CENG 1004: Introduction To Chemical Engineering Synopsis: Prof A Gavriilidis

Introduction
Synopsis
Aim is to provide the basic principles of process analysis together with an introduction to
CENG 1004: Introduction to Chemical Engineering

Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL
chemical engineering unit operations.

1
Introduction. Types of owsheet. Process variables and their units. Composition relationships. Ideal gases. Dalton's Law. Mass balances. Flowsheet analysis. Problems involving reaction and recycle streams. Phase equilibrium. Binary mixtures. Raoult's Law. Phase diagrams for simple binary mixtures. Mass balance problems involving change of phase. Heat capacity. Heat of formation. Enthalpy and its estimation. Enthalpy-composition charts. Energy balances: reaction and non-reaction applications. Problems involving combined mass and energy balances. Introduction to distillation. Heat exchangers: types and construction, log mean temperature dierence. Pipe ow: friction factors, ttings. Pumps, power for pumping. Introduction to chemical reactors. (Prof A Gavriilidis)
2 3
web:
HPH UTUW QVIU G xQQVIU email: eFfrgdulFFuk wwwFhomepgesFulFFukGueesfG

phone:
5 6 7 8 9
2011,
Revision : 1.20
Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical 2011, CENG 1004: Introduction to Chemical Engineering Engineering UCL .20 : 1phone: HPH/ UTUW QVIU G xQQVIU email: eFfrgdulFFuk web: wwwFhomepgesFulFFukGueesfG () 1 317 Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical 2011, CENG 1004: Introduction to Chemical Engineering Engineering UCL .20 : 1phone: HPH/ UTUW QVIU G xQQV 3 317
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Introduction
Introduction
Recommended textbooks
Engineering Calculations
It is assumed that you:
Elementary principles of chemical processes by R M Felder and R W Rousseau, John Wiley & Sons, 3rd Edition, 2000.
Understand units & dimensions Can handle conversions between units Understand scientic notation Understand concept of signicant digits Know how to calculate mean & variance Know how to interpolate and extrapolate data Know how to use a spreadsheet (e.g. MS Excel) We will also assume you know about molecular weights, density and pressure.
Unit operations of chemical engineering by W L McCabe, J C Smith and P Harriott, McGraw-Hill International, 5th Edition, 1993.
Chemical Engineering Volume 1 by J M Coulson and J F Richardson, Pergammon Press.
Heat Transfer by D Pitts and L Sissom, Schaum's Outlines, McGraw-Hill.
Heat transfer a practical approach by Y A Cengel, McGraw-Hill.
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Introduction
Introduction
Units
Calculations should be performed on consistent units, such as: Quantity Time Mass amount Notation t Dimension Units s
Validating results
m kg M Mass ow m kg/s T Molar amount n M mol M Molar ow n mol/s T M Pressure P bar LT ML Joule Energy H, Q, W T where M denotes mass, T time, and L length.
2 2 2
T M
back substitution order of magnitude estimation test of reasonableness
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Introduction
Introduction
Process analysis
Process
Denition
The aim of process analysis is to determine values of unknown quantities (e.g. ows, compositions, temperatures, . . . ) in a process given the process structure and some known quantities. The basis of process analysis is the use of both material and energy balances together with a number of relationships describing the properties of material in the process.
A set of operations or steps which results in a physical or chemical change in a substance or a mixture of substances.
Some useful terms

Material which enters a process: feed or input. Material which leaves: product or output. Each processing step is typically carried out in a process unit and each unit has associated with it input and output process streams.
Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical 2011, CENG 1004: Introduction to Chemical Engineering Engineering UCL .20 : 1phone: HPH/ UTUW QVIU G xQQVIU email: eFfrgdulFFuk web: wwwFhomepgesFulFFukGueesfG () 9 317 Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL 20 CENG 1004: Introduction to Chemical Engineering 2011, : 1. phone: 10 / UTUW QVIU G xQQV HPH 317
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Introduction
Introduction
Nomenclature
Variables that describe the condition of a process fall into two categories: extensive variables are proportional to the size of the system, such as mass and volume, and intensive variables are independent of quantity, such as temperature, pressure, density and specic volume, and mass and mole fractions of individual system components. The number of intensive variables that can be specied independently for a system at equilibrium is known as the degrees of freedom of the system. The number of signicant digits in measurements is also important.
Process types
batch Feed is added at beginning, products removed at end. continuous Inputs and outputs continuously added and removed. semibatch Anything in between
steady-state All variables do not change in time. transient One or more variables change in time. All batch processes are transient; continuous processes may be transient or steady-state.
Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL 20 CENG 1004: Introduction to Chemical Engineering 2011, : 1. phone: 11 / UTUW QVIU G xQQVIU email: eFfrgdulFFuk web: wwwFhomepgesFulFFukGueesfG () HPH 317 Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL 20 CENG 1004: Introduction to Chemical Engineering 2011, : 1. phone: 12 / UTUW QVIU G xQQV HPH 317
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Introduction
Mass balances
Process analysis procedure

1 2 3
Mass balance equations

The mass balance equation used depends on the process type and is based on a system box, a box drawn around the complete process or the part of the process of interest. Possible alternatives are In general: input + generation output consumption Steady state: input
Draw and label a diagram for the process. Choose a basis of calculation if required. Write down appropriate equations until zero degrees of freedom are achieved. Possible sources of equations include the following:
1
= accumulation
+ generation output consumption = 0 output = 0
2 3 4 5 6
Mass balances: for a system with n species, may be written down. Process specications and conditions. Denitions.
n mass balance equations
No reaction, steady state: input where:
input: Material entering through the system box. generation: Material produced within the system. output: Material which leaves through the system boundaries. consumption: Material consumed within the system. accumulation: Material which builds up within the system.
Identify the order in which the equations should be solved. Solve the equations for the unknown values. Possibly scale results (cf. item 2).
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Mass balances
Mass balances
Example: Continuous distillation
Solution
One thousand kilograms per hour (1000 kg/h) of a mixture of benzene ( 6
C H6 ) and toluene (C7 H8 ), containing 50% benzene by mass, is separated

1
by distillation into two fractions. The molar ow rate of benzene in the top stream is 5.8 kmol/h and that of toluene in the bottom stream is 5.2 kmol/h. The operation is at steady state. Calculate the unknown component ow rates in the output streams.
m1 = 1000 kg h
n2,b = 5.8 kmol h n2,t = ?
Draw process with system box, dening input and output streams.
2 3 4
Label known quantities. Identify desired variables. Basis of calculation not required as feed ow given.
x1,b = 0.50 kg
kg
n3,t = n3,b =
kmol 5.2 h ?
3
5
Specify equations . . .
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Mass balances
Mass balances
Solution: Gather equations

Write equations, indicating unknowns. Start with component mass balances (of the form input = output ) and add conversions and denitions. Then determine the order of solution.
Solution: solve equations
m1,b = x1,b m1
Benzene balance Toluene balance Conversion Denition Denition Conversion
= 0.50 = 500 = 6.4
kg kg
1000
kg
kg h
= 500
kg h
3 6 2 1 4 5
n3,b n2,t n1,b m1,b m1,t n1,t
n1,b
= n2,b + n3,b
n1,b = m1,b /MWb n3,b = n1,b n2,b m1,t = m1 m1,b n1,t = m1,t /MWt n2,t = n1,t n3,t
kg h h
/78
n1,t = n2,t + n3,t m1,b = MWb n1,b m1,b = x1,b m1 m1 = m1,b + m1,t m1,t = MWt n1,t
kmol
= 6.4
h
kmol h kmol h
kmol
5.8
kmol
= 0.6
kg h h
= (1000 500) = 500

kg h
kg h
= 500 = 5.4 = 0.2
/92
kg kmol kmol h
kmol kmol h
= (5.4 5.2)
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Mass balances
Mass balances
Modelling
Solving models
Process analysis consists of dening a model and then solving it. A model: Mathematical representation of reality Variables and equations May have constraints, especially for optimisation Equations may be algebraic, dierential and integral We will be concerned primarily with simple algebraic models in this course.
We will solve models mostly by hand in this course but you are welcome to use a number of tools: GAMS, the General Algebraic Modelling System Mathematica, Maple or Maxima for symbolic manipulation Some calculators which allow for solutions of systems of equations GAMS and Mathematica are available at UCL.
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Mass balances
Mass balances
GAMS example I
$title Continuous distillation set c components present /benzene, toluene/, s streams /feed, top, bottom/ ; positive variables n(s,c) molar flow rates of components in each stream in kmol per hour m(s,c) mass flow rates of components in each stream in kg per hour ; parameters FEED feed stream flow rate in kg per hour /1000/ MW(c) molecular weight of each species in kg per kmol / benzene 78 toluene 92 / ; equations balance(c) conversion(s,c) ;
GAMS example II
balance(c) .. n('feed',c) =e= n('top',c) + n('bottom',c); conversion(s,c) .. m(s,c) =e= MW(c) * n(s,c); * process specifications n.fx('top','benzene') = 5.8; n.fx('bottom','toluene') = 5.2; m.fx('feed','benzene') = 500; m.fx('feed','toluene') = 500; model distillation /all/; solve distillation using cns; display n.l;
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Mass balances
Mass balances
GAMS output
---35 VARIABLE n.L molar flow rates of components in each stream in kmol per hour benzene feed top bottom 6.410 5.800 0.610 toluene 5.435 0.235 5.200
Number of mass balance equations
Maximum number of independent equations that can be derived by writing balances on a non-reactive system equals the number of chemical species in the input and output streams. The only exception is when the system box contains only a splitter (where the composition of all streams involved is the same) in which case only one mass balance equation is possible.
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Mass balances
Mass balances
Degrees of freedom analysis
GAMS analysis
Dene the degrees of freedom of a system:
Tools like GAMS can help in degree of freedom analysis:
ndof = nunknowns nequations

The value of
MODEL STATISTICS BLOCKS OF EQUATIONS BLOCKS OF VARIABLES NON ZERO ELEMENTS DERIVATIVE POOL CODE LENGTH FIXED EQUATIONS 2 2 18 6 0 8 SINGLE EQUATIONS SINGLE VARIABLES NON LINEAR N-Z CONSTANT POOL FREE VARIABLES 8 12 0 16 8
ndof :
system can be solved uniquely. system is said to be under-specied. system is said to be over-specied.
=0 >0 <0
If
ndof > 0, we need to nd more equations to solve the system.
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Mass balances
Mass balances
Sources of equations
Example 4.2-3: Batch mixing process
1 2 3 4 5
Material balances Energy balances Process specications Physical properties and laws Physical constraints
Two methanol-water mixtures are contained in separate asks. The rst mixture contains 40.0 wt% methanol and the second contains 70.0 wt% methanol. If 200 g of the rst mixture is combined with 150 g of the second, what are the mass and composition of the product?
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Mass balances
Mass balances
Solution
Solution: equations
Start with mass balances, use denitions, and although we now have 0 degrees of freedom, not all desired variables are present.
1
Finally, determine
order of solution.
m1 = 200 g x1,m =
g 0.40 g
1 4 2 3 5 6
m3 = x3,m = x3,w =
? 3 ? ?
2 3 4
Label known quantities. Identify desired variables. Basis of calculation not required as input stream amounts given.
m2 = 150 g x2,m = 0.70 g g
m1 + m2 = m3 m1,m + m2,m = m3,m m1,m = x1,m m1 m2,m = x2,m m2 m3,m = x3,m m3 x3,m + x3,w = 1
total mass balance methanol balance denition denition denition denition
Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL 20 CENG 1004: Introduction to Chemical Engineering 2011, : 1. phone: 31 / UTUW QVIU G xQQV HPH 317 Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL 20 CENG 1004: Introduction to Chemical Engineering 2011, : 1. phone: 30 / UTUW QVIU G xQQVIU email: eFfrgdulFFuk web: wwwFhomepgesFulFFukGueesfG () HPH 317
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Mass balances
Mass balances
GAMS code I
$title Example 4.2-3 Batch mixing process set c components present /methanol, water/, s streams /feed1, feed2, output/ ; positive variables m(s) mass amount in each stream in g x(s,c) mass fraction of each species in each stream ; equations totalbalance methanolbalance massfractions(s) ;
GAMS code II
totalbalance .. m('feed1') + m('feed2') =e= m('output'); methanolbalance .. x('feed1','methanol')*m('feed1') + x('feed2','methanol')*m('feed2') =e= x('output','methanol')*m('output'); massfractions(s) .. sum(c,x(s,c)) =e= 1; * process specifications x.fx('feed1','methanol') = 0.40; x.fx('feed2','methanol') = 0.70; m.fx('feed1') = 200; m.fx('feed2') = 150; model distillation /all/; solve distillation using cns; display m.l, x.l;
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Mass balances
Mass balances
GAMS output
---31 VARIABLE m.L mass amount in each stream in g feed2 150.000, output 350.000 feed1 200.000, ----
Integral balances
31 VARIABLE x.L mass fraction of each species in each stream methanol water 0.600 0.300 0.471
For semi-batch and continuous processes, we may need to integrate over time. This may be complicated and is often not necessary. However, there are cases where this is required.
feed1 feed2 output
0.400 0.700 0.529
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Mass balances
Mass balances
Example 4.2-4
Solution: Draw and label diagram
Air is bubbled through a drum of liquid hexane at a rate of 0.100 kmol/min. The gas stream leaving the drum contains 10.0 mole% hexane vapour. Air may be considered insoluble in liquid hexane. Use an integral balance to estimate the time required to vapourise 10.0
x2,H = 0.10 kmol kmol VH = 10.0m3
2 3 4
Label known quantities. Identify desired variables. Basis of calculation not required as input stream amounts given.
3 of the liquid.
n1,A =
kmol 0.100 min
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Mass balances
Mass balances
Solution: equations
Start with mass balances ( input=output and input-output=accumulation ), use denitions and rules and determine order of solution.

n2,A = n1,A = 0.100
kmol min g
n1,A = n2,A n2,H dt = nacc,H macc,H = H VH MWH nacc,H = macc,H

0
Air balance
7 2 3 4 5 6
Hexane balance Denition Denition Rule Denition Denition
macc,H = H VH = 0.659 3 cm macc,H 6590 kg nacc,H = = MWH 86.17 kg x2,A = 1

n2 =
kmol kmol
10
cm3 1 kg 10m3 = 6590 kg 1 m3 1000 g

6
= 76.5 kmol
kmol kmol kmol min kmol min kmol min
kmol
x2,H = 0.90
0.100 kmol min
x2,A
+ x2,H = 1
kmol kmol
n2,A x2,A
kmol 0.90 kmol kmol kmol
= 0.111 0.111
x2,A = n2,A / n2 x2,H = n2,H /n2
n2,H = x2,H n2 = 0.10
= 0.0111
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Mass balances
Mass balances
Solution: solve equations (continued)
Example 4.3-5
n2,H dt = nacc,H 0 n2,H t = nacc,H
A liquid mixture containing 45.0% benzene (B) and 55.0% toluene (T) by mass is fed to a distillation column. A product stream leaving the top of the column (the overhead product) contains 95.0 mole% B and a bottom product stream contains 8.0% of the benzene fed to the column (meaning that 92% of the benzene leaves with the overhead product). The volumetric ow rate of the feed stream is 2000 L/h and the specic gravity 76.5 kmol kmol 0.0111 min of the feed mixture is 0.872. Determine the mass ow rate of overhead product stream and the mass ow rate and composition (mass fractions) of the bottom product stream.
n t = acc,H n2,H
= 6890 min
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Mass balances
Mass balances

m2 =
Solution: equations
Start with balances, add specications and denitions and make sure all required variables are included. 11
? 2
m3 m2,B m3,B m1 1
m1
= m2 + m3
3 6 6 7 7 7 8 9 10 11 11 12 13
1=2 2=4 3=3 4=3 5=2 6=1 7=1 8=1 9=1
dof
5 4 2 1 3 6 7 8 9 10 12 13
x2,B =
1
V1 = 2000 L h SG1 = 0.872
kmol 0.950 kmol
2 3 4
m1,B n2,B n2 n2,T m2,T m2 x3,B x3,T
x1,B = 0.45 kg kg kg x1,T = 0.55 kg
m3 =
? 3 ? ?
5
x3,T = x3,B =
m1,B = m2,B + m3,B m3,B = 0.08m1,B m 1 = 1 V1 1 = SG1 H O m1,B = x1,B m1 m2,B = MWB n2,B n2,B = x2,B n2 n2 = n2,B + n2,T m2,T = MWT n2,T m2 = m2,B + m2,T m3,B = x3,B m3 1 = x3,B + x3,T
2
10 = 1 11 = 0 12 = 0 13 = 0
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Mass balances
Mass balances
Multiple-unit processes
Example 4.5-1
Fresh air containing 4.00 mole% water is to be cooled and dehumidied to Balances over multiple units are handled by drawing boundaries around one or more units and applying the analysis to each boundary. Only take into account streams that intersect the boundary of a subsystem. We will illustrate this with a recycle example. Recycles are often required when reactions are present as reactions seldom go to full conversion. a water content of 1.70 mole%
H2 O .
A stream of fresh air is combined
with a recycle stream of previously dehumidied air and passed through the cooler. The blended stream entering the unit contains 2.30 mole%
H2 O .
In
the air conditioner, some of the water in the feed stream is condensed and removed as liquid. A fraction of the dehumidied air leaving the cooler is recycled and the remainder is delivered to a room. Taking 100 mol of dehumidied air delivered to the room as a basis of calculation, calculate the moles of fresh feed, moles of water condensed, and moles of dehumidied air recycled.
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Mass balances
Mass balances

n6 = x6,W
1 ? 6
Solution: box B4
= 0.017 mol
mol 3 Splitter
n1 = x1,W
Mixer
Cooler
n4 = 100 mol
= 0.017 mol
mol
Start with the system box containing all units, B4. Three streams, 1, 4 and
= 0.04 mol
mol
x2,W
= 0.023 mol
mol
x3,W
= 0.017 mol
mol
x4,W
x5,W
n5 =
5, intersect this box.

?
= 1.0
The equations can be solved for
n1 and n5 .
n1,A = n4,A + 5,A n n1,A = (1 x1,W )n1 n4,A = (1 x4,W )n4
n1
= n4 +
n5
Draw diagram, label known quantities, including the basis of calculation, and desired variables. There are a number of system boxes possible, including ones with multiple units. Apply mass balance procedure to one or more system boxes.
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Mass balances
Mass balances
Solution: box B1
Given
Chemical Reactions
n1 , we can now solve for the remaining variable, n6 , by using system

Mass balance analysis for processes involving reactions must include the
box B1:
n1 + n6 = n2 n1,A + n6,A = n2,A n6,A = (1 x6,W )n6 n2,A = (1 x2,W )n2
consumption and generation terms from the general mass balance equation: input
+ generation output consumption = accumulation
where accumulation is zero for steady state processes.
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Mass balances
Mass balances
Denitions I
Denitions II
stoichiometric proportion two reactants, A and B, are said to be in stoichiometric proportion if the ratio
stoichiometric equation statement of relative number of molecules of reactants and products that participate in a reaction A valid stoichiometric equation must be balanced: the number of atoms of each species must be the same on both sides of the reaction equation. stoichiometric coecients are the coecients in front of the species in the reaction equation and are indicated by reactants and positive for products. stoichiometric ratio of two molecular species is the ratio of their stoichiometric coecients.
moles A present moles B present equals the stoichiometric ratio for these species. limiting reactant the reactant that would run out if a reaction proceeded to completion. excess reactants any reactants other than the limiting reactant. stoichiometric requirement amount of an excess reactant actually required, dened by the limiting reactant amount. fractional excess
negative for
amount fed
stoichiometric
requirement
stoichiometric requirement
percentage excess is 100 times fractional excess.
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Mass balances
Mass balances
Denitions III
Example
Hydrogenation of acetylene to form ethane Given
C2 H2 + 2H2 C2 H6
Suppose 20.0 kmol/h of acetylene and 50.0 kmol/h of hydrogen are fed. Determine the limiting reactant and the fractional excess of the excess reactants. Solution:
1
fractional conversion of a reactant is
moles reacted moles fed
percentage conversion is 100 times fractional conversion
2mol 2 20.0 kmol C2 H2 requires 1molCHH 20 kmol C2 H2 = 40 kmol H2 so there is enough h h h 2 2 hydrogen present. 2 50.0 kmol H2 requires 1molCHH2 50 kmol H2 = 25 kmol C2 H2 so there is not enough h 2mol 2 h h acetylene present. Acetylene is the limiting reactant. kmol 40 kmol 50 h h = 0.25. Fractional excess of hydrogen is 40 kmol h
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Mass balances
Mass balances
Balances on reactive processes
Approach I: molecular species balance
For non-reactive processes, the maximum number of material balances you can write equals the number of independent species involved in the process. For reactive processes, we will also include equations for each reactive species. There are three dierent approaches:
ndof = Number of unknown labelled variables

+ Number Number Number
of independent chemical reactions of independent molecular species balances of other equations
molecular species balances atomic species balances extent of reaction
Seldom the most appropriate method.
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Mass balances
Mass balances
Approach II: atomic species balance
Approach III: Extent of reaction

Number Number
of independent atomic species balances of other equations

+ Number Number Number Number
of independent chemical reactions of independent reactive species balances of independent nonreactive species balances of other equations
Most straightforward, especially for multiple reactions.
Especially useful for equilibrium problems.
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Mass balances
Mass balances
Extent of reaction equation

Denition (Extent of reaction)
The amount which, when multiplied by the stoichiometric coecient of a species, determines the amount reacted or produced. Indicated by rate) and has same units as
Derivation of extent of reaction balance equation

For any given molecular species, we can start with the full mass balance equation (assuming steady state):
n (or n).
for
input
+ generation = output + consumption

re-arrange
In general, we can use extents of reaction to write down a more compact form of the general mass balance equation:
input
+ generation consumption = output

group
nout,i
or
= nin,i + i = nin,i + i
input
+ generation consumption = output

re-write input
nout,i
+ = output
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Mass balances
Mass balances
Illustrative example: Dehydrogenation of ethane
Solution
For all methods: Draw and label diagram
One hundred kmol/min of ethane are fed to the reactor. The molar ow rate of
H2 in the product stream is 40 kmol/min. C2 H6 C2 H4 + H2
key:
Ey + H
The reaction is
Determine the rates of the other species in the output stream.
n1,E = x1,E =
kmol 100 min kmol 1.0 kmol
n2,H = n2,E n2,Ey
kmol 40 min
2 3 4
= =
? ?
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Mass balances
Mass balances
Solution: Molecular species balances

Write equations, indicating unknowns. Start with component mass balances of the form input + generation = output + consumption remove zero valued terms, use the stoichiometry equation, determine the order of solution and solve the equations...
Solution: Atomic species balances

Write equations, indicating unknowns. Start with atomic species mass balances of the form input = output remove zero valued terms, determine the order of solution and solve the equations... Ethane balance Hydrogen balance Ethylene balance Ethane to Hydrogen Ethylene to Hydrogen 1 1
4 1 5 2 3
n1,E + ng ,E n1,H + ng ,H n1,Ey + ng ,Ey nc ,E ng ,Ey
= n2,E + nc ,E = n2,H + nc ,H = n2,Ey + nc ,Ey = ng ,H = ng ,H
2 6
n1,E = 0 n2,H + 2 n2,E + 2 n2,Ey n1,E = 2 n2,H + 6 n2,E + 4 n2,Ey
Carbon balance Hydrogen balance
solve simultaneously.
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Mass balances
Mass balances
Solution: Extents of reaction

Write equations, indicating unknowns. Start with component mass balances of the form output = input
Example 4.6-1
+i
Acrylonitrile is produced in the reaction of propylene, ammonia and oxygen:
remove zero valued terms, determine the order of solution and solve the equations...
C3 H6 + NH3 + O2 C3 H3 N + 3H2 O
2 The feed contains 10.0 mole% propylene, 12.0% ammonia and 78% air (assume 21% oxygen and 79% nitrogen). A fractional conversion of 30.0% of the limiting reactant is achieved. Taking 100 mol of feed as a basis of calculation, determine which reactant is limiting, the percentage by which each of the other reactants is in excess, and the molar amounts of all product gas constituents.
2 1 3
n2,E = n1,E 1 n2,H = n1,H + 1 n2,Ey = n1,Ey + 1
Ethane balance Hydrogen balance Ethylene balance
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Mass balances
Mass balances
Limiting reactant
n1,P = x1,P n1
= 0.10 = 0.12 = 0.21 0.78
mol mol mol mol 100 mol 100 mol
= 10 mol = 12 mol
key:
P + A + 3 O AN + 3W 2
n1,A = x1,A n1 n1,P n1,A n1,P n1,O

n1,O
3 2
n1,O = x1,O n1
= 0.833 < = 0.610 <
1 1 1
mol mol
100 mol
= 16.4 mol
x1,P = x1,A = x1,O = 0.21 0.78 mol mol x1,N = 0.79 0.78 mol mol
mol 0.10 mol mol 0.12 mol
n1 = 100 mol n2,P = n2,A = n2,O = n2,AN = n2,W = n2,N =

? ? ? ? ? ?
2 3 4
Label known quantities. Identify desired variables. Use suggested basis of calculation.
3 2
P A P = O
n1,A n1,P n1,P
Ammonia not limiting
Oxygen not limiting
Propylene is the limiting reactant with and
= 20%
excess of Ammonia
n1,P 3 n 2 1,P
= 9.3%
excess of Oxygen.
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Mass balances
Mass balances
Solution: equations
Start with component mass balances of the form output = input
GAMS model I
+i
, remove
zero valued terms, add process specication and determine the order of solution.
3 4 5 6 7 1 2
n2,A n2,O
n2,P n2,A n2,O n2,AN n2,W n2,N

0.30
= n1,P 1 = n1,A 1 = n1,O

3 2
Propylene balance Ammonia balance Oxygen balance Acrylonitrile balance Water balance Nitrogen balance Conversion
n2,AN n2,W n2,N n2,P
= n1,AN + 1 = n1,W + 3 = n1,N =
n1,P n2,P n1,P
$title Example 4.6-1 Acrylonitrile reaction set c components present /p, a, o, an, w, n/, s streams /feed, output/; positive variables n(s,c) molar amount of each species in each stream in mol xi extent of reaction in mol; equations balances(c) conversion; parameters FEED feed stream flow rate in mol per second /100/ NU(c) stoichiometric coefficients / p -1 a -1 o -1.5 an 1 w 3 n 0/ X fractional conversion /0.30/; balances(c) .. n('output',c) =e= n('feed',c) + NU(c)*xi;
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Mass balances
Mass balances
GAMS model II
GAMS solution I
conversion .. (n('feed','p') - n('output','p')) / n('feed','p') =e= X; * process specifications n.fx('feed','p') = 0.10 * FEED; n.fx('feed','a') = 0.12 * FEED; n.fx('feed','o') = 0.21 * 0.78 * FEED; n.fx('feed','an') = 0 * FEED; n.fx('feed','w') = 0 * FEED; n.fx('feed','n') = 0.79 * 0.78 * FEED; model distillation /all/; solve distillation using cns; display n.l, xi.l;
----
43 VARIABLE n.L molar amount of each species in each stream in mol p a 12.000 9.000 o 16.380 11.880 = an 3.000 w 9.000 n 61.620 61.620
feed output ----
10.000 7.000
43 VARIABLE xi.L
3.000 extent of reaction in mol
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Mass balances
Mass balances
Chemical equilibrium
Example 4.6-2
If the water-gas shift reaction
Given a set of reactive species and conditions, chemical equilibrium thermodynamics is concerned with determining the nal (equilibrium) composition of a reactive mixture and chemical kinetics are used to determine how long it will take to reach a specied state of equilibrium. Reactions are either (essentially) irreversible () or reversible ( usually indicated by ).
CO + H2 O
CO2 + H2 T
(degrees K),
(all in gas phase) proceeds to equilibrium at a temperature
the mole fractions of the four reactive species satisfy the relation
The equilibrium condition is described by the equilibrium constant, not really a constant!).
K , often a function of temperature or pressure (so
yCO yH = K (T ) yCO yH O At T = 1105 K, we know that K = 1.00.

2 2 2
Suppose the feed to a reactor contains 1.00 mol of CO, 2.00 mol of and no
H2 O CO2 or H2 , and the reaction mixture comes to equilibrium at 1105
K. Calculate the equilibrium composition and the fractional conversion of the limiting reactant.
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Mass balances
Mass balances
Solution: equations
Start with component mass balances of the form output = input denitions.
+i
remove zero valued terms, add equilibrium condition and add some
key:
CO + H2 O
CO2 + H2 T2 = 1105 K y2,CO = ? y2,H O = ? y2,CO = ? y2,H = ?

2 2 2
n1,CO = 1.00 mol n1,H O = 2.00 mol

2
2 3 4
Label known quantities. Identify desired variables. Basis of calculation not required.
y2,CO y2,CO
n2,CO n2,H O n2,CO n2,H y2,H y2,H O

2 2 2
= n1,CO 1 = n1,H2 O 1 = n1,CO2 + 1 = n1,H2 + 1 = K (T2 ) =
2 2
CO balance H2 O balance CO2 balance H2 balance

Equilibrium
y2,i
n2,i n2
i = {CO , H2 O , CO2 , H2 }
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Mass balances
Mass balances

Solve all equations simultaneously by substituting the rst four into the last 4 and then these last four into the equilibrium condition.
(continued)
y2,CO y2,H y2,CO y2,H O

2 2 2
= K (T2 )
n2,CO = 1.00 mol n2,H O = 2.00 mol

2
2 3 2 3
mol mol
= =
1 3 4 3
mol mol
= 1.00 (1 mol ) (2 mol )

2 =
2 mol
2 2
3 mol + 2 =
2 3 mol
n2,CO
= = = =
2 3 2 3
mol mol
2 mol
n2,H
3 mol
Conversion
n1,CO n2,CO n1,CO

1 mol
1 3 mol
1 mol
= 0.667
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Mass balances
Mass balances
Multiple reactions I
Many reactions do not occur in isolation. There are often a number of side reactions. For example, the following reactions may take place simultaneously when trying to produce ethylene ( 2
Multiple reactions II
yield is the ratio between the number of moles of desired product formed and the number of moles that would have been formed if there were no side reactions and the limiting reactant had reacted completely. Sometimes this is expressed as a ratio to the amount of the reactant fed or converted. selectivity is the ratio of the number of moles of the desired product (1) (2) (3) formed to the number of moles of an undesired product formed. Multiple reactions imply the existence of multiple extents of reaction so the amount of a species
C H4 ):
C2 H6 C2 H4 + H2 C2 H6 + H2 2 CH4 C2 H4 + C2 H6 C3 H6 + CH4
to emphasise one reaction over the others. For analysis, we require terminology for dierentiating between the individual reactions:
Only the rst reaction is desirable in this example. In general, we will want
after reaction can be described by
ni
(or
= ni ,0 +
nr j =1
i ,j j
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Mass balances
Mass balances
Multiple reactions III
Example 4.6-3: Dehydrogenation Reactor
The reactions
ni
for rates) where
= ni ,0 +
nr j =1
i ,j j
C2 H6 C2 H4 + H2 C2 H6 + H2 2 CH4
take place in a continuous reactor at steady state. The feed contains 85.0 mole% ethane ( 2 of ethane is 0.501 and the fractional yield of ethylene is 0.471. Calculate the molar composition of the product gas and the selectivity of ethylene to methane production.
nr
is the number of reactions.
C H6 ) and the balance inerts (I). The fractional conversion
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Mass balances
Mass balances
Solution: equations
nr i i ,j j
, remove zero
valued terms, add process specications and some denitions. Determine order of solution.
key:
E E +H
Ey + H 2M
Draw process with system box, dening input and output

8 9
5 1 n2,H n2,M n2,I n2,E
n1 = 100 mol s
streams.
y1,E = 0.85 mol mol y1,I = 0.15 mol mol
y2,E = y2,I = y2,Ey = y2,H = y2,M =
2 ? ? ? ? ?
2 3 4
Label known quantities. Identify desired variables. Basis of calculation required: choose value.
3 6
n2,Ey n1,i
1, 2
n2,E n2,Ey n2,H n2,M n2,I n1,E n2,E n1,E n2,Ey | ,Ey | | ,E | n1,E n1,i
1 1
= n1,E 1 1 1 2 = n1,Ey + 1 1 = n1,H + 1 1 1 2 = n1,M + 2 2 = n1,I = 0.501 = 0.471 = y1,i n1
Ethane balance Ethylene balance Hydrogen balance Methane balance Inerts balance Conversion
Yield
i = {E , I }
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Mass balances
Mass balances
Example 4.7-1: Incomplete combustion of methane

Methane is burned with air in a continuous steady state combustion reactor to yield a mixture of carbon monoxide, carbon dioxide and water. The reactions taking place are
key:
M + 3O 2 M + 2O
mol 1000 s
CM + 2W CD + 2W
CH4 + O2 CO + 2 H2 O 2 CH4 + 2 O2 CO2 + 2 H2 O N2 .

The feed to the reactor contains 7.80 mole%
n1 =
CH4 , 19.4% O2 and 72.8%
The percentage conversion of methane is 90.0% and the gas leaving
the reactor contains 8 mol
CO2 / mol CO .
Carry out a degree-of-freedom
y1,M = 0.078 mol mol y1,O = 0.194 mol mol y1,N = 0.728 mol mol
analysis on the process. Then calculate the molar composition of the product stream using molecular species balances, atomic species balances and extents of reaction.
y2,CM = y2,W = y2,CD = y2,N =
y2,M = y2,O =
2 ? ? ? ? ? ?
2 3 4
Label known quantities. Identify desired variables. Basis of calculation required: choose value.
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Mass balances
Mass balances
Solution: molecular species balances

Start with component mass balances of the form input+generation=output+consumption , remove zero valued terms, add process specications, some denitions and stoichiometry relations. Determine order of execution.
Solution: atomic species

Start with atomic species mass balances of the form input = output , add process specications and some denitions. Determine order of execution.
14 13
n2,M n2,O
5, 6, 7, 8 5, 6, 7, 8
n1,M n1,O
+ ng ,M = n2,M + nc ,M + ng ,O = n2,O + nc ,O
Methane balance Oxygen balance Carbon monoxide balance Carbon dioxide balance Water balance Nitrogen balance Conversion Specication
6, 7 8 9 4 5
n1,M = 1 n2,M + 1 n2,CM + 1 n2,CD

4
Carbon Hydrogen Oxygen Nitrogen Conversion Spec'n
12 11 4
n2,W n2,N nc ,M
5, 6, 7, 8
1, 2, 3
n1,i
5, 6, 7, 8 9 10
n1,CM + ng ,CM = n2,CM + nc ,CM n1,CD + ng ,CD = n2,CD + nc ,CD n1,W + ng ,W = n2,W + nc ,W n2,N = n1,N nc ,M = 0.90 n1,M n2,CD = 8 n2,CM n1,i = y1,i n1 nc ,M = ng ,CM + ng ,CD nc ,O = ng ,CM + 2ng ,CD 2 ng ,W = 2ng ,CM + 2ng ,CD
3
n2,W n2,O n2,N n2,M

6, 7 2
n1,M = 4 n2,M + 2 n2,W
n1,O = 2 n2,O + 1 n2,CM + 2 n2,CD + 1 n2,W
1, 2, 3
n1,i
n1,N = n2,N n1,M n2,M = 0.90 n1,M n2,CD = 8 n2,CM n1,i = y1,i n1
M, O, N
i = {M , O , N }
Methane consumption Oxygen consumption Water generation
nc ,O
ng ,W
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Mass balances
Mass balances
Solution: extents of reaction

nr i i ,j j
Product separation & Recycle

, remove zero
valued terms, add process specications and some denitions. Determine order of execution with simultaneous solution required for
n2,CM , n2,CD , 1 and 2 .
6, 7, 8, 9 10
n2,M n2,O
= n1,M 1 1 1 2 = n1,O
3 2
Unused reactants will often by recycled after separation from the desired
Methane balance Oxygen balance
products in order to increase the overall conversion, dened as: reactant input to process
n2,O
6, 7, 8, 9
1 2 2
n2,CM = n1,CM + 1 1 n2,W = n1,W + 2 1 + 2 2 n2,CD = n1,CD + 1 2 n2,N = n1,N n1,M n2,M = 0.90 n1,M n2,CD = 8 n2,CM n1,i = y1,i n1
CO
reactant
output from process
balance
11
n2,W
6, 7, 8, 9
reactant input to process where we dene the single-pass conversion as reactant input to reactor
Water balance
CO2 balance
Nitrogen balance Conversion Specication
4 5
n2,N n2,M
6, 7, 8, 9
reactant
output from reactor
reactant input to reactor
1, 2, 3
n1,i
i = {M , O , N }
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Mass balances
Mass balances
Process with recycle
Example 4.7-2: Dehydrogentation of Propane
Propane is dehydrogenated to form propylene in a catalytic reactor:

75 mol/min A 100 mol/min A REACTOR 75 mol/min B 25 mol/min A SEPARATOR 75 mol/min B
C3 H8 C3 H6 + H2
The process is to be designed for a 95% overall conversion of propane. The reaction products are separated into two streams: the rst, which contains
25 mol/min A
H2 , C3 H6 and 0.555% of the propane that leaves the reactor, is taken o

propane and 5% of the propylene in the rst stream, is recycled to the reactor. Calculate the composition of the product, the ratio (moles recycled)/(moles fresh feed), and the single-pass conversion.
as product; the second stream, which contains the balance of the unreacted
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Mass balances
Mass balances

P Py + H
Reactor 3 Separator 4
Solution: box B4
Start with the system
Key:
n1 = 100 mol x1,P =

mol 1 mol
Mixer 2
n4,H = ? n4,P = ? n4,Py = ?
box containing all units, B4. Two streams, 1 and 4, intersect this box. Use extent of reaction
x5,H = 0 mol mol
balance equations. Include process specications and denitions, remove 0 terms and solve.
n4,P = n1,P n4,Py = n1,Py + n4,H = n1,H + n1,P n4,P = 0.95 n1,P n1,P = x1,P n1
composition of product stream
Draw diagram, label known quantities, including the basis of calculation, and desired variables. There are a number of system boxes possible, including ones with multiple units. Apply mass balance procedure to one or more system boxes.
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Mass balances
Mass balances
Solution: box B3
Solution: box B1
Look at separator, box B3. Three streams, 3, 4 and 5, intersect this box. Use input=output mass balance equations. Include process specications, remove 0 terms and solve for desired quantity.
n3,P = n4,P + n5,P n3,H = n4,H + n5,H n3,Py = n4,Py + n5,Py n4,P = 0.00555n3,P n5,Py = 0.05n4,Py n5,P + n5,Py ratio = n1
To calculate single pass conversion, we need stream 2 composition so use box B1. Three streams, 1, 2 and 5, intersect this box. Use input=output mass balance equations. remove 0 terms and solve for desired quantity.
n1,P + n5,P = n2,P n1,Py + n5,Py = n2,Py n1,H + n5,H = n2,H n2,P n3,P conversion = n2,P
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Mass balances
Properties
Purging
Estimates of density
Liquids and solids are essentially incompressible. We can estimate the average density of a mixture, Suppose a material that enters with the fresh feed or is produced in a reaction remains entirely in a recycle stream rather than being carried out in a process product. If nothing were done about this situation, the substance would continually build up within the process. The prevent this build-up, a percentage of the recycle stream can be withdrawn as an output stream and this stream known as a purge stream. 1
by =
i
xi
i
if we assume volume additivity and
=
i
xi i
otherwise. The rst estimate is more often the more accurate one.
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Properties
Properties
Ideal Gases
Want to relate temperature, pressure and volume for gases. Solids and liquids we can often handle by assuming constant properties. Equation of state: relates molar quantity and volume of a gas to temperature and pressure.
Applicability
The ideal gas equation works well for
> 0 C
and
P < 1atm.
If
is the error, we expect
Xideal Xtrue 100 Xtrue

if
< 1%
The ideal gas equation of state
Videal = = nRT
(4) for diatomic gases and
RT P
>5
L mol
PV
(or
PV
= nRT
) is a good approximation for ideal or perfect gases.
absolute pressure, constant,
R=
m3 Pa 8.314 mol K
volume,
J 8.314 mol K .
n molar amount (n molar rate) and R
is for other gases.
Videal > 20
the gas
L mol
Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL 20 CENG 1004: Introduction to Chemical Engineering 2011, : 1. phone: 99 / UTUW QVIU G xQQVIU email: eFfrgdulFFuk web: wwwFhomepgesFulFFukGueesfG () HPH 317 Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL phone:100 / UTUW QVIU G xQQV CENG 1004: Introduction to Chemical Engineering 2011, : 1.20 HPH 317
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Properties
Properties
Standard temperature and pressure

STP, standard temperature (0 as a reference condition.
Example 5.2-3
C ) and pressure (1 atm), is often used PV = nRT Ps Vs = RTs T PV =n s Ts Ps V

10
ft 3 of air at 70 F , 1 atm is heated to 610 F
and compressed to
2.50 atm. What volume does the gas occupy at the end? Assume ideal gas behaviour. Note: 0 at STP. for
so do not need to remember
460R
(Rankin) and 0
R 0K
(absolute 0).
m R . Vs 22.4 kmol
3
L = 22.4 mol
You will often be given a specication in the form
m3 (STP)
volume which is not the actual volume but the volume the mixture would have if it were at STP.
Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL phone:101 / UTUW QVIU G xQQVIU email: eFfrgdulFFuk web: wwwFhomepgesFulFFukGueesfG () CENG 1004: Introduction to Chemical Engineering 2011, : 1.20 HPH 317 Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL phone:102 / UTUW QVIU G xQQV CENG 1004: Introduction to Chemical Engineering 2011, : 1.20 HPH 317
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Properties
Properties
Solution: The equations

Write equations, indicating unknowns. Start with mass balances of the form input = output , add process conditions, determine the order of solution and solve the equations...
1
2 1 3
V1 = 10 ft T1 = 70 F P1 = 1 atm
3
V2 = ? T2 = 610 F P2 = 2.50 atm
2 3 4
Label known quantities. Identify desired variables. Basis of calculation not required as volume given.
n1 = n2 P1 V1 = n1 RT1 P2 V2 = n2 RT2
Mass balance Ideal gas law Ideal gas law
Alternatively, combine all three equations to end up with
P1 V1 T1
pressure.
P2 V2 T2
V2 =
P1 V1 T2 T1 P2
In either case, remember to use absolute values for temperature and
Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL phone:104 / UTUW QVIU G xQQV CENG 1004: Introduction to Chemical Engineering 2011, : 1.20 HPH 317 Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL phone:103 / UTUW QVIU G xQQVIU email: eFfrgdulFFuk web: wwwFhomepgesFulFFukGueesfG () CENG 1004: Introduction to Chemical Engineering 2011, : 1.20 HPH 317
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Properties
Properties
Ideal gas mixtures
Example 5.2-5
nA moles of A nA is the amount of species A in a mixture, in some volume V and at temperature T . pure component volume, vA is the volume that would be occupied by nA moles of A alone at total pressure P and temperature T .
partial pressure, is the pressure that would be exerted by alone, where If we assume ideal gas behaviour,
pA
Liquid acetone ( 3
C H6 O ) is fed at a rate of 400 L/min into a heated
chamber where it evaporates into a nitrogen stream. The gas leaving the heater is diluted by another nitrogen stream owing at a measured rate of
m3 (STP)/min. The combined gases are then compressed to a total pressure P = 6.3 atm gauge at T = 325 C . The partial pressure of acetone in this stream is pA = 501 mm Hg. Atmospheric pressure is 763
419 determine the volumetric ow rate of the nitrogen stream entering the evaporator if Note:
mm Hg. Find the molar composition of the stream leaving the system and
pA = yA P vA = yA V vA V
is the volume fraction.
(5) (6)
= 27 C and P = 475 acetone = 0.791g /cm3 .
mm Hg gauge.
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Properties
Properties

P1 = 475mm Hg T1 = 27 C V1 = ? Evaporator
vapour 1 3
Solution: equations
Start with component mass balances of the form input = output , remove zero valued terms and add some denitions. Determine order of solution.
(STP V4 = 419 m min )

3
y4,N = 1.0 mol mol

5 6
P6 = 6.3 atm gauge T6 = 325 C

Compressor
6 8
n6,A n1,N
9
n1,A n1,N
+ n2,A + n4,A = n6,A + n2,N + n4,N = n6,N P1 V1 = n1,N RT1 V4 = n4,N Vs 2,A m2,A = A V m2,A = MWA n2,A p6,A = y6,A P6 y6,A + y6,N = 1 n6,A y6,A = n6,A + n6,N
Acetone balance Nitrogen balance Ideal Gas Law STP denition Denition Denition Denition Denition Denition
y1,N = 1.0 mol mol

L V2 = 400 min
liquid
Mixer
x2,A = 1.0 mol mol
p6,A = 501mm Hg y6,A = ? y6,N = ?
V1
1 2 3 4 5 7
n4,N m2,A n2,A y6,A y6,N n6,N
Draw diagram, label known quantities, including the basis of calculation, and desired variables. There are a number of system boxes possible, but probably only need one with all units.
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Properties
Properties
Critical temperature and pressure
Phase diagrams
Highest temperature and pressure at which a species can co-exist in two phases (liquid and vapour). Said to be at critical state when law does not apply in this case. vapour gaseous species with gas
T = Tc and P = Pc . A supercritical uid exists when T > Tc and P > Pc . Ideal gas T gaseous species with T (P Pc ).
< Tc > TC
A plot of one system variable against another showing conditions at which a substance exists as a solid, liquid, vapour and gas.
x -axis.
but with
Typically we will have pressure on the
y -axis and temperature on the
low enough
Lines on the graph will indicate conditions of co-existence of multiple phases.
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Properties
Properties
Phase diagram for water

P
Denitions
Supercritical Fluid
218.3 atm Critical Point
1 atm
Liquid
So li d
Gas
ur po Va
Triple point
T and T is the boiling point P = 1 atm, T is the normal boiling point. Solid-liquid curve T is melting point or freezing point and solid-vapour curve T is sublimation point.
(VLE) curve, temperature at
If
and
correspond to a point on the vapour-liquid equilibrium
P.
is the vapour pressure at If
4.58 mm Hg
The point at which all three phases can exist is the triple point.
0.0 0.0098
100.0
647.4
T (C)
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Properties
Properties
Estimation of vapour pressure

Volatility
Degree to which a species tends to transfer from liquid (or solid) to vapour state. As
Vg Vl Vg
and if we assume that
Hv
is independent of
T:
Clausius-Clapeyron equation
ln where
Clapeyron equation
Vapour pressure is a measure of volatility and is dened by the Clapeyron equation:
p =
Hv
d p = dT T Vg Vl
where
Hv
RT
+B
varies from substance to substance.
is absolute and
Hv
is the latent heat of vapourisation (energy
required to vapourise 1 mole of liquid).
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Properties
Properties
Example 6.1-1
More on estimating vapour pressure
The vapour pressure of benzene is measured at two temperatures, with the following results:
Vapour pressure can be estimated from the COX chart which plots log
p versus T .
We can also use the Antoine equation.
T1 = 7.6 C T2 = 15.4 C
p1 = 40 mm Hg p2 = 60 mm Hg
Antoine equation
log10
Calculate the latent heat of vapourisation and the parameter B in the Clausius-Clapeyron equation and then estimate equation.
at 42.2
p = A
using this
A, B
and
T +C
(7)
are known as the Antoine coecients and these values are
known for a large number of species.
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Properties
Properties
Gibbs Phase Rule

The number of independent intensive variables (e.g. represents the degrees of freedom in a system.
Gas-liquid systems
T , P ) at equilibrium
Raoult's law for single condensable species
If a mixture is saturated vapour at a temperature contains a species
The Gibbs phase rule

The degrees of freedom in a system is given by
i , with mole fraction is yi , and if this species is the only pi (T ) at the system temperature. yi P = pi (T )
and a pressure
P , if it
where
ndof = 2 + c
is the number of chemical species and
species that would condense if the temperature were slightly lowered, then (8) the partial pressure of the species in the vapour mixture equals the pure-component vapour pressure
is the number of phases
at equilibrium.
Examples:
solid water
ndof = 0.
pure liquid water
ndof = 2;
pi
mixture of liquid, vapour and
(9)
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Properties
Properties
Example 6.3-1
Q. Air and liquid water are contained at equilibrium in a closed chamber at 75
Note: A vapour present in a gas at less than its saturation amount is referred to as a superheated vapour:
and 760 mm Hg. Calculate the molar composition of the gas
phase. A.
yW P = pW (T ) yW + yA = 1 B log10 pW = A T +C A = 7.96681 B = 1668.210 C = 228.000
(Raoult's law (9)) (Denition) (Antoine's eq. (7))
pi
yi P < pi (T )
If a gas containing a single superheated vapour is cooled at constant pressure, the temperature at which the vapour becomes saturated is referred to as the dew point of the gas:
(Data: Appendix B.4) The degrees of superheat is
pi
yi P = pi (Tdp )
T Tdp .
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Properties
Properties
Example 6.3-2
Solution I
1
To determine degrees of superheat, we need to nd rst what the partial pressure of water is:
A stream of air at 100

volume.
1 2
and 5260 mm Hg contains 10.0% water by
yW P = 0.10 5260 mm Hg = 526 mm Hg

2
Calculate the dew point and the degrees of superheat of the air. Calculate the percentage of the vapour that condenses and the nal
If the system were at equilibrium, the partial pressure must be the vapour pressure (Raoult's Law):
composition of the gas phase if the air is cooled to 80

pressure.
3
at constant
Calculate the percentage condensation and the nal gas-phase composition if, instead of being cooled, the air is compressed isothermally to 8500 mm Hg.
3
yW P = pW (Tdp ) pW (Tdp ) = 526 mm Hg
Look up temperature
Tdp
( Table B.3 , say) for which vapour
pressure is 526 mm Hg.

4
Tdp 90 C
so we have 10
of superheat.
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Properties
Properties
Solution 2: Draw and label diagram
Solution 2: Equations
Write equations, indicating unknowns. Start with mass balances of the form input = output , remove zero valued terms, add equilibrium condition and denitions and look up data. Determine the order of solution and solve...
P2 = 5260 mm Hg T1 = 100 C 2 P1 = 5260 mm Hg n1 = 100 mol

vapour 1 vapour
T2 = 80 C
y2,W
4 7 2 3 5 6 1
n2,A = 90 mol n3,W = 3.2 mol y2,W = 0.07 y2,A = 0.93 n2 = 97 mol
pW
n1,A = n2,A + n3,A n1,W = n2,W + n3,W y2,W P2 = pW (T2 ) y2,A + y2,W = 1 n2,A = y2,A n2 n2,W = y2,W n2 pW (80 C ) = 355.1 mm Hg
Air balance Water balance Raoult's law
y1,W
= 0.10 mol
mol 3
Cooler
2 3 4
Label known quantities. Identify desired variables. Basis of calculation required.
T3 = x3,W
80
C
mol
n2,W = 6.8 mol
liquid
Table B.3
= 1.0 mol
Finally calculate
n3,W n1,W
100 =
3.2 mol 10 mol
100 = 32%
to answer the question.
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Properties
Properties
Solution 3: Draw and label diagram
Solution 3: Equations
Write equations, indicating unknowns. Start with mass balances of the form input = output , remove zero valued terms, add equilibrium condition and denitions and look up data. Determine the order of solution and solve...
P2 = 8500 mm Hg T1 = 100 C 2 P1 = 5260 mm Hg n1 = 100 mol

vapour 1 vapour
T2 = 100 C
y2,W
4 7 2 3 5 6 1
n2,A = 90 mol n3,W = 1.1 mol y2,W = 0.09 y2,A = 0.91 n2 = 99 mol
pW
n1,A = n2,A + n3,A n1,W = n2,W + n3,W

y2,W P2 = pW (T2 ) y2,A + y2,W = 1 n2,A = y2,A n2 n2,W = y2,W n2 pW (100 C ) = 760 mm Hg
Air balance Water balance Raoult's law
y1,W
= 0.10 mol
mol 3
Compressor
2 3 4
Label known quantities. Identify desired variables. Basis of calculation required.
T3 = x3,W
100
n2,W = 8.9 mol
liquid
Table B.3
= 1.0 mol
mol
Finally calculate
n3,W n1,W
100 =
1.1 mol 10 mol
100 = 11%
to answer the question.
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Properties
Properties
Multicomponent gas-liquid systems

Raoult's law
pA = yA P = xA pA (T )
which is most valid when
Example 6.4-2
Q. An equimolar liquid mixture of benzene (B) and toluene (T) is in equilibrium with its vapour at 30.0
C.
What is the system pressure
and the composition of the vapour? A. (10)
xA is almost 1.
yB
+ yT = 1
(Denition) (Raoult's law (10)) (Raoult's law (10)) (Antoine's eq. (7))
yB P
= xB pB (T )
Henry's law
pA = yA P = xA HA (T )
where valid when
(11)
HA (T ) is Henry's law constant for A in a specic solvent and is most xA is almost 0.
yT P = xT pT (T ) BB log10 pB = AB T + CB BT log10 pT = AT T + CT
(Antoine's eq. (7))
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Properties
Properties
Vapour liquid equilibrium calculations

Bubble-point temperature
Temperature at which rst vapour bubbles form when heating:
Vapour-liquid equilibrium diagram
P=
Dew-point temperature
n
1
xi pi (Tbp )
(12)
Temperature at which rst drops form when cooling:
n
1
yi P =1 pi Tdp )
(
(13)
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Energy Balances
Energy Balances
Energy Balances
Example 7.2-1
Q. Water ows into a process through a 2 cm ID (internal diameter) pipe at a rate of 2.00
Forms of energy: kinetic due to motion relative to some frame of reference:
m3 . h
Calculate
Ek
for this system in
J /s .
A. where
Ek = 1 mv 2 2
is the velocity (and
Ek = 1 mv 2 ). 2
Ek
1 2
m v2
1 2
0.556
potential due to position within a potential eld, such as magnetic or gravitational:
Ep = mgz where z is the height above some reference point (and Ep = mgz ).
due to, for instance, the motion of molecules relative to the centre of mass, vibrational motion, . . . represented by
= 0.870 V v= A
internal possessed by a system, other than kinetic and potential, and
1h 3600s m = 1m 2 = 1.77 s (1cm 100cm )

2.0
J s
kg m 1J (1.77 )2 kg m s s 1 s
2
m3 h
U.
m = W V
= 1000
kg m3 1h 2 m3 h 3600s
= 0.556
kg s
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Energy Balances
Energy Balances
Transfer of energy
Energy balance for a closed system
In a closed system (i.e. no mass transfer), energy can be transferred in the form of: heat energy, input
output = accumulation =
net energy transfer
Q , that ows as a result of temperature dierence; W Uf

, that ows in response to any other driving force
nal system energy
a positive value indicates a ow into the process from the surroundings. work energy,
initial system energy
+ Ek ,f + Ep,f
Ui + Ek ,i + Ep,i
=Q W
(e.g. a piston); a positive value indicates work done by the system on the surroundings.
U + Ek + Ep = Q W
First law of thermodynamics.
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Energy Balances
Energy Balances
Simplications
Example 7.3-1
U 0 Ek = 0 Ep = 0
A gas is contained in a cylinder tted with a movable piston. The initial if no temperature change, phase change, or chemical reaction and pressure changes small if no acceleration if system not rising or falling if system and surroundings are at same temperature or system perfectly insulated gas temperature is 25
C.
The cylinder is placed in boiling water with the
piston held in a xed position. Heat in the amount of 2.00 kcal is transferred to the gas, which equilibriates at 100
(and a higher pressure).
The piston is then released and the gas does 100 J of work in moving the piston to its new equilibrium position. The nal gas temperature is 100
Q=0
=0
C.
adiabatic
Write the energy balance equation for each of the two stages of this process and, in each case, solve for the unknown energy term in the equation. In solving this problem, consider the gas in the cylinder to be the system, neglect the change in potential energy of the gas as the piston moves vertically, and assume the gas behaves ideally. Express all energies in Joules.
if no moving parts, no electrical currents and no radiation at system boundary
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Energy Balances
Energy Balances
Solution: equations
Box 1 Start with closed system energy balance, remove zero terms and solve.
W1 =
W2 = 100J
U1 + Ek ,1 + Ep,1 = Q1 W1 U1 = Q1
& 1000 & cal
1 kcal 1
T1 = 25 C
T2 = 100 C
2
T3 = 100 C
= 2.00 kcal
3
= 8368 J
0.23901cal & &
Box 2 Start with closed system energy balance, remove zero terms and solve.
Q1 = 2.00kcal
Q2 =
Mass ? Energy
U2 + Ek ,2 + Ep,2 0 = Q2 W2
Q2 = W2 = 100 J
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Energy Balances
Energy Balances
Open systems
An open system is one in which mass crosses the boundaries. Work must be done to push mass into the system and work is done on the surroundings by mass that leaves the system:
Energy balance for open systems
input (14)
= output Ej + W
output streams
(conservation) (all energy types)
= Ws + W
Q+
input streams
Ej = Ej = Q W
input streams
(net rate of work is the shaft work together with the ow work)
W = rate
Ej
output streams
(group terms)
of work at outow
rate
of work at inow
= Pout Vout Pin Vin
H + Ek + Ep = Q W
(15) (balance equation)
A property that appears often in open systems is the specic enthalpy, dened as
H U + PV
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Energy Balances
Energy Balances
Reference states
Absolute values for
Reference data
(and hence
works with changes in
(ditto
H ) are not often known. Instead ) with respect to a specic state H
one
Steam tables
For some species, data on enthalpies and internal energies are well known. A good example is water. Reference tables for water are known as the saturated steam tables ( Table B.5 and Table B.6 in the textbook) and
(temperature and pressure) known as the reference state. For example, for
CO
Supercritical Fluid
218.3 atm Critical Point
( Table B.8 ):
1 atm
0 100 500
0 2919 15,060
So
T ( C ) H (J /mol )
Liquid
lid
Gas
ur po
4.58 mm Hg Triple point
Va
0.0 0.0098
100.0
647.4
the superheated steam table ( Table B.7 ).
T (C)
in going from 100
to 500
is
(15060 2919) J /mol .
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Energy Balances
Energy Balances
Example 7.6-1

W
Two streams of water are mixed to form the feed to a boiler. Process data are as follows: Feed stream 1 Feed stream 2 Boiler pressure 120 kg/min @ 30 17 bar (absolute)
175 kg/min @ 65
C C
kg m1 = 120 min T1 = 30 C kg m2 = 175 min T2 = 65 C
P3 = 17 bara d3 = 6 cm ID
vapour 3
2 3 4
Label known quantities. Identify desired variables. Basis of calculation not required as feed ows given.
The exiting stream emerges from the boiler through a 6 cm ID pipe. Calculate the required heat input to the boiler in kilojoules per minute if the emerging stream is saturated at the boiler pressure. Neglect the kinetic energies of the liquid input streams.
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Energy Balances
Energy Balances
Solution: equations
Start with mass and energy balances, remove zero terms and add denitions and table data.
Example 7.6-3
m1 + m2 = m3 H + Ek + Ep = Q W H = H3 H1 H2 H1 = m1 Hl (T1 ) H2 = m2 Hl (T2 ) H3 = m3 Hv (P3 ) b b Ek = Ek ,3 && && Ek ,& Ek ,& 1 2 E3 = m3 v3 2

2 1 0 0 Table B.5 Table B.5 Table B.6
Saturated steam at 1 atm is discharged from a turbine at a rate of 1150 kg/h. Superheated steam at 300
is needed as a feed to a heat
exchanger. To produce the steam, the turbine discharge stream is mixed with superheated steam available from a second source at 400 superheated steam at 300
and 1
atm. The mixing unit operates adiabatically. Calculate the amount of
rate of the 400
produced and the required volumetric ow
stream.
v3 =
V3 A
m3 V (P3 ) d3 2
2
Table B.6
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Energy Balances
Energy Balances

W m1 = 1150 h P1 = 1 atm
1 kg
Solution: equations
Start with mass and energy balances, remove zero terms and add denitions and table data.
saturated vapour
T3 = 300 C P3 = 1 atm
vapour 3
2 3
m3 =
Draw process with system box, dening input and output streams. Label known quantities. Identify desired variables. Basis of calculation not required as feed ows given.
m1 + m2
= m3
H + Ek + Ep = 0 Q W H = H3 H1 H2 H1 = m1 Hv (T1 ) H2 = m2 Hv (T2 ) H3 = m3 Hv (T3 ) V2 = m2 V (T2 )

Table B.7 Table B.7 Table B.7 Table B.7
V2 = ? T2 = 400 C P2 = 1 atm
superheated vapour
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Energy Balances
Energy Balances
Energy as heat
Sensible heat
Sensible heat is calculated using the heat capacity (at constant
In working with materials, we can classify heat in two ways depending on what eect it has on material: sensible heat which signies heat that must be transferred to raise or lower the temperature of a substance, assuming no change in phase (solid, liquid, gas), and latent heat which is the heat necessary to change from one phase to another.
pressure),
Cp (T ) (units of energy per mass)
Heat capacity for each component is typically estimated by
Cp (T ) = a + bT + cT 2 + dT 3
Change in enthalpy from
(16)
T2 :
T1 to T2 is the integral of Cp (T ) from T1 to

=
T2 T1
Cp (T ) dT
aT + b
T2
2
+c
T3
3
+d
T4
4
T2 T1
(17)
Coecients of (16) can be found in Table B.2 .
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Energy Balances
Energy Balances
Latent heat
Change in enthalpy
For latent heats: look up the corresponding entry in tables ( Table B.1 ): latent heat of vapourisation (or simply the heat of vapourisation) for liquid to/from vapour phase change heat of fusion for solid to/from liquid quantities are in units of energy per unit mass . . . . . . and are given for a specic reference state, typically the 1 atm boiling point or melting point of the substance). The calculation of the change in enthalpy: Identify a path of pressure and temperature changes from state 1 to state 2 passing through states for which we have reference data. Any sections of the path that do not involve phase changes require the calculation of sensible heat. Phase changes make use of the appropriate latent heat quantity.
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Energy Balances
Energy Balances
Example. Vapourisation and heating

W
1 kilomole per hour of liquid n-hexane, at 25 and heated to 150
and 1 bar, is vapourised 1
at constant pressure. Neglecting the eect of
n1 = 1 kmol h T1 = 25 C P1 = 1 bar
T2 = 150 C P2 = 1 bar
pressure on enthalpy, estimate the rate at which heat must be supplied.
2 3 4
Q=
Solve . . .
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Energy Balances
Energy Balances
Solution: Gather data

Mass balance, energy balance, remove zero terms, add equations for Table B.1 individual energy terms and solve the equations.
Tb =69 C
(boiling point)
l Cp =0.2163 v Cp
kJ
mol
C
5
n1 = n2
0.13744
+ 40.85 10
T + 23.92 10 T
8
H + Ek + Ep = Q W H = Hliquid + Hboil + Hvapour

Table B.2
+ 57.66 1012 T 3
kJ
mol
Hliquid = n1 Hvapour = n1
Tb T1
l Cp (T ) dT
Hboil = n1 Hv
T2
phase change ( Table B.1 ): kJ mol
Input is liquid and output is vapour
Tb
v Cp (T ) dT
Hv = 28.85
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Energy Balances
Energy Balances
Solution: Calculate Hliquid
Solution: Calculate Hboil
Hliquid = n =1 =1 =1
h
Tb T1
Cp (T ) dT
69 C 25 C
216.3
kmol kmol h kmol h
kJ
kmol
dT
Hboil = n Hv
(216.3 69 216.3 25) 9517.2
kJ
kmol
=1
kmol h
2.885 104
kJ
kmol
kJ
kmol
kJ = 2.885 104 h
kJ = 9.5172 103 h
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Energy Balances
Energy Balances
Solution: Calculate Hvapour

Hvapour = n =1
h
Solution: Calculate Q
T2 Tb
Cp (T ) dT
150 C 69 C
137.44
kmol
+ 40.85 10
Q = H = Hliquid + Hboil + Hvapour
+ 23.92 105 T 2 + 57.66 109 T 3 =1

kmol h
kJ
kmol
C dT
9.5172
103 + 2.885 104 + 1.500571 104
1.500571 10
kJ
kmol
= 5.337291 104 = 5.34 104
kJ = 1.500571 104 h
kJ h
kJ h
kJ h
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Energy Balances
Energy Balances
Heat of reaction
Denition
Hr (T , P )
is the enthalpy change for a process in which stoichiometric quantities of reactants at temperature
Observations
Hr (T , P ) Hr (T , P ) Hr (T , P )
and pressure
negative
reaction is exothermic which means it
react completely
generates energy. positive reaction is endothermic which means it
in a single reaction to form products at the same temperature and pressure.
requires energy. Also known as Enthalpy of reaction. Units are in energy per unit mass where mass is the extent of reaction; specically: is nearly independent of pressure at low and moderate
pressures and will be written often as
Hr (T ).
H = Hr (T , P ) =
where
nA,r
|A |
Hr (T , P )
Standard heat of reaction

(18)
Hr
is the heat of reaction at specied reference temperature and pressure.
is the stoichiometric coecient of species
A and nA,r
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is
amount consumed or produced.
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Energy Balances
Energy Balances
Eect of Stoichiometry on value of Hr (T , P )

The value of
Eect of state on value of Hr (T , P )

The states of aggregation (gas, liquid, solid) of the reactants and products aects the value of
Hr (T , P )
depends on how reaction is written in terms of
stoichiometric coecients. For instance:
Hr (T , P ).
For instance:
CH4 (g ) + 2O2 (g ) CO2 (g ) + 2H2 O (l ) kJ Hr 1 (25 C ) = 890.3

kmol 2
CH4 (g ) + 2O2 (g ) CO2 (g ) + 2H2 O (l ) kJ Hr (25 C ) = 890.3

kmol
CH4 (g ) + 4O2 (g ) 2CO2 (g ) + 4H2 O (l ) kJ Hr 2 (25 C ) = 1780.6

kmol
CH4 (g ) + 2O2 (g ) CO2 (g ) + 2H2 O (g ) kJ Hr (25 C ) = 802.3

kmol
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Energy Balances
Energy Balances
Internal energy of reaction

Denition
The internal energy of reaction,
Heats of formation
is dened by (19)
Ur (T ),
A formation reaction of a compound is the reaction in which the compound is formed from its elemental constituents as they normally occur in nature (e.g.
Ur (T ) = Uproducts Ureactants
if stoichiometric quantities of reactants react completely at temperature
O2 rather than O ).
The enthalpy change at
specic reference temperature and pressure is known as the standard
T.
heat of formation of the component,
Hf .
Assuming ideal gas behaviour and that specic volumes of liquid and solid reactants/products are negligible:
Heat of reaction in terms of heats of formation:
Ur (T ) = Hr (T ) RT
Hr = =
(20)
i Hf,i |i | Hf,i
reactants
|i | |i | gaseous gaseous products reactants
|i | Hf,i
products
Heats of formation are useful when working with multiple reactions.
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Energy Balances
Energy Balances
Energy balances on reactive processes: Procedure
Example: Ammonia oxidizer
1 2 3
Draw and label a owchart. Choose basis of calculation, if necessary. Use material balances and phase equilibrium relationships to determine as many stream component amounts and owrates as possible. The standard heat of reaction, 4 is
Hr ,
for the oxidation of ammonia
NH3 (g ) + 5O2 (g ) 4NO (g ) + 6H2 O (v )

mol
4 5 6 7 8
Choose reference state for enthalpy calculations Prepare an inlet/outlet enthalpy table. Calculate
25
kJ 904.7 mol .
(or equivalent).
300
C . Ammonia is completely consumed. The product gas emerges at C . Calculate the rate at which heat must be transferred to or from the
The feed to the reactor is 100
NH3 and 200 mol O2 at s
Apply and solve energy balance equation. Complete any remaining calculations (from mass and energy balances).
reactor, assuming operation at approximately 1 atm.
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Energy Balances
Energy Balances

key: 4

Mass balances (extent of reaction), energy balance, remove zero terms, solve mass balances and collect necessary data to calculate
1
A + 5O 4N + 6W W= ?
25
H .
n2,A 0 = n1,A 4 n2,O n2,N n2,W = n1,O 5 = n1,N + 4 = n1,W + 6
mol = 25 s
T1 = C P1 = 1 atm
n1,A = 100 mol s n1,O = 200 mol s Q=
?
T2 = C P2 = 1 atm
300
= 75
mol s mol s mol s
n2,A = 0 mol s
2 3 4
= 100 = 150
H + Ek + Ep = Q W
Solve . . .
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Energy Balances
Energy Balances
Solution. Dene enthalpy table
Solution. Enthalpy calculations

For
O2 and H2 O , we can retrieve actual enthalpies at 300 C
relative to
the reference state from Table B.8 in textbook. If this were not available, we would use the heat capacity equations ( Table B.2 ) and latent heats Species Inlet Outlet
i
A O N W
NH3 O2 NO H2 O
n1,i
mol s 100 200
H1,i
kJ mol
0 0
n2,i
mol s 75 100 150
H2,i
kJ mol
( Table B.1 ) where appropriate.
a reference state of 25
H2,O H2,N H2,W
assuming
H2,O = 8.470 H2,W

For
and 1 atm.
kJ mol kJ = 9.570 mol
NO :
use heat capacity equation, integrating from 25
to 300
to
yield:
H2,N = 8.453
kJ mol
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Energy Balances
Energy Balances
Solution. Update enthalpy table
Solution. Change in enthalpy

Determine change in enthalpy:
Species
Inlet
Outlet
i
A O N W
NH3 O2 NO H2 O
n1,i
mol s 100 200
H1,i
kJ mol
0 0
n2,i
mol s 75 100 150
H2,i
kJ mol
8.470 9.570 8.453
H = Hr +
mol s
n2,i H2,i
n1,i H1,i
from enthalpy table
= 25
904.7
= 19 700 =Q
Therefore, 19 700
kJ s
kJ mol
75
mol s
8.470
kJ mol
+ ...
kW
must be transferred out of the reactor.
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Equipment
Equipment
Objectives
Distillation
The most common or prevalent method of separating mixtures for purication is distillation: Flash Distillation versus Rectication Distillation:
Separations: how do we design a distillation column to separate two species? Heat transfer: what is it, how is it done and what equipment is used? Fluid ow: wow do we move uids and how much power is required?
both based on boiling of liquid mixtures but latter includes reux. distillation unit typically consists of a number of plates, known as stages.
We will consider only binary mixtures so will use variables such as
y , z , . . . all referring to the most volatile component (i.e.

the lowest boiling point). W L McCabe, J C Smith & P Harriott (1993),
x,
the one with
Unit Operations of Chemical Engineering 5th Edition, McGraw-Hill Inc.
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Equipment
Equipment
Flash vessel
Distillation unit
V, y
Rectifying Section
V
Condenser
D, xD
Reflux Feed plate
Tops product Distillate Overhead
F, z
T, P
Feed stream
F, xF
Stripping Section
Reboiler
L, x
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Equipment Equipment
B, xB
Bottom Product
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Distillation unit: Notes
The design problem
Given a feed stream, Stripping section includes the feed plate, the plate in which the feed enters the unit. Plates are numbered from the top downwards. The condenser shown is a total condenser as all of the vapour out of the column is condensed to liquid. A partial condenser would have the top product drawn o in vapour form and only the reux would be condensed.
2 1
xF , and the operating pressure, P : determine the reux ow rate, L, and the number of stages, nS , for a distillation unit which achieves the product purity requirements, xD and xB .
and Subsequently, design the heat exchangers (the condenser and the reboiler) which will provide the cooling and heating required (cf. next section of the course).
We will develop a graphical method to address step 1.
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Equipment
Equipment
Distillation plate
Degrees of Freedom for distillation
Assuming vapour-liquid equilibrium (VLE) on each plate of the Plate and
yi
with composition
xi
sends vapour stream
L i1, x i1
Vi , yi
column, the Gibbs Phase rule tells us that dof For a binary mixture ( (
upwards (amount composition
stream downwards ( (
yi ) and liquid Li , xi )
Li xi Vi+1 yi+1
Vi ,
=2+c
(21)
c = 2) with vapour and liquid simultaneously
and gets liquid from above
= 2),
we have 2 degrees of freedom.
Li 1 , xi 1 ) and vapour from below (Vi +1 , yi +1 ).
These degrees of freedom can be satised by two values from a choice of composition (vapour or liquid of either species), temperature and pressure.
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Equipment
Equipment
Vapour-Liquid Equilibrium Diagram

T Vapour composition Equilibrium temperature
Driving forces on a plate

T
The VLE diagram shows the compositions of a plate with input stream compositions and direction of move towards equilibrium from
Liquid Composition
Given an operating pressure, we can represent the single remaining degree of freedom using a vapour-liquid equilibrium
x , y and T . Choosing any one of x , y or T

diagram, relating two.
other plates. The input streams will
automatically denes the other

0 x y 1 x, y
eventually to an equilibrium temperature.
Composition of lighter species
xi
xi1
yi+1 y i
1 x, y
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Equipment
Equipment
Relative volatilities
The vapour pressure,
Equilibrium curve I
pc
1
of a component,
c1 , gives an indication of
We can generate an equilibrium curve which relates the vapour composition of a component to its liquid composition. Start with denition of relative volatility and recall Raoult's law:
the volatility of the component. In a multi-component system, we can dene the relative volatility of one species
c1 to another c2 by
c1 c2
p = c pc
yc P = xc pc
1 1
(24)
(22)
where
is the total system pressure.
We will typically use Antoine's equation to determine the vapour pressure of a component:
For a binary mixture, note that
log10
p = A
T +C
(23)
xc yc
2 2
= 1 xc1 = 1 yc1
(25) (26)
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Equipment
Equilibrium curve II
Combining equations 22 and 24:
Example: Benzene and Chlorobenzene mixture
c1 c2
p = c pc
1 2
yc xc = xc yc
1 1
2 2
yc = xc
(1 xc1 ) (1 yc1 ) 1
1
Benzene is lighter of the two components. (27) Antoine coecients ( Table B.4 ) are: Species benzene chlorobenzene (28) Picking a reasonable temperature, say gives a relative volatility of Now generate values of A 6.89272 7.10690 B 1203.531 1500.0 C 219.888 224
For a binary mixture, we can drop the subscripts, letting each mole fraction variable be with respect to the lighter species. Re-arranging the result:
y
This assumes that systems.
x = 1 + ( 1)x
is constant throughout the range of compositions
which, although not true in reality, is a reasonable assumption for ideal
UFVT.
= 25 C ,
and using eq. 22,
for values of
x [0, 1] using eq.
28.
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Equipment
Equipment
Example Equilibrium curve

Benzene/Chlorobenzene Equilibrium curve
1.0
Equilibrium diagram for handout

y, Benzene vapour mole fraction 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.9
0.0 0.1
0.8
Benzene/Chlorobenzene Equilibrium curve
0.2
y, Benzene vapour mole fraction
0.7
0.3
Generated using R (http://www.r-project.org/) but could have been generated using, for instance, a spreadsheet calculator.
0.6
x, Benzene liquid mole fraction
0.4
0.5
0.5
0.4
0.6
0.3
0.7
0.2
0.8
0.1
0.9
0.0
1.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
x, Benzene liquid mole fraction
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Equipment
Equipment
Mass balances
Distillate, 1
D , xD
To design a distillation unit, we need to describe the behaviour of the species within the column. We use mass balances around dierent system boxes:
Notes on mass balances
n Vn+1 , yn+1 n+1

Feed,
Ln , xn
Whole column:
F xF F
Rectifying section
=D +B
= xD D + xB B
(29) (30)
By convention,
n indicates trays in the rectifying section and m trays
in the stripping section.
F , xF
Feed plate
m Vm+1 , ym+1 m+1 Ns

Bottoms,
Lm , xm
Vn+1 = D + Ln yn+1 Vn+1 = xD D + xn Ln

Stripping section, not including the feed plate:
D + Ln is the net ow rate of material upwards in the rectifying

(31) (32)
column section.
Lm = B + Vm+1 xm Lm = xB B + ym+1 Vm+1
(33) (34)
B , xB
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Equipment
Operating lines
Operating lines describe the composition at any stage. From mass balances, we can dene an equation for each section of the column: Rectifying section
Equilibrium and operating lines

Equilibrium curve yn1
Ln + xn yn+1 = xD Vn + 1 Vn+1 Ln D = x + x Ln + D n Ln + D D D
where Stripping section
y n
The combination of the equilibrium curve and an operating line denes a single plate. The equilibrium curve
(35)
y n+1 Operating line
xD
is a constant so this is an equation of a line.
relates to
operating line relates
ym+1 =
where again
xB
Lm B
Lm
xm
Lm B
xB
xn
One plate
yn+1 .
xn and yn and the xn
is a constant.
xn1
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Equipment
Distillation column design
The McCabe-Thiele Graphical Method

1 2 3
Generate and draw the equilibrium curve for the binary mixture. Locate and draw the feed line. Calculate the
Recall that the goal of the rst step in a distillation unit design problem is to identify the reux ow rate, stages,
nS .
L, and the number of
4 5
R. y -intercept of the rectication section operating line for R . Draw a line from the y -intercept to the distillate product, (xD , xD ): this is the
Determine the minimum reux ratio and choose the actual reux ratio, operating line for the rectifying section. Draw a line from
We will use a graphical method based on the equilibrium curve and the operating lines. We assume a constant molar overow which says that the molar ow rates of vapour and liquid in each section of the column are nearly constant:
(xB , xB )
to the intersection point of the rectifying operating
line and the feed line.

7
Draw stages in starting at the distillate point working downwards in the column towards the bottoms product, tting stages in between the equilibrium curve and the operating lines and switching from the rectifying operating line to the stripping operating line when the feed line is passed.
drop subscripts on Vn and Ln results in a single straight line for each column section.
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Equipment
Example: Separate Benzene-Chlorobenzene mixture
Example: relative volatility

Antoine coecients: Benzene A 6.89272 1203.531 219.888 Chlorobenzene 7.10690 1500.0 224.
Determine the minimum reux ratio,
Rmin , and the number of stages, nS ,
B C
required for separating an equimolar liquid feed of benzene and chlorobenzene using a reux ratio factor of 2.5 and a reference temperature of 75
Relative volatility:
for vapour pressure calculations. The products of the distillation
unit should each have a purity of 95%.
=
at
pchlorobenzene
pbenzene
= = 5.2629
= 75 C .
Draw equilibrium curve using eq. (28):
y=
x + ( 1)x
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Equipment
Example: equilibrium curve
Feed line
y
= 5.26
The feed line is a line from the at the point
(xF , xF )
y =x
line on the equilibrium diagram
to a point on the equilibrium line based on the
feed condition. The feed condition,
q , (also known as the q -value), is dened by
q=
enthalpy required to vapourise 1 mol of feed specic molar latent enthalpy of feed
A vertical line corresponds to a feed as liquid at its bubble point, q = 1. A horizontal line corresponds to a feed as vapour at its dew point, q = 0.
0.05 0.5 0.95
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Equipment
Feed lines
q=1.00 q=0.75 q=0.50 q>1.00
Example: feed line
yF
= 0= 5.26 .84033
q=0.25
q=0.00
q<0.00
0.05
0.5
0.95
x F
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Equipment
Reux ratio
Choosing
The reux ratio is often used to describe the amount of reux. There are two denitions used: Typically,
L RD = D
and
RV
L = V.
There is a trade-o between reux and the number of stages. Limits on these values can be determined from the equilibrium diagram (36) for both minimum reux ratio and minimum number of stages.
L R=D
is used which, when combined with eq. 35, gives:
yn+1 =
through the point
R +1
xn +
R +1
xD
This is the equation of the rectication operating line which goes
R R +1 .
(xD , xD )
as a function of the reux ratio with slope
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Equipment
Minimum reux ratio

Find slope,
Example:
Rmin
(xD , xD ), (xF , yF ).
to the intersection of the
m, of operating line in
Draw a line from the distillate point,
rectifying section which goes through the point of intersection between the feed line at the equilibrium curve. From the slope, as dened in eq. 36, determine ratio:
equilibrium curve
feed line and the equilibrium curve,
Rmin , the minimum reux

operating line
For
yF
= 0.84,
we get
m = 0.24
From equation 38, we see that
m=
Rmin + 1 m Rmin = 1m
Rmin
(37) (38)
Feed line
0.05 0.5 0.95
Rmin = x
0.32
(39)
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Equipment
Actual reux ratio

The trade-o between the number of stages and the reux ratio is addressed by choosing a reux ratio as a factor of the minimum reux ratio,
Example: operating lines
nd slope and intercept for rectifying operating line:
Rmin .
For example:
R = 1.5 Rmin
The reux ratio can now be used to dene the rectication operating line
R = 2.5 Rmin
= 0.81
y = mx + b by:
m=
R R +1 x b= D R +1
m = 0.45 b = 0.53
0.05 0.5 0.95
and now draw the stripping section operating line.
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Equipment
Minimum number of stages
McCabe-Thiele Method Revisited

1
Generate and draw the equilibrium curve for the binary mixture. Locate and draw the feed line. Calculate the
y
2
Assume a total reux condition,
2 3 4 5
R = .
slope 1:
This denes an operating line of
R. y -intercept of the rectication section operating line for R . Draw a line from the y -intercept to the distillate product, (xD , xD ): this is the
Determine the minimum reux ratio and choose the actual reux ratio, operating line for the rectifying section. Draw a line from
R +1 Starting at (xD , xD ), draw stages

R
until we reach the bottom product
lim
(xB , xB )
to the intersection point of the rectifying operating
=1
line and the feed line.

7
Draw stages in starting at the distillate point working downwards in the column towards the bottoms product, tting stages in between the equilibrium curve and the operating lines and switching from the rectifying operating line to the stripping operating line when the feed line is passed.
(xB , xB ).
xB
xF
xDx
The number of stages calculated is the minimum number of stages.
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Equipment
for handout only

1 0.95 0.9 0.85 0.8 0.75 0.7 0.65 0.6 0.55 0.5 0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
The full method
y
3 4
All the steps

1 2 3
Draw graph with diagonal. Equilibrium curve. Feed line (
q = 1).
5 6 Feed plate 0.05 0.5
4 5 6
Minimum reux operating line. Rectifying section operating line. Stripping section operating line. Plates in rectication section. and in stripping section.
0.95
7 8
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Equipment
Heat transfer
How is heat transferred?
Heat transfer is concerned with temperature: represents the thermal energy, or heat, that is available, and ow of heat: represents the movement of thermal energy from one place to another. Heat transfer is thermal energy in transit due to a temperature dierence. Temperature dierence is the driving force that causes heat to be transferred. Heat transfer plays a major role in the design of process equipment.
Heat may be transferred in three dierent ways: conduction transfer of heat as a result of molecular motion and the subsequent transfer of kinetic energy. Conduction is predominant in solid materials and in static uids. convection the ow of heat as a result of macroscopic movement of matter from a hot to a cool region radiation transfer of energy in the form of rays or waves or particles (,
, )
We will consider only conduction and convection.
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Equipment
Conduction through a wall

Consider a wall of thickness temperature
T1 on one side and T2 on the other:
and surface area
A that has a uniform
Thermal conductivity
Materials with a large thermal conductivity, copper.
k , are good thermal
conductors. These will transfer large amounts of heat over time, e.g.
Conversely, materials with low thermal conductivities are poor thermal conductors. These will transfer small amounts of heat over time, e.g. concrete.
The heat transfer,
q (W ), through the wall is k q = A T x

(40)
The ratio
k x
is called the heat transfer coecient.
The inverse of the heat transfer coecient, resistance.
x k,
is the thermal
where
(in
measure of the ability of the material to conduct heat and
W mK )
is the thermal conductivity of the material which gives a
T T1 T2 .
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Equipment
Composite wall example

Applying eq. 40 to each section of the composite wall:
Heat transfer through convection

Example (Heating a pot of water)
At rst, when the water is cold and still, it behaves as a solid and heat is transferred by conduction through the bottom of the pot. Bubbles, when created, will transfer heat from the bottom to the top by convection due to buoyancy. Cooler, more dense water at the top will sink to the bottom.
k q = i A(Ti Ti +1 ) i = 1, . . . , 3 xi 1 q = xi A T
ki
so overall thermal resistance is sum of the individual resistances (analogous to electrical circuits).
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Equipment
Types of convection
Natural convection occurs when the motion of uid is due to buoyancy eects. Example, the cooling of a heated pipe:
Convective heat transfer
Heat transfer by convection,
q , is q = hAT
(41)
where
Forced convection is when the uid motion is produced by an external agent.
A (m2 ) is the characteristic area of contact. T (K ) is the temperature dierence between the solid and the uid. h ( mWK ) is the convective heat transfer coecient and is a property of
2
the system, not a property of the uid as is the thermal conductivity,
k.
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Equipment
Convective heat transfer coecient

The value of
What aects convective heat transfer?
h depends on the surface geometry, the properties of the uid

Type of convection Natural Material Gases Liquids Forced Gases Liquids
and the uid motion regime:
W m2 K
2-25
h is a function of the properties of the system and depends on: geometry of the system, i.e. a characteristic length L.
physical properties of the uid: i.e. viscosity, capacity,
50-1000 25-250 100-20000
cp , and thermal conductivity, k .
density,
heat
uid regime, i.e. a characteristic velocity To determine
h is therefore a complex task and we rely on experiments.
v.
Liquids transfer greater amounts of heat than gases, which are good thermal insulators and forced convection gives greater heat transfer than natural convection for both gases and liquids.
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Equipment
Prandtl and Nusselt numbers

The properties of the uids and the dierent forms of heat transfer can be described by some dimensionless numbers: Prandtl is the ratio between uid ability to store heat and to transfer heat through conduction, independent of the system geometry:
Flow patterns and temperature proles

Consider the ow of air over an innite at plate.
Ts
is the temperature of the plate, while
temperature away from the plate, with
Ts > Tf .
Tf
is the air ow
Pr = Nu =
cp
Nusselt is the ratio between heat transfer through convection and conduction:
hL k
Regardless of the type of convection, we analyse the ow pattern and the temperature proles at the wall and away from it.
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Equipment
Flow layers
Overall heat transfer coecient

Given a at wall of uniform, homogeneous material having constant thermal conductivity,
Tc , on either side:
k , exposed to uids h, at temperature Th , and c , at
Adjacent to the wall, a laminar sub-layer forms with no uid mixing. Heat transfer across the sub-layer is by conduction only with large resistance to heat transfer and large temperature change. Away from the wall, turbulent ow with large eddies and high uid mixing. Heat transfer is by convection with low resistance to heat transfer and small temperature change. with convective heat transfer coecients conductivity, coecient,
U ( mWK ), for the combined conductive-convective heat transfer:

2
k , and wall thickness, x .
hh and hc , wall thermal
What is the overall heat transfer
q = UAT
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(42)
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Equipment
Assumptions
Overall heat transfer
In steady state, the same amount of heat section.
q must pass through each
Heat transfer is by convection across the hot and cold lm and by conduction through the solid wall. The uid temperatures suciently far from the wall, unaected by the heat transfer and are known. The surface temperatures The heat transfer area,
q = hh A(Th T1 ) k q = A(T1 T2 ) x q = hc A(T2 Tc )
hot lm solid wall cold lm (solve)
Th and Tc , are
Note:
q= U
A(Th Tc )
hh
1
A, is the same for all sections.
T1 and T2 are unknown.
x 1 + k + hc
= UAT
can be calculated in a manner similar to resistances in electrical 1 1
networks:
Ui
(43)
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Equipment
Example: double-paned glass window
Solution: Diagram
Consider a 0.8m-high and 1.5m-wide double-pane glass window consisting of two 4 mm thick layers of glass ( by a 10 mm wide stagnant air space (
ka =
W 0.026 mK ).
kg
W = 0.78 mK )
separated
Determine the steady rate of heat transfer,
q , through the C
while the
double-pane window and the temperature of its inner surface,
a day during which the room is maintained at 20 . temperature outside is 10
T1 , for
Take the convection heat transfer coecients on the inner and outer surfaces of the window to be
h1 = 10 mWK
2
and
h2 = 40 mWK .
2
Assume that the heat transfer through the window is steady state since the surface temperatures remain constant.
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Equipment
Solution: overall thermal resistance

From eq. 43,
Solution: heat transferred
U
where
h1
= = = = =
L1 L2 L1 1 + + + kg k2 kg h2
1
h1 L1 kg L2 k2 L3 kg h2
1
m2 K W W 10 2 m K 0.004m m2 K W = 0.00513 W 0.78 m K 0.01m m2 K W = 0.385 W 0.026 m K 0.004m m2 K W = 0.00513 W 0.78 m K 1 m2 K W = 0.025 W 40 2 m K
1
= 0.100
and
U W U = 1.92 2 mK A = 0.8 m 1.5 m = 1.2 m2 q = UA(Ti To ) W = 1.92 2 1.2m2 30 K mK = 69.12W
= 0.52026
m2 K W
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Equipment
Solution: inner surface temperature
Non-uniform heat transfer area
q = h1 A(Ti T1 )
In some cases, the area for transfer applicable to each media could dier. For example, the radial ow of heat through a thick pipe wall or 69.12 10
T1 = Ti
q h1 A
W m2 K
= (20 + 273) K = 14.24 C = 287.24 K
1.2 m2
cylinder. The area of transfer in these cases is a function of position.
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Equipment
Example: curved wall

Consider a curved solid wall with constant thermal conductivity k exposed to a convective hot outer uid and a convective cold inner uid:
Derivation
Start with eq. 40,
q = k AT , and let x r . x dT q dr kA
ro
Consider heat transfer over a small part of the pipe and the corresponding change in temperature:
Integrate over the pipe wall:
To and Ti are the temperatures at ro and ri respectively. ho and hi are the convective heat transfer coecients in the outer and
inner lm, and impact of the thickness of these lms is assumed to be negligible.
ro q q dr = r dr Ti ri kA i 2 rLk q To Ti = (ln ro ln ri ) 2 Lk k q= 2 L (To Ti ) ln(ro /ri ) To
dT
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Equipment
Combined system
Engineers and heat transfer
Assuming thin lms on either side of the pipe, we can write three equations:
q = ho 2ro L(Th To ) k q= 2 L(To Ti ) ln(ro /ri ) q = hi 2ri L(Ti Tc )

which have three unknowns, specic reference area.
In practice, engineers often have to design equipment to eect heat transfer, say to achieve a specic temperature change in a uid stream of known mass ow rate, Such equipment will typically be in the form of a heat exchanger and the engineer will need to
To , Ti
and
q , so we can solve as usual.
Note: the heat transfer coecient will often be given with respect to a
determine the surface area to transfer heat at a given rate for given uid temperatures and ow rates. predict the outlet temperatures of hot and cold uid streams for a specied heat transfer.
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Equipment
Heat exchangers
Double pipe heat exchanger

The simplest form of an heat exchanger consists of two concentric cylindrical tubes, the double pipe heat exchanger:
A heat exchanger is any device that eects transfer of thermal energy between two uids that are at dierent temperature. The two uids do not come in direct contact but are separated by a solid surface or tube wall. Common heat exchangers include:
Shell-and-tube (single pass or multi-pass) Flat-plate Finned tubes

Heat transfer involves convection in each uid and conduction through the wall separating the two uids.
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Equipment
Parallel or co-current ow

The uids both ow in the same direction:
Counter-current ow
The uids ow in opposite directions:
In both cases, the uids are forced to ow using pumps or fans.
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Equipment
Shell and tube single pass
Example
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Equipment
Multi-pass shell and tube
Multi-pass ow arrangement
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Equipment
Example
Plate heat exchangers

Plate heat exchangers are built up from individual plates separated by gaskets, assembled in a pack and clamped in a frame.
They are applied in the energy recovery section of many processes because of low initial cost, high eciency and low maintenance costs.
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Equipment
Plates
Finned tube heat exchangers
Finned tubes exchangers are employed Thin sheet material, resulting in economic units, particularly when expensive material is involved. Plates are especially corrugated to promote turbulence also at low in large air/liquid heat exchanger systems to give greater heat transfer area because gases, which are good thermal insulators, transfer smaller amounts of heat than liquids. There are various types of nned tubes, depending on the application:
very high heat transfer coecients reduces fouling

facilitates chemical cleaning
Re , resulting in:
large air conditioning systems radiators for large truck.
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Equipment
Heat transfer in a heat exchanger

Heat exchangers operate for long periods of time with no change in the operating conditions. They can be modelled as steady-ow devices:
1
Energy balance
Under these assumptions, it follows that the rate of heat transfer from the hot uid to be equal to the rate of heat transfer to the cold one. The basic design equations for heat exchangers are therefore the energy balance for each uid:
The overall heat transfer coecient, exchanger.
U , is constant throughout the
2 3 4
The mass ow rate of each uid remains constant. The specic heats of the uids are constant. The temperature of the two uids are constant over a specic cross-section.
q = mh cph (Tho Thi ) q = mc cpc (Tco Tci )
(Energy given up by hot uid) (Energy gained by cold uid)
The outer surface is perfectly insulated, so that any heat transfer occurs between the two uids only.
where
kJ m (kg/s) is the mass ow rate and cp ( kg K ) is the specic heat. But what is the driving force, T ?
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Equipment
Temperature prole: co-current ow
Temperature prole: counter-current ow
The temperature dierence
is large at the inlet but decreases
exponentially towards the outlet. Temperature of the hot uid decreases and the temperature of the cold uid increases along the heat exchanger. The outlet temperature of the cold uid can never exceed that of the hot uid, no matter how long the heat exchanger.
The hot and cold uids enter the heat exchanger from opposite ends. The outlet temperature of the cold uid may exceed the outlet temperature of the hot uid, temperature cross. The outlet temperature of the cold uid can never exceed the inlet temperature of the hot uid.
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Equipment
Design
Log mean temperature dierence derivation I
q = UAT . Need to calculate T for either

Recall eq. 42, co-current or counter-current exchange. However, the temperature dierence varies across the range of operation. We introduce the log mean temperature dierence (LMTD), expression of
At any point along the exchanger:
q = mh cph Th q = mc cpc Tc q = U (Th Tc ) A

(44)
T .
TLM ,
as an
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Equipment
LMTD II
Rearrange for
LMTD III
T
in each equation and nd the dierence: Let the
terms be dierentials and integrate along the length of the
exchanger:
Th =
mh cph q Tc = mc cpc mh cph

1
ln (
Tho Tco ) ln (Thi Tci ) = UA
mh cph
mc cpc
which, when combined with overall energy balance on each uid (solve for
mcp + mc cpc mh cph mc cpc

1 1 1
term and substitute):
+(44) :
Th Tc = q
(Th Tc ) = U A(Th Tc ) (Th Tc ) = U A (Th Tc ) mh cph

1
mc cpc
ln (
Tho Tco ) ln (Thi Tci ) = UA
ln
(Thi Tho ) + (Tco Tci )
T2 ln T1 = UA
T2 T1
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Equipment
LMTD IV
T2 T1 ln T2 ln T1 T2 T1
ln
Correction factor for complex heat exchangers

TLM ,
or
q = UA q = UA
Determination of the average temperature dierence, dicult for complex heat exchangers. It is practice to introduce a correction factor, rate is then given by:
is
Ft .
The heat transfer
T2 T1
q = UA Ft TLM
LM is that for the counter ow double-pipe heat exchangers with the same uid inlet and outlet temperatures as in the more
where The term in the box is (LMTD). For counter-current exchangers, the same result is obtained although for dierent
TLM ,
the log mean temperature dierence
complex design.
Ft
values for several congurations are given in reference books (cf.
Perry or Kern).
T1
and
T2 .
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Equipment
Example: area comparison
Solution
co-current
T1 = 200 C 80 C = 120 C T2 = 150 C 120 C = 30 C Tco-current = T1 = Tcounter-current

30
Suppose we wish to exchange heat between a hot stream, with
counter-current
C 120 C
30
Thi
= 200 C and Tho = 150 C , and Tco = 120 C .
and a cold stream, with
Tci
= 80 C
Assuming the same heat transfer coecient, same amount of heat, exchange?
U , in both cases and the q , to be exchanged, what is the ratio of area
C C = 80 C T2 = 150 C 80 C = 70 C 70 C 80 C = 75 C
ln 120 C 200 120
65 C
required for co-current exchange to area required for counter-current
Aco-current Acounter-current
ln 80 C
70
U Tco-current q U Tcounter-current Tcounter-current = Tco-current

=
1.15
C q
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Equipment
Example: Cooling a hot process uid in a counter-ow heat exchanger

A counter-ow double-pipe heat exchanger is used to cool a hot process uid using water. The process uid ows at 18
Solution: Diagram
105
to 45
entering at 25
1
C . The water ows counter-currently to the process uid, C and leaving at 50 C .

kJ 3.4 kg K . kJ kg K
and that of the
kg s
and is cooled from
Assuming no heat losses, calculate the required ow-rate for the cooling water. The specic heat for water is 4.2 process uid is
Neglecting the tube wall curvature, calculate the required area for heat exchange. Under these conditions, the process uid side lm heat transfer coecient is 2500 coecient is
W 1200 2 . m K
W m2 K ,
the cooling water side heat transfer
The tube wall thickness is 3 mm and the
thermal conductivity is 220
W mK .
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Equipment
Solution: 1. required water ow rate
Solution: 2. heat exchanger area
q = Gf cpf (Tho Thi ) = 3672kW = Gw cpw (Tco Tci )
(heat from hot stream) (energy balance)
TLM =
1
q = UATLM T2 T1
ln
Gw
34.97
kg s
(water ow rate required)
x 1 + U hf k hw W U = 802 2 mK q A= = 132.3m2 U TLM

=
1
T2 T1
= 34.6 K
(thermal resistance)
(overall htc)
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Fouling
The performance of a heat exchanger depends upon surfaces being clean but deposits form over time. The layer of deposits presents additional resistance to heat transfer and must be accounted for by a fouling factor, 1
Pumping of liquid uids
Rf
Pumps are the devices used to add energy to a uid in order to maintain ow. Fluids ow in the direction of decreasing pressure.
(cf. Perry, Kern).
= Rconv,hot
uid
+ Rcond,wall +
Rf
+ Rconv,cold
uid
Pumps direct a uid from one vessel to another or through a long pipeline. The energy added to the uid compensates for the mechanical energy losses due to friction and provides an increase in the velocity, the pressure, or the height of the uid.
Deposits can occur by the precipitation of solid deposits (e.g. calcium in a kettle), corrosion or chemical fouling due to chemical reactions, and the growth of algae, biological fouling. Can apply water treatment, coatings and chemical treatments. Periodic cleaning of exchangers and the resulting down time are additional penalties associated with fouling.
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Equipment
Valves
Pumping devices for liquids
Valves are used to control the ow rate: On/O valves: gate (30% of all on/o valves) and ball Throttling valves: globe (50%), needle and diaphragm Check valves: allow ow only in one direction Automatic valves Relief valves (for safety): spring loaded, bursting disk. Liquids used in the chemical industry dier considerably in physical and chemical properties so a variety of pump types exists. Most pumps fall into one of two major classications:
Positive-displacement pumps Centrifugal pumps
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Equipment
Positive-displacement pumps
Examples
Reciprocating pumps involve a back-and-forth motion of a piston in a cylinder. Rotary pumps depend upon a rotating motion. The ow from these pumps is pulsating. The higher the speed of the pump, the higher the ow rate delivered. Deliver a controlled amount of liquid for each stroke or revolution. Used when nearly constant delivery rates are required.
Reciprocating pumps:
Diaphragm pump Piston pump

Rotary pumps:
Gear pump Lobe pump Peristaltic pump Screw pump

For details on other types of pump refer to Coulson & Richardson.
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Equipment
The Piston pump
Piston pumps
Piston pumps may be single-acting, with the liquid admitted only to the portion of the cylinder in front of the piston.
In these pumps, the motion of a rotor is converted into a back-and-forward motion of a piston. The rate of liquid delivery is a function of the volume swept out by the piston in the cylinder and the number of strokes the piston make per unit time. For each stroke of the piston, a xed volume of liquid is discharged from the pump. When the piston moves towards the disk it creates a partial vacuum in the chamber. This allows atmospheric pressure to push the uid from below. On the return half of the cycle the top check valve opens and the
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bottom one closes. The water is forced up through the pipe.
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Equipment
Equipment
Double-acting piston pumps

Piston pumps can also be double-acting, in which case the feed is admitted to both sides of the piston.
Piston pump applications
These pumps can deliver the highest pressure of any other pump. Piston reciprocating pumps have long been used in many applications, including pumping of oil, feed water and mud. However, their capacities are relatively small compared to centrifugal pumps. As the piston moves downwards, it forces the uid out through the bottom right valve and creates at the same time a partial vacuum in the upper chamber, pushing the uid through the top left valve. When the piston is moving upwards it forces the uid out through the top right valve, while creates at the same time a partial vacuum in the lower chamber, pushing the uid in through the bottom left valve. Not used with liquid containing abrasive material as it can damage the machined surfaces of the cylinder and piston.
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Equipment
Equipment
Diaphragm pump
Rotary pumps: the Gear pump
In one section a piston operates in a cylinder in which an inert liquid is displaced. The movement of the uid is transmitted by means of the exible diaphragm. They have been developed to handle corrosive liquids or suspensions with abrasive solids. They are used for example to move gasoline from the gas tank to the carburetor. They are not used for high pressure applications.
Two gears operate within a casing. Small packages of uids are carried between the teeth and the casing from the low pressure inlet side to the high pressure delivery side. Has been developed to deal with viscous uids.
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Equipment
Equipment
The 3 lobe pump
The Peristaltic pump
Works on the same principle of the gear pump but the gear teeth are replaced by two or three lobes. A small clearance between the lobes can be maintained and wear is reduced. Delivers ow precisely controlled by the speed of a rotor compressing an elastic tube. The rollers atten the tube against the track at the points of contact and these ats move the uid along the tube. They are mainly used in labs as they are particularly good in handling
biological uids, where all forms of contacts must be avoided.
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Equipment
Equipment
The screw pump
Screw pump
One of the oldest pumps: its usage goes back 2000 years. It consist of a helical screw. Suitable for very viscous uids (e.g. polymers) and also for sewage uids. The uid is sheared in the screw channel and so is raised to the delivery side.
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Figure: Pumps used in a waste water treatment plant.
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Equipment
Equipment
Centrifugal pumps
Centrifugal pumps II
A Centrifugal pump has an impeller enclosed by a casing or volute. The
Pumps that cause the pumped uid to rotate are called centrifugal pumps. Centrifugal pumps are the most widely applied in the chemical and petroleum industry. They are applied for large capacity applications. They pump liquids with very wide-ranging properties and suspensions with high solids content. They cannot handle highly viscous uids.
impeller consists of a series of curved vanes. The greater the number of vanes, the greater is the control over the direction of motion of the uid.
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Equipment
Equipment
Centrifugal pumps III
Turbine pump
The uid is fed to the centre of the rotating impeller and is thrown from the impeller vanes into the casing by centrifugal force. As a result, the liquid acquires a high kinetic energy. This velocity energy is converted in pressure as the uid leaves the impeller and enters the casing.
In the turbine pump, the liquid ows from the impeller into a series of xed vanes, called diusers. These give more gradual change in direction to the uid and more ecient conversion of kinetic energy into pressure energy.
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Equipment
Equipment
Summary of types
Pump characteristics
Centrifugal Reciprocating (piston) Head High, single stage up to 600 ft Multistage up to 6000 psi Capacity Low (100 gal/min) to very high (200,000 gal/min) Liquids Clear or dirty, non viscous Clean no solids Intermediate (500 gal/min) Low (1 gal/min) to intermediate (500 gal/min) High viscosity, non abrasive Highest available 100,000 psi Rotary (gear or screw) Intermediate up to 600 psi
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Equipment
Equipment
Summary of characteristics
Operating characteristics of centrifugal pumps
Pump
Pressure delivered
Flow delivered pulsating pulsating pulsating continuous
Capacity
Fluid
Centrifugal pumps are the most widely applied in the chemical and petroleum industry. Centrifugal pumps operate at constant speed and the capacity depends upon the total head,
Piston Diaphragm Rotating Centrifugal
very high not high not high not high
not high not high not high very high
non-corrosive corrosive highly viscous not viscous
H , the design and the suction conditions.
Pumps usually achieve maximum eciency at one particular ow rate. Operating characteristics are described through use of characteristic curves.
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Equipment
Equipment
Characteristic curves
Characteristic curve graph
For a pump at a particular speed, the characteristic curves show the inter-relation between:
Total head and capacity, the H Q curve. Power input and pump capacity, the P Q curve. Pump eciency and capacity, the Q curve. This is the point where the head curve cuts the ordinate through the point of maximum eciency.
The duty point shows the optimum conditions for operation.
For a pump having the characteristics shown above: maximum eciency would occur at a capacity of 2500 gal/min and a total head of 80ft.
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Equipment
Equipment
Variable speeds
Pump design
The energy required for a pump will depend on the height through which the uid raises, the pressure required at the delivery point, the length and diameter of the pipe, the rate of ow, and the physical properties of the uid, density and viscosity.
When a pump is capable of being operated at variable speeds, then, at higher speed of rotation gives higher capacity and requires more horsepower to supply the increased supply of liquid.
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Equipment
Equipment
General scenario for pumping
Energy balance
The work done on a uid by a pump is expressed as head, the mechanical specic energy balance,
(m). From
H=
p u2 + + z + hfT g 2g 2 2 P2 P1 u2 u1 + + (z2 z1 ) + hfT = g 2g

vertical position, and
(45)
where
u is velocity, p pressure, z
hfT
represents the
total friction loss in the system and is the sum of the losses in the whole pipe length and other losses due to ttings:
hft = hf + htting
where
loss
hf
is the frictional head loss.
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Equipment
Equipment
Reynolds and Grashof numbers

These dimensionless numbers describe uid ow properties: Reynolds The ratio between inertial and viscous forces in the uid which identies the uid ow regime:
Frictional losses
hf
(46)
is expressed as a frictional pressure drop over a pipe of length
l:
Re =
vL
hf = 2cf
where the Fanning friction factor, number,
High values correspond to turbulent ow regime, and therefore to high convection h.t.c. Grashof replaces
Re
when uid motion is driven by thermal expansion
Laminar ow
of the uid:
16 cf = Re 0.25 Turbulent ow cf = 0.079Re

Rough pipes use Moody diagram to estimate the value
Re
cf , is given as a function of the Reynolds
l u2 dg
pf g
(eq. 46):
Gr =
where
T 2 gL3 2
is the volumetric thermal expansion coecient.
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Equipment
Equipment
Fitting losses
Total friction losses
Loss due to ttings, such as bends and valves, can generate large-scale turbulence in which energy is dissipated as heat. For turbulent ow, these losses are proportional to the square of the uid velocity and can be expressed as the frictional loss due to an equivalent length of straight pipe, pipe diameter:
Total friction loss is therefore equal to
le , estimated as a multiple of the
hfT = 2cf
which in terms of pressure losses is
l + le u 2 d g l + le 2 u d
(47)
le = nd
htting
loss
so that
= 2cf
le u 2 d g
pfT = g hfT = 2cf
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Equipment
Equipment
Power requirements
Example
Thus, from eq. 45, the head,
H , that must be supplied by the pump is:

2 2 2 1
2.32
P P u u H= 2 1+ g 2g
Power where
l + le u + (z2 z1 ) + 2cf d g H
is given by:
distance of 125 m in a horizontal direction and then up through a vertical height of 12 m. The friction loss in the 90
m3 h
of water is pumped in a 35 mm internal diameter pipe through a
square elbow may be taken as
equivalent to 60 pipe diameters. Also in the line there is a control valve fully open and frictional losses may be taken equivalent to 200 pipe diameters. Calculate the total head
The power required by the pump to deliver
= Pp Q =
H g Q
hfT
to be developed to overcome the total
frictional losses in the pipeline. You may assume that for this pipe
is the volumetric owrate of the uid that the pump moves and is
= 0.079Re 0.25 .
mN s m2
Assume the water to ow in turbulent regime through
known as the capacity of the pump.
the pipe. Density and viscosity of water in the pipe are 1000 0.65 respectively.
kg m3
and
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Equipment
Solution: data collection

Quantity Volumetric Flow rate Density of water Viscosity of water Value 2.32 1000 0.65 Units
Solution
The total friction losses, eq. 47, in the pipeline for turbulent ow regime is expressed as:
Internal pipe diameter Horizontal pipe length Vertical pipe length 90
d lh lv cf
103
0.65
35 0.035 125 12
mm m
m m m m
m3 h kg m3 mN s m2 N m2 s
cf (l + le )u 2 gd with l = lh + lv = 125m + 12m = 137m and le from the denition of the

hfT =
2 equivalent pipe length:
le = 200d + 60d = 200x 0.035m + 60x 0.035m = 9.1m

The velocity of the water in the pipe is given by the volumetric ow rate divided by the pipe cross-section area:
square elbow friction loss
Control valve friction loss Friction coecient
d 200d 0.25 0.079Re

60
u=
d 2 2
2.32
m3 h
1h 3600s 0.035m 2 2
= 0.67
m s
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Equipment
Equipment
Solution
The friction coecient depends on
Cavitation in centrifugal pumps
Re , the Reynolds number (eq.

3
46):
Cavitation is the formation of cavities or bubbles in a pumped uid when the pressure on the uid falls below the vapour pressure of the liquid,
Re =

du
0.035
cf
= 0.079Re
0.25
kg m 0.67 m 1000 m s N 0.65 103 m s

2
= 36076 = 0.0057
Pv
(or
p ).
When a centrifugal pump is operated at high capacity, low pressure may develop at the impeller eye or vane tips and so vapourisation may occur. Cavitation leads to:
= 0.079 36076
0.25
hfT = =
cf (l + le )u 2 gd
0.0057 (137 + 9.1)m (0.67 m )2 s = m 9.81 2 0.035m s
2.17
m N m2
pfT = hfT g = 2.17m 9.81
m kg 1000 3 s2 m
= 21287
A reduction in pump capacity. A reduction in the head of the pump. A noise that can be heard when the pump is running. Mechanical damage that can be seen on the pump impeller and volute.
To avoid cavitation, the pressure at the pump inlet must exceed the vapour pressure of the liquid.
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Equipment
Equipment
Pump congurations
Negative suction head
Pump is placed above the reservoir of uid to be pumped, drawing uid up with suction:
Net positive suction head (NPSH)

Positive suction head
Pump is placed below the reservoir of uid to be pumped and is fed by gravity action: To avoid cavitation, the pressure at the pump inlet must exceed the vapour pressure of the liquid. NPSH is the amount by which the pressure at the suction point of the pump must exceed the vapour pressure of the liquid and is expressed as a head of the liquid to be pumped. For any pump, the manufacturers specify the minimum value of the NPSH required at the impeller eye to avoid cavitation.
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Equipment
Equipment
Typical conguration
Available NPSH
Start with energy balance (per unit mass):
P1 , pressure at the tank liquid

surface.
h1 , height of the liquid surface

above the pump centre-line at the suction inlet.
If the reference plane is taken at h2 , and the liquid velocity in the reservoir, u1 , is negligible compared with u2 :
P1 g
2 u1 2g
+ h1 hf =
P2 g
2 u2 2g
+ h2
(48)
u1 , liquid velocity on the surface. u2 , velocity at the pump inlet. hf , total piping friction loss
between (1) and (2).
P1 g
+ h1 hf =
P2 g
2 u2 2g
(49)
The available NPSH is the dierence between the static head and the head corresponding to the vapour pressure of the liquid at the suction inlet.
NPSHA
P2 g
2 u2 2g
Pv g
P1 Pv g
+ h1 hf
(50)
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Equipment
Required NPSH - I
From eq. 49, the total head at the suction inlet is:
Required NPSH II
Cavitation is probable if the total head at the impeller eye (rhs of eq. 51 minus eq. 52) is equal to or less than the vapour pressure:
P2 g
than at the suction inlet by
P1 = g
u2 + h1 hf 2 2g
(51)
P1 g
+ h1 hf
2 u2 2g
2 u3 2g
Pv g
2 u3 2g
Cavitation usually occurs at the impeller eye where the pressure will be less
Limiting case therefore is
P =
Where
2 u3 2g
(52)
P1 Pv g
+ h1 hf =
2 u2 2g
where the right hand side is the NPSH required at the impeller eye:
u3 is the uid velocity at the eye.
is a pressure drop coecient characteristic of pump geometry and NPSHR
2 u2 2g
2 u3 2g
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Equipment
Avoiding cavitation
In order to avoid cavitation, the NPSHA available has to be greater than the NPSHR required at impeller eye: NPSHA
> NPSHR
The value of the required NPSHR for the particular pump being used may be obtained from the pump manufacturer. If NPSHA is too low, then cavitation can be avoided by increasing This is why pumping uids that are close to saturated conditions require that the vessel upstream be elevated . . . . . . or, more generally, that the pump be lowered.
h1 .
Professor Eric S Fraga Room 2.05 Engineering Front Building Department of Chemical Engineering UCL phone:317 / UTUW QVIU G xQQVIU email: eFfrgdulFFuk web: wwwFhomepgesFulFFukGueesfG () CENG 1004: Introduction to Chemical Engineering 2011, : 1.20 HPH 317
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Introduction

CENG 1004: Introduction to Chemical Engineering

chemical engineering unit operations.

HPH UTUW QVIU G xQQVIU email: eFfrgdulFFuk wwwFhomepgesFulFFukGueesfG

Chemical Engineering  Volume 1 by J M Coulson and J F Richardson, Pergammon Press.

Heat Transfer by D Pitts and L Sissom, Schaum's Outlines, McGraw-Hill.

Heat transfer a practical approach by Y A Cengel, McGraw-Hill.

back substitution order of magnitude estimation test of reasonableness

Some useful terms

Process analysis procedure

Mass balance equations

+ generation output consumption = 0 output = 0

n mass balance equations

No reaction, steady state: input where:

Example: Continuous distillation

One thousand kilograms per hour (1000 kg/h) of a mixture of benzene ( 6

C H6 ) and toluene (C7 H8 ), containing 50% benzene by mass, is separated

n2,b = 5.8 kmol h n2,t = ?

Solution: Gather equations

Solution: solve equations

= 0.50 = 500 = 6.4

n3,b n2,t n1,b m1,b m1,t n1,t

= (1000 500) = 500

= 500 = 5.4 = 0.2

Number of mass balance equations

Degrees of freedom analysis

Dene the degrees of freedom of a system:

Tools like GAMS can help in degree of freedom analysis:

ndof = nunknowns nequations

ndof > 0, we need to nd more equations to solve the system.

Example 4.2-3: Batch mixing process

m2 = 150 g x2,m = 0.70 g g

total mass balance methanol balance denition denition denition denition

feed1 feed2 output

0.400 0.700 0.529

Solution: Draw and label diagram

x2,H = 0.10 kmol kmol VH = 10.0m3

kmol 0.100 min

Solution: solve equations

n1,A = n2,A n2,H dt = nacc,H macc,H = H VH MWH nacc,H = macc,H

Hexane balance Denition Denition Rule Denition Denition

macc,H = H VH = 0.659 3 cm macc,H 6590 kg nacc,H = = MWH 86.17 kg x2,A = 1

cm3 1 kg 10m3 = 6590 kg 1 m3 1000 g

kmol 0.90 kmol kmol kmol

x2,A = n2,A / n2 x2,H = n2,H /n2

n2,H = x2,H n2 = 0.10

Solution: solve equations (continued)

n2,H dt = nacc,H 0 n2,H t = nacc,H

Solution: Draw and label diagram

1=2 2=4 3=3 4=3 5=2 6=1 7=1 8=1 9=1

V1 = 2000 L h SG1 = 0.872

kmol 0.950 kmol

m1,B n2,B n2 n2,T m2,T m2 x3,B x3,T

x1,B = 0.45 kg kg kg x1,T = 0.55 kg

A stream of fresh air is combined

Solution: Draw and label diagram

5, intersect this box.

The equations can be solved for

n1,A = n4,A + 5,A n n1,A = (1 x1,W )n1 n4,A = (1 x4,W )n4

Chemical Engineering Volume 1 by J M Coulson and J F Richardson, Pergammon Press.

Heat Transfer by D Pitts and L Sissom, Schaum's Outlines, McGraw-Hill.

Heat transfer a practical approach by Y A Cengel, McGraw-Hill.

Dene the degrees of freedom of a system:

ndof > 0, we need to nd more equations to solve the system.

total mass balance methanol balance denition denition denition denition

Hexane balance Denition Denition Rule Denition Denition