Work and the First Law of

Thermodynamics + some useful

mathematical relations
32TDY - Lecture 2

Janne-Mieke Meijer - 32TDY - Lecture 2 1

To do
Reading: CH 2: 2.2-2.4, CH 3: 3.1-3.2,
Appendix B: B1-B3
Assignments:
CH 2: 2.1, 2.5, 2.6, 2.7, 2.9, 2.11, 2.12, 2.15, 2.17
CH 3: 3.1, 3.2, 3.3, 3.4, 3.5

Janne-Mieke Meijer - 32TDY - Lecture 2 2

Contents
• Recap Lecture 1
• Properties of exact differentials
• Work in thermodynamic processes
• Calculating work in a reversible process
• First law of Thermodynamics
• History
• Internal energy, heat and work

Janne-Mieke Meijer - 32TDY - Lecture 2 3

 Recap Lecture 1
• We considered a system, its surroundings and its walls (that can be adiabatic or diathermal)
• Zeroth law of Thermodynamics: if two systems are in thermal equilibrium with a third, they
are in thermal equilibrium with one another and have the same temperature T
• State variables/functions: Set of variables including temperature (X,Y,T) that uniquely
describe a systems equilibrium state and are path independent
• Equation of state: There is functional relationship between the state variables describing an
equilibrium state in a closed system, only two are independent and any one can be expressed
in terms of the other two X(Y,T), Y(X,T) or T(X,Y)
clamped wire
moveable piston (F, L, T)

State variables Gas system

(P, V, T)

Equation of state 𝑓 𝑃, 𝑉, 𝑇 = 0 𝑓 𝐹, 𝐿, 𝑇 = 0
Ideal gas: 𝑃𝑉 = 𝑛𝑅𝑇
Janne-Mieke Meijer - 32TDY - Lecture 2 4
Recap Lecture 1
• Quasistatic process: a process that can be thought of as a succession of equilibrium states
• Reversible process: a process whose direction can be reversed such that the system returns
to its original state, and the surroundings are unchanged too.
• Irreversible process: involves finite changes in a state variable and includes dissipation
(energy loss)
• State variable changes during different processes:

Isothermal compression Cooling with fixed length Thermal expansion

P1, V1, T Ideal gas clamped wire 1 𝑑𝐿

𝛼=
isotherms (F, L, T) 𝐿 𝑑𝑇 𝑃
System
𝑃 = 𝑛𝑅𝑇1 /𝑉
Deformation

𝐿 𝜕𝐹
P2, V2, T 𝑌=
𝑇2
𝜕𝐹 𝐴 𝜕𝐿
Δ𝐹 = න 𝑑𝑇 = −𝑌𝐴𝛼(𝑇2 − 𝑇1 ) 𝑇
𝑇1 𝜕𝑇
System 𝐿

Janne-Mieke Meijer - 32TDY - Lecture 2 5

 Useful Mathematical Relations in Thermodynamics

Exact differentials in Thermodynamics

• Differential coefficients relating the rate of change of one state
variable/function with another are very important in thermodynamics
• In thermodynamics all state functions are exact differentials
PV diagram: isotherms
For the gas system with Equation of state:
P, V and T:
𝑓 𝑃, 𝑉, 𝑇 = 0
moveable piston
A
Gas system 𝑃, 𝑇
(P, V, T)
𝑃 = 𝑃 𝑉, 𝑇 𝑃, 𝑉

𝑉, 𝑇
Janne-Mieke Meijer - 32TDY - Lecture 2 6
Credit: Atkins' Physical Chemistry, 9th ed.
 Appendix B
Properties of exact differentials I
Suppose three variables that are related:
(𝜕𝑋/𝜕𝑍)𝑌

𝐹 𝑋, 𝑌, 𝑍 = 0 (𝜕𝑋/𝜕𝑌)𝑍

Rearrange with two of the variables as independent X(Y,Z)

𝑋 = 𝑋 𝑌, 𝑍
Differentiating by parts:
Z
𝜕𝑋 𝜕𝑋
𝑑𝑋 = 𝑑𝑌 + 𝑑𝑍
𝜕𝑌 𝑍
𝜕𝑍 𝑌
Y

Change in X in a process is path independent

𝐵
∆𝑋 = න 𝑑𝑋 = 𝑋𝐵 − 𝑋𝐴
𝐴 Janne-Mieke Meijer - 32TDY - Lecture 2 7
Modified based on Atkins' Physical Chemistry, 10th ed.
 Appendix B
Properties of (exact) differentials II
Suppose three variables that are related:

𝐹 𝑋, 𝑌, 𝑍 = 0
Rearrange with two of the variables as independent
𝑋 = 𝑋 𝑌, 𝑍 also 𝑌 = 𝑌 𝑋, 𝑍
Differentiating by parts: =0

𝜕𝑋 𝜕𝑋 𝜕𝑋 𝜕𝑌 𝜕𝑌 𝜕𝑌 𝜕𝑋
𝑑𝑋 = 𝑑𝑌 + 𝑑𝑍 𝑑𝑋 = 𝑑𝑋 + + 𝑑𝑍
𝜕𝑌 𝑍
𝜕𝑍 𝑌
𝜕𝑌 𝑍
𝜕𝑋 𝑍
𝜕𝑋 𝑍
𝜕𝑍 𝑋
𝜕𝑍 𝑌

Consequence 1: Reciprocal relations

𝜕𝑌 𝜕𝑌 𝜕𝑋 𝜕𝑌
𝑑𝑌 = 𝑑𝑋 + 𝑑𝑍 =1
𝜕𝑋 𝑍
𝜕𝑍 𝑋 𝜕𝑌 𝜕𝑋
𝑍 𝑍
Janne-Mieke Meijer - 32TDY - Lecture 2 8
 Appendix B
Properties of (exact) differentials II
Suppose three variables that are related:

𝐹 𝑋, 𝑌, 𝑍 = 0
Rearrange with two of the variables as independent
𝑋 = 𝑋 𝑌, 𝑍 also 𝑌 = 𝑌 𝑋, 𝑍
Differentiating by parts: =0 =0

𝜕𝑋 𝜕𝑋 𝜕𝑋 𝜕𝑌 𝜕𝑌 𝜕𝑌 𝜕𝑋
𝑑𝑋 = 𝑑𝑌 + 𝑑𝑍 𝑑𝑋 = 𝑑𝑋 + + 𝑑𝑍
𝜕𝑌 𝑍
𝜕𝑍 𝑌
𝜕𝑌 𝑍
𝜕𝑋 𝑍
𝜕𝑋 𝑍
𝜕𝑍 𝑋
𝜕𝑍 𝑌

Consequence 2: Cyclical relations

𝜕𝑌 𝜕𝑌 𝜕𝑋 𝜕𝑍 𝜕𝑌
𝑑𝑌 = 𝑑𝑋 + 𝑑𝑍 = −1
𝜕𝑋 𝑍
𝜕𝑍 𝑋 𝜕𝑌 𝜕𝑋 𝜕𝑍
𝑍 𝑌 𝑋
Janne-Mieke Meijer - 32TDY - Lecture 2 9
Pay attention!
 Appendix B
Properties (exact) differentials IV
Variable X is determined by Y and Z and vice versa

𝑋 = 𝑋 𝑌, 𝑍 also 𝑌 = 𝑌 𝑋, 𝑍 𝑍 = 𝑍 𝑋, 𝑌

There is variable 𝜙 = 𝜙 𝑋, 𝑌, 𝑍 = 𝜙 𝑋, 𝑌
𝜕𝑋 𝜕𝑋
𝑑𝑋 = 𝑑𝑌 + 𝑑𝜙
𝜕𝑌 𝜙
𝜕𝜙 𝑌
Chain rule
𝜕𝑋 𝜕𝑋 𝜕𝑌
=
𝜕𝑍 𝜙
𝜕𝑌 𝜙
𝜕𝑍 𝜙
Janne-Mieke Meijer - 32TDY - Lecture 2 10
 Appendix B
Properties of exact differentials I
Suppose three variables that are related:
(𝜕𝑋/𝜕𝑍)𝑌

𝐹 𝑋, 𝑌, 𝑍 = 0 (𝜕𝑋/𝜕𝑌)𝑍

Rearrange with two of the variables as independent X(Y,Z)

𝑋 = 𝑋 𝑌, 𝑍
Differentiating by parts:
Z
𝜕𝑋 𝜕𝑋
𝑑𝑋 = 𝑑𝑌 + 𝑑𝑍
𝜕𝑌 𝑍
𝜕𝑍 𝑌
Y

Successive partial derivatives

may be taken in any order
𝜕 𝜕𝑋 𝜕 𝜕𝑋
=
𝜕𝑍 𝜕𝑌 𝑍 𝑌
𝜕𝑍 𝜕𝑍 𝑌 𝑍 Janne-Mieke Meijer - 32TDY - Lecture 2 11
Modified based on Atkins' Physical Chemistry, 10th ed.
 Appendix B
Properties of exact differentials V
If we have a differential of the form:
𝜕𝑋 𝜕𝑋
𝑑𝑋 = 𝑀𝑑𝑌 + 𝑁𝑑𝑍 𝑀= 𝑁=
𝜕𝑌 𝜕𝑍 𝑌
𝑍
If 𝑑𝑋 is an exact differential, then:

𝜕𝑀 𝜕 𝜕𝑋
=
𝜕𝑍 𝑌
𝜕𝑍 𝜕𝑌 𝑍 𝑌 𝜕𝑀 𝜕𝑁
=
𝜕𝑍 𝜕𝑌
𝜕𝑁 𝜕 𝜕𝑋 𝑌 𝑍
=
𝜕𝑌 𝑍
𝜕𝑌 𝜕𝑍 𝑌 𝑍

Janne-Mieke Meijer - 32TDY - Lecture 2 12

Back to Thermodynamic processes

Janne-Mieke Meijer - 32TDY - Lecture 2 13

 Work in reversible processes
A = Area of piston
Work done during compression of a gas:
• No friction: all work is performed on gas moveable piston

• If reversible process (quasistatic) Gas system

(P1, V1)
• Express work in state variables of the gas:
At intermediate equilibrium state:

Force 𝐹 = 𝑃𝐴 Area of piston Force, F

Pressure Gas system
F (P2, V2)
For infinitesimal increase in F work done by surroundings on gas:

𝑑𝑊 = 𝑃𝐴𝑑𝑥 = −𝑃𝑑𝑉 (reversible)

To ensure work is positive while gas volume goes down dx

Janne-Mieke Meijer - 32TDY - Lecture 2 14

 Work in reversible processes
A = Area of piston
Work done during compression of a gas:
• Express work in state variables of the gas: moveable piston

For infinitesimal increase in F work done by surroundings on gas: Gas system

(P1, V1)
𝑑𝑊 = 𝑃𝐴𝑑𝑥 = −𝑃𝑑𝑉 (reversible)
Total work done on system:
𝑉2 Force, F
Gas system
𝑊 = − න 𝑃𝑑𝑉 (reversible) F (P2, V2)

𝑉1

Note: this is in fact the maximum work that can be done

dx

Janne-Mieke Meijer - 32TDY - Lecture 2 15

Work in reversible processes
quasistatic expansion:
Applied to some irreversible processes : No pressure drop across piston

• The expression for work:

𝑉2

𝑊 = − න 𝑃𝑑𝑉 (reversible)
𝑉1 𝑉2 𝑉2

𝑊 = − න 𝑃𝑑𝑉 = − න 𝑃0 𝑑𝑉 = −𝑃0 (𝑉2 − 𝑉1 )

can be applied to some irreversible 𝑉1 𝑉1
processes if:
quasistatic compression:
• Compression or expansion process by
itself is considered quasistatic but there
is irreversibility somewhere else in the
system 𝑉2

𝑊 = − න 𝑃𝑑𝑉
Janne-Mieke Meijer - 32TDY - Lecture 2 16
𝑉1
 The work needed
to get from point

Work is path dependent

A to point B
depends on how
B you go there

Work for different paths:

• Is the integral below PV curve and thus
path dependent A
𝑉2

𝑊 = − න 𝑃𝑑𝑉 (reversible)
𝑉1

• Three common paths:

• Isothermal (constant T)
• Isochoric (constant V)
• Isobaric (constant P)
work work
Work cannot be expressed as a difference
between end points of some state function

Janne-Mieke Meijer - 32TDY - Lecture 2 17

Work is path dependent Infinitesimal increase in work
should be written as:

đ𝑊
Work for different paths:
• (1→2) Isothermal compression 𝑃𝑉 = 𝑛𝑅𝑇
Inexact differential

𝑉2 𝑉2
1 𝑉2
𝑊 = − න 𝑃𝑑𝑉 = −𝑛𝑅𝑇 න 𝑑𝑉 = −𝑛𝑅𝑇 ln
𝑉 𝑉1
𝑉1 𝑉1
Direction of the path matters too:
𝑉2 𝑉2
𝑉2 > 𝑉1 ln >0 𝑉2 < 𝑉1 ln <0
𝑉1 𝑉1

• (1→3) isochoric decrease in pressure +

(3→2) isobaric increase in volume
𝑊 = −𝑃0 (𝑉2 − 𝑉1 )

Janne-Mieke Meijer - 32TDY - Lecture 2 18

Work in a free expansion?
Free expansion:
• Special case: partition is broken, and gas
expands to fill space 𝑉2

• How much work is done? 𝑊 = − න 𝑃𝑑𝑉

𝑉1

• No work! ∆𝑉 = 0, so 𝑊 = 0
Partition break

Two important points in thermodynamics:

1. Be clear about what is the system
2. đ𝑊 = −𝑃𝑑𝑉 is applicable only to reversible
processes (or the two special quasistatic
cases without a finite pressure drop)
Janne-Mieke Meijer - 32TDY - Lecture 2 19
Sign convention for Work
Definition of work (physics): Older definition of work (engineering):
• W is the work done on a system by its • W is the work done by a system on its
surroundings surroundings
positive work in compression đ𝑊 = 𝑃𝑑𝑉
đ𝑊 = −𝑃𝑑𝑉 negative work in expansion • Useful for applications: how much work can be
done by an engine (and for efficiency)

Gas system Surroundings Gas Surroundings

system
F (P, V, T) F (P, V, T)

Important: one must stick consistently with one or the other

Janne-Mieke Meijer - 32TDY - Lecture 2 20
Dissipative Work Stirring of a viscous liquid

Dissipative work
• Stirring of a viscous liquid

Temperature, T will increase

• State of system is changed

Other example of dissipative work
• Work is performed irreversibly
• Is called dissipative work
• Not possible to find expression for work in battery
terms of the state variables of the system
Janne-Mieke Meijer - 32TDY - Lecture 2 21
 Other kinds of work
The appropriate form of the infinitesimal work term in different reversible processes
Extensible wire Surface film
• Isothermal stretching • Isothermal stretching
area
đ𝑊 = 𝐹𝑑𝑥 đ𝑊 = Γℓ𝑑𝑥 = Γ𝑑𝐴
Surface tension

Surroundings Surroundings
Stretched wire
L
F
ℓ Γℓ
Tension, F dx Soap film

dx
Janne-Mieke Meijer - 32TDY - Lecture 2 22
 Other kinds of work
The appropriate form of the infinitesimal work term in different reversible processes
Reversible electrolytic cell Simple magnetizable material
• Increasing the charge with external • Increasing the magnetic moment
charging circuit ℳ = 𝑀𝑉
đ𝑊 = 𝐵0 𝑑ℳ
emf
Applied field magnetic moment
magnetization
đ𝑊 = 𝜀𝑑𝑍

charge

Note: in thermodynamics
symbol Q is reserved for heat
B0 Surroundings
Janne-Mieke Meijer - 32TDY - Lecture 2 23
Credit: Wikimedia commons
Infinitesimal work in various reversible processes
Overview of all state variables and work terms:

Gas system

(P, V*)

(P, V)

Intensive Extensive If we take only part of the system

the intensive state variable is independent
the extensive state variable is proportional

Janne-Mieke Meijer - 32TDY - Lecture 2 24

Work in reversible processes
Effect of work on surroundings: Surroundings

• All forms of work discussed so far can

be considered can be thought of as
raising or lowering a weight in the
surroundings weight

• OR: equivalent of mechanical work Gas system

(P, V, T)
• This idea is useful in distinguishing work
and heat

F
Janne-Mieke Meijer - 32TDY - Lecture 2 25
Calculating work in a reversible process
Change in state of compressible fluid:
• Reversible process P1, V1, T1 P2, V2, T2

Initial state: (𝑃1 , 𝑇1 )

System System
Final state: (𝑃2 , 𝑇2 )

Infinitesimal work done in part of the process

đ𝑊 = −𝑃𝑑𝑉 We need to find dV

Typical example: determine change in state function given the change in the other two

Technique to solve this problem is always the same:

Janne-Mieke Meijer - 32TDY - Lecture 2 26

Calculating work in reversible process
So let’s solve:
1. We know it is reversible process
2. Write the equation of state in the form that gives the state function we wish to find
3. Write the differential
4. Find solutions for the partial derivatives
5. Rewrite for work term
6. Perform integrations (if possible)

Janne-Mieke Meijer - 32TDY - Lecture 2 27

Calculating work in reversible process
So let’s solve:
1. We know it is reversible process
2. Write the equation of state in the form that gives the state function we wish to find

𝑉 = 𝑉(𝑃, 𝑇)

3. Write the differential

𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑃 + 𝑑𝑇
𝜕𝑃 𝑇
𝜕𝑇 𝑃

4. Find solutions for the partial derivatives

𝜕𝑃 1 1 𝜕𝑉 𝑉
𝐵 = −𝑉 ≡ 𝛽= 𝑑𝑉 = − 𝑑𝑃 + 𝛽𝑉𝑑𝑇
𝜕𝑉 𝑇
𝜅 𝑉 𝜕𝑇 𝐵
𝑃
Janne-Mieke Meijer - 32TDY - Lecture 2 28
Calculating work in reversible process
So let’s solve:
5. Rewrite for work term
𝑃2 𝑇2
𝑃𝑉 𝑃𝑉
đ𝑊 = −𝑃𝑑𝑉 đ𝑊 = 𝑑𝑃 + 𝑃𝛽𝑉𝑑𝑇 𝑊= න 𝑑𝑃 + න 𝑃𝛽𝑉𝑑𝑇
𝐵 𝐵
𝑃1 𝑇1

6. Perform integrations (if possible)

In this case only possible for simplified case: isothermal change
𝑃2
𝑃𝑉 𝑃22 − 𝑃12
Then: 𝑊= න 𝑑𝑃 = 𝑉
𝐵 2𝐵
𝑃1

If V and B stay approximately constant during process,

Janne-Mieke Meijer - 32TDY - Lecture 2 29
The First law of Thermodynamics
• Essentially statement of conservation of energy
• Gives precise relationships between

Work, W

Internal Energy, U Heat, Q

State Function

Janne-Mieke Meijer - 32TDY - Lecture 2 30

History Joseph Black - “Methods of mixtures”

Start 19th century: Caloric theory T1 T2

• Heat = indestructible substance (caloric)

System 1 System 2
• Heat flows from a hot body to a cold
body naturally T 1 > T2

• Heat was quantified by the temperature Thermal contact

rise it produces in a unit mass of water
T1 → T1 - ΔT T 2→ T2 + ΔT
• Heat transfer between two bodies
heat
suggested heat was conserved entity
System 1 System 2

heat lost = heat gained

Janne-Mieke Meijer - 32TDY - Lecture 2 31

The work of Thompson
New theory: heat is inexhaustible
Benjamin Thompson
• Thompson observed production of great (1775)
heat during drilling of canon holes
• Measured T increase in cooling water
• Found that change in the amount of work
changed the amount of heat produced
• Direct relation:
work done ∝ heat produced
heat
Work

Janne-Mieke Meijer - 32TDY - Lecture 2 32

 James Joule
The work of Joule (1840-1849)

Precise relation work and heat:

• Very careful & accurate experiments
• Measured increase in heat of water in response
to mechanical stirring Work
→ Irreversible adiabatic process
• 4,2 kJ of work is required to increase 1 kg water
with 1 oC or K
heat
→ Mechanical equivalent of heat J
• No matter how adiabatic work was performed
(weights or electric) it always required the
same amount of work to take water system
between two equilibrium states
Janne-Mieke Meijer - 32TDY - Lecture 2 33
The First law of thermodynamics
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.

In other words:
• Work in an adiabatic process, 𝑊adiabatic is path independent

• There must be a state function that is equal to adiabatic work:

→ Internal energy, U
𝑊adiabatic = 𝑈2 − 𝑈1

Janne-Mieke Meijer - 32TDY - Lecture 2 34

The First law of thermodynamics
Internal Energy, U
• Is related to the kinetic and potential
energy of molecules
• The molecular motion and relative
positions constitute internal energy U
Kinetic energy: random motion

Potential energy: mutual attraction

Janne-Mieke Meijer - 32TDY - Lecture 2 35

The first law of thermodynamics
Heat, Q Fixed:
• For non-adiabatic process work is path dependent ∆𝑈 ≠ 𝑊 ∆𝑈 = 𝑈2 − 𝑈1
• The difference between ∆𝑈 and 𝑊 is called the heat 𝑄

The first law of thermodynamics: a sign convention for heat:

the internal energy can
positive when it enters the system
be increased ∆𝑈 = W + Q
Supply heat to system
work on system by
from surroundings
surroundings

• Heat is the non-mechanical exchange of energy between the system and the
surroundings because of their temperature difference
Janne-Mieke Meijer - 32TDY - Lecture 2 36
The first law of thermodynamics
The first law of thermodynamics:
∆𝑈 = 𝑊 + 𝑄 Q Surroundings

work on system by Supply heat to system from

surroundings surroundings
Gas system W
• For an infinitesimal process:
F (P, V, T)
𝑑𝑈 = đ𝑊 + đ𝑄

Is a state
function and This is to indicate that work
Only in the special case of adiabatic
thus an exact and heat are path dependent,
work is dW path indedent!
differential they are inexact differentials
W is not a state function
Janne-Mieke Meijer - 32TDY - Lecture 2 37
The first law applied to a compressible fluid
For a reversible infinitesimal process:
• Work is: Q Surroundings
đ𝑊 = −𝑃𝑑𝑉

• The first law becomes:

Gas system W

F (P, V, T)
𝑑𝑈 = −𝑃𝑑𝑉 + đ𝑄

đ𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 (reversible)

Janne-Mieke Meijer - 32TDY - Lecture 2 38

Heat or work?
Difference between heat and work can be obvious:
Example of gas compression under different conditions:
Change in internal energy: 𝑑𝑈 = đ𝑊 𝑑𝑈 = đ𝑊 + đ𝑄
đ𝑄 = 0

Surroundings Q Thermal reservoir (T)

Gas system W Gas system W

F (P, V, T) F (P, V, T)

Janne-Mieke Meijer - 32TDY - Lecture 2 39

 Heat or work? Question:
What about a microwave?
Heat or work?
For some systems it is not so clear:
• Heating coils with current 𝐼 through resistance 𝑅
Q

Work is done on W Energy flow across

system at a rate system boundary in
𝐼2 𝑅 the form of heat

• Very important to be clear about what constitutes the system!

Janne-Mieke Meijer - 32TDY - Lecture 2 40

Summary
• The first law of thermodynamics:
the internal energy can
be increased ∆𝑈 = W + Q
Supply heat to system
work on system by
from surroundings
surroundings

• State variables and functions are exact differentials

• Heat and work are inexact differentials

𝑑𝑈 = đ𝑊 + đ𝑄

Janne-Mieke Meijer - 32TDY - Lecture 2 41