CLL121 : Chemical Engineering

Thermodynamics
Lecture 1
Gaurav Goel
• Objectives:
– Relevance to chemical engineers
– Definitions of thermodynamic properties/terms
– Zeroth and first law of thermodynamics

• Learning guides:
– Ch 1 & 2 of Smith, Van Ness (6th Ed)
– Review physical chemistry notes
 Origin of Thermodynamics
• Developed by engineers to describe conversion of
chemical energy stored in fossil fuel into heat and
useful work

– how much energy in coal, steam, etc. (first law)

– How efficiently can energy be converted from one
form to another (entropy)
– Feasibility (second law)
Why ChE need thermo?

Thermodynamics
Reactor

Chem. Engg.
Operation Plant
 Why ChE need thermo?
• We transform natural raw materials into
useful products
Distillation products
such as,, Gasoline,
s ical n
atio Diesel etc.
Phy sform
Crude oil Refinery Tran
Ch
Tra emic
ns al
for
ma
tio Petrochemicals, e.g.
n Nylon
 Why ChE need thermo?
• Address questions pertaining to feasibility and
efficiency of transformations

• Estimation of material properties required for

design

• Phase and reaction equilibria

 Thermodynamics at nanoscale: Structure
(phase)-Property-Function
Static Assembly Dynamic Assembly
Folding

By TimVickers on Wikipedia
• Folding shields hydrophobic
groups from water
– Folded 3D structure of
enzymes catalyzes the
reaction
• Self-assembled ant raft is
more hydrophobic
– Entrapped air pocket
allows the raft to float
Mlot N J et al. PNAS 2011;108:7669-7673
 Thermodynamics at nanoscale: Structure
(phase)-Property-Function
ARTICLE
Nanoemulsion system based on US FDA approved components
NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-019-10749-1

a Nanoemulsion via low b c

energy method 10 °C 50 °C
RT

Oil

Adding Pluronic
solution Heating

PEO-PPO-PEO
~ 50 nm

Dl water

Pluronic
PEG 400 CH3
H O O OH
O Pluronic attached
a b a
Surfactant micelle Mixed micelle to oil droplet

Fig. 1 Schematic diagram of the nanoemulsion system and hypothesized gelation mechanism. a Formation of the oil-in-water nanoemulsion prepared using
a low energy process containing oil, surfactant (Tween 80 and Span 80, HLB = 13) and PEG 400 as a cosurfactant. b Addition of mixed Pluronic solution

Hashemnejad et al., Nature Communications, 2019

into the nanoemulsion suspension to impart thermoresponsive behavior. Final concentration of Pluronic is 4.7% wt. c Gel formation at 50 °C through
adsorbing midblock of Pluronic onto the droplet interface and mixed micelles formation between Pluronic and excess emulsifiers in the aqueous solution

a 104
b 104
c
Thermodynamic property classification
• Intensive properties: P, T, µ
– Independent of quantity of material

• Extensive properties: Vt, Ut, Ht, St, Gt

– Depend on quantity of material (N, M)

• Molar & Specific properties: xi, wi, r, V, U, H, S, G

– are intensive
Thermodynamic property classification
• State properties: P, T, V, U, H, S, G etc.
– Do not depend on “path”

• Path properties
– Dependent on the path/process connecting initial
and final states
 Types of System
• Closed
– Opaque to mass energy

– Transparent to energy
mass
 Types of System
• open
– Transparent to mass energy

– Transparent to energy
mass
 Types of System
• Isolated
– Opaque to mass energy

– Opaque to energy
mass
 Types of System
• It is very important to be careful in
thermodynamics about the type of system
that you are considering: the thermodynamic
rules that apply change in very subtle ways
depending on whether a system is at constant
pressure, absorbs no heat, etc.
– For instance, to discuss a quantity as simple as the
heat capacity, one needs to make very precise
specifications about how the physical experiment
is actually performed.
Know your variables: Temperature
• Temperature
– Zeroth law provides a mechanism for defining
temperature: “if two objects are in thermal
equilibrium with a specified object, then the two
objects would be in thermal equilibrium with each
other– and in fact they have the same
temperature”
Know your variables: Temperature
• Temperature
– Zeroth law provides a mechanism for defining
temperature: “if two objects are in thermal
equilibrium with a specified object, then the two
objects would be in thermal equilibrium with each
other– and in fact they have the same
temperature”
Know your variables: Temperature
• Temperature
– Zeroth law provides a mechanism for defining
temperature: “if two objects are in thermal
equilibrium with a specified object, then the two
objects would be in thermal equilibrium with each
other– and in fact they have the same
temperature”

Temperature, heat capacity, and heat: Three

interrelated, but distinct variables.
Know your variables: Temperature
• Temperature
Metric unit: Kelvin (K); other units: oC, oF, R
 Know your variables: Pressure
• Pressure: Force per unit perpendicular area
Metric unit: Pa = Nm-2; other units: atm, bar, torr, psi
We define either a gauge pressure or absolute
pressure
Know your variables: Pressure
 Know your variables: Energy
• Energy
Metric unit: J; Other units: BTU, ft-lbf

Types of Energies:
Stored energies: Internal energy (stored in molecules)
Potential energy (configurational)
Kinetic energy (motion)
Transient Energies: Work
Heat
 Know your variables: Energy
• Energy
Metric unit: J; Other units: BTU, ft-lbf

Types of Energies:
Stored energies: Internal energy (stored in molecules)
Potential energy (configurational)
Mechanical
Energy Kinetic energy (motion)
Transient Energies: Work
Heat
 Know your variables: Energy
• Kinetic Energy: energy stored in moving objects
– Can be thought of as arising from net work done on an
object
 Know your variables: Energy
• Potential energy: energy stored in objects due
to their relative position or configuration

Gravitational PE = mgz
Elastic PE = ½ kx2
 Know your variables: Energy
• Internal Energy: stored in internal degrees of
freedom of object, viz. momenta and
positions
– energy that cannot be 4 Energy
accounted for by specifying Force
2
macroscopic position or 2 r1
1
2
macroscopic velocity 0

-2

1.0 1.5 2.0 2.5

Separation, r/s
 Know your variables: Energy
• Internal Energy: stored in internal degrees of
freedom of object, viz. momenta and
positions
– energy that cannot be accounted for by specifying
macroscopic position or macroscopic velocity
𝑈 = 𝑓 𝑃, 𝑇
 Know your variables: Energy
• Work & Heat: the only means available for
energy transfer across a boundary
 Know your variables: Energy
• Work & Heat: the only means available for
energy transfer across a boundary
Heat: Energy transfer by virtue of temperature
difference. From high T to low T (second law)
Work: Energy transfer by either mechanical (-PdV,
Fdl) or chemical (µdN) means
System & Surrounding

System
Q: − 𝑾: + compressed
Q: + 𝑾: − System
System expanded

Surrounding
 Joule’s Experiment
• Interconversion of heat and work

Harper's New Monthly

Magazine, No. 231,
August, 1869.