phys 241

Thermodynamics

CH2
Reversible processes
and work
 Processes
Thermodynamics focuses on the change in different state functions that occur when a system changes from one
equilibrium state (initial) to another equilibrium state (final)

State Variable vs state function

state variables (easy to measure in lab)
state function (function of state variables)
y=2x-3 and x=(y+3)/2 are the same
process
• A process is the mechanism of changing a system from an initial equilibrium
state to a final equilibrium state. These initial and final equilibrium states
are called the end points of the process
• There are two types of processes form a reversibility point of view:
1. Reversible
2. Irreversible
• There are many types of processes from holding one of the variable (state
or process) constant point of view:
1. isothermal
2. isobaric
3. isochoric
4. adiabatic
 Processes Which one is/isn’t reversible?

Reversible processes
Reversible processes are idealized processes which change a system from initial to a
final state; but system must be capable of being reversed to its initial state and the
surroundings must be unchanged too

Reversible processes are quasistatic processes (slow processes which maintain

equilibrium along the process) where no dissipative forces such as friction are
present

we can calculate changes in the state functions for any

process using reversible process
 Processes Ideal gas
𝑃𝑉=𝑛𝑅𝑇
Common thermodynamics processes
1. Isothermal: a process in which T is held
constant (e.g. a gas cylinder in good
thermal contact with heat reservoir at a
specific T)

2. Isobaric: a process in which P is held

constant (e.g. a gas cylinder with free
piston against atmosphere pressure)

3. Isochoric: a process in which V is held

constant (e.g. a gas cylinder with a fixed
piston)

4. Adiabatic: a process in which the system

is isolated (e.g. an isolated gas cylinder)
Reversible isothermal process
Processes
• The cylinder is fitted with a frictionless piston with initial state (P1 , V1)
• A force ƒ = P1 A (A is the area of the piston) is applied to the piston to
oppose the gas pressure
• The walls of the cylinder are in thermal contact with the surrounding
• The surrounding is so large that its temperature T cannot be changed by
the system state changes (heat reservoir)
• The applied ƒ is now increased infinitesimally and the system is allowed to
come to a new equilibrium state at the same T
• This process is repeated until the final state (P2 , V2) is reached
we can plot the process on an indicator diagram since P,V, and T are well defied
through the process
The ideal gas equation of state hold for each point in the process

Irreversible isothermal process

• by pushing in the piston violently from V1 to V2 ,initially there will be turbulence with
some T and P gradient within the system and between the system and the surrounding
• Eventually such gradient will fade and the final state of the gas system will be exactly as
the one reached by the reversible process
we cannot plot the process on an indicator diagram since P,V, and T are not well defied
through the process
The ideal gas equation does not hold for each point in the process (only for the end points)
 More state variables
Thermal expansion β and α
The volume thermal expansion β : is the fractional increase in volume V divided by the temperature rise

1 𝜕𝑉 P outside the partial differential

β= reminds us that the expansivity is

𝑉 𝜕𝑇 𝑃
measured at constant pressure

The length thermal expansion α : is the fractional increase in length L divided by the temperature rise

1 𝜕𝐿 ƒ outside the partial differential

α= reminds us that the expansivity is

𝐿 𝜕𝑇 ƒ
measured at constant pressure

The bulk Modulus Κ

Moduli of elasticity are always given as stress/strain or force/unit area divided by the fractional deformation
𝜕𝑃 1 The negative sign ensures that K is a positive number (all known
For a solid or fluid , the bulk modulus K Κ = −𝑉 = substances dV is - for + increase in dP
𝜕𝑉 𝑇
κ The inverse of the bulk modulus is the compressibility κ

For a stretched wire of cross-sectional 𝐿 𝜕ƒ (Note that, as dL is positive for positive

area A, the modulus of elasticity is Y= 𝐝ƒ , we do not need a negative sign in
Young s modulus 𝐴 𝜕𝐿 𝑇
front
 Important Math concepts
If a closed system can be specified by two of three variables, then the total differential is

𝜕𝑃 𝜕𝑃
g(𝑃,V,T) = 0 𝑃 = 𝑃(V,T) 𝑑𝑃 = 𝑑𝑉 + 𝑑𝑇
𝜕𝑉 𝑇
𝜕𝑇 𝑉
If there is a well behaved function 𝑃(V,T), then this differential is exact and path independent
𝑃2
න 𝑑𝑃 = 𝑃 𝑉2 , 𝑇2 − 𝑃 𝑉1 , 𝑇1 = 𝑃2 − 𝑃1 = Δ𝑃 ර 𝑑𝑃 = 0
𝑃1

How to check if there is a function 𝑷(V,T)?

𝜕𝑃 𝜕𝑃
1. it should be exactly the same function either by integrating or
𝜕𝑉 𝑇 𝜕𝑇 𝑉

2. Since integration generally is not as easy as differentiation, the same conclusion

could be reached if
𝜕 𝜕𝑃 𝜕 𝜕𝑃
= Condition for an exact differential
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑉 𝑇
𝜕𝑇 𝑉
This is because these two partial differentials are equal and the order of the
differentiation doesn’t change the final answer if there is a function 𝑃(V,T)
 Important Math relations
𝜕ƒ 𝜕ƒ
g(ƒ,L,T) = 0 ƒ = ƒ(L,T) 𝑑ƒ = 𝑑𝑇 + 𝑑𝐿
𝜕𝑇 𝐿
𝜕𝐿
𝑇
𝜕𝑳 𝜕𝑳
𝐿 = 𝐿 (ƒ,T) 𝑑𝐿 = 𝑑𝑇 + 𝑑ƒ
𝜕𝑇 ƒ
𝜕ƒ
𝑇

𝜕ƒ 𝜕ƒ 𝜕𝑳 𝜕𝑳
𝑑ƒ = 𝑑𝑇 + [ 𝑑𝑇 + 𝑑ƒ]
𝜕𝑇 𝐿
𝜕𝐿 𝜕𝑇 ƒ
𝜕ƒ
𝑇 𝑇
We can choose ƒ and 𝑇 to be the independent variables. This means that dT = 0 and still have a non-zero value
for dƒ, as ƒ an dT are independent
reciprocal relation
𝜕ƒ 𝜕𝑳
𝑑ƒ = 𝑑ƒ −1
𝜕𝐿 𝜕ƒ 𝜕ƒ 𝜕𝑳
𝑇 𝑇 =
Alternatively, we could choose dƒ = 0 wit h dT ≠ 0 𝜕𝐿 𝑇
𝜕ƒ 𝑇
cyclical rule
𝜕ƒ 𝜕ƒ 𝜕𝑳 𝜕ƒ 𝜕𝑇 𝜕𝐿
0= 𝑑𝑇 + 𝑑𝑇 = −1
𝜕𝑇 𝜕𝐿 𝜕𝑇 𝜕𝐿 𝑇
𝜕ƒ 𝐿
𝜕𝑇 ƒ
𝐿 𝑇 ƒ
 Application of the thermodynamic method
clamped wire between two rigid wall
Let us calculate the increase in tension ƒ of a wire clamped
between two rigid supports, a distance L apart , when it is
cooled from T1 to T2

g(ƒ,L,T) = 0

ƒ = ƒ(L,T)

𝜕ƒ 𝜕ƒ
𝑑ƒ = 𝑑𝑇 + 𝑑𝐿
𝜕𝑇 𝐿
𝜕𝐿
𝑇
𝑇2
𝜕ƒ 1 𝜕𝐿 𝐿 𝜕ƒ 𝜕ƒ 𝜕𝐿 𝜕𝑇
ƒ2 − ƒ1 = න 𝑑𝑇 α= Y= = −1
𝑇1 𝜕𝑇 𝐿 𝐿 𝜕𝑇 𝐴 𝜕𝐿 𝑇
𝜕𝑇 𝐿
𝜕ƒ 𝜕𝐿
ƒ 𝑇 ƒ
𝑇2 𝑇2 𝜕ƒ 𝜕ƒ 𝜕𝐿
ƒ2 − ƒ1 = − න 𝑌𝐴α 𝑑𝑇 = −𝑌𝐴α න 𝑑𝑇 =− = −𝑌𝐴α
𝜕𝑇 𝐿
𝜕𝐿 𝜕𝑇
𝑇1 𝑇1 𝑇 ƒ

ƒ𝟐 − ƒ𝟏 = −𝒀𝑨α (𝑻𝟐 − 𝑻𝟏 )
In practice the cooling will not be reversible because we
simply heat the wire and let it cool. This will result in large
temperature gradients both within the wire itself and
between the wire and the surroundings. As the
intermediate states are not equilibrium states , we cannot
apply the equation of state:

ƒ = ƒ(L,T)

Is our analysis invalid??

The answer is that our analysis is still sound because the wire is
being taken between equilibrium states. It does not matter
how we go from state 1 to state 2 to determine the change in ƒ𝟐 − ƒ𝟏 = −𝒀𝑨α (𝑻𝟐 − 𝑻𝟏 )
the state function ƒ

We use this elegant trick time and time again in thermodynamics

to calculate changes in state functions for processes between a
pair of equilibrium states
From PHY110:

Linear 𝑭
Elasticity in Y = 𝑡𝑒𝑛𝑠𝑖𝑙𝑒 𝑠𝑡𝑟𝑒𝑠𝑠 = 𝑨
thermal tensil𝑒 𝑠𝑡𝑟𝑎𝑖𝑛 𝜟𝑳
Length
expansion 𝑳𝒊

𝐹𝐿𝑖
𝛥𝐿 = α 𝐿𝑖 𝛥𝑇 𝛥𝐿 =
𝑌𝐴
𝐹𝐿𝑖
α 𝐿𝑖 𝛥𝑇 =
𝑌𝐴
𝑌 𝐴 α 𝛥𝑇 = 𝐹
Since tension change 𝛥𝐹 will increase when 𝛥𝑇 is
negative (cooling), we need a minus sign: 𝜟𝑭 = −𝒀 𝑨α 𝜟𝑻
 Work
pressure-volume work ƒ
𝑷𝑨
• a gas in the initial equilibrium state (P1 , V1) is expanding to a
final equilibrium state (P2 , V2)
• If this is done by infinitesimally decreasing the external
balancing force and if there is no friction between the piston
and the cylinder wall, the system will be doing a reversible
work against the surrounding 𝒅𝒙
• During one of the intermediate equilibrium states, the
forces balancing the piston are:

ƒ = 𝑃𝐴
• If the external force is decreased by an infinitesimal amount
the piston will be pushed a distance dx. The work done by
the system on the environment is:
This minus sign is a convention so
ҧ = 𝑃𝐴 𝑑𝑥 = −𝑃𝑑𝑉
𝑑𝑊 (only for reversible) that the W is positive when it is
done on the system
𝑉2 This reversible work is in fact the
𝑊= − ‫𝑉𝑑𝑃 𝑉׬‬ (only for reversible) maximum work that can be obtained
1
from the expansion
isothermal work for an ideal gas (12)
𝑉
𝑊 = − ‫ 𝑉׬‬2 𝑃𝑑𝑉 (only for reversible)
1
𝑉2
1
𝑊 = − න 𝑛𝑅𝑇 𝑑𝑉
𝑉1 𝑉
𝑉2 1 𝑉2
𝑊= −𝑛𝑅𝑇 ‫𝑉𝑑 𝑉׬‬ = −𝑛𝑅𝑇 ln( )
1 𝑉 𝑉1

isobaric work for an ideal gas (132)

𝑉2
𝑊= − ‫𝑉𝑑𝑃 𝑉׬‬ (only for reversible)
1
𝑉2
𝑊 = −𝑃2 න 𝑑𝑉 = −𝑃2 (𝑉2 − 𝑉1 )
𝑉1
 The Free Expansion
free expanding gas
• Consider a gas in the state (P, V) being
contained in the left-hand part of a double-
sectioned chamber
• There is a vacuum in the right-hand part
• take the volumes of each part as V
• If the partition is broken, the gas rushes
into the right-hand half before eventually
settling down to a new equilibrium state

How much work is done by the gas in this process ? Zero

This example illustrates two important points in thermodynamics

1. It is important to be clear about what the system is . Here it is the chamber as a whole
and not just the left-hand part initially containing all the gas

ҧ = PdV is applicable only to reversible processes and to those special irreversible

2. 𝐝𝐖
processes (see section 2.5) where there is no finite pressure drop across the piston
 Dissipative Work
falling weight
• a viscous fluid which can be stirred by the action of the falling weigh:
w=mgh
• Because of the dissipative viscous effects in the fluid, the
temperature will rise changing the state of the system
• This work is irreversible (dissipative work) since you can’t take heat
spontaneously from the fluid to rise the weight

passing “I” through “R”

• the work performed in the time “t” is: w=I2Rt
Current
• This work is irreversible (dissipative work) since you can’t take
I
heat spontaneously from the fluid to recharge the battery

Unlike reversible work considered in section 2.5, it is not possible R

to find an expression for dissipative wok in terms of the state
variables of the system
 Other Kinds of Work
There are other systems ( other than compressible gas or fluid ) which are common in thermodynamics.
The following are appropriate forms for the infinitesimal work term in a reversible process:

simple
Compressible extensible reversible dielectric
system surface film magnetizable
fluid wire electrolytic cell material
material

Work ҧ = 𝑃 dV
𝑑𝑊 ҧ = ƒ dx
𝑑𝑊 ҧ = Γ dA
𝑑𝑊 ҧ = ℇ dZ
𝑑𝑊 ҧ = 𝐵0 dM
𝑑𝑊 ҧ = 𝐸 dP
𝑑𝑊

P ƒ Γ ℇ 𝐵0 E
Intensive
variable Surface tension Magnetic field Electric field
Pressure (N/m2) force (N) Emf (V)
(N/m) (T ) (N/C)
V x A Z M P
Extensive
variable Magnetic Dipole moment
Volume (m3) Length (m) Area (m2) The charge (C)
moment (A.m2) (C.m)
 Calculation of Work in Rev-process
calculating the work done in changing the state of a compressible fluid from (P1 ,T1) to (P2 , T2 ) in a reversible process:
ҧ = −𝑃𝑑𝑉
𝑑𝑊
Need to find dV and then integrate

Since this is a reversible process, which is a succession o f equilibrium states , the equation of state holds at every stage
in the process
Write the equation of state in the form that gives the state function whose
change we wish to find in terms of the other two whose changes are given

𝝏𝑽 𝝏𝑽 𝜕𝑃 1 𝜕𝑉
𝑉 = 𝑉(P,T) 𝒅𝑽 = 𝒅P + 𝒅𝑻 Κ = −𝑉 β=
𝝏𝑷 𝑻
𝝏𝑻 𝑷
𝜕𝑉 𝑉 𝜕𝑇
𝑇 𝑃

𝑉
𝑑𝑉 = − 𝑑P + β 𝑉 𝑑𝑇
𝑲
𝑃𝑉
ҧ
𝑑𝑊 = −𝑃𝑑𝑉 = 𝑑P − P β 𝑉 𝑑𝑇
𝑲
𝑃2
𝑃𝑉 𝑇2 IF: 𝑉1 2
𝑊=න 𝑑P − න P β 𝑉𝑑𝑇 T is constant 𝑊= (𝑃2 − 𝑃12 )
𝑃1 𝑲 𝑇1 V and K dependence on P is very small 𝑲2
 compressibility factors for N and O as a function of
Real Gases pressure at 298 K

Real gas atoms or molecules have

1. some intermolecular force between them
2. finite volume
𝑃𝑉
compressibility factor Z 𝑍=
𝑛𝑅𝑇
Z =1 (for an ideal gas)
Z1 as P0 (for all real gases)
Z > 1 at high P (real V is bigger than ideal)
Z < 1 at low P (attraction reduces real P)
AS T is reduced, real V and P deviation from ideality is large
As T increases and P decreases real gas  ideal gas
As T decreases and P increases  high deviation from ideality

Virial Equation
𝑃𝑉 𝐵 2
𝐶
𝑍= =1+n +𝑛 2+⋯
𝑛𝑅𝑇 𝑉 𝑉
Van Der Waals Equation
𝑛2 compressibility
(𝑃 + 𝑎)(𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇 factor dependence

𝑉2 on T (for nitrogen )
Exercises
Can you calculate Wirrev?