Thermodynamics

Today: Introduction to Separations

Lecture 2: Review of equilibrium thermodynamics (not covered in class).
Lecture 3: Thermodynamics of Separations
Instructor: Charles Musgrave
261 Keck
725-9176
charles@chemeng.stanford.edu
http://chemeng.stanford.edu/~charles/cheme120/
Office Hour: Tuesday 3-4pm
TA: Junsic Hong
03 Stauffer I
723-0980
junsic@stanford.edu
Office hour: Thursday 4-5pm
Book:
Separation Process Principles
Seader and Henley
Homework Assigned on Friday/Due on Friday

Lecture 1: Introduction to Separations

Introduction to Separations
The goal of a separations process is to purify solutions.
To do this we must cause differential transport of species or conversion of species so that the
purer mixtures can be collected. Most separations processes involve differential transport.

Examples:
Separation of blood
Purification of drugs
Purification of Au, Si, GaAs
Refining of crude oil
DNA testing
Purification of organics
Purification of water
Smog control
mixed

separated

However, mixing is inherent in nature: The increase in entropy associated with the randomness of a mixture
lowers the Gibbs free energy.
Therefore, to unmix a solution we must overcome the entropic driving force to mix.

Lecture 1: Introduction to Separations

Why Separate?
There are many reasons for wanting pure substances. Some of these reasons include:
Need for pure material in engineering application (semiconductors)
Preparation of raw materials into their components
Need for pure material for materials processing
Need to remove toxins or inactive components from solution (drugs)
Need for ultrapure samples for testing
Need for analysis of the components of the mixture (DNA testing)
Based on these motivations for separations, we can divide separations up into three main areas:
Analytical
Separations

Preparative
Separations

Industrial
Separations

small scale
quantitative
analysis

small scale
materials for
R&D

large scale
economical

Example:
Chromatography

Example:
Centrifugation

Example:
Distillation

The list of different existing separations methods is limitless. Therefore

we will emphasize the fundamentals of separations.
Note: 50 to 90 percent of capital investment in chemical plant is for separations equipment.
Lecture 1: Introduction to Separations

Background Material for Separations

The fundamentals that we will apply to study separations in this course involve:
Materials and energy balances: conservation of energy and matter
Thermodynamics: phase equilibrium and solution thermodynamics (Chapter 2)
Transport phenomena (Chapter 3; not emphasized)
Chemical reaction kinetics: rate of conversion of one species to another (not emphasized)

For the most part our analysis of various separations processes will
focus on using phase equilibrium and materials and energy balances.

Lecture 1: Introduction to Separations

Basic Description of Operations

Separations processes can be run in various modes of operation:
Batchwise: no flows
Continuous: continuous flows in and out of separators
Semicontinuous: pauses in flows.

Operations are classified as key operations and auxiliary operations

Key Operation: involves reaction or separations
Examples: distillation, leaching, reactor
Auxiliary Operation: involves no change in chemical composition
Examples: pumps, heaters, compressors
Block Flow Diagrams indicate:
Key Operations by rectangles and
Flows and Streams by lines
Process Flow Diagrams indicates processes by:
Realistic symbols of process equipment
Including auxiliary operations
Lecture 1: Introduction to Separations

Basic Description of Operations

Process Flow Diagram

Block Flow Diagram

S1

P1
Total condenser

Distillation

Distillation
Reflux drum
Overhead vapor

1
2

Distillate

Feed Stage

Feed

Stripping section stages

Reflux

Boilup
Partial reboiler

P2

Lecture 1: Introduction to Separations

S2

Bottoms

Example
Example: Recovery of hydrocarbons from wet natural gas (wng)
These types of separations generally exploit the differences in volatility to cause a separation

methane

C2+

ethane

Feed: wng
C2+/abs
C3+

absorber
i-butane
n-butane

C4

C4+

C5+

propane

Notice that this process involves a train of separators:

This is common in industrial processes.
Lecture 1: Introduction to Separations

Mechanism of Separations
UNMIXING is not a spontaneous process in nature
A process requiring no external driving force
Reduces randomness and thus the entropy of the system
Separations involve nonspontaneous processes
Usually the mixture to separate is a homogeneous, single phase:
If not, then often one will phase separate first
gravity
centrifugation
filtration.

Feed
S, L,V {ci}

Product 1
Product 2
Product 3
Differ in concentrations,
may differ in phase state

Separator: Causes different chemical

components to move to different spatial
locations to be collected as more pure
mixtures: Differential Transport.
Lecture 1: Introduction to Separations

Main Separations Techniques

Phase Creation: Use ESA (heat or depressurize)
Phase Addition: Use MSA (add solvent or absorber)
Barrier Separation: Use membrane (semipermeable membrane)
Solid Agent separations: Use particles (reaction, absorbent film, direct absorption, chromatography)
Separation by gradient: Use electric field, magnetic field, gravity (Hall effect, electrophoresis, mass spec)

Most Common
Gaining popularity
Often in labs

Phase Creation
Phase Addition
Barrier Separation
Solid Agent separations
Separation by gradient

All five techniques rely on the ability to enhance the rate of mass transfer of certain
species relative to others to effect a spatial separation of components.

Thus, all separations processes must introduce a thermodynamic driving force

to overcome the decrease in the entropy of the system as the components are separated.

Lecture 1: Introduction to Separations

Thermodynamics of Separations
Remember that there is an infinite driving force associated with removing
the last impurity atom from a pure substance:

SM

S B

S A

G' B 0
G' A 0

GA
GB

XB

0
1

XB

Since the driving force to mix will eventually equal the driving force
we introduced to cause the separation the extent of separation will be
limited by thermodynamics equilibrium!
Lecture 1: Introduction to Separations

10

Rate of Separations
Although the extent of a separation is determined by thermodynamics, the rate of separations
is limited by the differential rate at which the different species are moved. That is:
The Rate of Separation is limited by Mass Transport.

Limits:

Extent = Thermodyanmics
Rate = Transport

In this course we will generally focus on the thermodynamic fundamentals

governing separations. Transport issues will be addressed, but not a focus.

Lecture 1: Introduction to Separations

11

Thermodynamics

Next: Thermodynamics of Separations

Lecture 2: Review of equilibrium thermodynamics (not covered in class).
Lecture 3: Thermodynamics of Separations
Before Next lecture Read Lectures 2 and 3 (see course webpage)
Review Thermodynamics (some notes available on course webpage)
Equilibrium
Entropy
Solution Thermodynamics
Activity and Activity Coefficients
Equilibrium Phase Diagrams

Lecture 1: Introduction to Separations

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