ENCH-633: Chemical

Thermodynamics
Sathish Ponnurangam
Fall 2018

Week – 1:
(Reading: Chap-1,2,3,4 Molecular Thermodynamics Of Fluid-Phase Equilibria by Prausnitz et. al.,
Chap-I,II,III, IV from Lecture Notes, P. R. Bishnoi)
[Additional reading: Chap-1,2,3,4,5 Engineering and Chemical thermodynamics by Milo Koretsky]
• Thermo+Dynamics = Heat  mechanical motion
• Why study thermodynamics?
• Chemical and petroleum industry
• Enthalpies and fugacities needed for designing unit
operations and equipment
• Phase equilibrium
• Reaction engineering
• Predicting flow in pipelines
• Rating on heat exchangers, compressors, blowers..,
• Maximum achievable efficiency of power plants, internal
combustion engines..,
Phase equilibrium problem
• Why study phase equilibrium?
• Natural raw materials occur as mixtures
• Most products are mixtures
• Examples of phase equilibrium in chemical
engineering unit operations?
• Extraction
• Distillation
• Adsorption
• Leaching
• Absorption ..,
 Phase equilibrium problem
• Separation processes:
• Remove undesired raw materials,
• Purify products
• Separate products from reactants to recycle
• distillation, solvent extraction ..,
• 40-80 % of investment of chemical plants

Prausnitz et. al.,

Bitumen Upgrading

Phase equilibrium thermodynamics:

establishes relationship between
thermodynamic properties – important
for designing chemical plants

http://www.oilsandsmagazine.com/technical/bitumen-upgrading
Phase equilibrium problem
• Consider, two homogeneous phases at equilibrium

Prausnitz et. al.,

Perpetual Motion Machine

You can't get anything without working for it.

7
3-steps of phase equilibrium problems

• Translate to abstract
mathematical problem
• Solve the mathematical
problem (i = iβ)
• Translate to real world
variables
• T, P, x1β,x2β.. = f(T, P, x1,x2.. )

Prausnitz et. al.,

 Step 3: Classical thermodynamics alone is not useful
 need equation of state and/or apply statistical thermodynamics and physical
chemistry concepts

𝝏𝑼
 Consider the solution to a process to be, 𝑻 =
𝝏𝑺 𝑽
 Need to know functional form of U(S) to translate to T
Statistical Thermodynamics
• Statistical thermodynamics  tool for relating
thermodynamic properties to molecular properties
(counting and averaging)

𝟏
Temperature, 𝑻 ≈ 𝒆𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓
𝒌 = 𝒎𝑽 𝟐
𝟐

• Molecular properties (molecular mass, bond lengths,

angles, vibrations, intermolecular forces..,)
• Thermodynamic properties (U, H, P, G..,)
Milo Koretsky
Course Schedule
• Week-1: Review of Chemical thermodynamics (work, heat, energy, terminologies, laws of
thermodynamics, measured and derived properties,)
• Week-2: Thermodynamic relations, thermodynamic equilibrium, and fugacity
• Week-3: Volumetric properties of fluids and Intermolecular forces
• Week-4: Fugacities in gas mixtures
• Week-5: Fugacities in liquid mixtures: Excess functions
• Week-6: Introduction to computational thermodynamics
• Week-7: Mid-term exam (October 26, 5-7 pm)
• Week-8: Chemical reaction equilibrium
• Week-9: Introduction to statistical thermodynamics
• Week-10: Fugacities in liquid mixtures: Model and theories of solution
• Week-11: Polymers: Solutions, Blends, Membranes, and Gels
• Week-12: Electrolyte solutions, Solubility and High pressure equilibria??
• Final Exam
Course readings
 Week1-3:
o Chap-1-4 from Prausnitz et. al.,
o Chap-I,II,III,IV from Lecture Notes, P. R. Bishnoi
o Additional reading: Chap 1-5 Engineering and Chemical
thermodynamics - Koretsky
 Week-4: Chap-5 from Prausnitz et. al.,
 Week-5: Chap-6 from Prausnitz et. al.,
 Week-6: Lecture Notes
 Week-8: Chap-VIII from P. R. Bishnoi & Chap-8 from Koretsky
 Week-9: Lecture Notes & Appendix-B from Prausnitz et. al.,
 Week-10: Chap-7 from Prausnitz et. al.,
 Week-11: Chap-8 from Prausnitz et. al.,
 Week-12: Chap-9,10 from Prausnitz et. al.,
Course learning outcomes
By the end of this course, you should be able to,
• Thermodynamic relations
• Solve problems using PVT-relations and the laws of thermodynamics
• Interpret PVT-behavior in terms of intermolecular forces
• Define the chemical potential and fugacity and criterion for phase
equilibrium
• Comprehend methods for the fugacity calculation in different phases as
well as for pure vs. mixed systems
• Perform thermodynamic calculations for non-ideal systems including gas-
liquid, liquid-liquid, and solid-liquid equilibria;
• Define and apply chemical reaction equilibria
Course learning outcomes
By the end of this course, you should be able to,
• Comprehend the basics of statistical thermodynamics including the
redefinition of entropy in statistical terms, as well as the relations between
different thermodynamic functions and partition functions;
• Perform simple thermodynamic calculations for different phase equilibria
using statistical thermodynamics;
• Get familiar with statistical simulation tools such as molecular dynamics.
Course information
• Instructor: Sathish Ponnurangam,
sathish.ponnurangam@ucalgary.ca
• TA information:
• ???
• Days, Time & Location:
• Lecture: TR, 3:30 PM - 4:45 PM, ST 064
• Office hours: Monday: 3:30 – 4:30 PM, ENB 204L
Examination dates, grading and details
Final Grade Determination:
• Homework assignments (6-7 assignments, 3-4 will be
graded): 30 %
• Class participation: 5 %
• Mid-term exam: 30 %
• Final exam: 35 %
Dates:
• Midterm: the week of October 29th 5-7 pm (2 hours)
• Final exam (3 hours): Will be set by the University
Main textbooks
Classical thermodynamics:
• Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd
edition, by J.M. Prausnitz, R.N. Lichtenthaler, and E. G. de
Azevedo, Prentice-Hall, Englewood Cliffs (1999). Ebook is
available at library website

Additional reading:
Classical Thermodynamics
• Engineering and Chemical Thermodynamics, 2nd edition (2013), by
Milo D. Koretsky, published by John Wiley & Sons, Inc., Check with the
book store for availability.
Statistical thermodynamics
• Molecular driving forces, statistical thermodynamics in chemistry
and biology by Ken Dill and Sarina Bromberg
History of thermodynamics

• In 19th century, engineers and physicists tried to

answer two important questions
• Nature of heat
• How exactly heat is related to work
• Nature of heat
• Calorique theory of heat
• Fluid flowing from hot to cold body
• Conservation of heat
• Francis Bacon: “is motion and nothing else”

https://www.sussex.ac.uk/webteam/gateway/file.php?name=a-thermodynamics-history.pdf&site=35
Nature of heat
• Mechanical theory of heat
• First breakthrough: Canon boring experiments by
Count Rumford in 1798
• While boring hole in a cannon, blunter instrument generated
more heat than sharper instrument
• For same hole size: no difference in weight of shavings and
its heat capacity
• More heat  less boring depth/diameter
•  mechanical work is converted to heat and idea of heat as
a fluid overturned
• Mechanical equivalent of heat
https://www.sussex.ac.uk/webteam/gateway/file.php?name=a-thermodynamics-history.pdf&site=35
Idea of Energy
• Joule – converted mechanical or electrical
energy into heat
• 1 calorie = 4.184 J
• Different forms of energy can be interconverted

• Clausius, 1850 – Conservation of energy Joule’s apparatus – 1843

(Harper's New Monthly Magazine,
• Heat  kinetic energy of particles inside matter No. 231, August, 1869)

‘Friedrich Mohr in 1837,”Besides the fifty four chemical elements, there exists in
nature only one agent more, and this is called force (he meant energy); it can
under suitable conditions appear as motion, cohesion, electricity, light, heat, and
magnetism. Heat is thus not a particular kind of matter, but an oscillatory motion
of the smallest parts of bodies”.’
https://www.sussex.ac.uk/webteam/gateway/file.php?name=a-thermodynamics-history.pdf&site=35
Energy
• Ability to perform work
• Classically, energy is divided into
• Kinetic energy: macroscopic and microscopic
• Potential energy: position of the object in a force field (gravity, electrical,
magnetic…,)
• Mixed form of energies
• Mechanical energy: For e.g. a ball falling under gravity (macroscopic
kinetic + gravitational potential energy)
• Elastic energy, chemical energy: electrical potential energy of atoms and
molecules + kinetic energy
• Thermal energy/internal energy, U:
• microscopic kinetic energy + microscopic potential energy
Heat & Work
• What is heat?
• Exchange of energy due to motion and collision of particles
• Heat is chaotic form of energy transfer
Heat

• Work: Ordered form of energy transfer

Work
Gravitational potential energy Kinetic energy of turbine

• Both work and heat: mechanisms of energy transfer

• Appears when energy is passed from one system into another 22
http://www.youtube.com/watch?v=66_O9E5YdCg http://www.ecolink.com/info/hydro-electric-generator/
Work
• Work?
• 𝜹𝒘 = 𝒇𝒂𝒑 𝒅𝒙
𝒙𝟐
•𝑾= 𝒇 𝒅𝒙
𝒙𝟏 𝒂𝒑

• Force?
𝒅𝟐 𝒙
• 𝑭𝒐𝒓𝒄𝒆 = 𝒎𝒂 = 𝒎 𝟐
𝒅𝒕
Type of work
• volume, extension, flow, shaft, surface, electrical,
gravitational, magnetic
Volume work
Pext

dx
P

𝑑𝑉 = 𝐴. 𝑑𝑥
𝐹𝑜𝑟𝑐𝑒, 𝑓𝑎𝑝 = 𝑃𝑒𝑥𝑡 × 𝐴
𝑤𝑜𝑟𝑘, 𝛿𝑤 = 𝑃𝑒𝑥𝑡 𝑑𝑉
 First Law of Thermodynamics
• Change in system's internal energy is equal to sum of heat added to system
from its surroundings and work on system by its surroundings.
• Although energy can be transferred from one system to another in many
forms, it can neither be created nor destroyed.
• Conservation of energy
• Total energy in universe (System + Surroundings) is constant
• Universe = isolated system

dU = δQ + δW
Sign convention?

Work, δW
δQ > 0; heat supplied to system
Internal energy
change, dU Heat, δQ δW > 0; work performed on system

25
Classical thermodynamics – review of
basics
• Thermodynamics?
• Conservation of energy, transfer of energy, direction
of transfer, how much is transferred in ordered form
(work) vs. disordered form (heat)
• Zeroth law of thermodynamics
• If A is in thermal equilibrium with B and B with C,
then A is in thermal equilibrium with C
Review
• Heat?
• Exchange of energy due to motion and collision of particles
• Heat is chaotic form of energy transfer
• Work?
• Ordered form of energy transfer
• Types of work?
• volume, extension, surface, electrical, gravitational, magnetic
• Energy?
• Ability to perform work
• How is energy classified?
• Generally as kinetic and potential energy
• Internal energy?
• Thermal energy?
• Not-well defined term in thermodynamics – so not used.
 Internal energy, U
• What is U microscopically?
• U = molecular potential energy + molecular kinetic energy
• Excludes kinetic and potential energies of the system as a whole
• Different forms of potential energy (gravitational, electrical,
magnetic, inter and intra molecular attraction/repulsion..,)
• Molecular potential energy depends on the position of the
molecules w.r.to other molecules or external field
𝒒𝟏 𝒒𝟐 𝒎𝟏 𝒎𝟐
• 𝑪𝒐𝒍𝒖𝒎𝒃𝒊𝒄 𝒆𝒏𝒆𝒓𝒈𝒚 ∝ , 𝒈𝒓𝒂𝒗𝒊𝒕𝒂𝒕𝒊𝒐𝒏𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚 ∝
𝒓 𝒓
• Molecular kinetic energy,
• Ukin = Utranslational + Urotational + Uvibrational
28
1. Temperature rises with U
U = molecular PE + molecular KE

For ideal gas: will molecular potential energy change with T?

No intermolecular forces  Molecular potential energy is constant
U = Ukin+Upot (Upot=0)
Energy added  kinetic energy of molecules   T 
Ukin = Utranslational + Urotational + Uvibrational

For monoatomic ideal gas, which of these kinetic energy terms = 0?

 Urot, Uvib = 0
For ideal gases: U depends on T only not on the position of molecules
He 𝑼 = 𝒇(𝑻)

Real gases, 𝑼 = 𝒇(𝑻, 𝒑𝒐𝒔𝒊𝒕𝒊𝒐𝒏 𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔)

How to quantify position of molecules?
P or , 𝑼 = 𝒇 𝑻, 𝑷 = 𝒇(𝑻, 𝛖)

29
2. Can U be increased without increasing T?
Sublimation of dry ice: internal energy 

• Yes, during phase transition

• Energy needs to be supplied to
break the bonds of CO2
molecules in dry ice
https://commons.wikimedia.org/wiki/File:Dry_Ice_Sublimation_1.jpg

30
3. Change in U vs. chemical reaction
• Consider N2 + 3H2  NH3
• 3 single bonds of H2 and one triple bond of N2 broken
• 3 single bonds of NH formed.
• Depending on the strength of the bonds of reactants and
products, U can increase or decrease
• Contribution from entropy

31
Directionality of the
process

𝒅𝑼 = 𝜹𝒒 + 𝜹𝒘

32
Milo D. Koretsky
Carnot cycle |
|
|
|
• Ideal gas and reversible processes
• 12: isothermal expansion
• 23: adiabatic expansion
• 34: isothermal compression
• 41: adiabatic compression 𝑸𝑯 + 𝑸𝑪 = 𝑸 𝑯 − 𝑸𝑪

𝑾𝒏𝒆𝒕 = 𝑸𝒏𝒆𝒕 = 𝑸𝑯 − 𝐐𝐂

𝑸𝑯 − 𝐐 𝐂 𝐐𝐂 𝑻𝑪
𝜼= = 𝟏− =𝟏−
𝐐𝐇 𝐐𝐇 𝑻𝑯
For reversible process,
|𝑸𝑪 | 𝑻
= 𝑻𝑪
|𝑸𝑯 | 𝑯
Carnot cycle

Isothermal
expansion
Adiabatic
T1=T2=TH
P compression

Adiabatic
expansion
Isothermal
compressionT3=T4=TC
33
T
 Second law of thermodynamics

• Kelvin-Planck statement
• It is impossible to construct a device which, operating in a cycle,
will produce no other effect than the extraction of heat from a
reservoir and the performance of an equivalent amount of work.
• Clausius statement
• It is impossible to construct a device which, operating in a cycle,
will produce no other effect than the transfer of heat from a
cooler to a warmer body.

34
Entropy, S
• Can a property be defined that quantifies
• Directionality of nature so we can tell if a
process is spontaneous or not
• How far real process is from reversible process.
• Can this property be also a state function?
• A thermodynamic property, entropy, s, allows to
achieve these goals,
𝜹𝒒𝒓𝒆𝒗
• 𝐝𝐬 =
𝑻
𝑓𝑖𝑛𝑎𝑙 𝜹𝒒𝒓𝒆𝒗
• Δs = 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑻
35
Adiabatic expansion/compression
• Reversible adiabatic expansion and compression
of a insulated piston pump
• Δ𝑠𝑢𝑛𝑖𝑣 = Δ𝑠𝑠𝑦𝑠 + Δ𝑠𝑠𝑢𝑟𝑟
𝑓𝑖𝑛𝑎𝑙 𝜹𝒒𝒓𝒆𝒗
• Δssys = 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑻
= 0, and Δss𝑢𝑟𝑟 = 0, since there is no
heat transfer from the surroundings
Adiabatic State 1
expansion

• Δ𝑠𝑢𝑛𝑖𝑣 = 0 P
reversible

• Also, Δ𝑢 = 𝑤𝑟𝑒𝑣
State 2
Part of energy
transformed to heat
instead of work

T
36
Irreversible adiabatic expansion and compression
• For irreversible adiabatic expansion for the same driving force (Δ𝑃) as rev.
• q = 0, 𝑤𝑖𝑟𝑟𝑒𝑣 > 𝑤𝑟𝑒𝑣 or |𝑤𝑖𝑟𝑟𝑒𝑣 | < |𝑤𝑟𝑒𝑣 |
• ⇒ Δ𝑢𝑖𝑟𝑟𝑒𝑣 > Δ𝑢𝑟𝑒𝑣 or |Δ𝑢𝑖𝑟𝑟𝑒𝑣 | < |Δ𝑢𝑟𝑒𝑣 |
• 𝑢3 − 𝑢1 > 𝑢2 − 𝑢1
• 𝑢3 > 𝑢2 ⇒ for ideal gas, 𝑇3 > 𝑇2
• To calculate s3, construct hypothetical path since entropy is defined for reversible paths only:
• Step-1: reversible adiabatic expansion from state 1 to state 2,
• Step-2: Reversible isobaric expansion from state 2 to state 3
𝑠𝑡𝑎𝑡𝑒 2 𝜹𝒒𝒓𝒆𝒗 𝑠𝑡𝑎𝑡𝑒 3 𝜹𝒒𝒓𝒆𝒗
• But Δssys = s3 − s1 = state 1
+ 𝑠𝑡𝑎𝑡𝑒 2 𝑻
Adiabatic
expansion
State 1
𝑻
𝑇3 𝑐𝑝 𝑑𝑇 𝑇3 𝑐𝑝 𝑑𝑇 reversible
• =0+ 𝑇2 𝑻
= 𝑇2 𝑻
P
State 2
irreversible

• Since 𝑇3 > 𝑇2 , ⇒ Δssys > 0 State 3

Part of energy
transformed to heat
instead of work

37
T
Irreversible adiabatic expansion and compression
• Since 𝑇3 > 𝑇2 , ⇒ Δssys > 0

• Δss𝑢𝑟𝑟 = 0, (no heat from/to surroundings)

• Δ𝑠𝑢𝑛𝑖𝑣 = Δ𝑠𝑠𝑦𝑠 + Δ𝑠𝑠𝑢𝑟𝑟 = Δ𝑠𝑠𝑦𝑠 = 𝑠3 − 𝑠1 > 0

This implies: to perform adiabatic irrev. work, the system converts some of
the internal potential energy (-ve) into a more chaotic form of internal Adiabatic State 1
expansion
energy (molecular kinetic energy or T), thereby increasing entropy .
reversible
P irreversible
If the gas is ideal, then it simple means that the mechanisms of transfer of State 2
energy through work is hindered in irreversible process such that entropy Part of energy State 3
lost by decrease in temperature is more than offset by entropy gain by the transformed to heat
instead of work

volume increase T 38
Combined first and second law
• 𝒅𝑼 = 𝜹𝑸 + 𝜹𝑾
• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝒑𝒅𝑽
Molecular view of entropy
• Entropy: Molecular probability
• For given thermodynamic state (for e.g., given T,P), the microscopic
ensemble of states corresponds to maximum possible microscopic
configurations
 Consider two ideal gases, A and B with atoms each in a chamber
 Initially, A and B separated by porous membrane
 All states are equally likely (ergodic hypothesis)
 Probability all A on left = 1/6 A B
 1 A and 1 B = 4/6 A B
 No A on left = 1/6

A B B A B B A A A B B A
A B A B A A B B B A B A
1/6 4/6 1/6
40
• 128 As and Bs
each: Probability
of 52-76 A
atoms on the
left ≈ 1075
(99.8%)
• Avogadro
number of
atoms!!
• This probability
is defined as
entropy
• Irreversibility of
macroscopic
process 
mixing at
molecular level
41
Milo Koretsky
Maximizing molecular configurations over space (mixing of space)
Chemical Directionality

Mechanical Directionality

42
Milo Koretsky
Maximizing molecular configurations over energy
(mixing of energy levels)

• Not only maximizing spatially probability but

also probability of energy distribution

Spontaneous reaction of H2 and

O2 to form H2O  increases
temperature and entropy

43
Milo Koretsky
• Review of terminology of thermodynamics
• System
• Intensive/extensive properties
• Thermodynamic process and path
• State and path functions
• Measured thermodynamic properties and Equation of
state
• Thermodynamic equilibrium
• Phase equilibrium and Gibbs phase rule (and state postulate)
• Equilibrium state vs. steady state
• Reversible, irreversible, and quasi-static processes
• Exact, inexact differentials
Thermodynamic Equilibrium
Mechanical equilibrium: PA = PB
No tendency for bulk movement of material

Thermal equilibrium:. TA = TB
No tendency for transport of thermal energy

Material equilibrium: Chemical potential µA = µB

no tendency for material to change form (eg., phase transformation or a chemical reaction)

45
Equilibrium vs. Steady state
• Equilibrium:
• internal equilibrium and
• equilibrium with its surroundings.
• Steady state: A system that relies on its surrounding to
remain unchanged
Steady state
Bar on hot plate
Metal bar in a room
Thermal equilibrium

Steady state

http://tll.mit.edu/help/equilibrium-vs-steady-state 46
Quasi-static process?
• Internal vs. external equilibrium?
• Quasi-static processes are arbitrarily slow such
that the system is at internal equilibrium
• For example, consider a very slow compression in a
piston-cylinder, then internally the pressure remains
same at all spatial points in the system
• Heat transfer is slow that temperature remain similar
any point in the system
• Changes in the external stimuli is much slower than
internal processes – hence internal equilibrium
Reversible process?
• A reversible process is so slow that system is both in internal equilibrium with itself and external
equilibrium with surroundings at each small step
• Quasi-static process reversible or irreversible process
• Reversible process: Any process system can be restored to initial states with no net effects on
surroundings. Processes are considered reversible only if they are executed very slowly, i.e. the driving
force for the process is infinitesimally small.
• No increase in entropy of the system
• In the real world, all processes are irreversible.

• Sources of irreversibility
• Friction
• Spontaneous chemical reactions
• Electric current flowing through a finite resistance
• Inelastic deformation of solids
• Viscous dissipation in liquids

• Then, why do we care for reversible process?

rev. process gives a limit for maximum work that can be extracted or minimum energy needed. For
𝑾 𝑻
e.g., consider Carnot efficiency of internal combustion engine: 𝜼 = 𝑸 = 𝟏 − 𝑻 𝑪
𝑯

48
Exact and inexact differentials
𝜕𝑓 𝜕𝑓
• Exact differential: 𝑑𝑓 = 𝑑𝑥 + 𝑑𝑦 ; 𝑑𝑓 = 0
𝜕𝑥 𝑦 𝜕𝑦 𝑥

𝜕𝑓 𝜕𝑓
• Inexact differential: f can not be expressed as, 𝑑𝑓 = 𝑑𝑥 + 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
• 𝑑𝑓 ≠ 0

• Traveling from point A to B and returning

• Net traveled is distance is 0 – exact differential
• Total distance traveled 2(B-A) – inexact differential
• Internal energy change remains the same for State 1  2, however
heat and work depends on the path we took

49
Test for exact differential

𝝏𝒛 𝝏𝒛
• 𝜹𝒛 𝒐𝒓 𝒅𝒛 = 𝑴 𝒙, 𝒚 𝒅𝒙 + 𝑵 𝒙, 𝒚 𝒅𝒚; 𝑴 𝒙, 𝒚 = and 𝑵 𝒙, 𝒚 =
𝝏𝒙 𝒚 𝝏𝒚 𝒙

• If dz is exact differential then,

𝝏𝑴 𝝏𝑵
• =
𝝏𝒚 𝒙 𝝏𝒙
𝒚

• Inexact differential
𝝏𝑴 𝝏𝑵
• ≠
𝝏𝒚 𝒙 𝝏𝒙
𝒚

50
 𝝏𝑷
Compressibility (), thermal expansion coefficient () and pressure coefficient
𝝏𝑻 𝑽
• Isothermal compressibility: relative volume change with respect to pressure or
stress at constant T. How to represent ?
∆𝑽
• 𝜿=− 𝑽
∆𝑷
𝟏 𝝏𝑽
• 𝜿 = −𝑽 𝝏𝑷 𝑻

• Volumetric thermal expansion coefficient: relative volume change with respect to

temperature at constant P. How to represent ?
∆𝑽
• 𝜷= 𝑽
∆𝑻
𝟏 𝝏𝑽
• 𝜷=
𝑽 𝝏𝑻 𝑷

𝝏𝑷
• Pressure coefficient: =?
𝝏𝑻 𝑽

51
Other mathematical relationships
Chain rule:
𝝏𝒛 𝝏𝒛 𝝏𝒚
= ; for e.g, z(y,a) and x(y,a)
𝝏𝒙 𝒂 𝝏𝒚 𝒂 𝝏𝒙 𝒂

Inverse rule:
𝝏𝒙 𝟏
=
𝝏𝒛 𝝏𝒛
𝒚
𝝏𝒙 𝒚

Cyclic relation
𝝏𝒙 𝝏𝒚 𝝏𝒛 𝝏𝟏 𝝏𝟐 𝝏𝟑
= −𝟏 = −𝟏
𝝏𝒚 𝒛 𝝏𝒛 𝒙 𝝏𝒙 𝒚 𝝏𝟐 𝟑 𝝏𝟑 𝟏 𝝏𝟏 𝟐

𝝏𝒛 𝝏𝟑
𝝏𝒙 𝝏𝒚 𝒙 𝝏𝟏 𝝏𝟐 𝟏
=− ; =−
𝝏𝒚 𝝏𝒛 𝝏𝟐 𝝏𝟑
𝒛 𝟑
𝝏𝒙 𝒚 𝝏𝟏 𝟐

52
 𝝏𝑷
Relationship between , , and and pressure coefficient ?
𝝏𝑻 𝑽

𝟏 𝝏𝑽
• 𝜿=−
𝑽 𝝏𝑷 𝑻

𝟏 𝝏𝑽
• 𝜷=
𝑽 𝝏𝑻 𝑷

𝝏𝑷
• =?
𝝏𝑻 𝑽

• Using cyclic relations: 𝝏𝒙 𝝏𝒚 𝝏𝒛

= −𝟏
𝝏𝑷 𝝏𝑇 𝝏𝑽
𝝏𝒚 𝒛
𝝏𝒛 𝒙
𝝏𝒙 𝒚
• = −1 𝝏𝒛
𝝏𝑻 𝑽 𝝏𝑉 𝑷 𝝏𝑷 𝑻
𝝏𝒙 𝝏𝒚 𝒙
𝝏𝑽 =− ;
𝝏𝑷 𝝏𝑻 𝑷 𝝏𝒚 𝝏𝒛
• =− 𝝏𝑽
𝒛
𝝏𝒙 𝒚
𝝏𝑻 𝑽
𝝏𝑷 𝑻
𝟏 𝝏𝑽
𝝏𝑷 𝑽 𝝏𝑻 𝑷 𝜷
• = 𝟏 𝝏𝑽 =
𝝏𝑻 𝑽 −𝑽 𝝏𝑷 𝜿
𝑻

53
 Thermodynamic property relationships
• Three types of thermodynamic properties
• Measured (𝑷, 𝒗, 𝑻, 𝒄𝒐𝒎𝒑𝒐𝒔𝒊𝒕𝒊𝒐𝒏, β, κ, 𝑪𝒑)
• Fundamental (𝒊𝒏𝒕𝒆𝒓𝒏𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚 𝒖, 𝒆𝒏𝒕𝒓𝒐𝒑𝒚 𝒔)
• Derived (𝑬𝒏𝒕𝒉𝒂𝒍𝒑𝒚 (𝒉), 𝑯𝒆𝒍𝒎𝒉𝒐𝒍𝒕𝒛 (𝒂), 𝑮𝒊𝒃𝒃𝒔 (𝒈))
• How do we perceive measured property (𝒗, 𝑻, 𝑷, 𝒄𝒐𝒎𝒑𝒐𝒔𝒊𝒕𝒊𝒐𝒏)?
• How to perceive and determine the fundamental properties (u,s)?
• Only through generalization of heat and work equivalence and with help 1st
and 2nd postulates of thermodynamics
• What about derived properties (h,a,g)?
• They are derived from measured and fundamental properties out of
convenience (for e.g., to avoid measuring/knowing u, s, or q)
• Derived properties are invented quantities and can’t be measured directly in
lab and they are not fundamental.
54
Constant-Pressure Process (isobaric)
isobaric
Pressure
State A State B

Volume
𝒅𝒖 = 𝜹𝒒 + 𝜹𝒘
Constant P and only PdV work 𝒅𝒖 + 𝒅(𝑷𝒗) = 𝜹𝒒
𝒅𝒖 = 𝜹𝒒 − 𝑷𝒅𝒗 𝒅(𝒖 + 𝑷𝒗) = 𝜹𝒒
𝒅𝒖 + 𝑷𝒅𝒗 = 𝜹𝒒 𝒅𝒉 = 𝜹𝒒
𝒅𝒖 + 𝑷𝒅𝒗 + 𝒗𝒅𝑷 − 𝒗𝒅𝑷 = 𝜹𝒒
𝒅𝒖 + 𝒅(𝑷𝒗) = 𝜹𝒒 𝒉 = 𝒖 + 𝑷𝒗 55
Enthalpy: 𝒉 = 𝒖 + 𝑷𝒗
• Convenient way to represent the combination u+P.
• 𝒉 = 𝒖 + 𝑷𝒗;
• h is state variable, 𝑑ℎ = 0
• since it is combination of state variables
• Why it is convenient?
• Under certain conditions (constant P and boundary work
only), q becomes path independent (equals to change in 𝒉, a
state variable)
• 𝒖 + 𝑷𝒗 combination occurs several times in open chemical
systems
56
Constant-Temperature Process (isothermal)
State B
𝒅𝒖 = 𝜹𝒒 + 𝜹𝒘
isothermal
Pressure 𝒅𝒖 = 𝑻𝒅𝒔 + 𝜹𝒘
State A 𝒅𝒖 − 𝑻𝒅𝒔 = 𝜹𝒘
𝒅𝒖 − 𝑻𝒅𝒔 − 𝒔𝒅𝑻 + 𝒔𝒅𝑻 = 𝜹𝒘
𝒅𝒖 − 𝒅 𝑻𝒔 + 𝒔𝒅𝑻 = 𝜹𝒘
Volume
At constant T, dT=0
𝒅 𝒖 − 𝑻𝒔 = 𝜹𝒘
𝒅𝒂 = 𝜹𝒘 (can be Pdv and/or non-Pdv work)

57
Helmholtz free energy: 𝒂 = 𝒖 − 𝑻𝒔
• Also known as work function
• 𝒂 = 𝒖 − 𝑻𝒔;
• a is state variable, 𝑑𝑎 = 0
• since it is combination of state variables

• Why it is convenient?
• Under constant T,
• 𝒅𝒂 = 𝜹𝒘 (PV work or otherwise)

58
Constant T, P process

• Under constant T, and P

• dg = w (non-PdV work)

• 𝒅𝒖 = 𝑻𝒅𝒔 + 𝜹𝒘, 𝜹𝒘 = −𝐏𝐝𝛖 + 𝜹𝒘′

• 𝒅𝒖 − 𝑻𝒅𝒔 + 𝐏𝐝𝛖 = 𝜹𝒘′
• 𝒅𝒖 − 𝑻𝒅𝒔 − 𝒔𝒅𝑻 + 𝒔𝒅𝑻 + 𝑷𝒅𝝊 + 𝝊𝒅𝑷 − 𝝊𝒅𝑷 = 𝜹𝒘′
• 𝒅𝒖 − 𝒅 𝑻𝒔 + 𝒅 𝑷𝝊 + 𝒔𝒅𝑻 − 𝝊𝒅𝑷 = 𝜹𝒘′
• At constant T, P
• 𝒅 𝒖 − 𝑻𝒔 + 𝑷𝝊 = 𝜹𝒘′
• 𝒅𝒈 = 𝜹𝒘′

59
Gibbs free energy: 𝒈 = 𝒉 − 𝑻𝒔 𝒐𝒓 𝒈 = 𝒖 + 𝑷𝒗 − 𝑻𝒔

• Most important for phase equilibrium problems

• 𝒈 = 𝒖 − 𝑻𝒔 + 𝑷𝒗;
• g is state variable, 𝑑𝑔 = 0
• since it is combination of state variables

• Why it is convenient?
• Under constant T, and P
• 𝒅𝒈 = 𝜹𝒘’ (non-PV work)

60
Gibbs free energy: 𝒈 = 𝒉 − 𝑻𝒔 𝒐𝒓 𝒈 = 𝒖 + 𝑷𝒗 − 𝑻𝒔

• Under constant T, and P

• dg = w (non-Pdv work)

• 𝒅𝒖 = 𝑻𝒅𝒔 + 𝜹𝒘
• 𝜹𝒘 = −𝐏𝐝𝛖 + 𝜹𝒘′
• 𝜹𝒘′ - non-Pdv work, examples?
• F.dx: string (kx), flow/shaft work (dP), surface tension (dA),
electrical (dq)
• most important non-PdV work for us?
• 𝝁𝒊 𝒅𝒏𝒊

61
 Method to solve thermodynamic problems

• Check which properties are available

• Depending on the properties, choose the paths
and the boundaries carefully so that necessary
properties of the final (or initial) state can be
calculated

62
Example methods in classical thermodynamics
𝒅𝑼 = 𝜹𝒒 + 𝜹𝒘

• Method 1: Adiabatic boundaries, 𝒅𝑼 = 𝜹𝒒 + 𝜹𝒘

• 𝒅𝑼 = 𝜹𝒘

• Method 2: Closed system,

• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝒑𝒅𝑽
• We would like to know u(T,P) or u(T,v): 𝒅𝒖 =
𝝏𝒖
𝝏𝒔 𝒗
𝒅𝒔 +
𝝏𝒖
𝝏𝒗 𝒔
𝒅𝒗
𝝏𝒖
• All possible combinations of slope: as a function of
𝝏𝒙 𝒚
𝑻, 𝑷, 𝒂𝒏𝒅 𝒗
• 𝒘𝒉𝒆𝒓𝒆 𝒙, 𝒚 = 𝑻, 𝑷, 𝒗, 𝒐𝒓 𝒔
• (𝑻, 𝒔) 𝒂𝒏𝒅 (𝑷, 𝒗) are conjugate variables
• Other examples (, 𝒏), (𝒔𝒕𝒓𝒆𝒔𝒔, 𝒔𝒕𝒓𝒂𝒊𝒏)
63
 Thermodynamic property relationships
• Purpose is to derive inter-relationships among
• 𝒖, 𝒔, 𝒉, 𝒂, 𝒈 𝒗𝒔. 𝑷, 𝒗, 𝑻, 𝒙𝒊 ,
• (as well as 𝒄𝒗, 𝒄𝒑, , )

• Consider a single phase single component homogenous system, how many

independent intensive variables are needed?
• Two (in other words any of the two intensive variables can be independent and rest of all
can be expressed as a function of the two)
• For eg., u= u(T,P) or u(T,) or u(s,) or u(h,s), or u(g,h) etc.,
• Which of the above u would be most convenient to use?
• u(T,P) or u(T, )

• Four variables of interest

• 𝑷, 𝒗, 𝑻, 𝒂𝒏𝒅 𝒙𝒊 , (𝒔)

• Since variables are state functions and their differentials are exact,
𝝏𝒛 𝝏𝒛
• 𝒅𝒛 = 𝒅𝒙 + 𝒅𝒚
𝝏𝒙 𝒚 𝝏𝒚 𝒙
𝝏𝒖 𝝏𝒖
• For e.g, 𝒅𝒖 = 𝒅𝒔 + 𝒅𝒗
𝝏𝒔 𝒗 𝝏𝒗 𝒔

64
Relationship between u, h. q, cp and cv
• 𝒅𝒖 = 𝜹𝒒 − 𝑷𝒅𝒗

At constant pressure?
• 𝒅𝒖 + 𝑷𝒅𝒗 + 𝒗𝒅𝑷 − 𝒗𝒅𝑷 = 𝒅𝒖 + 𝒅 𝑷𝒗 = 𝒅(𝒖 + 𝑷𝒗) = 𝜹𝒒
• 𝒅𝒉 = 𝜹𝒒
𝜹𝒒 𝝏𝒉
• Therefore, 𝒄𝑷 = =
𝒅𝑻 𝑷 𝝏𝑻
𝑷

At constant volume,
• 𝒅𝒖 = 𝜹𝒒
𝜹𝒒 𝝏𝒖
• Therefore, 𝑐𝒗 = =
𝒅𝑻 𝒗 𝝏𝑻
𝒗
65
 Fundamental groupings – {u,s,}
𝝏𝒖 𝝏𝒖
• 𝒅𝒖 = 𝒅𝒔 + 𝒅𝒗
𝝏𝒔 𝒗 𝝏𝒗 𝒔
• From the combined first and second laws
• 𝒅𝒖 = 𝑻𝒅𝒔 − 𝑷𝒅𝒗
𝝏𝒖 𝝏𝒖
• Thus, 𝑻 = 𝒂𝒏𝒅 𝑷 = −
𝝏𝒔 𝒗 𝝏𝒗 𝒔

• Why is this group {u,s,} called fundamental grouping?

• Direct consequence of first and second law
• Relates to measurable quantities, T, P

66
Fundamental groupings – {s,u,}
• s = s(u,)
𝝏𝒔 𝝏𝒔
• 𝒅𝒔 = 𝒅𝒖 + 𝒅𝒗
𝝏𝒖 𝒗 𝝏𝒗 𝒖
𝟏 𝑷
• 𝒅𝒔 = 𝒅𝒖 + 𝒅𝒗
𝑻 𝑻

67
 Fundamental groupings – {h,s,p}, {a,T,}, {g,T,p}

• 𝒉 = 𝒖 + 𝑷𝒗
 𝒂 = 𝒖 − 𝑻𝒔  𝒈 = 𝒖 − 𝑻𝒔 + 𝑷𝒗
• 𝒅𝒉 = 𝒅𝒖 + 𝑷𝒅𝒗 + 𝒗𝒅𝑷  𝒅𝒂 = 𝒅𝒖 − 𝑻𝒅𝒔 − 𝒔𝒅𝑻  𝒅𝒈 = 𝒅𝒖 − 𝑻𝒅𝒔 − 𝒔𝒅𝑻 + 𝑷𝒅𝒗 + 𝒗𝒅𝑷
= 𝑻𝒅𝒔 − 𝑷𝒅𝒗 + 𝑷𝒅𝒗 + 𝒗𝒅𝑷 = 𝑻𝒅𝒔 − 𝑷𝒅𝒗 − 𝑻𝒅𝒔 − 𝒔𝒅𝑻 = 𝑻𝒅𝒔 − 𝑷𝒅𝒗 − 𝑻𝒅𝒔 − 𝒔𝒅𝑻 +𝑷𝒅𝒗 + 𝒗𝒅𝑷
= 𝑻𝒅𝒔 + 𝒗𝒅𝑷 𝒅𝒂 = −𝒔𝒅𝑻 − 𝑷𝒅𝒗 𝒅𝒈 = −𝒔𝒅𝑻 + 𝒗𝒅𝑷

• h=h(s,P)  a=a(T,)  g=g(T,P)

𝝏𝒉 𝝏𝒉 𝝏𝒂 𝝏𝒂 𝝏𝒈 𝝏𝒈
𝒅𝒉 = 𝒅𝒔 + 𝒅𝑷 𝒅𝒂 = 𝒅𝑻 + 𝒅𝝊 𝒅𝒈 = 𝒅𝑻 + 𝒅𝑷
𝝏𝒔 𝝏𝑷 𝝏𝑻 𝝊
𝝏𝝊 𝑻
𝝏𝑻 𝑃
𝝏𝑷 𝑻
𝑃 𝒔

𝝏𝒉 𝝏𝒉 𝝏𝒂 𝝏𝒂 𝝏𝒈 𝝏𝒈
= 𝑇; =𝒗 = −𝑠; = −𝑷 = −𝑠; =𝝊
𝝏𝒔 𝝏𝑷 𝝏𝑻 𝝊
𝝏𝝊 𝑻
𝝏𝑻 𝑃
𝝏𝑷 𝑻
𝑃 𝒔

68
 Fundamental and Maxwell relations
𝝏 𝝏𝒁 𝝏 𝝏𝒁
dU = TdS – PdV;
𝝏𝒚 𝝏𝒙 𝒚
= 𝝏𝒙 𝝏𝒚 𝒙
𝒙 𝒚

• dH?
• dG? • dA?
• Fundamental grouping of H?
• dU? • Fundamental grouping of G? • Fundamental grouping of A?
• Fundamental grouping of U?
• For dH, we want heat as a state function at
dU = TdS – PdV • For dG, we want non PdV work as a state • For dA, we want any work as a state
{U,S,V} constant P
function at constant T and P function at constant T
• Both variables (S,V) are extensive • from dU switch dV to dP :
• from dU switch dS to dT and dV to dP: • from dU switch dS to dT :
• One fundamental and other measurable • 𝒅𝑼 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 +
• 𝒅𝑼 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷 = 𝑻𝒅𝑺 −
variables 𝑷𝒅𝑽 + 𝑽𝒅𝑷
𝑷𝒅𝑽 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻 +𝑷𝒅𝑽 + 𝑽𝒅𝑷 • 𝐝𝐀 = −𝑺𝒅𝑻 − 𝑷𝒅𝑽
𝝏𝑼 𝝏𝑼 • 𝒅 𝑼 + 𝑷𝑽 = 𝒅𝑯 = 𝑻𝒅𝑺 + 𝑽𝒅𝑷
𝒅𝑼 = 𝒅𝑺 + 𝒅𝑽 • 𝐝 𝐔 − 𝐓𝐒 + 𝐏𝐕 = 𝐝𝐆 = −𝑺𝒅𝑻 + 𝑽𝒅𝑷 • Eliminated fundmanetal variable (S); both
𝝏𝑺 𝑽 𝝏𝑽 𝑺 • One fundamental (S) and other measurable
variable (P) • Both variables (T,P) are intensive and (T,V) are measurable
𝝏𝑼 𝝏𝑼 measurable • One intensive (T) and other extensive (V)
𝑻= ; −𝑷 = • One intensive (P) and other extensive (S)
𝝏𝑺 𝑽 𝝏𝑽 𝒔 • {G,T,P}: variables
variables
𝝏𝑻 𝝏𝑷 𝝏𝑮 𝝏𝑮 • {A,T,V}:
=− • {H,S,P}: • 𝒅𝑮 = 𝒅𝑻 + 𝒅𝑷
𝝏𝑽 𝒔 𝝏𝑺 𝝏𝑻 𝑷 𝝏𝑷 𝑻 𝝏𝑨 𝝏𝑨
𝑽 • 𝒅𝑯 =
𝝏𝑯
𝒅𝑻 +
𝝏𝑯
𝒅𝑷 𝝏𝑮 𝝏𝑮 • 𝒅𝑨 = 𝒅𝑻 + 𝒅𝑽
𝝏𝑻 𝑽 𝝏𝑽 𝑻
𝝏𝑺 𝑷 𝝏𝑷 𝑺 −𝑺 = ;𝑽 =
𝝏𝐻 𝝏𝐻 𝝏𝑻 𝑃 𝝏𝑷 𝝏𝐴 𝝏𝐴
T= ;𝑉 = 𝑻 −𝑺 = ; −𝑃 =
𝝏𝑆 𝝏𝑃 𝝏𝑺 𝝏𝑽 𝝏𝑻 𝑉
𝝏𝑉 𝑻
𝑃 𝑆 − = 𝝏𝑺 𝝏𝑷
𝝏𝑻 𝝏𝑽 𝝏𝑷 𝑻 𝝏𝑻 𝑃
= − =−
𝝏𝑃 𝝏𝑆 𝝏𝑉 𝑻 𝝏𝑻 𝑉
𝑆 𝑃
𝝏𝑺 𝝏𝑷
=
𝝏𝑉 𝑻 𝝏𝑻 𝑉

69
Z (U,H,A and G) vs. PVT
𝝏𝒁 𝝏𝒁 𝝏𝒁 𝝏𝒁 𝝏𝒁 𝝏𝒁
• Find: , , , , ,
𝝏𝑻 𝑷 𝝏𝑻 𝑽 𝝏𝑽 𝑻 𝝏𝑷 𝑻 𝝏𝑽 𝑷 𝝏𝑷 𝑽

𝝏𝒁 𝝏𝒁 𝝏𝒁 𝝏𝒁 𝝏𝒁 𝝏𝒁
• , , , , 𝒗𝒔. ,
𝝏𝑻 𝑷 𝝏𝑷 𝑻 𝝏𝑻 𝑽 𝝏𝑽 𝑻 𝝏𝑽 𝑷 𝝏𝑷 𝑽

• P,T or V,T as variables most useful not P,V

• No fundamental grouping relation has P and V as only
variables
• Easy to transform using chain rule, e.g.,
𝝏𝑼 𝝏𝑼 𝝏𝑻
• = ×
𝝏𝑷 𝑽 𝝏𝑻 𝑽 𝝏𝑷 𝑽

70
 𝝏𝑼 𝝏𝑼 𝝏𝑼 𝝏𝑼
, , ,
𝝏𝑻 𝑽
𝝏𝑻 𝑷
𝝏𝑽 𝑻
𝝏𝑷 𝑻
𝝏𝑼 𝝏𝑼
=? = 𝑪𝑽
𝝏𝑻 𝑽
𝝏𝑻 𝑽

𝝏𝑼
𝝏𝑼 𝝏𝑼 =?
=? =? 𝝏𝑃 𝑻
𝝏𝑻 𝑷 𝝏𝑉 𝑻
• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽
• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 • 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 𝒅𝑼 𝒅𝑺 𝒅𝑽
𝒅𝑼 𝒅𝑺 𝒅𝑽 • 𝒅𝑷 = 𝑻 𝒅𝑷 − 𝑷 𝒅𝑷
𝒅𝑼 𝒅𝑺 𝒅𝑽
• 𝒅𝑻 = 𝑻 𝒅𝑻 − 𝑷 𝒅𝑻 • 𝒅𝑽 = 𝑻 𝒅𝑽 − 𝑷 𝒅𝑽
• At constant T
• At constant T 𝝏𝑼 𝝏𝑺 𝝏𝑽
•
𝒅𝑼
=
𝒅𝑺
𝑻 𝒅𝑻 −
𝒅𝑽
𝑷 𝒅𝑻 at constant P 𝝏𝑼 𝝏𝑺 • =𝑻 −𝑷
𝒅𝑻 • =𝑻 −𝑷 𝝏𝑷 𝑻 𝝏𝑷 𝑻 𝝏𝑷 𝑻
𝝏𝑽 𝑻 𝝏𝑽 𝑻

𝝏𝑼 𝝏𝑺 𝝏𝑽 • Maxwell to rescue
• 𝝏𝑻
=𝑻 𝝏𝑻 𝑷
−𝑷 𝝏𝑻 𝑷 • Maxwell to rescue 𝝏𝑺 𝝏𝑽
𝝏𝑼
𝑷
𝑪𝑷 𝝏𝑽 𝝏𝑺 𝝏𝑷 • =−
• =𝑻 −𝑷 • = 𝝏𝑷 𝑻 𝝏𝑻 𝑷
𝝏𝑻 𝑻 𝝏𝑻 𝑷 𝝏𝑽 𝑻 𝝏𝑻 𝑽 𝝏𝑼 𝝏𝑽 𝝏𝑽
𝝏𝑼
𝑷
𝝏𝑽 𝝏𝑼 𝝏𝑷 • = −𝑻 𝝏𝑻 −𝑷
• = 𝑪𝑷 − 𝑷 • = 𝑻 𝝏𝑻 −𝑷 𝝏𝑷 𝑻 𝑷 𝝏𝑷 𝑻
𝝏𝑻 𝝏𝑻 𝑷 𝝏𝑽 𝑻 𝑽 𝝏𝑼
𝝏𝑼
𝑷
𝝏𝑼 𝑻𝜷 • = −𝑻𝑽𝜷 + 𝑷𝑽𝜿
• = 𝑪𝑷 − 𝑷𝑽𝜷 • = −𝑷 𝝏𝑷 𝑻
71
𝝏𝑻 𝝏𝑽 𝑻 𝜿
𝑷
 𝝏𝒁 𝝏𝒁 𝝏𝒁 𝝏𝒁
𝝏𝑻 𝝏𝑻 𝑷 𝝏𝑽 𝝏𝑷
𝑽 𝑻 𝑻

1. For U and A: (V,T) as independent

variables give simpler relations
2. For H and G: (P,T) as independent
variables give simpler relations
3. For S, will depend on details of the
process
4. These equations apply both for extensive
and intensive properties. Why?
1. Extensive – homogenous (degree
one)
5. For extensive variables, for e.g, H,
𝝏∆𝐻 𝝏𝐻2 𝝏𝐻1
• = −
𝝏𝑻 𝑃 𝝏𝑻 𝑃 𝝏𝑻 𝑃

72
Gibbs – Helmholtz equation
𝝏𝑮 𝝏𝑨
• = −𝑺 = −𝑺
𝝏𝑻 𝑷 𝝏𝑻 𝑽
𝝏𝑮 𝝏𝑷 𝝏𝑨 𝝏𝑽
• = −𝑺 + 𝑽 = −𝑺 − 𝑷
𝝏𝑻 𝑽 𝝏𝑽 𝑻 𝝏𝑻 𝑷 𝝏𝑷 𝑻
𝑮 =?
𝑮 = 𝑼 − 𝑻𝑺 + 𝑷𝑽
𝑮 = 𝑯 − 𝑻𝑺
𝑮 𝑯
= −𝑺
𝑻 𝑻 𝑨
𝝏 𝑻 𝑼
Show that = − 𝑻𝟐
𝝏𝑻 𝑽
Differentiate with T 𝑮
𝑮 𝑯 𝝏 𝑻 𝑯
𝝏(𝑻) 𝝏( 𝑻 ) 𝝏𝑺
• = − =−
𝝏𝑻 𝑷 𝝏𝑻 𝑷 𝝏𝑻 𝑷 𝝏𝑻 𝑷 𝑻𝟐
𝑯
𝝏( 𝑻 ) 𝟏 𝝏𝑯 𝟏 𝟏 𝑯
• =𝑻 − 𝑻𝟐 𝑯 = 𝑻 𝑪𝑷 − 𝑻𝟐 𝚫𝑮
𝝏𝑻 𝑷 𝝏𝑻 𝑷 𝝏
𝝏𝑺 𝑪𝑷 𝑻 𝚫𝑯
• = =−
𝝏𝑻 𝑷 𝑻 𝝏𝑻 𝑷 𝑻𝟐
73
Gibbs – Helmholtz equation
𝑮
𝝏 𝑻 𝑯
=− 𝟐
𝝏𝑻 𝑷 𝑻

𝚫𝑮
𝝏 𝚫𝑯
𝑻
=−
𝝏𝑻 𝑷 𝑻𝟐

Useful in thermochemical measurements of reactions: integrating between T1

and T2 at constant pressure (with respect to a standard reference state)

𝚫𝑮⊖ 𝑻𝟐 𝚫𝑮⊖ 𝑻𝟏 ⊖ 𝟏 𝟏
• − =𝚫𝑯 −
𝑻𝟐 𝑻𝟏 𝑻𝟐 𝑻𝟏

74
 Applications

Calculate 𝚫𝑼, 𝚫𝑺, 𝚫𝑯, 𝒂𝒏𝒅 𝚫𝑮 𝒇𝒐𝒓 𝒕𝒉𝒆 𝒊𝒔𝒐𝒕𝒉𝒆𝒓𝒎𝒂𝒍 𝒆𝒙𝒑𝒂𝒏𝒔𝒊𝒐𝒏 𝒐𝒇 𝒐𝒏𝒆
𝒎𝒐𝒍𝒆 𝒐𝒇 𝒊𝒅𝒆𝒂𝒍 𝒈𝒂𝒔 𝒂𝒕 𝑻 = 𝟑𝟎𝟎 𝑲, 𝒇𝒓𝒐𝒎 𝑷𝟏 = 𝟎. 𝟏 𝑴𝑷𝒂 𝒕𝒐 𝑷𝟐 = 𝟎. 𝟐 𝑴𝑷𝒂

∆𝑼

Maxwell relation

75
76
• 𝐺𝑖𝑣𝑒𝑛 𝑇, 𝑣 𝑎𝑛𝑑 𝑞, 𝑢𝑠𝑖𝑛𝑔 𝑣𝑑𝑊 − 𝐸𝑂𝑆, 𝑓𝑖𝑛𝑑 𝑤
• 1st law: Δu = q + w
• Find Δ𝑢?
𝜕𝑢 𝜕𝑢 𝜕𝑃
• 𝑑𝑢 = 𝑑𝑇 + 𝑑𝑣 = 𝑐𝑣 𝑑𝑇 + 𝑇 − 𝑃 𝑑𝑣
𝜕𝑇 𝑣 𝜕𝑣 𝑇 𝜕𝑇 𝑣
𝜕𝑃
• At constant T, Δ𝑢 = 𝑇 − 𝑃 𝑑𝑣
𝜕𝑇 𝑣
𝜕𝑃
• From vdW-EOS: 𝑎𝑛𝑑 𝑃
𝜕𝑇 𝑣
𝑅𝑇 𝑎 𝜕𝑃 𝑅
• 𝑃 = 𝑣−𝑏 − 𝑣 2 ; = 𝑣−𝑏
𝜕𝑇 𝑣

𝜕𝑃 0.04𝑚3 𝑎 J
• Δ𝑢 = 𝑇 − 𝑃 𝑑𝑣 = 0.001𝑚3 𝑣 2
𝑑𝑣 = 936 mol
𝜕𝑇 𝑣
𝑗
• 𝑤 = 936 − 10400 = −9464 𝑚𝑜𝑙

77
Koretsky
Phase Equilibrium

• mechanical and thermal

driving force, P and T
differences
• For chemical or reaction
equilibria?
• Can it be mole fraction or
concentration drive the phase
equilibrium?
• Why not?
78
 Criteria for equilibrium
Mechanical equilibrium: PA = PB
No tendency for bulk movement of material

Thermal equilibrium:. TA = TB
No tendency for transport of thermal energy

Material equilibrium: Chemical potential µA = µB

no tendency for material to change form (eg., phase transformation or a chemical reaction)

79
 Fundamental criterion for equilibrium
• 𝒅𝒔𝒖𝒏𝒊𝒗 = 𝒅𝒔 + 𝒅𝒔𝑺𝒖𝒓𝒓 ≥ 𝟎
• Reversible process, dsuniv=0
• Spontaneous process, dsuniv >0
−𝜹𝒒
• 𝒅𝒔 + ≥𝟎
𝑻
• 𝑻𝒅𝒔 ≥ 𝜹𝒒 (and −𝑷𝒅𝒗 ≤ 𝜹𝒘, −𝑷𝒅𝒗 ≤ −𝑷𝒆𝒙𝒕 𝒅𝒗)
• 𝑻𝒅𝒔 − 𝜹𝒒 ≥ 𝟎
• Find maximum of 𝑻𝒅𝒔 − 𝜹𝒒
• Adiabatic irrev. process: 𝑻𝒅𝒔 > 𝟎
• We need to know entropy change of surroundings dssurr or the heat
interaction

80
Criteria for equilibrium under specific conditions
• For any closed system,
• 𝜹𝒒 = 𝒅𝒖 − 𝜹𝒘 or 𝑻𝒅𝒔 = 𝒅𝒖 + 𝑷𝒅𝒗
• From 𝒅𝒔𝒖𝒏𝒊𝒗 = 𝒅𝒔 + 𝒅𝒔𝑺𝒖𝒓𝒓 ≥ 𝟎
• 𝒇𝒐𝒓 𝒐𝒏𝒍𝒚 𝒃𝒐𝒖𝒏𝒅𝒂𝒓𝒚 𝒘𝒐𝒓𝒌 𝜹𝒘 = −𝑷𝒆𝒙𝒕 𝒅𝒗
• −𝑷𝒅𝒗 ≤ 𝜹𝒘, 𝒊. 𝒆., −𝑷𝒅𝒗 ≤ −𝑷𝒆𝒙𝒕 𝒅𝒗
• 𝑻𝒅𝒔 ≥ 𝜹𝒒
• Restricting to only boundary work
• 𝜹𝒒 = 𝒅𝒖 + 𝑷𝒆𝒙𝒕 𝒅𝒗
• Substituting 𝜹𝒒 = 𝒅𝒖 + 𝑷𝒆𝒙𝒕 𝒅𝒗 𝒊𝒏 𝑻𝒅𝒔 ≥ 𝜹𝒒
• 𝑻𝒅𝒔 ≥ 𝜹𝒒
• 𝑻𝒅𝒔 ≥ 𝒅𝒖 + 𝑷𝒆𝒙𝒕 𝒅𝒗
𝒓𝒆𝒂𝒓𝒓𝒂𝒏𝒈𝒊𝒏𝒈
• 𝒅𝒖 − 𝑻𝒅𝒔 ≤ −𝑷𝒆𝒙𝒕 𝒅𝒗 or 𝒅𝑼 − 𝑻𝒅𝑺 ≤ −𝑷𝒆𝒙𝒕 𝒅𝑽
At constant, s,v
• 𝒅𝒖 ≤ 𝟎 or 𝒅𝑼 ≤ 𝟎 81
• Find criteria for constant S, P
• 𝒅𝑼 − 𝑻𝒅𝑺 ≤ −𝑷𝒆𝒙𝒕 𝒅𝑽
• 𝑯 = 𝑼 + 𝑷𝑽
• 𝒅𝑯 = 𝒅𝑼 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷
• (𝒅𝑯 − 𝑷𝒅𝑽 − 𝑽𝒅𝑷) = 𝒅𝑼
• (𝒅𝑯 − 𝑽𝒅𝑷 − 𝑷𝒅𝑽) − 𝑻𝒅𝑺 ≤ −𝑷𝒆𝒙𝒕 𝒅𝑽
• 𝒅𝑯 − 𝑽𝒅𝑷 − 𝑻𝒅𝑺 ≤ 𝑷𝒅𝑽 − 𝑷𝒆𝒙𝒕 𝒅𝑽

At constant S and P, P=Pext

• 𝒅𝑯 ≤ 𝟎

82
• Find criteria for constant T, V and no boundary work
• 𝒅𝑼 − 𝑻𝒅𝑺 ≤ −𝑷𝒆𝒙𝒕 𝒅𝑽
• 𝑨 = 𝑼 − 𝑻𝑺
• 𝒅𝑨 = 𝒅𝑼 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻
• (𝒅𝑨 + 𝑻𝒅𝑺 + 𝑺𝒅𝑻) = 𝒅𝑼

• (𝒅𝑨 + 𝑻𝒅𝑺 + 𝑺𝒅𝑻) − 𝑻𝒅𝑺 ≤ −𝑷𝒆𝒙𝒕 𝒅𝑽

• 𝒅𝑨 + 𝑺𝒅𝑻 + 𝑷𝒆𝒙𝒕 𝒅𝑽 ≤ 𝟎
At constant T and V,
• 𝒅𝑨 ≤ 𝟎
• For any kind of work, 𝛿𝑤, (no boundary work)
• 𝒅𝑼 − 𝑻𝒅𝑺 ≤ 𝜹𝒘
• (𝒅𝑨 + 𝑻𝒅𝑺 + 𝑺𝒅𝑻) − 𝑻𝒅𝑺 ≤ 𝜹𝒘
At constant T and V,
• 𝒅𝑨 ≤ 𝜹𝒘
83
• Find criteria for constant T, P and only boundary work
• 𝒅𝑼 − 𝑻𝒅𝑺 ≤ −𝑷𝒆𝒙𝒕 𝒅𝑽
• 𝑮 = 𝑼 − 𝑻𝑺 + 𝑷𝑽
• 𝒅𝑮 = 𝒅𝑼 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷
• (𝒅𝑮 + 𝑻𝒅𝑺 + 𝑺𝒅𝑻 − 𝑷𝒅𝑽 − 𝑽𝒅𝑷) = 𝒅𝑼

• (𝒅𝑮 + 𝑻𝒅𝑺 + 𝑺𝒅𝑻 − 𝑽𝒅𝑷 − 𝑷𝒅𝑽) − 𝑻𝒅𝑺 ≤ −𝑷𝒆𝒙𝒕 𝒅𝑽

• 𝒅𝑮 + 𝑺𝒅𝑻 − 𝑽𝒅𝑷 + 𝑷𝒅𝑽 ≤ −𝑷𝒆𝒙𝒕 𝒅𝑽
• 𝒅𝑮 + 𝑺𝒅𝑻 − 𝑽𝒅𝑷 ≤ 𝑷𝒅𝑽 − 𝑷𝒆𝒙𝒕 𝒅𝑽
At constant T and P,
• 𝒅𝑮 ≤ 𝟎

If a non-PV work is also involved?

• 𝒅𝑮 ≤ 𝜹𝒘′

84
Phase equilibria of pure species

• How liquid water and vapor

equilibrates?
Find criteria for constant T, P
• Pure species in how many
phases at equilibrium?
• Which combination has Suniv
maximum
• 𝒅𝑮 ≤ 𝟎
• If a non-PV work is involved?
• 𝒅𝑮 ≤ 𝜹𝒘′ 85
Phase equilibria of pure species
• Total Gibbs free energy for pure species in two phases (,)
𝜷 𝜷
• 𝑮𝒊 = 𝒏𝜶𝒊 𝒈𝜶𝒊 + 𝒏𝒊 𝒈𝒊 ,
𝜷
• where 𝒏𝜶𝒊 𝒂𝒏𝒅 𝒏𝒊 are number of moles of i in  and  phases
𝜷 𝜷 𝜷 𝜷
• 𝒅𝑮𝒊 = 𝒏𝜶𝒊 𝒅𝒈𝜶𝒊 + 𝒈𝜶𝒊 𝒅𝒏𝜶𝒊 + 𝒏𝒊 𝒅𝒈𝒊 + 𝒈𝒊 𝒅𝒏𝒊 ≤ 𝟎
𝜷 𝜷
• 𝒅𝑮𝒊 = 𝒈𝜶𝒊 𝒅𝒏𝜶𝒊 + 𝒈𝒊 𝒅𝒏𝒊 ≤ 𝟎, for a given T and P, g is constant
𝜷
• Since it is a closed system, 𝒅𝒏𝜶𝒊 = −𝒅𝒏𝒊
𝜷
• (𝒈𝜶𝒊 −𝒈𝒊 )𝒅𝒏𝜶𝒊 ≤ 𝟎
• Consider water -steam at (90 C , 1 atm) and (110 C, 1 atm)
• Condition for phase equilibrium
𝜷
• 𝒈𝜶𝒊 = 𝒈𝒊 ; molar Gibbs free energy should be equal
• not the concentration
• water-steam at T=100 C and 1 atm

86
Roles of energy and entropy in phase equilibria

• Since Suniv >0, why not all solid atoms

sublimate?
• To view phase equilibria from
energetic vs. entropic effects
• ∆𝑮 = ∆𝑯 − 𝑻∆𝑺 ≤ 𝟎 ?
• Solid  gas
• What happens to H and S
• As bonds are broken, H and S
• If ∆𝑯 < 𝑻∆𝑺; spontaneous process
• If ∆𝑯 > 𝑻∆𝑺; non-spontaneous process
• If ∆𝑯 = 𝑻∆𝑺; Phase equilibrium
• Our life depends on precise balance
between these two terms
• Protein folding and denaturation
87
 Clapeyron equation
• If a pure species is in equilibrium in two of its phases,
• T and P are not independent variables?
• Why it is true physically?
• Since at phase equilibrium, P and T are same for both phases, when T
, P has to 

• Psat(T)
𝜷
• 𝒈𝜶𝒊 = 𝒈𝒊

88
Clapeyron equation – Psat(T)
𝑷𝜶 = 𝑷𝜷
𝜷
𝑻𝜶 = 𝑻𝜷 • 𝒇𝒐𝒓 𝒑𝒐𝒊𝒏𝒕 𝟏: 𝒈𝜶𝒊 = 𝒈𝒊
𝜷
𝒈𝜶𝒊 = 𝒈𝒊 𝜷
• 𝒇𝒐𝒓 𝒑𝒐𝒊𝒏𝒕 𝟐: dP, dT and 𝒅𝒈𝜶𝒊 , 𝒅𝒈𝒊
𝜷 𝜷
• 𝒈𝜶𝒊 + 𝒅𝒈𝜶𝒊 = 𝒈𝒊 + 𝒅𝒈𝒊
𝜷
• 𝒅𝒈𝜶𝒊 = 𝒅𝒈𝒊
𝜷 𝜷
• −𝒔𝜶𝒊 𝒅𝑻 + 𝒗𝜶𝒊 𝒅𝑷 = −𝒔𝒊 𝒅𝑻 + 𝒗𝒊 𝒅𝑷

𝜷
𝒅𝑷 𝒔𝜶
𝒊 −𝒔𝒊
• = 𝜷
𝒅𝑻 𝒗𝜶
𝒊 −𝒗𝒊

𝜷 𝜷
• 𝒉𝜶𝒊 − 𝑻𝒔𝜶𝒊 = 𝒉𝒊 − 𝑻𝒔𝒊
𝜷
𝒅𝑷𝒔𝒂𝒕 𝒉𝜶
𝒊 −𝒉𝒊
• = 𝜷
𝒅𝑻 𝑻 (𝒗𝜶
𝒊 −𝒗𝒊 )
89
Vapor-liquid equilibrium: Clausius–Clapeyron equation
𝒅𝑷𝒔𝒂𝒕 𝒉𝒗𝒊 −𝒉𝒍𝒊
• =
𝒅𝑻 𝑻 (𝒗𝒗𝒊 −𝒗𝒍𝒊 )

• How to transform so that we get only P vs. T?

• Assumption 1: molar volume of liquid negligible,
• 𝒗𝒍𝒊 ≪ 𝒗𝒗𝒊  𝒗𝒍𝒊 = 𝟎
𝒅𝑷𝒔𝒂𝒕 ∆𝒉𝒗𝒂𝒑,𝒊
• =
𝒅𝑻 𝑻 𝒗𝒗𝒊
𝑹𝑻
• Assumption 2: Ideal gas, 𝒗𝒗𝒊 =
𝑷𝒔𝒂𝒕

𝒅𝑷𝒔𝒂𝒕 ∆𝒉𝒗𝒂𝒑,𝒊 𝑷𝒔𝒂𝒕 ∆𝒉𝒗𝒂𝒑,𝒊

• = =
𝒅𝑻 𝑻 𝒗𝒗𝒊 𝑹𝑻𝟐
𝒅𝑷𝒔𝒂𝒕 ∆𝒉𝒗𝒂𝒑,𝒊 𝒅𝑷𝒔𝒂𝒕 ∆𝒉𝒗𝒂𝒑,𝒊
• = 𝒅𝑻; = 𝒅𝑻
𝑷𝒔𝒂𝒕 𝑹𝑻𝟐 𝑷𝒔𝒂𝒕 𝑹𝑻𝟐 90
Vapor-liquid equilibrium: Clausius–Clapeyron equation

𝒅𝑷𝒔𝒂𝒕 ∆𝒉𝒗𝒂𝒑,𝒊
• = 𝒅𝑻
𝑷𝒔𝒂𝒕 𝑹𝑻𝟐

• Assumption 3: hvap,i is independent of T

𝒅𝑷𝒔𝒂𝒕 𝒅𝑻
• = ∆𝒉𝒗𝒂𝒑,𝒊
𝑷𝒔𝒂𝒕 𝑹𝑻𝟐

𝒔𝒂𝒕 1
• ln 𝑷 = −∆𝒉𝒗𝒂𝒑,𝒊 +𝑪
𝑹𝑻
Or
𝑷𝒔𝒂𝒕 ∆𝒉𝒗𝒂𝒑,𝒊 1 1
• ln 𝟐𝒔𝒂𝒕 =− −
𝑷𝟏 𝑹 𝑻𝟐 𝑻𝟏 91
 Vapor-liquid equilibrium: Clausius–Clapeyron equation
𝒔𝒂𝒕 1
• ln 𝑷 = −∆𝒉𝒗𝒂𝒑,𝒊 +𝑪
𝑹𝑻

• Assumptions cancel total error, 𝒅𝑷𝒔𝒂𝒕

𝒅𝑻
=
𝒉𝒗𝒊 −𝒉𝒍𝒊
𝑻 (𝒗𝒗𝒊 −𝒗𝒍𝒊 )
• Let us assume T
• Assumption 3: hvap ↓ (bonds in liquid become weaker)
• Assumption 1: molar volume of liquid negligible,
• Real 𝒗𝒍𝒊 
𝑅𝑇
• Assumption 2: Ideal gas, 𝑣𝑖𝑣 = 𝑃𝑠𝑎𝑡
• Real gas Psat < ideal gas Psat; real 𝒗𝒗𝒊 ↓
• Assumption 1 and 2 leads to denominator ↓
https://en.wikipedia.org/wiki/Enthalpy_of_vaporization

• Most accurate and commonly reported

functional form is Antoine equation
B
• ln 𝑷𝒔𝒂𝒕 = 𝑨 −
𝑪+𝑻
92
dG=-SdT+VdP
dG  0
• Refining of crude oil?
• Waste water treatment?
• Environmental remediation?

• Why not use the criteria for equating g from pure species
to mixtures,
• Pure species phase equilibrium
𝜷
• 𝒈𝜶𝒊 = 𝒈𝒊

93
94
 Thermodynamics of mixtures

• Any state function of a pure substance depends on molecular PE

and KE (any two state variable can fix this, e.g., P and T)
• Only i-i interactions are present
• Mixtures: i-i, j-j, and i-j interactions are important
• Depends on the nature of components and their quantity

Need to develop formal thermodynamic equations for mixtures 95

Partial molar properties
• For mixtures, we want to establish how state
properties vary as a function of number of moles
of each species along with T, P

96
Partial molar properties

• Defined always at constant T, P and nj≠i

• Partial molar property defined with number of

moles NOT mole fraction
97
Partial molar properties

• Partial molar property

98
Partial molar properties

Partial molar properties: contribution of given species to

the properties of a mixture, at a constant T,P and nj≠i

99
• Determine C by
• physical argument or
• Euler’s theorem on homogenous functions

• Extensive property K depends on total number of

moles
• K=nTk
• As nT  0, K=0  as ni  0, K=0  C=0

100
• Extensive total solution property, K is sum of partial molar property
adjusted by its moles
• Intensive property, k, is weighted average of partial molar property

101
𝑲𝒊 − 𝒌𝒊
102
Gibbs-Duhem equation
• Most useful equation relating partial molar
properties of different species

103
Gibbs-Duhem equation

104
Summary of nomenclature

105
Summary of nomenclature

106
Property changes of mixing
• Δ𝐾𝑚𝑖𝑥 = 𝐾 − ∑𝑛𝑖 𝑘𝑖
• e.g., Δ𝑉𝑚𝑖𝑥 = 𝑉 − ∑𝑛𝑖 𝑣𝑖 , Δ𝐻𝑚𝑖𝑥 = 𝐻 − ∑𝑛𝑖 ℎ𝑖
• Δ𝐾𝑚𝑖𝑥 = ∑𝑛𝑖 𝐾𝑖 − ∑𝑛𝑖 𝑘𝑖 = ∑𝑛𝑖 (𝐾𝑖 − 𝑘𝑖 )
• Δ𝑉𝑚𝑖𝑥 = ∑𝑛𝑖 (𝑉𝑖 − 𝑣𝑖 ), Δ𝐻𝑚𝑖𝑥 = ∑𝑛𝑖 (𝐻𝑖 − ℎ𝑖 )

• Δ𝑘𝑚𝑖𝑥 = 𝑘 − ∑𝑥𝑖 𝑘𝑖
• Δ𝑣𝑚𝑖𝑥 = 𝑣 − ∑𝑥𝑖 𝑣𝑖 , Δℎ𝑚𝑖𝑥 = ℎ − ∑𝑥𝑖 ℎ𝑖
Enthalpy of mixing
• At constant T, P Δℎ𝑚𝑖𝑥 > 0, < 0, = 0?
• What is enthalpy?
• Adding sulfuric acid heats up the solution?
• Why water cools when a salt is dissolved?
• Why add salt to thaw ice?

Milo Koretsky
Enthalpy of solution
• Enthalpy change per mole of solute, Δℎ𝑠
Entropy of mixing
• Mixing ideal gases at constant T, P?
• Example 6.11
• Let gases ‘a’ and ‘b’ mix with each other
• Δ𝑆𝑚𝑖𝑥 = Δ𝑆𝑎𝐼 + Δ𝑆𝑏𝐼 + Δ𝑆 𝐼𝐼
P, T 𝒑𝑶𝟐 , 𝑻
P, T
Isothermal Isothermal mixing
expansion

𝚫𝑺𝑰𝑶𝟐
𝚫𝑺𝑰𝑰 = 𝟎
𝒑𝑵𝟐 , 𝑻
P, T
𝚫𝑺𝑰𝑵𝟐

Isothermal
expansion
• Step 1: Constant T and volume expansion
𝑝𝑎 𝑝𝑏
𝐼
• Δ𝑆 = Δ𝑆𝑎𝐼 + Δ𝑆𝑏𝐼 = 𝑛𝑎 −𝑅𝑙𝑛 + 𝑛𝑏 −𝑅𝑙𝑛
𝑃 𝑃

• Step 2: Constant T & P

• Δ𝑆 𝐼𝐼 = 0
𝑝𝑎 𝑝𝑏
• Δ𝑆 = −𝑅 𝑛𝑎 𝑙𝑛 + 𝑛𝑏 𝑙𝑛
𝑃 𝑃

𝑝𝑎 𝑝𝑏 𝑝𝑖
• Δ𝑠 = −𝑅 𝑦𝑎 𝑙𝑛 + 𝑦𝑏 𝑙𝑛 = −R ∑𝑚
𝑖=1 𝑦𝑖 ln = Δ𝑠𝑚𝑖𝑥
𝑃 𝑃 𝑃
Regular solution vs. Ideal solution
• Ideal solution: Enthalpy of mixing = 0 and entropy of
mixing = −R ∑𝑚 𝑖=1 𝑥𝑖 ln 𝑥𝑖
• Regular solution: Ideal gas mixing is assumed for
liquid mixture (fully random mixing) but enthalpy of
mixing non-zero (but non-specific interactions)
• Which liquid mixtures can be approximated as regular
mixture?
• Liquids with vdW interactions and simple fluids
Multicomponent multi-phase system
• Include composition changes across phases
in fundamental energy equation?
• 𝒅𝑼 = 𝜹𝒒 + 𝜹𝒘
• 𝒅𝑼 = 𝑻𝒅𝑺 + 𝜹𝒘
• 𝛅𝐰 = 𝒅𝒓𝒊𝒗𝒊𝒏𝒈 𝒇𝒐𝒓𝒄𝒆 × 𝒓𝒆𝒔𝒖𝒍𝒕𝒊𝒏𝒈 𝒂𝒄𝒕𝒊𝒐𝒏
• e.g., -PdV, 𝒄𝒉𝒆𝒎𝒊𝒄𝒂𝒍 𝒅𝒓𝒊𝒗𝒊𝒏𝒈 𝒇𝒐𝒓𝒄𝒆 × 𝒅𝒏𝒊

• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 + ∑𝒊 𝒄𝒉𝒆𝒎𝒊𝒄𝒂𝒍 𝒅𝒓𝒊𝒗𝒊𝒏𝒈 𝒇𝒐𝒓𝒄𝒆 × 𝒅𝒏𝒊

• Chemical driving force each component

114
Other examples of work and generalized energy equation

• Surface forces?
• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 + 𝜸𝒅𝑨
• Rubber band?
• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 + 𝒇𝒅𝑳
• Electrical forces?
• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 + 𝚿𝒅𝑸
• Magnetic forces?
• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 + 𝑩𝒅𝑰
• Generalized equation:
• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 + 𝒇𝒅𝑳 + 𝜸𝒅𝑨 + 𝚿𝒅𝑸 + 𝑩𝒅𝑰 + ∑𝒊 ℱ𝒊 𝒅𝑿𝒊
115
 Chemical processes T,P as a controlled variable

• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 + ∑𝒊 𝒄𝒉𝒆𝒎𝒊𝒄𝒂𝒍 𝒅𝒓𝒊𝒗𝒊𝒏𝒈 𝒇𝒐𝒓𝒄𝒆 × 𝒅𝒏𝒊

• 𝑮 = 𝑼 − 𝑻𝑺 + 𝑷𝑽
• 𝒅𝑮 = 𝒅𝑼 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷

• 𝒅𝑮 = −𝑺𝒅𝑻 + 𝑽𝒅𝑷 + ∑𝒊 𝒄𝒉𝒆𝒎𝒊𝒄𝒂𝒍 𝒅𝒓𝒊𝒗𝒊𝒏𝒈 𝒇𝒐𝒓𝒄𝒆 × 𝒅𝒏𝒊

Let us call the driving force for chemical components to escape
as chemical potential, 𝛍𝒊
• 𝒅𝑮 = −𝑺𝒅𝑻 + 𝑽𝒅𝑷 + ∑𝒊 𝛍𝒊 𝒅𝒏𝒊
• Extended form of Gibbs equation
116
 Chemical processes T,P as a controlled variable

• 𝒅𝑮 = −𝑺𝒅𝑻 + 𝑽𝒅𝑷 + ∑𝒊 𝛍𝒊 𝒅𝒏𝒊

• Include composition in dG
• 𝑮 = 𝒇(𝑻, 𝑷, 𝒏𝟏 , 𝒏𝟐 , … )

𝝏𝑮 𝝏𝑮 𝝏𝑮
• 𝒅𝑮 = 𝒅𝑻 + 𝒅𝑷 + ∑𝒊 𝒅𝒏𝒊
𝝏𝑻 𝑷,𝒏𝑖 𝝏𝑷 𝑻,𝒏𝑖 𝝏𝒏𝒊 𝑻,𝑷,𝒏
𝒋≠𝒊

𝝏𝑮 𝝏𝑮 𝝏𝑮
• −𝑺 = ;𝑽 = ; 𝛍𝒊 = = 𝐺𝑖
𝝏𝑻 𝑷,𝒏𝑖 𝝏𝑷 𝑻,𝒏𝑖 𝝏𝒏𝒊 𝑻,𝑷,𝒏
𝒋≠𝒊

Applying Maxwell relations?

𝝏(𝑮𝒊 /𝑻) 𝟏 𝝏 𝑮𝒊 𝑮 𝒊 𝑻 𝑺𝒊 − 𝑮 𝒊 𝑯𝒊
𝝏 𝑮𝒊 𝝏 𝑮𝒊 = − = = −
−𝑺𝒊 = 𝑽𝒊 = 𝝏𝑻 𝑻 𝝏𝑻 𝑻𝟐 𝑻𝟐 𝑻𝟐
𝝏𝑻 𝑷,𝒏𝑖
𝝏𝑃 𝑇,𝒏𝑖
𝑷,𝒏𝑖 𝑷,𝒏𝑖
117
• 𝒅𝑮 = −𝑺𝒅𝑻 + 𝑽𝒅𝑷 + ∑𝒊 𝛍𝒊 𝒅𝒏𝒊
• At constant T, P
• 𝒅𝑮 = ∑𝒊 𝛍𝒊 𝒅𝒏𝒊

• 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 + ∑𝒊 𝛍𝒊 𝒅𝒏𝒊

• U=f(S,V,n1,n2…); H=f(S,P,n1,n2…); A=f(T,V,n1,n2…)
𝝏𝑼 𝝏𝑼 𝝏𝑼
• 𝒅𝑼 = 𝒅𝑺 + 𝒅𝑽 + ∑𝒊 𝒅𝒏𝒊
𝝏𝑺 𝑽,𝒏 𝝏𝑽 𝑺,𝒏 𝝏𝒏𝒊 𝑺,𝑽,𝒏
𝒋≠𝒊

𝝏𝑯 𝝏𝑯 𝝏𝑯
• 𝒅𝑯 = 𝒅𝑺 + 𝒅𝑷 + ∑𝒊 𝒅𝒏𝒊
𝝏𝑺 𝑷,𝒏 𝝏𝑷 𝑺,𝒏 𝝏𝒏𝒊 𝑺,𝑷,𝒏
𝒋≠𝒊

𝝏𝑨 𝝏𝑨 𝝏𝑨
• 𝒅𝑨 = 𝒅𝑻 + 𝒅𝑽 + ∑𝒊 𝒅𝒏𝒊
𝝏𝑻 𝑽,𝒏 𝝏𝑽 𝑻,𝒏 𝝏𝒏𝒊 𝑻,𝑽,𝒏
𝒋≠𝒊

𝝏𝑮 𝝏𝑼 𝝏𝑯 𝝏𝑨
• 𝛍𝒊 = = = =
𝝏𝒏𝒊 𝑻,𝑷,𝒏 𝝏𝒏𝒊 𝑺,𝑽,𝒏 𝝏𝒏𝒊 𝑺,𝑷,𝒏 𝝏𝒏𝒊 𝑻,𝑽,𝒏
𝒋≠𝒊 𝒋≠𝒊 𝒋≠𝒊 𝒋≠𝒊

118
Relationship among partial molar quantities
𝑯 = 𝑼 + 𝑷𝑽

𝝏𝑯 𝝏𝑼 𝝏𝑽 𝝏𝑷
= +𝑷 +𝐕
𝝏𝒏𝒊 𝑻,𝑷,𝒏𝒋≠𝒊
𝝏𝒏𝒊 𝑻,𝑷,𝒏𝒋≠𝒊
𝝏𝒏𝒊 𝑻,𝑷,𝒏𝒋≠𝒊
𝝏𝒏𝒊 𝑻,𝑷,𝒏𝒋≠𝒊

𝑨𝒕 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝑻, 𝑷, 𝒏𝒋≠𝒊

𝝏𝑯 𝝏𝑼 𝝏𝑽
= +𝑷
𝝏𝒏𝒊 𝑻,𝑷,𝒏𝒋≠𝒊
𝝏𝒏𝒊 𝑻,𝑷,𝒏𝒋≠𝒊
𝝏𝒏𝒊 𝑻,𝑷,𝒏𝒋≠𝒊

𝑯 𝒊 = 𝑼 𝒊 + 𝑷 𝑽𝒊
𝑨 𝒊 = 𝑼 𝒊 − 𝑻𝑺 𝒊

𝑮𝒊 = 𝑯𝒊 − 𝑻𝑺𝒊 119
 Multi-component phase equilibria
• phase equilibria
• 𝒅𝑮 = 𝟎 = 𝒅𝑮𝜶 + 𝒅𝑮𝜷
𝝏𝑮
• 𝒅𝑮𝜶 = −𝑺𝜶 𝒅𝑻 + 𝑽𝜶 𝒅𝑷 + ∑𝒊 𝛍𝜶𝒊 𝒅𝒏𝜶𝒊 , where, 𝛍𝒊 =
𝝏𝒏𝜶
𝒊 𝑻,𝑷,𝒏𝜶
𝒋≠𝒊

𝜷 𝜷 𝝏𝑮
• 𝒅𝑮 = −𝑺 𝒅𝑻 + 𝑽 𝒅𝑷 + ∑𝒊 𝛍𝒊 𝒅𝒏𝒊 , where, 𝛍𝒊 =
𝜷 𝜷 𝜷
𝜷
𝝏𝒏𝒊 𝜷
𝑻,𝑷,𝒏𝒋≠𝒊
• at constant T, P
𝜷 𝜷
• 𝒅𝑮 = 𝒅𝑮𝜶 + 𝒅𝑮𝜷 = ∑𝒊 𝛍𝜶𝒊 𝒅𝒏𝜶𝒊 + ∑𝒊 𝛍𝒊 𝒅𝒏𝒊 = 𝟎
𝜷
• 𝒅𝒏𝜶𝒊 = −𝒅𝒏𝒊
𝜷
• ∑𝒊(𝛍𝜶𝒊 −𝛍𝒊 )𝒅𝒏𝜶𝒊 = 𝟎
𝜷
• 𝛍𝜶𝒊 = 𝛍𝒊 , for each species across all phases
120
 Multi-component phase equilibria
• phase equilibria at constant T, P
𝜷
𝜶
• 𝛍𝒊 = 𝛍𝒊 , for each species across all
phases

121