Srinivas Vanapalli

Thermodynamics toolkit – part I 05-12-2021

Note: Thermodynamic laws and equations always refer to

system variables.

System or state variables

§ Pressure, p
§ Temperature, T
§ Volume, V or density
§ Internal Energy, U
§ Entropy, S
§ Enthalpy, H
§ Helmholtz free energy, F
§ Gibbs free energy, G

and more depending on the domain, e.g. electrical system; charge

and potential

Stationary & closed system Sign convention: Q, W or

First law Wother into the system is
∆𝑈 = 𝑄 + 𝑊!" + 𝑊#$%&' positive

net heat transfer

net other work (like
Work expressed with system variables: turbine, shaft work)

Only fluid systems domain W

covered in this course NOTE: Mechanical work by
fluid -p V -pdV
definition is,
Elastic rod f L fdL
dielectric E pE E.dpE 𝑊!" = * 𝐹#$% , 𝑑𝑥
magnetic B m B.dm
quasistatic

𝑊!" = * 𝑝𝐴 , 𝑑𝑉/𝐴
Second law 𝑄 ≤ ( 𝑇𝑑𝑆

Third law 𝑇 = 0, 𝑆 = 0

Quasistatic process and no other work)

Note: Quasistatic does not mean a slow process
(it means equilibrium between system and
surroundings and system variable can be clearly
defined)

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 Srinivas Vanapalli
Thermodynamics toolkit – part I 05-12-2021

1
Equipartition theorem 𝑈%)#*+,- = 𝑁𝑓 𝑘𝑇
2

Ideal gas

adiabat

isotherms isotherms
(increasing
temperature)

𝑝𝑉 = 𝑁𝑘𝑇

𝑝𝑉 = 𝑛𝑅𝑇
Constant
1 1
𝑈 = 𝑓 𝑛𝑅𝑇 = 𝑓 𝑝𝑉
2 2 isotherm T pV = constant
1 1 Adiabat S pVγ = constant
∆𝑈 = 𝑓 ∆(𝑛𝑅𝑇) = 𝑓 ∆(𝑝𝑉)
2 2 isobar p V = f(T)
isochor V p = f(T)

Heat capacity

Note: heat capacity Small changes

J/[mol.K] J/[kg.K]
Any process ∆𝑈 = 𝑛𝑐" ∆𝑇 = 𝑚𝑐"& ∆𝑇 𝑑𝑈 = 𝑛𝑐" 𝑑𝑇 = 𝑚𝑐"& 𝑑𝑇
Only for 𝑄 = 𝑛𝑐! ∆𝑇 = 𝑚𝑐!& ∆𝑇 𝑄 = 𝑛𝑐! 𝑑𝑇 = 𝑚𝑐!& 𝑑𝑇
isobaric process
Only for 𝑄 = 𝑛𝑐" ∆𝑇 = 𝑚𝑐"& ∆𝑇 𝑄 = 𝑛𝑐" 𝑑𝑇 = 𝑚𝑐"& 𝑑𝑇
isochoric process

Quasistatic process:
( (
p W = − * 𝑝𝑑𝑉 T 𝑄 <= * 𝑇𝑑𝑆
' '

V S
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 Srinivas Vanapalli
Thermodynamics toolkit – part I 05-12-2021

isobaric 𝑊 = −𝑝. (𝑉/ − 𝑉. ) Note:

- Only quasistatic processes
∆𝑈 = 𝑛𝑐3 (𝑇/ − 𝑇. ) can be shown on a property
𝑄 = 𝑛𝑐! 𝑇/ − 𝑇. diagram
- Any process, ∆𝑈 = 𝑛𝑐3 ∆𝑇
𝑇/ - If volume increases in a
∆𝑆 = 𝑛𝑐! ln process, W is negative
𝑇.

𝑊=0
isochoric Note:
∆𝑈 = 𝑛𝑐3 (𝑇/ − 𝑇. ) - Practice plotting T-s
diagrams of these processes.
𝑄 = 𝑛𝑐3 (𝑇/ − 𝑇. )
𝑇/
∆𝑆 = 𝑛𝑐3 ln
𝑇.

𝑉/
isothermal 𝑊 = −𝑛𝑅𝑇. ln
𝑉.
∆𝑈 = 0
𝑄 = −𝑊
𝑉/
∆𝑆 = 𝑛𝑅 ln
𝑉.

1
adiabatic 𝑊 = −𝑝. 𝑉.
0
1−𝛾 1
(𝑉
.20 .20
− 𝑉. )

∆𝑈 = 𝑛𝑐3 (𝑇/ − 𝑇. ) If temperatures are given and n

and f are know calculate ∆U, which
𝑄=0 is equal to W.

∆𝑆 = 0 If p, V and f are given calculate ∆U,

which is equal to W.
!"
Check if you can calculate ∆U and
𝑊 = − $ 𝑝𝑑𝑉
arbitrary !!
then W. Apply first law to calculate
Q.
∆𝑈 = 𝑛𝑐3 (𝑇/ − 𝑇. )
i 𝑄 = ∆𝑈 − 𝑊
𝑇' 𝑇/
∆𝑆./ = ∆𝑆.' + ∆𝑆'/ ∆𝑆./ = 𝑛𝑐! ln + 𝑛𝑐3 ln
𝑇. 𝑇'
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 Srinivas Vanapalli
Thermodynamics toolkit – part I 05-12-2021
Heat transfer
Quasistatic and non-quasistatic
Wother =0
In a quasistatic process, the S inside S
S inside
entropy change of the system is Irreve…
only because of the heat transfer.

In a non-quasistatic process, the

entropy change of the system is
the sum of entropy change due to ∆S ∆S
heat transfer and irreversible
entropy produced in the process.
quasi non-quasi

Thermodynamic cycles

p Process 1 ∆𝑈#→% = 𝑄#→% + 𝑊#→%

Process 2 ∆𝑈%→# = 𝑄%→# + 𝑊%→#

Cycle ∆𝑈#→% + ∆𝑈%→# = ' 𝑄 + ' 𝑊

∆𝑈#→% + ∆𝑈%→# = 0
V
'𝑄 + '𝑊 = 0

' ∆𝑈 = 0 ' ∆𝑆/0/ = 0 ' ∆𝑆/122 ≥ 0 ' ∆𝑆+'+-( ≥ 0

Maximum efficiency: All processes in the cycle are quasistatic

𝑏𝑒𝑛𝑒𝑓𝑖𝑡
Ef+iciency =
𝑐𝑜𝑠𝑡
Note: In practice reservoir temperatures are known
(not system temperatures) maximum efficiencies can
be derived as,
𝑊 𝑇&
Heat engine ef+iciency = 𝜂,-. = 1 − Maximum
𝑄*'+ 𝑇*

𝑄&'() 𝑇&
Cooler ef+iciency = 𝐶𝑂𝑃,-. =
𝑊 𝑇* − 𝑇&

𝑄*'+ 𝑇*
Heat pump ef+iciency = 𝐶𝑂𝑃,-. =
𝑊 𝑇* − 𝑇&

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 Srinivas Vanapalli
Thermodynamics toolkit – part I 05-12-2021

Microstates, microstate and multiplicity

Multiplicity and entropy

Multiplicity of two interacting Einstein solids

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 Srinivas Vanapalli
Thermodynamics toolkit – part I 05-12-2021

Definition of temperature

Cup of tea cooling exercise

We assume this process to be isochoric. Although note that the
pressure is constant (tea is exposed to atmospheric pressure). We
neglect the change in density of the tea with temperature.

𝐶3 = 600 J/K

6 899∗;<
∆𝑆45** = 7
= 1=>
= 148.5 J/K

6 ?! @7 @7 7
∆𝑆%#, = ∫ 7 = ∫ 7
= 𝐶3 ∫ 7
= 𝐶3 ln 7" = −132.7 J/K
#

∆𝑆5/'3#*4# = 148.5 − 132.7 = 15.8 J/K

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 Srinivas Vanapalli
Thermodynamics toolkit – part I 05-12-2021

Entropy of mixing