝑉2 − 𝑉1 ) 0 W=
P1 V1 − P2 V2
1−γ
ΔU = 𝑊 + 𝑄
Q Yes Yes Yes No
𝑉2 Ideal gas
reversible 𝑄 = 𝑛𝑅𝑇 ln( ) 𝑄𝑃 = CP Δ𝑇 𝑄𝑉 = CV Δ𝑇 0
𝑉1
ΔU 0 Yes Yes Yes
ΔU(T) = CV ΔT
 isothermal isobaric isochoric adiabatic

What to do
 Reversible an Irreversible work
During a reversible work, pressures (forces) are always in equilibrium between the
system and environment  we can use the equation of state, which provides the correct
path on the P-V diagram, and calculate the work by integrating
ഥ 𝑹 = −𝑷𝒅𝑽
𝒅𝑾
If work is irreversible, pressure (forces) are not in equilibrium between the system and
environment, then work cannot be calculated by integrating the equation of state
(doesn’t provide the correct path on the P-V diagram)

However, work can be calculated even if its is irreversible. If the environment pressure
is assumed to be constant during an irreversible process
Work done by (or on) the system is the opposite of that of the environment

𝑾𝑰𝑹 = −𝑷𝒆𝒙𝒕 Δ𝑽
reversible irreversible

5 kg

2 and 4
 THE JOULE-KELVIN EFFECT (throttling process)
The effect is used in the liquefaction of gases and is often called the throttling process
• Gas is forced at a constant pressure and at a steady rate
through a small hole, or series of holes (a plug of cotton
wool), to emerge at a constant pressure.
• There is a finite pressure drop across the plug, so the
process is irreversible
• The walls of the chamber are thermally insulating and so the
process is also adiabatic
Because there is no finite pressure drop across the left-hand piston and as
there is no friction, the work we do in forcing the gas through the plug is
0
𝑊𝐿𝐻𝑆 = − ‫𝑖𝑉 𝑖𝑃 = 𝑉𝑑 𝑖𝑃 𝑉׬‬ (reversible)
𝑖
𝑉𝑓
𝑊𝑅𝐻𝑆 = − ‫׬‬0 𝑃𝑓 𝑑𝑉 = −𝑃𝑓 𝑉𝑓 (reversible)

𝑈𝑓 − 𝑈𝑖 = 0 + 𝑃𝑖 𝑉𝑖 −𝑃𝑓 𝑉𝑓 both heating and

cooling can occur in
𝑈𝑖 + 𝑃𝑖 𝑉𝑖 = 𝑈𝑓 + 𝑃𝑓 𝑉𝑓 the throttling process
𝜕𝑇
throttling process is an isenthalpic μJk = Joule-Kelvin coefficient
𝐇𝐢 = 𝐇𝐟 𝜕𝑝 𝐻
 THE JOULE-KELVIN EFFECT (throttling process)
For real gases and using,
𝑛2
Van Der Waals Equation (𝑃 + 2 𝑎)(𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇
𝑉
𝜕𝐻 𝑎
∝ 𝑏− Proof?
𝜕𝑝 𝑇
𝑅𝑇
𝜕𝑇
Using cyclic rule and since Cp is positive μJk = Joule-Kelvin coefficient
𝜕𝑝 𝐻
𝜕𝑇 𝑎
μJk = ∝ −𝑏
𝜕𝑝 𝐻 𝑅𝑇
Note that
𝑎
1. heating occurs above an inversion Tinv ( < 𝑏 → μJk = negative)
𝑅𝑇
𝑎
2. cooling can occur below Tinv ( > 𝑏 → μJk = positive)
𝑅𝑇
𝑎
3. at Tinv the real gas behaves as an ideal gas ( = 𝑏 → μJk = 0)
𝑅𝑇
Gas Expansions

process Joule Free Expansion The Joule-Kelvin Effect

constant U H
coefficient 𝜕𝑇 𝜕𝑇
μJ = μJk =
ΔT 𝜕𝑉 𝑈 𝜕𝑝 𝐻

ideal gas μJ = 0 μJk = 0

μJK = positive (cooling)
μJ = negative (cooling)
real gas μJK = negative (heating)
• cooling is slight • There is an inversion T for each gas, above which the
• All known real gasses cools down with free gas will be heating up and below which the gas will be
expansion cooling down
• The inversion temperature for nitrogen is 607 K, for
hydrogen 204 K, and for helium 43 K
• Below the inversion temperature, this effect can be
used for refrigeration
 Steady flow process (turbine)

This section will be left as independent reading