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# 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

## 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.
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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 small scale quantitative analysis Example: Chromatography Preparative Separations small scale materials for R&D Example: Centrifugation Industrial Separations

## large scale economical

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.
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## 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.

## 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
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## Basic Description of Operations

Block Flow Diagram
S1 P1
Total condenser

## Process Flow Diagram

Distillation

Distillation

F
Feed
Stripping section stages

1 2

Reflux

Distillate

Feed Stage

P2

S2

Bottoms

## Lecture 1: Introduction to Separations

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 Feed: wng C2+/abs absorber i-butane n-butane C4 C4+

C2+

ethane

C3+

C5+

propane

Notice that this process involves a train of separators: This is common in industrial processes.
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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.

## 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 A

S B

G
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!
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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

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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

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