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Chapter 1 INTRODUCTION

INTRODUCTION
1. Introducing Chemical Engineering
Chemical Engineering covers a wide scope that is difficult to put in one definition. However, a good definition is that chemical engineering is concerned with the design, construction, and operation of chemical process plants. In general, chemical plants perform the following :

Raw Materials (input) Energy

The operation in the chemical plant may involve physical steps (separation) and/or chemical steps (reactions) Products (o u t p u t)

Basically, there are 3 distinctive functions for a chemical plant.

(1)

(2)

(3)

Purification of raw materials

Separation into products

Chemical conversion

- Crude Oil dehydration desalting - Dehydration and

- Distillation of crude oil

Steam reforming of N.G H2, CO

- Separation of
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sweetening of natural gas

C1, C2, C3 and C4 - Fresh water from saline sources

- NH3 synthesis - Hydrotreating and hydrocraking in petroleum refining

Notice the difference between a physical separation process and a chemical conversion step.
Fresh Water Sea Water M.S.F. Brine N2 + H2

NH3 Synthesis (Reactor)

NH3

(Input)

(Output)

(Reactant)

(Product)

2. Classification of Processes
Processes are classified according to different classifications as follows:

2.1. Physical Versus Chemical Processes


Physical processes include mixing, heat exchange (heating or cooling), condensation, evaporation, separation and purification processes such as distillation, extraction, and absorption. In these processes, there is no molecular change and thus no new species formed or consumed. Chemical processes, on the other hand, involve chemical reactions in which atoms are rearranged or redistributed to form new molecules or products and some reactants are partially or totally consumed. As shown in the diagram below, process industries usually consist of chemical processes as the heart of the plant preceded and followed by physical processes :
2

Raw Material

Physical process typically mixing or heat exchange

Chemical process

Physical process typically heat exchange or separation

Products

2.2. Continuous Versus Batch Processes


Batch process The feed is charged into the system at the beginning and removed at one at the end.

Continuous processes

Inputs and outputs flow continuously throughout the duration of the process.

Semi-batch processes

Also referred to as semi-continuous process, is any process that is neither batch nor continuous.

2.3. Steady-State Versus Transient Processes


In the steady-process, all process variables such as temperature, pressure, flow rates, etc. do not change with time. If any of the process variables change with time, the process is transient or unsteady-state process. Accordingly, the batch and semi-batch processes are unsteady-state operations by their nature, because it would not be possible to maintain all process variables constant with time. On the other hand, continuous processes may either be steady or unsteady state. Usually, continuous process plants operate under steady state conditions. Typical situations under which unsteady-state operations is obtained include process start-up, shutdown, or process upset.

3. Overview of the Principles of Chemical Engineering


3.1. Basis Courses (subjects) Covered In A Chemical Engineering Program In a chemical plant:

Transformation of both materials (matter) and energy occur. To study these changes, use is made of the following basic courses:

Thermodynamics Laws

Stoichiometry Principles

Material Balance Energy Balance

Transport Phenomena, (Unit Operations, Momentum, Heat, Mass Transfer)

Kinetics, Reactor Design, Control

3.2. The Design of Chemical Processes: Stages and Approaches

Approach and method of attacking Stages Chemical Process design 1. Construction of qualitative flow diagram

Problem synthesis

CHE And other fundamentals used to obtained solution

Simple block diagram for all steps involved in the process, indicating which are u.o. and which are c.c.

2. Calculations involving Material balance - Law of conservation of process streams (in/out mass calculations of equipment) based on Energy balance (for - Stoichiometry given specs and process both nonreacting and - Thermodynamic laws variables - Gas laws reacting systems) - Others 3. Sizing of equipment Treatment of processes used in process (as per involving: step 1) a) Physical separation, fluid handling and heat transfer (unit operations) b) Chemical reactions and conversion processes (use of rate equations). 4. Construction of quantitative flow diagram Transport phenomena: Fluid, heat and mass Application of u.o. principles Chemical reactions kinetics Reactor design

Results of steps (2) and (3) Plant layout for are blended to form both optimum organization block & symbolic Cost estimate and quantitative flow diagrams. economic analysis for profitability measures Process instrumentation and control.

3.3. Functions of Chemical Engineers


(with the help of others)

Develop, design and engineer the complete process (process design & the equipment)

Choose the proper raw materials

Operate the plant efficiently, safely and economically

Assure that the products are in specifications

Chapter 2 DIMENSIONS AND UNITS

DIMENSIONS AND UNITS


Dimension is a property that can be measured, e.g. length (L), time (t), Mass (M), or temperature (T). These are the basic dimensions relevant to chemical engineering. From these, other dimensions can be calculated by multiplying or dividing the basic dimensions, such as velocity (L/t), volume (L3), or density (M/L3). Units are specific values of dimensions that have been defined by convention, custom, or law, such as grams for mass, seconds for time, and centimeters for length. Treat the units as ALGEBRAIC symbols, i.e. you can add, subtract, or equate like units but not unlike units. 3 kg + 5 kg = 8 kg 15 cm - 12 cm = 3 cm But 3 kg + 4 seconds = ? meaningless like 3x + 4y = ? 3x + 5x = 8x 15x - 12x = 3x

On the other hand, numerical values and their corresponding units may always be combined by multiplication or division:

100 km km = 50 2h h
90 km x 4 h = 360 km h

12 km x 6 (dim ensionless quantity) 2 km 3 ft x 4 ft = 12 ft2

1. System of Units
There are three systems of units. These are the CGS, SI, and the American Engineering Systems of units. Each system of units has the following components relevant to chemical engineering:

Base units

- units of length, mass, time, and temperature

Multiple units - multiples or fractions, e.g. cm, m, km. Derived units - obtained by multiplying or dividing base units such as ft3 and kg m lb . ft or defined equivalents, e.g. N = kg. 2 and 1 lbf = 32.2 m2 3 s s m
Table (1) shows a comparison of the various base and some selected derived units used in the above mentioned systems of units. Table (2) gives more comprehensive details.

Table (1) Base Units Quantity


Length Mass Time Temperature

CGS
centimeter gram seconds Kelvin (cm) (g) (s) (K) meter

SI
(m)

American Eng.
foot (ft)

kilogram (kg) seconds Kelvin (s) (K)

pound mass (lbm) seconds Rankine (s) (R)

Derived Units Quantity


Volume Force Pressure Energy, work Power erg gram-calorie watt (W) liter dyne

CGS
( l or 1) liter newton pascal joule watt

SI
( l or 1) (N) (Pa) (J) (W)

American Eng.
cubic feet (ft3) pound force (lbf) lbf/in2 (psi)

horsepower (hp)

2. Force and Weight


From Newtons law, F = ma (where F is force, m mass, and a is acceleration).

Units of force kg American Eng.

m s2

in SI units, g .

cm ft in CGS units and lb m . 2 2 s s

in

For simplicity, use derived force unit. 1 newton (N) 1 kg


m s2 cm 1 dyne 1 g 2 s

In American Engineering, the derived force unit lbf (pound-force) is defined as the product of a unit mass (l lbm) and the acceleration of gravity at sea level and 40o latitude which is 32.174
ft . s2

1 lbf 32.174 lbm

ft . s2

Since both units of mass and force in American Engineering system are called pounds, there is some confusion about this. So, always distinguish them in your mind, lbm / lbf. Force conversion factor, gc = 1
kg. m / s 2 N

g c m / s2 or = 1 dyne
lb m .ft / s 2. lbf

or = 32.174

Thus, the equation for force in defined units is:


F= ma gc

The weight of an object is the force exerted on the object by gravitational attraction. Weight, W =
mg . g is the acceleration of gravity and is equal to : gc m N g / g c 9.8066 2 kg s cm dyn g / g c 980.66 2 g s ft lb g / gc 1 f 2 lb m s

g = 9.8066

g = 980.66

g = 32.174

Note that g is acceleration due to gravity which varies according to position on earth and height while gc is conversion factor and is constant. This is a source of confusion in American Engineering units.

3. The Mole Unit


The number of moles =
mass , so, depending on the units of mass used, molecular weight

the unit of moles is determined. When grams are used for mass, the resulting mole unit is gram-moles, or simply moles, mass in kilograms will give mole unit in kgmole, mass in pound-mass will give moles in lb-moles and so on. In the CGS and SI systems of units, the mole unit is gram-mole (mole or g-mole) while in the American Engineering, the pound-mole (lb-mole) is used.

4. Conversion of Units
A measured quantity can be expressed in terms of any units having the appropriate dimension. For example, velocity =
length (cm, ft, km, mile) time (s, min h ) etc.

Thus, the units of velocity may be

ft km , , etc. s h

Numerical value of velocity depends on units chosen.

BEWARE of errors due to improper use of units. Using units with your number help
guide you to the correct answer. The Conversion Factor is a ratio used to convert a certain quantity with certain unit to its equivalent in another unit. e.g.
1m 60 s 10 mm ) 100 mm 2 ( , , and = 100 cm 1 min 1 cm 2 1 cm 2
2

For conversion to the new units, multiply the old unit by the conversion factor which new unit should be the equivalent of . old unit e.g. convert 500 g to kg 500 g x
1 kg = 0.5 kg 1000 g

Alternatively, this may be done by using a dimensional equation as follows :

500 g 1 kg = 0.5 kg 1000 g This should avoid mistakes, compare with

500 g 1000 g g2 = 500,000 1kg kg of course this is meaningless, and certainly does not result in the desired units.
km g , , etc. , set up a When converting a quantity having a compound unit e.g. 3 h cm

dimensional equation. Table 3 gives the conversion factors you will need .

Example :
1. Convert a flow rate of 5 ft3/s to its equivalent in m3/day:
5 ft 3 0.028317 m3 60 s 60 min 24 h m3 = 12 , 233 s 1ft 3 1 min 1h 1 day day

2.

Convert a density of 1000 kg/m3 to its equivalent in lbm/ft3 : lb m 1000 kg 2.20462 lbm 1 m3 = 62 . 4 m3 1kg 35.3145 ft 3 ft 3

So, the dimensional equation has vertical lines set up to separate each ratio (conversion factor), and these lines retain the same meaning as multiplication sign placed between each ratio. At any point in the dimensional equation, you can determine the consolidated net units and see what conversions are still required.

Dimensional Homogeneity:
As a rule, every valid equation must be dimensionally homogeneous; that is, all additive terms on both sides of the equation must have the same dimensions. m e.g. V (m / s) = Vo (m / s) + g 2 t (s) s dimensionally homogeneous while V = Vo + g is not homogeneous This is also consistent in its unit.

If an equation is dimensionally homogeneous but its term are inconsistent in units, these terms and hence equation can be made consistent in units by multiplying by the conversion factor. Thus, dimensional analysis can also be used to help identify the dimensions of terms in an equation. The opposite of the above rule is not necessarily true. An equation may be dimensionally consistent but invalid.

e.g. If M mass of an object, then M = 2 M is dimensionally homogeneous but incorrect.

Example :
Consider the equation D(ft) = 3t(s) + 4 1. If the equation is valid, what are the dimensions of the constant 3 and 4?
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2. If the equation is consistent in its units, what are the units of 3 and 4?

Solution
1. For the equation to be valid, it must be dimensionally homogeneous, so that each term must have the dimension of length. The constant 3 must therefore have the dimension length/time , and 4 must have the dimension length. 2. For consistency of units, the constants must be 3 ft/s and 4 ft.

Table 2. SI units
Physical Quantity Name of Unit Basic SI Units Length Mass Time Temperature Amount of substance Energy Force Power Density Velocity Acceleration Pressure Heat Capacity metre, meter kilogramme, kilogram second kelvin mole Derived SI Units joule newton watt kilogram per cubic meter meter per second meter per second squared newton per square meter, pascal joule per (kilogram . kelvin) Alternative Units Time Temperature Volume Mass minute, hour, day, year degree Celsius litre, liter (dm3) tonne, ton (Mg), gram min, h, d, y o C L t, g m kg s K mol J N W kg . m2 . s-2 kg . m . s-2 J . m-1 kg . m2 . s3 J. s-1 kg . m-3 m . s-1 m . s-2 N . m-2, Pa J . kg-1 . K-1 Symbol for Unit * Definition of Unit

American Engineering System Units


Physical Quantity Name of Unit Basic Units Length Mass Force Time Temperature feet pound (mass) pound (force) second, hour degree Rankine Derived Units Energy Power Density Velocity Acceleration Pressure Heat capacity British thermal unit, foot pound (force) horsepower pound (mass) per cubic foot feet per second feet per second squared pound (force) per square inch Btu per pound (mass) per degree F Btu, (ft) (lbf) hp lbm/ft3 ft/s ft/s2 ft lbm lbf s, hr o R Symbol

lbf/in.2 Btu/(lbm) (oF)

Chapter 3 PROCESS VARIABLES

PROCESS VARIABLES

1. Liquid and Solid Densities


Density is the ratio of mass per unit volume, for example, kg / m3, g / cm3, lbm/ft3. It has both numerical values and units. To determine the density of a substance, you must find both its mass and its volume. If the substance is solid, the common method to determine its volume is to displace a measured quantity of inert liquid. For example, a known weight of a material can be placed into a container of liquid of known weight and volume, and the final weight and volume of the combination be measured. The density (or specific gravity) of a liquid is commonly measured with a hydrometer which consists of a body of known weight and volume which is dropped into a liquid and the depth to which it penetrates into the liquid is noted. Specific gravity is a dimensionless ratio of two densities - that of substance (A) of interest to that of a reference substance.
lbm 3 ft A lbm 3 ft ref g 3 kg 3 cm A m A = = g 3 kg 3 cm ref m ref

Specific gravity =

(1)

The reference substance of liquids and solids is normally water. Gas densities are quite difficult to measure; one device used is the Edwards Balance which compares the weight of a bulb filled with air to the same bulb filled with the unknown gas. The specific gravity of a gas is frequently referred to air but may be referred to other gases. In petroleum industry the specific gravity of petroleum products is usually reported in terms of hydrometer called API, defined as,

API =

141. 5 . 1315 60o SpGr o 60

(2)

or

60o 141. 5 SpGr o = o 60 API + 1315 .

(3)

The density of liquids and solids does not change very much with pressure. For common substances data is reported in literature. When a liquid or solid is heated, it normally expands (i.e. its density decreases). In most process applications, however, it can usually be assumed with little error that solid and liquid densities are independent of temperature, provided that no phase change occur. Similarly changes in pressure don not cause significant changes in the liquid or solid densities; these substances are therefore termed incompressible.

2. Flow Rate
The flow rate of a process stream may be expressed as a mass flow rate (mass/time) or as a volumetric flow rate (volume/time). Suppose a fluid (gas or liquid) flows in the cylindrical pipe shown below, where the shaded area represents a section perpendicular to the direction of flow.

m (kg fluid /sec) v (m3 fluid /sec)

Figure1. Flow of a fluid in a pipe If the mass flow rate of the fluid is m (kg/sec), then every second m kilograms of fluid pass through the cross section. If the volumetric flow rate of the fluid at the given cross-section is v (m3 /sec), then every second, v cubic meters of fluid pass
2

through the cross-section. However, the mass flow rate m and volumetric flow rate v are not independent quantities but are related through density.

3. Chemical Composition
3.1. Moles and Molecular Weight
The atomic weight of an element is the mass of an atom on a scale that assigns 12C (the isotope of carbon whose nucleus contains six protons and six neutrons) a mass of exactly 12. The molecular weight of a compound is the sum of atomic weights of the atoms that constitute a molecule of the compound. A gram-mole( gmole or mole in SI units system) of a species is the amount of that species whose mass in grams is numerically equal to its molecular weight. Other types of moles (e.g. kg-mole or kmol, lb-mole, ton-mole etc.) are similarly defined. Carbon monoxide (CO), for example, has a molecular weight of 28. One mole of CO therefore contains 28 grams; 1 lb-mole contains 28 lbs.; 1 ton-mol contains 28 tons). The molecular weight of a substance, M, can be expressed as M kg/kmol, M g/gmol., M lbs/lb-mol etc. The molecular weight may thus be used as a conversion factor that relates mass and number of moles of the quantity of the substance. Therefore, 34 kg ammonia (NH3) are equivalent to:

1 kmol NH3 34 kg NH3 = 2 kmol NH3 17 kg NH3

(4)

3.2. Mass and Mole Fractions


Process streams occasionally contain one substance but more often consist of mixture of liquids or gases or solutions of one or more solutes in liquid solvent. Following
3

terms may be used to define the composition of a mixture of substances including a species A.

Mass Fraction

xA =

mass of A kg of A g of A lbm of A , or Total mass total kg total g total lbm

(5)

Mole Fraction

yA =

moles of A kmol of A mol of A lb mol of A , or Total moles total kmol total mol total lb moles

(6)

For example, if a solution contains 15% A by mass (xA = 0.15) and 20% B (xB = 0.20), calculation of the mass of A in 175 kg of solution:

015 . kg A 175 kg solution = 26 kg A kg of sol .

(7)

similarly, the mass flow rate of A in a stream of solution flowing at the rate of 53 lbm/ hr is given as,

Flow rate of A = 53

lbm 015 . lbm hr lbm

A lb A = 8.0 m hr

(8)

3.3. Conversion from a Composition by Mass to Molar Composition


Example: O2 = 16%, A mixture of gases has the following composition by mass: CO = 4%, CO2 = 17% N2 = 63%

Define the molar composition. Solution: Basis: 100 g of the mixture

016 . g O2 1 mol O2 nO2 = 100 g total = 0.5 mol g total 32 g O2


Similarly,

1 . mol nCO = 100 ( 0.04) = 0143 28 1 . ) = 0.386 mol nCO2 = 100 (017 44 1 nN 2 = 100 (0.63) = 2.25 mol 28

nT = nO2 + nCO + nCO2 + nN 2 = 3.279 mol


Therefore,

yO2 =

nO2 nT nT

0.5 mol O2 = 015 . 3.279 total mol = = mol CO 0143 . = 0.044 3.279 total mol 0.386 mol CO2 = 012 . 3.279 total mol

yCO = yCO2 = yN2 =

nCO nCO2 nT nT =

nN 2

2.25 mol N2 = 0.69 3.279 total mol

yi = 015 . + 0.044 + 012 . + 0.69 = 1.0

3.4. Average Molecular Weight


The average molecular weight or mean molecular weight of a mixture, M (kg/kmol) is the ratio of the mass of sample of the mixture (mtotal) to the moles (ntotal) of all the species in the mixture, i.e.

M =
or

mtotal = y1 M1 + y2 M 2 + y3 M 4 + LLL ntotal


N

(9)

M = yi Mi
i =1

(10)

where N = total number of components


Also,
N 1 x x x x = 1 + 2 + 3 + LLL + i M M1 M 2 M 3 i =1 M i

(11)

3.5. Concentration
The mass concentration of a component of a mixture or solution is the mass of this component per unit volume of the mixture (g/cm3, kg/m3, lbm/ft3). The concentration can also be expressed as molar concentration which is the number of moles of the component per unit volume of the mixture (gmol/cm3, kmol/m3, lbmol/ft3). The molarity of the solution is the value of the molar concentration of the solute expressed in gram moles of solute per liter of solution. The density of a mixture of liquids can be estimated by assuming that component volumes are additive: e.g. if 2 ml of liquid A and 3 ml of liquid B are mixed, the resulting volume would be assumed to be 5 ml. This leads to a simple averaging formula for the mixture density ();

x1

2
6

x2

(12)

where 1 and 2 are the densities of component A and B respectively while x1 and x2 are their mass fractions respectively.

4. Pressure
Pressure is the ratio of a force to the area on which it acts. Therefore, the pressure units are force units divided by area units (N / m2, dynes / cm2, or lbf / ft2). The SI unit of pressure is N / m2 and is known as Pascal. In most investigations we are concerned with absolute pressure. Most pressure measuring devices read the difference between absolute pressure and atmospheric pressure existing at the gauge and this is referred to as gauge pressure. This is shown graphically in the figure below:
Pressure above Atmospheric Pressure

Ordinary Pressure gauge reading

Ordinary vacuum gauge reads difference between atmospheric and absolute pressure Atmospheric Pressure

Absolute pressure that is less than atmospheric pressure Zero Pressure

Figure 2. Illustration of terms used in pressure measurement

From the principles of hydrostatics, it is possible that pressure may be expressed as head of a particular fluid - i.e. as a height of a hypothetical column of this fluid that will exert the given pressure at its base if pressure at the top were zero. You can thus speak of a pressure of 14.7 lbf /in2 as equivalent of 33.9 ft of water (33.9 ft of H2O) or 76 cm of mercury (76 cm Hg)

P = g h
where, g = density of fluid = acceleration due to gravity

(13)

h = head of the fluid.


If P = 2.0 105 Pa, the corresponding head of mercury can be calculated using the above equation:

h = 2.0 105

N m3 kg 103 mm . 103 mm = 15 2 m 13600 kg 9.807 N m

5. Temperature
The temperature is a measure of the degree of hotness or coldness of the body. There are two commonly used scales for measuring temperature, namely the Fahrenheit and Celsius scales. The Celsius scale was formerly called the Centigrade scale. Until 1954 each of these scales was based on two fixed and easily duplicated points, the ice point and the steam point. The temperature of the ice point is defined as the temperature of a mixture of ice and water which is in equilibrium with saturated air at the pressure of 1 atm. The temperature of the steam point is the temperature of water and steam which are in equilibrium at the pressure of 1 atm. On the Fahrenheit scale,

these two points are assigned the number 32 and 212 respectively. On the Celsius scale the respective points are numbered 0 and 100. Letters F and C denote the Fahrenheit and Celsius scales respectively. In 1954 the Celsius scale was redefined in terms of a single fixed point and the magnitude of the degree. The triple point of water (the state where the solid, liquid and vapor phases of water exist together in equilibrium) assigned the value 0.01C. On the scale the steam point is experimentally found to be 100.0C. Thus there is essential agreement between the old and new temperature scales. The absolute scale of temperature related to Celsius scale is referred to as the Kelvin scale designated as K.

K = o C +27315 .

(14)

The absolute scale related to the Fahrenheit scale is referred to as the Rankine scale designated as R. The relation between the two scales is

R = o F +459.67

(15)

The following relationships may be used to convert a temperature expressed in one defined scale unit to its equivalent in another:

T ( K ) = T ( o C ) + 27315 . T ( R ) = T ( o F ) + 459.67 T ( R ) = 18 . T (K)

(16) (17) (18) (19)

T o F = 18 . T

( )

( C) + 32
o

Chapter 4 MATERIAL BALANCES AND APPLICATIONS

MATERIAL BALANCES AND APPLICATIONS

4.1. Introduction

Material balances are important first step when designing a new process or analyzing an existing one. They are almost always prerequisite to all other calculations in the solution of process engineering problems. Material balances are nothing more than the application of the law of conservation of mass, which states that mass can neither be created nor destroyed. Thus, you cannot, for example, specify an input to a reactor of one ton of naphtha and an output of two tons of gasoline or gases or anything else. One ton of total material input will only give one ton of total output, i.e. total mass of input = total mass of output. A material balance is an accounting for material. Thus, material balances are often compared to the balancing of current accounts. They are used in industry to calculate mass flow rates of different streams entering or leaving chemical or physical processes.

4.2. The General Balance Equation

Suppose propane is a component of both the input and output streams of a continuous process unit shown below, these flow rates of the input and output are measured and found to be different.

Process unit

qin (kg propane/h)

qout (kg propane/h)

If there are no leaks and the measurements are correct, then the other possibilities that can account for this difference are that propane is either being generated, consumed, or accumulated within the unit. A balance (or inventory) on a material in a system (a single process unit, a collection of units, or an entire process) may be written in the following general way:

Input + (enters through system boundaries)

generation (produced within system boundaries)

output (leaves through system boundaries)

consumption (consumed within system)

accumulation (buildup within system)

This general balance equation may be written for any material that enters or leaves any process system; it can be applied to the total mass of this material or to any molecular or atomic species involved in the process. The general balance equation may be simplified according to the process at hand. For example, by definition, the accumulation term for steady-state continuous process is zero. Thus the above equation becomes: Input + generation = output + consumption For physical process, since there is no chemical reaction, the generation and consumption terms will become zero, and the balance equation for steady-state physical process will be simply reduced to: Input = Output

4.3. Balances on Single and Multiple Physical Systems

4.3.1. Procedure for Material Balance Calculations In material balance problems, you will usually be given a description of a process, the values of several process variables, and a list of quantities to be determined. In order to be trained on using a systematic procedure to solve material balance problems, you are advised to follow the steps summarized below: 1. Draw and label the process flow chart (block diagram). When labeling, write the values of known streams and assign symbols to unknown stream variables. Use the minimum number possible of symbols. 2. Select a basis of calculation. This is usually the given stream amounts or flow rates, if no given then assume an amount of a stream with known composition.

3. Write material balance equations. Note in here the maximum number of independent equations you can write for each system is equal the number of species in the input and output streams of this system. Also note to first write balances that involve the fewest unknown variables. 4. Solve the equations derived in step 3 for the unknown quantities to be determined.

Notes i. Minimize the symbols assigned to unknown quantities by utilizing all the given process specifications and using laws of physics. ii. After doing calculations on certain basis, you may scale up or scale down (convert to new basis) while keeping the process balanced. This is done by multiplying all streams (except mass or mole fractions) by the scale factor which is equal to the ratio of the new stream amount or flow rate to the old one. You can only scale between mass amount or flow rates regardless of units used but not from mass to molar quantity or flow rate. The examples below will illustrate the procedure of balances on physical processes:

EXAMPLE: Balance on a mixing unit An aqueous solution of sodium hydroxide contains 20% NaOH by mass. It is desired to produce an 8% NaOH solution by diluting a stream of the 20% solution with a stream of pure water. 1. Calculate the ratios (g H2O/g feed solution) and (g product solution/g feed solution). 2. Determine the feed rates of 20% solution and diluting water needed to produce 2310 lbm/min of the 8% solution.

Solution We could take a basis of 2310 lbm product/min, but for illustrative purposes and to have neater numbers to work with let us choose a different basis and scale the final results. Basis: 100 g Feed Solution

Draw and label the flowchart, remembering that the amount of the product stream is now unknown.

100 g 0.20 g NaOH/g 0.80 g H2O/g Q1 (g H2O)

Q2 (g) 0.080 g NaOH/g 0.920 g H2O/g

(Since the known stream amount is given in grams, it is convenient to label all unknown amounts with this unit.)

There are two unknowns - Q1 and Q2 - and since there are two substances - NaOH and H2O in the input and output streams, two balances may be written to solve for them. The total mass balance and the water balance involve both unknowns, but the NaOH balance involves only one.

NaOH Balance

(g

NaOH )in

= (g NaOH )out Q 2 = 250 g

(0.20)(100 g ) = 0.080 Q2

It is a good practice to write calculated variable values on the flowchart as soon as they are known for ease of use in later calculations; at this point, 250 would therefore be written in place of Q2 on the chart. Total Mass Balance
100 g + Q1 = Q 2

= 250 g

Q1 = 150 g H 2 O

The desired ratios can now be calculated:

Q1 (g H 2 O) 100 g feed solution


Q2 (g H 2 O) 100 g feed solution

Q1 = 150

1.5

g H 2O g feed solution
g product g feed solution

Q2 = 250

2.5

The scale factor is obtained as the true flow rate of the product stream divided by the rate calculated on the assumed basis.
2310 lb m product/min lb /min = 9.24 m 250 g product g

Feed Solution Flow Rate

lb feed solution 100 g 9.24 lb m /min = 924 m g min

Dilution Water Flow Rate

lb H O 150 g 9.24 lb m /min = 1386 m 2 min g

Check:

(924 + 1386) lbm/min = 2310 lbm/min

EXAMPLE: Scale up of a separation process flowchart

A 60 - 40 mixture (by moles) of A and B is separated into two fractions. A flowchart of the process is shown here.
50.0 mol 0.95 mol A/mol 0.05 mol B/mol

100.0 mol 0.60 mol A/mol 0.40 mol B/mol

12.5 mol A 37.5 mol B

It is desired to achieve the same separation with a continuous feed of 1250 lb-moles/h. Scale the flowchart accordingly.
Solution

The scale factor is


1250 lbmoles / h lbmoles / h = 12.5 mol 100 mol

The masses of all streams in the batch process are converted to flow rates as follows:
100 mol 12.5 lb - moles/h lb - moles (as specified) = 1250 h mol

Feed:

Top product stream: Bottom product stream:

(50.0)(12.5) (12.5)(12.5) (37.5)(12.5)

= 625 lb-moles/h = 156 lb-moles A/h = 469 lb-moles B/h

The units of the mole fractions in the top product stream may be changed from mol/mol to lbmole/lb-mole, but their values remain the same. The flowchart for the scaled-up process is shown here.
625 lb-moles/hr 1250 lb-moles/hr 0.60 lb-mol A/lb-mole 0.40 lb-mol B/lb-mole 156 lb-moles A/hr 469 lb-moles B/hr 6 0.95 lb-mole A/b-mole 0.05 lb-mole B/b-mole

EXAMPLE: Material balances on a distillation column

A mixture containing 45% benzene (B) and 55% toluene (T) by mass is fed to a distillation column. An overhead stream of 95 wt% B is produced, and 8% of the benzene fed to the column leaves in the bottom stream. The feed rate is 2000 kg/h. Determine the overhead flow rate and the mass flow rates of benzene and toluene in the bottom stream
Solution

Basis : Given Feed Rate


The labeled flowchart is as follows.
D kg/h 2000 kg/h 0.45 kg B/kg 0.55 kg T/kg 0.95 kg B/kg 0.05 kg T/kg

Contains 8% of the B in the feed

wB kg B/kg wT kg T/kg

There are three unknowns on the chart - D, wB, and wT - and therefore three equations are needed. We are entitled to write only two material balances since two species are involved in the process; the third equation must therefore come from additional given information (the amount of benzene in the bottom stream.) The latter relation is.
B in bottom stream = 0.080 (B in feed) wB (kg B/h) = 0.080 [(0.45)(2000) kg/h] wB = 72 kg B/h (Write 72 in place of wB on the chart)

Toluene and total mass balances each involve two unknowns, D and wT, but a benzene balance involves only one, D. Benzene Balance

(0.45)(2000) kg

= 0.95 D + wB wB = 72 kg B/h D = 870 kg/h (Write it on the chart)

Total Mass Balance (A toluene balance could be used equally well)


2000 kg = D + w B + wT h D = 870 kg/h wB = 72 kg/h wT = 1060 kg T/h

EXAMPLE: Two Unit Distillation Process


A labeled flowchart of a continuous steady-state two-unit distillation process is shown below. Each stream contains two components, A and B, in different proportions. Three streams whose flow rates and/or compositions are not known are labeled 1, 2 and 3.
40 kg/h 0.900 kg A/kg 0.100 kg B/kg 100 kg/h 0.500 kg A/kg 0.500 kg B/kg 30 kg/h 0.300 kg A/kg 0.700 kg B/kg 1 2 30 kg/h 0.600 kg A/kg 0.400 kg B/kg 3

Calculate the unknown flow rates and compositions of streams 1, 2, and 3.

Solution
The systems about which balances might be taken are shown on the following representation of the flowchart.
40 kg/h 0.900 kg A/kg 0.100 kg B/kg 30 kg/h 0.600 kg A/kg 0.400 kg B/kg

100 kg/h 0.500 kg A/kg 0.500 kg B/kg

Q1 (kg/h) x1 (kg A/kg) 1- x1 (kg B/kg)

Q2 (kg/h) x2 (kg A/kg) 1- x2 (kg B/kg)

Q3 (kg/h) x3 (kg A/kg) 1- x3 (kg B/kg)

30 kg/h 0.300 kg A/kg 0.700 kg B/kg

The outer boundary encompasses the entire process. Two of the interior boundaries surround the individual process units, and the fourth boundary encloses a stream junction point. Basis: Given Flow Rates There are two unknowns in the streams that enter and leave the total process, Q3 and x3, and since there are two independent components in these streams (A and B) we may write two balances. Overall Mass Balance

(100 + 30) kg
h

= (40 + 30 )

kg + Q3 h

Q3 = 60 kg/h Overall Balance On A

(0.500)(100) + (0.300)(30) = (0.900)(40) + (0.600)(30) + (60)(x 3 )


x 3 = 0.0833 kg A/kg To determine the flow rate and composition of a connecting stream, we must write balances on a subsystem whose boundary intersects this stream. Of the three such boundaries shown in the flowchart, the middle one (about the stream junction) would not be a good one to use at this point since its input and output streams contain four unknown quantities (Q1, x1, Q2, x2), while the boundaries about the process units each intersect streams that contain two unknowns. Let us choose the boundary about unit 1 for the next set of balances. There are two unknowns, Q1 and x1, in the streams that intersect this boundary, and up to two balances may be written. Total Mass Balance on Unit 1
100 kg / h = 40 Q1 = 60 kg / h kg + Q1 h

Balance on A in Unit 1 (0.500)(100) = (0.900)(40) + 60x1 x1 = 0.233 kg A/kg To find Q2 and x2, we could write balances about either the stream mixing point or Unit 2. Let us choose the first alternative. Mass Balance About Mixing Point
Q1 + 30 kg/h = Q2 Q1 = 60 kg/h Q2 = 90 kg/h Balance on A About Mixing Point
Q1 x1 + (0.300)(30) kg A/h = Q2 x 2 Q1 = 60 kg/h x1 = 0.233 kg A/kg Q2 = 90 kg/h x2 = 0.255 kg A/kg

4.4. Balances on Reactive Systems 4.4.1. Stoichiometry, Limiting and Excess Reactants
For reactive systems, in addition to input and output of materials, generation and consumption terms should be considered in the general mole balance equation. Theory of proportions in which chemical compounds react is called stoichiometry. A statement of the relative number of moles or molecules reacting to produce products is given by a chemical equation known as stoichiometric equation. For example, 2 moles of SO2 and one mole of O2 react to produce 2 moles of SO3. Then the stoichiometric equation will be 2SO2+O22SO3. Numbers that precede the formulas are known as stoichiometric coefficients.

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EXAMPLE:

2SO2+O2 2SO3.

What is the stoichiometric coefficient of SO2?

Solution The number that precede SO2 is 2. Therefore, stoichiometric coefficient of SO2 is 2.
In a stoichiometric equation, the number of atoms in both sides of the equation must be balanced. In this example, the number of atoms of S and O are 2 and 6, respectively, in both sides of equation. Ratio of stoichiometric coefficients of two species is known as stoichiometric ratio.

EXAMPLE: Solution

2SO2+O2 2SO3.

What is the stoichiometric ratio of SO2 to SO3?

stoichiometric ratio of SO2 to SO3 =

2 mole of SO 2 reacted 2 mole of SO 3 produced

= 1

If proportion of chemical species fed to a reactor is same as the stoichiometric ratio, then chemical species combine in stoichiometric proportion, otherwise one or more species will be in excess of the other. The chemical compound which is present less than its stoichiometric amount, will disappear first. This reactant will be the limiting reactant and all the others will be excess reactants. Fractional and percentage excess are given by the following formulas.

n nS nS n nS percentage excess = 100 nS where n = number of moles fed


fractional excess =

ns = number of moles corresponding to stoichiometric amount


EXAMPLE: 100 moles of SO2 and 100 moles O2 are fed to a reactor and they react according to 2SO2+O2 2SO3. Find the limiting reactant, excess reactant, fractional excess and percentage excess? Solution

ratio of SO2 to O2 fed = 100/100 = 1 stoichiometric ratio of SO2/O2 = 2/1=2 Therefore, SO2 is fed less than the stoichiometric proportion (or stoichiometric ratio). SO2 is the limiting reactant. The other reactant (O2) will be the excess reactant.
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n = number of moles of excess reactant (O2) fed = 100 ns = stoichiometric amount of O2 to react with 100 moles of the limiting reactant SO2 = 50 n n S 100 50 Therefore, fractional excess = = = 1.0 nS 50
percentage excess =
n nS 100 = 100% nS

4.4.2. Fractional Conversions, Extent of Reaction, Chemical Equilibrium

In many cases, chemical reactions do not go to completion and only a fraction will be converted. Therefore, fractional and percentage conversions are used. They are defined as follows, fractional conversion (f) = mole reacted mole fed to the reactor

percentage conversion = f 100 fraction unreacted = (1-f)

EXAMPLE: 200 moles of SO2 and 100 moles O2 are fed to a reactor. Only 100 moles of SO2 react according to 2SO2+O22SO3 Find fractional conversion, percentage conversion and fraction unreacted? Solution

fractional conversion of SO2 (f) =

mole reacted =100/200=0.5 mole fed to the reactor

percentage conversion = f 100=0.5100=50% fraction unreacted = (1-f)=1-0.5=0.5

When a reaction is not complete, remaining amount in the reactor will be given by
n i = n io + i

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where,

= extent of reaction (mole reacted or produced/i) i = compound i, ni = remaining amount nio = amount initially put in the reactor i = +i, stoichiometric coefficient of a product = -i , stoichiometric coefficient of a reactant = 0 , inert

The same equation is true if quantities (i.e., moles) are replaced by flow rates (mole/hr).

EXAMPLE: 200 moles of SO2 and 100 moles O2 are fed to a reactor. Only 50 moles of O2 react according to 2SO2+O22SO3 Find the moles remaining for all species? Solution

For O2, For SO2, For SO3,

= 50, nio = 100, i = -i = -1, n i = n io + i = 100-150=50 moles = 50, nio = 200, i = -i = -2, ni = 200-250=100 moles = 50, nio = 0, i = +i = +2, ni = 0+250=100 moles

When the chemical reaction proceeds in one direction only, we call it irreversible. If the reaction proceeds in forward and backward directions then it is reversible. When forward reaction rate and reverse reaction rate becomes equal, reaction is said to be in equilibrium. Equilibrium constant (K) for a gas phase reaction, A(gas) + B(gas)<=> C(gas) + D (gas), is given by K= yCyD , yA yB where y is the mole fraction of the components in the gas phase.

EXAMPLE: Reaction Stoichiometry

Acrylonitrile is produced by the reaction of propylene, ammonia, and oxygen.

C3 H 6 + NH3 +

3 O 2 C3H 3 N + 3 H 2 O 2

The feed contains 10 mole% propylene, 12% ammonia, and 78% air. A fractional conversion of 30% of the limiting reactant is achieved. Determine which reactant is limiting, the percentage by which each of the other reactants is in excess, and the molar flow rates of all product gas constituents for a 30% conversion of the limiting reactant, taking 100 mol of feed as a basis.

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Solution
Basis : 100 mol Feed
100 mol 0.100 mol C3H6/mol 0.120 mol NH3/mol 0.780 mol air/mol (0.21 mol O2/mol air 0.79 mol N2/mol air)

n C 3 H 6 mol C3 H 6 n NH 3 mol NH3 n o 2 mol O 2 n N 2 mol N 2 n C 3 H 3 N mol C3H 3 N n H 2 O mol H 2O

The feed to the reactor contains

(C

(NH 3 )in (O 2 )in

H 6 )in = 10.0 mol = 12.0 mol = 78.0 mol air 0.210 mol O 2 = 16.4 mol mol air

(NH 3 /C 3 H 6 )in = 12.0/10.0 = 1.20 NH 3 is in excess (NH 3 /C 3 H 6 )stoich = 1/1 = 1 (O 2 / C 3 H 6 )in = 16.4/10.0 = 1.64 O 2 is in excess (O 2 / C 3 H 6 )stoich = 1.5/1 = 1.5
Since propylene is fed in less than the stoichiometric proportion relative to the two other reactants, propylene is the limiting reactant. To determine the percentages by which ammonia and oxygen are in excess, we must first determine the stoichiometric amounts of these reactants corresponding to the amount of propylene in the feed (10 mol).

(NH3 )stoich

10.0 mol C3 H 6 1 mol NH 3 = 10.0 mol NH 3 1 mol C3H 6

(O 2 )stoich

10.0 mol C3 H 6 1.5 mol O 2 = 15.0 mol O 2 1 mol C3H 6

(% excess)NH

(NH 3 )0

(NH 3 ) stoich

= [(12 10 )/10] 100% = 20% excess NH 3


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(NH 3 ) stoich

100%

(% excess)O

= [(16.4 15.0)/15.0] 100% = 9.3% excess O 2

If the fractional conversion of C3H6 is 30% (C3H6)out = 0.700(C3H6)in = 7.0 mol C3H6 But Then,
n NH 3 = 12.0 n O2 n N2 = 16.4 1.5 = (N 2 ) 0 n C3H 6 N = n H 2 O = 3 = = = 9.0 mol NH 3 3.00 mol C 3 H 3 N 9.0 mol H 2 O = 11.9 mol O 2 = 61.6 mol N 2

n C3 H 6 = 10.0 . The extent of reactions is therefore :

= 3.0.

EXAMPLE: Calculation of an Equilibrium Composition


If the water-gas shift reaction, CO(g) + H2O(g) CO2(g) + H2(g) proceeds to equilibrium at a temperature T(K), the mole fractions of the four reactive species satisfy the relation y CO 2 y H 2 y CO y H 2 O = K (T)

where K (T) is the reaction equilibrium constant. At T = 1105 K (832C), K = 1.00. Suppose the feed to a reactor contains 1.00 mol CO, 2.00 mol of H2O, and no 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.

Solution
The strategy is to express all mole fractions in terms of a single variable (e, the extent of reaction at equilibrium), substitute in the equilibrium relation, solve for e, and backsubstitute to calculate the mole fractions and any other desired quantity.

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n CO = 1.00 e n H 2O = 2.00 e n CO 2 = e n H 2 = 1 e n total = 3.00 from which

(number of mols of CO present at equilibrium)

y CO

= (1.00 e )/3.00

y H 2O = (2.00 e )/3.00 y CO 2 = e /3.00 y H2 = e /3.00

Substitution of these expressions in the equilibrium relation (with K = 1.00) yields


2 e

(1.00 e )(2.00 e )

= 1.00

This may be rewritten as a standard quadratic equation and solve to yield e = 0.667. This quantity may in turn be substituted back into the expressions for yi(e) to yield

y CO = 0.111,

y H 2O = 0.444,

y CO 2 = 0.222, y H 2 = 0.222

The limiting reactant in this case is CO (verify). At equilibrium, n CO = 1.00 0.667 = 0.333 The fractional conversion of CO at equilibrium is therefore fCO = (1.00 - 0.333) mol reacted/(1.00 mol fed) = 0.667

4.4.3. Multiple Reactions, Yield and Selectivity

In a chemical process, our objective is to produce a certain product (desired product), but there may be several unwanted reactions which will produce undesirable by products. Therefore, we must maximize the production of a desired product in the process. Two quantities, yield and selectivity, are used for this purpose and they are defined as follows,

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yield =

moles of desired product formed moles of desired product formed if there were no side reactions and the limiting reactant reacts completely moles of desired product formed moles of undesired product formed

selectivity =

When we have multiple reactions, the remaining amount or flow rate will be given by

n i = n io + ij j
j

where

i = compound i j = reaction j j = extent of reaction for the jth reaction ij = +i, stoichiometric coefficient of a product i in the jth reaction = -i, stoichiometric coefficient of a reactant i in the jth reaction = 0, inert

EXAMPLE: Consider the following pair of reactions.

A 2B (desired) A C (undesired) 100 moles of A are fed to a batch reactor and the final product contains 10 mol of A, 160 mol of B and 10 mol of C. Calculate (1) percentage yield of B, (2) the selectivity of B relative to C and (3) the extents of the reactions.
Solution
Percentage Yield

moles of desired product (B) formed = 160 moles of desired product formed if there were no side reactions and the limiting reactant 2 moles of B produced reacts completely = 100 moles of A = 200 moles 1 mole of A reacted
yield (%) = 160/200*100 = 80%
Selectivity

moles of desired product (B) formed = 160

17

moles of undesired product (C) formed = 10 selectivity = moles of desired product formed = 160/10 = 16. moles of undesired product formed

Extent of Reactions

n i = n io + ij j
j

for two reaction system as above, n i = n io + i1 1 + i 2 2 applying this equation for B, for C,
10 = 0 + 2

160 = 0 + 21 ,

this gives

1 = 80

this gives

2 = 10.

check: for A,
10 = 100 1 2 ,

10 = 100 80 10 = 10

EXAMPLE: Yield and Selectivity in a Dehydrogenation Reactor

The reactions

C2 H 6 C2 H 4 + H 2 C 2 H 6 + H 2 2 CH 4

take place in a continuous reactor at steady state. The feed contains 85.0 mole% ethane (C2H6) and the balance inerts (I). The fractional conversion 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.
Solution
Basis: 100 mol Feed
100 mol 0.850 C2H6

0.150 I

n 1 (mol C 2 H 6 ) n 2 (mol C 2 H 4 ) n 3 (mol H 2 ) n 4 (mol CH 4 ) n 5 (mol I)

The outlet component amounts in terms of extents of reaction are as follows:

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n1 (mol C2H6) = 85.0 - 1 - 2 n2 (mol C2H4) = 1 n3 (mol H2) = 1 - 2 n4 (mol CH4) = 22 n5 (mol I) = 15.0
Ethane Conversion

n1 =

(1.000 0.501) mol C 2 H 6 unreacted 85.0 mol C 2 H 6 fed mol C 2 H 6 fed

= 42.4 mol C 2 H 6 = 85.0 1 2


Ethylene Yield

Maximum possible ethylene = n 2 = 0.471 (85.0 mol C 2 H 4

85.0 mol C 2 H 6 fed 1 mol C 2 H 4 = 85.0 mol 1 mol C 2 H 6 C 2 H 4 = 1

) = 40.0 mol

Substituting 40.0 for 1 in (1) yield 2 = 2.6 mol. Then

n 3 = 1 2

= 37.4 mol H 2

n 4 = 2 2 = 5.2 mol CH 4 n 5 = 15.0 mol I n tot = (42.4 + 40.0 + 37.4 + 5.2 + 15.0) = 140.0 mol 30.3% C 2 H 6 , 28.6% C 2 H 4 , 26.7% H 2 , 3.7% CH 4 , 10.7% I

Selectivity = (40.0 mol C2H4)/(5.2 mol CH4) = 7.7

mol C 2 H 4 mol CH 4

4.4.4. Atomic and Molecular Balances

In a chemical process, molecules are either generated (produced) or consumed. Therefore, one should take into account the amounts (moles) generated, consumed, fed and remaining in molecular balances.
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EXAMPLE: In a steady state process, 100 moles ethane (C2H6) react to produce ethylene (C2H4) and hydrogen (H2) according to C2H6C2H4 + H2. Product gas shows 40 moles of hydrogen remaining. Perform molecular balances for all species. Solution:

100 mol C2H6

40 mol of H2 q1 mol of C2H6 q2 mol of C2H4

Then, the molecular balance of H2 is as follows, input + generated (produced) = output + consumed (reacted) input = 0.0 output = 40 consumed = 0 0 + generated (produced) = 40+ 0 H2 (generated) = 40 moles. Molecular balance of C2H6 is as follows, input + generated (produced) = output + consumed (reacted) input = 100 generated = 0 output = q1 100 + 0 = q1 + consumed C2H6 (consumed) = 100-q1 q1 = 60 moles

H2 (generated) = 40 moles=C2H6 (consumed) = 100-q1 Molecular balance of C2H4 is as follows,

input + generated (produced) = output + consumed (reacted) input = 0 output = q2 consumed = 0 0 + generated = q2 + 0 C2H4 (generated) = q2 q2 = 40 moles

C2H4 (generated) = q2 = H2 (generated) = 40 moles


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According to conservation principle, atoms can neither be created (produced) nor destroyed (consumed). Therefore, in atomic balances there is no generation or consumption terms. Simply, input = output.

EXAMPLE: For the same problem as above, do atomic balances? Solution

Atomic carbon balance: Atomic hydrogen balance

1002 = q12 + q22 1006 = 402 + q16 + q24

Solving these two atomic balance equations, you will get the same answer as above.

EXAMPLE: Combustion of Methane

Methane is burned with oxygen to yield carbon dioxide and water. The feed contains 20 mole% CH4, 60% O2, and 20% CO2, and a 90% conversion of the limiting reactant is achieved. Calculate the molar composition of the product stream using (1) balances on molecular species, (2) atomic balances, (3) the extent of reaction.
Solution
Basis : 100 mol Feed
100 mol 0.200 CH4 0.600 O2 0.200 CO2

n CH 4 (mol CH 4 ) n O 2 (mol O 2 ) n CO 2 (mol CO 2 ) n H 2 O (mol H 2 O)

CH 4 + 2 O 2 CO 2 + 2 H 2 O

Since a 2:1 ratio of O2 to CH4 would be stoichiometric and the actual ratio is 3:1, CH4 is the limiting reactant and O2 is in excess. Before the balances are written, the given process information should be used to determine the unknown variables or relations between them. In this case, the methane conversion of 90% tells us that 10% of the methane fed to the reactor emerges in the product, or

21

n CH 4 = 0.100 (20.0 mol CH 4 fed) = 2.0 mol CH 4 Now all that remains are the balances. We will proceed by each of the indicated methods.
1. MolecularBalances

CH 4 reacted =

20.0 mol CH 4 fed 0.900 mol react = 18 mol CH 4 react mol fed

CO2 Balance (input + generation = output)

18 mol CH 4 react 1 mol CO 2 produced 100 mol 0.200 mol CO 2 + = n CO 2 mol fed 1 mol CH 4 n CO 2
H 2 O Balance (generation = output) 18 mol CH 4 react 2 mol H 2 O produced = n H 2O 1 mol CH 4 react n H 2O = 36 mol H 2 O

= 38 mol CO 2

O2 Balance (input = output + consumption)


18 mol CH 4 react 2 mol O 2 react 100 mol 0.600 mol O 2 = n O2 + mol 1 mol CH 4 react n O2 = (60 36) mol O 2 = 24 mol O 2

In summary, the output quantities are 2 mol CH4, 24 mol O2, 38 mol CO2, and 36 mol H2O, for a total of 100 mol. (Since 3 moles of products are produced for every 3 moles of reactants consumed, it should come as no surprise that total moles in = total moles out.) The mole fractions of the product gas components are thus: 0.02 mol CH4/mol, 0.24 mol O2/mol, 0.38 mol CO2/mol, 0.36 mol H2O/mol
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2. Atomic Balances
Referring to the flowchart, we see that a balance on atomic carbon involves only one unknown ( n CO 2 ), and a balance on atomic hydrogen also involves one unknown ( n H 2 O ), but a balance on atomic oxygen involves three unknowns. We should therefore write the C and H balances first, and then the O balance to determine the remaining unknown variable. All atomic balances have the form input = output. (We will just determine the component amounts; calculation of the mole fractions then follows as in part 1.)

C Balance
20.0 mol CH 4 20.0 mol CO 2 1 mol C 1 mol C + 1 mol CO 2 1 mol CH 4 n mol CO 2 1 mol C 2.0 mol CH 4 1 mol C CO 2 = + 1 mol CO 2 1 mol CH 4 = 38 mol CO 2

n CO 2

H Balance
20 mol CH 4 2 mol CH 4 4 mol H 4 mol H = 1 mol CH 4 1 mol CH 4 n H 2 O mol H 2 O 2 mol H + 1 mol H 2 O n H 2 O = 36 mol H 2 O

O Balance
60 mol O 2 20 mol CO 2 2 mol O 2 mol O + 1 mol O 2 1 mol O 2 = (n O 2 mol O 2 ) (2) + (38 mol CO 2 ) (2) + (36 mol H 2 O)(1) = 24 mol O 2

n O2

confirming the results obtained using molecular balances.

3. Extent of Reaction
As discussed earlier, for all reactive species n out = n in + i For the species in this problem, we may write

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n CH 4 n C2 n C2 n H 2O

= 20.0 mol = 18.0 mol = 60.0 mol 2 = 60.0 (2)(18.0) = 24.0 mol O 2 = 20.0 mol + = 20.0 + 18.0 = 38.0 mol CO 2 = 0 + 2 = (2)(18.0) = 36.0 mol H 2 O

n CH 4 = 2 mol CH 4

again, the previous solutions are obtained.

4.5. The Case of Recycle and Purge 4.5.1. Overall and Single Pass Conversion
Two definitions of conversion are used in the analysis of chemical reactors with product separation and recycle of unconsumed reactants:

overall conversion =

reactant input to the process - reactant output from the process reactant input to the process
reactant input to the reactor - reactant output from the reactor reactant input to the reactor

single pass conversion =

EXAMPLE : Find the overall and single pass conversion of A ?


75 mol A/min 100 mol A/min 25 mol A/min 75 mol B/min Product Separator 75 mol B/min

Reactor

overall conversion of A =

(75 mol A/min) in - (0 mol A/min) out 100 = 100% (75 mol A/min) in (100 mol A/min) in - (25 mol A/min) out 100 = 75% (100 mol A/min) in

single pass conversion of A =

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4.5.2. Recycle and Purge


A material such as an inert gas or impurities which enter with the feed will remain in the recycle stream. This material will accumulate and the process will never reach steady state. To prevent this buildup, a portion of the recycle stream must be withdrawn as a purge stream.

EXAMPLE: Dehydrogenation of Propane


Propane is dehydrogenated to from propylene in a catalytic reactor C3 H 8 C3 H 6 + H 2 The process is to be designed for a 95% overall conversion of propane. The reaction products are separated into two streams: the first, which contains H2, C3H6, and 0.555% of the propane that leaves the reactor, is taken off as product; the second stream, which contains the balance of the unreacted propane and 5% of the propylene in the product stream, is recycled to the reactor. Calculate the composition of the product, the ratio (moles recycled)/(moles fresh feed), and the single-pass conversion.

Solution

Basis : 100 mol Fresh Feed

Fresh feed 100 mol C3H8

100 + Qr1 mol C3H8 Qr2 mol C3H6

Reactor

P1 mol C3H8 P2 mol C3H6 P3 mol H2

Separation Unit

Q1 mol C3H8 Q2 mol C3H6 Q2 mol H2

Qr1 mol C3H8 Qr2 mol C3H6

Note: In labeling the feed stream to the reactor, we have implicitly used balances on propane and propylene about the stream junction.
In terms of the labeled variables, the quantities to be calculated are

Mole Fractions of Product Stream Components: Recycle Ratio:


Qr1 + Qr 2 100

Q1 , ... etc. Q1 + Q2 + Q3

25

Single-Pass Conversion:

( 100 + Qr 1 ) P1 ( 100 + Qr 1 )

100%

We must therefore calculate the values of Q1, Q2, Q3, Qr1, Qr2 and P1. Let us first examine the overall process. Overall conversion = 95% 100 mol C 3 H 8 Q1 = 0.95 100 mol C 3 H 8

Q1 = 5 mol C 3 H 8 Overall Propane Balance:


input = output + consumption

100 mol C3H8 = 5 mol C3H8 + C (mol C3H8 reacted) C = 95 mol C3H8 reacted

Overall Propylene Balance: Q2 =

output = generation

95 mol C3H8 reacted 1 mol C3H 6 formed 1 mol C3H8 reacted

Q2 = 95 mol C3H 6 Similarly, overall H2 balance yields

Q3 = 95 mol H2
The analysis of the product is, therefore, 5 mol C3H8 95 mol C3H 6 95 mol H 2 195 mol total We may now proceed to the analysis of the interior streams including the recycle stream. First, we summarize the information given in the problem statement. 2.6 % C3H8 48.7% C3H 6 48.7% H 2

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Q1 = 0.00555 P1 Qr 2 = 0.05 Q2

Q1 = 5 mol C 3 H 8

P 1 = 900 mol C3H 8 Qr 2 = 4.75 mol C3H 6

Q2 = 95 mol C 3 H 6

Next, write balances around the separation unit (which is nonreactive, so that input = output for all species.) C3H8 Balance About Separation Unit P 1 = Q1 + Qr1 P 1 = 900 mol C3 H 8 Q1 = 5 mol C3H8

Qr1 = 895 mol C3H8 We now have all the variable values we need. The desired quantities are Re cycle ratio = 9.00 (Qr1 + Qr 2 ) mol recycle 100 mol fresh feed Qr1 = 895 mol Qr 2 = 4.75 mol mol recycle mol fresh feed
(100 + Qr 1 ) P1 100% (100 + Qr 1 ) Qr 1 = 895 mol C 3 H 8 P1 = 900 mol C 3 H 8

Single pass conversion =

9.55%

EXAMPLE: Recycle and Purge in the Synthesis of Ammonia


The fresh feed to an ammonia production process contains 24.75 mole % nitrogen, 74.25 mole% hydrogen, and the balance inerts (I). The feed is combined with a recycle stream containing the same species, and the combined stream is fed to a reactor in which a 25% single-pass conversion of nitrogen is achieved. The products pass through a condenser in which essentially all of the ammonia is removed, and the remaining gases are recycled. However, to prevent buildup of the inerts in the system, a purge stream must be taken off. The recycle stream contains 12.5 mole% inerts. Calculate the overall conversion of nitrogen, the ratio (moles purge gas/mole of gas leaving the condenser), and the ratio (moles fresh feed/mole fed to the reactor).

27

Solution
Basis : 100 mol Fresh Feed. N2 + 3H2 2NH3

n8(mol recycled)
0.125 I x N2 0.875 - x H2 100 mol 0.2475 N2 0.7425 H2 0.0100 I n1 (mol N2) n2 (mol H2) n3 (mol I) n3 (mol. I) n4 (mol N2) n5 (mol H2)

n7(mol purged)
0.125 I x N2 0.875 - x H2

Reactor

n4 (mol N2) n5 (mol H2) n6 (mol NH3) n3 (mol I)

Condenser

n6 (mol NH3)

Strategy:

Overall N, H, I balances n6, n7, x overall conversion of N2 n6, 25% single pass conversion n1, n4 n7, x, n4, n2 balance around purge-recycle split point n8 H2, I balances around recycle-fresh mixing point n2, n3

Overall I balance:

(0.0100)(100) = 0.125 n7 n7 = 8.00 mol purge gas

n 6 = 46.0 mol NH 3 x = 0.219 mol N 2 /mol Overall H balance : (100)(0.7425)(2) = 8.00 (0.875 x) (2) + 3n 6 24.75 mol fed (0.219)(8.00) mol in effluent Overall N 2 balance = x 100% = 92.9% 24.75 mol fed

Overall N balance : (100)(0.2475)(2) = 8.00 ( x) (2) + n 6

25% Single Pass Conversion :

n 1 mol N 2 fed 0.25 mol react 2 mol NH 3 = 46.0 mol NH 3 1 mol fed 1 mol N 2 n 1 = 92.0 mol N 2 feed to reactor n 4 = (0.75)(92.0) = 69.0 mol N 2

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N2 balance around purge-recycle split point:

69.0 = (0.219)n8 + (0.219)(8.00) n8 = 307 mol recycled

H2 balance around mixing point:

(100)(0.7425) + (307) (0.875 - 0.219) = n2 n2 = 276 mol H2

I balance around mixing point: (100)(0.01) + (307)(0.125) = n3 n3 = 39.4 mol I

moles purge 8 = = 0.025 moles leaving condenser 8 + 307

100 moles fresh feed = 0.245 92 + 276 + 39.4 mol fed to reactor

EXAMPLE: Recycle and Purge in the Synthesis of Methanol

Methanol may be produced by the reaction of carbon dioxide and hydrogen.

CO 2 + 3 H 2 CH 3OH + H 2O The fresh feed to the process contains hydrogen and carbon dioxide in stoichiometric proportion, and 0.5 mole% inerts (I). The reactor effluent passes to a condenser, which removes essentially all of the methanol and water formed, none of the reactants or inerts. The latter substances are recycled to the reactor. To avoid build-up of the inerts in the system, a purge stream is withdrawn from the recycle. The feed to the reactor contains 2% inerts, and the single-pass conversion is 60%. Calculate the molar flow rates of the fresh feed, the total feed to the reactor, and the purge stream for methanol production rate of 1000 mol/h.

Solution

Basis: 100 mol Combined Feed to the Reactor

As a general rule, the combined feed to the reactor is a convenient stream to use as a basis of calculation for recycle problems, provided that its composition is known. Since in this process the reactants are fed in stoichiometric proportion and they are never separated from each other, they must be present in stoichiometric proportion throughout the process; that is, (CO2/H2) = 1/3. The feed thus contains 2 mol I (2% of 100 mol), and 98 mol CO2 + H2, of which 24.5 mol are CO2 (1/4 of 98) and 73.5 mol are H2.

29

n5 mol x4 mol CO2 /mol 3x4 mol H2 /mol (1-4x4) mol I/mol

n5 mol x4 mol CO2 /mol 3x4 mol H2 /mol (1-4x4) mol I/mol n4 mol CO2 /mol x4 mol CO2 /mol 3x4 mol H2 /mol (1-4x4) mol I/mol

n0 mol
0.249 mol CO2 /mol 0.746 mol H2 /mol 0.005 mol I/mol

100 mol 24.5 mol CO2 75.5 mol H2 2 mol I

Reactor

Condenser

n1 mol CO2 3n1 mol H2 n2 mol CH3OH n3 mol H2O 2 mol I

n2 mol CH3OH n3 mol H2O

Take a moment to examine the chart labeling. In particular, notice that we have built in facts that CO2 and H2 are always present in a 1:3 ratio and that the compositions of gaseous effluent from the condenser, the purge stream, and the recycle stream are identical. The more of this sort of information you can incorporate in the chart labeling, easier the subsequent calculations become. Let us outline the solution, referring to flowchart.

the the all the the

1. Calculate n1, n2, and n3, from the feed to the reactor, the single-pass conversion and reactor balances. 2. Calculate n4, from a total mole balance about the condenser, and then x4 from a CO2 balance about the condenser. 3. Calculate n0, and n6, from balances on total moles and I about the recycle-fresh-feed mixing point. (Two equations, two unknowns.) Then calculate n5, from a mole balance about the recycle-purge split point. 4. Scale up the calculated flows of fresh feed, combined reactor feed, and purge streams by the factor (1000/n2). The results will be the flow rates in mol/h corresponding to a methanol production of 1000/h.

60% Single-Pass Conversion


n1 = 0.400(24.5) = 9.80 mol CO 2 0.600(24.5) = 14.7 mol CO 2 react Balances on CH 3OH, H 2 O : output = generation n2 = 14.7 mol CH 3OH n3 = 14.7 mol H 2O 3n1 = 29.4 mol H 2

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Mole Balance About Condenser

2 4 n1 + n2 + n3 = n2 + n3 + n4 substitute for n1
n4 = 41.2 mol CO2 Balance About Condenser n1 = n4 x4

x4 = (9.80 / 41.2) = 0.2379 mol CO 2 / mol


Mole Balance About Mixing Point n0 + n6 =100 I Balance About Mixing Point

0.00500 n0 + n6 (1 4 x4 ) = 2 x4 = 0.2379 0.00500n0 + 0.0484n6 = 2 Solving the above two equations simultaneously yields
no = 65.4 mol fresh feed n6 = 34.6 mol recycle Mole balance About Purge Takeoff n4 = n5 + n6

n5 = 41.2 34.6 = 6.6 mol purge The required scale factor is

[(1000 mol / h ) / n2 mol]

n2 = 14.7

68.03 h 1

31

The desired flow rates are therefore 65.4 68.06 = 4450 mol fresh feed/h 100.0 68.03 = 6803 mol/h fed to reactor 6.6 68.03 = 449 mol/h purge

4.6. Combustion Reactions and Their Material Balances 4.6.1. Complete and Partial Combustion

Combustion is a rapid reaction of fuel with oxygen. Combustion products are CO2, NO, CO, H2O, and SO2. In a combustion reaction if CO is formed, then the reaction is incomplete and referred as incomplete combustion or partial combustion. During a complete combustion of a fuel, carbon will be oxidized to CO2, hydrogen will be oxidized to H2O, and sulfur will be oxidized to SO2. C + O2 CO2 C + O2 CO, H2+O2 H2O S+O2 SO2

Complete and incomplete combustion of C3H8 are given by the following chemical reactions, complete C3H8 +5O2 3CO2 + 4H2O incomplete C3H8 + 7/2O2 3CO + 4H2O

4.6.2. Wet and Dry Basis

Product gas that leaves the combustion chamber is called stack or flue gas. Composition of a flue gas is given on a wet (including water ) or dry basis (excluding water).

EXAMPLE: Suppose a stack gas contains equimolar amounts of CO2, N2 and H2O. Find the composition on wet and dry basis? Solution

Suppose we have n moles of each, then

32

composition of CO2 on wet basis =

moles of CO 2 100 = (n/3n)100 = 33.33% total moles on wet basis

composition of CO2 on dry basis =

moles of CO 2 100 = (n/2n)100 = 50%. total moles on dry basis

EXAMPLE: A stack gas contains 60 mole% N2, 15% CO2, 10% O2, and the balance H2O. Calculate the molar composition of the gas on a dry basis. Solution

Basis: 100 mol Wet Gas

60 mol N 2 15 mol CO 2 10 mol O 2 85 mol dry gas 60 mol N 2 = 0.706 85 mol dry gas mol CO 2 15 = 0.176 mol dry gas 85 mol O 2 10 = 0.118 mol dry gas 85

EXAMPLE: Dry Basis Wet Basis

An Orsat analysis (a technique for stack gas analysis) yields the following dry basis composition: N2 CO 2 CO O2 65% 14% 11% 10%

A humidity measurement shows that the mole fraction of H2O in the stack gas is 0.07. Calculate the stack gas composition on a wet basis.

33

Solution

Basis: 100 lb-moles Dry Gas

0.07

lb mole H 2O lb mole dry gas 0.93 lb mole wet gas lb mole wet gas

0.07 lb mole H 2O / lb mole wet gas lb mole H 2O = 0.0753 0.93 lb mole dry gas / lb mole wet gas lb mole dry gas 100 lb mole dry gas 0.0753 lb mole H 2O = 7.53 lb moles H 2O lb mole wet gas 100 lb mole dry gas 0.650 lb mole N 2 = 65.0 lb mole N 2 lb mole dry gas (100)(0.140) = 14.0 lb mole CO 2 (100)(0.110) = 11.0 lb mole CO 10.00 lb mole O 2 (100)(0.100) = 107.5 lb mole wet gas

The mole fractions of each stack gas component may now easily be calculated:
y H 2O = 7.53 lb moles H 2 O lb moles H 2 O = 0.070 ,. . . etc. lb moles wet gas 107.5 lb moles wet gas

4.6.3.

Theoretical and Excess Air

Theoretical oxygen is the amount needed for complete combustion of reactants to form CO2 and H2O. Air that contains the theoretical amount of oxygen is called theoretical air. Theoretical air does not depend on how much of a reactant is converted. The difference between the amount of air initial fed and the theoretical air is known as excess air. Therefore, percentage excess air is defined as,

% excess air = {[Air (fed) - Air (theoretical)]/Air (theoretical)}100.


EXAMPLE: Theoretical and Excess Air

One hundred mol per hour of butane (C4H10) and 5000 mol per hour of air are fed into a combustion reactor. Calculate the percent excess air.

34

Solution

First, calculate the theoretical air from the feed rate of fuel and the stoichiometric equation for complete combustion of butane. 13 O 2 4 CO 2 + 5 H 2O 2 100 mol C 4 H10 6.5 mol O 2 required (O 2 ) theoretical = h mol C 4 H10 C 4 H10 + = 650 (air ) th Hence % excess air = mol O 2 h 650 mol O 2 4.76 mol air mol air = = 3094 h mol O 2 h

(air) fed (air) th 5000 3094 100% = 100% = 61.6% (air) th 3094

If instead you had been given 61.6% excess air, you could have calculated (air)fed = 1.616 (air)th = 1.616 (3094) = 5000 mol/h.

4.6.4. Combustion Material Balances

When doing material balances for combustion reactions, one should consider balances of the followings: a. inert N2 at both inlet and outlet b. unreacted fuel c. excess oxygen d. combustion products CO2, H2), CO etc. Suppose 15% excess of oxygen is fed, oxygen fed = 1.15 theoretical oxygen nitrogen fed = (79/21) oxygen fed air fed = (100/21) oxygen fed

35

EXAMPLE: Combustion of Ethane

Ethane (C2H6) is burned with 50% excess air. The percentage conversion of the ethane is 90%; of the ethane burned, 25% reacts to form CO and the balance to form CO2. Calculate the composition of the fuel gas and the ratio of water to dry fuel gas.
Solution

Basis: 100 mol Ethane Fed


100 mol C2H6 50% excess air Q mol O2 3.76Q mol N2

q1 mol C 2 H 6 q 2 mol O 2 q 3 mol N 2 q 4 mol CO q 5 mol CO 2 q 6 mol H 2 O

7 O 2 2 CO 2 + 3 H 2O 2 5 C2H 6 + O 2 2 CO + 3 H 2O 2 C2H 6 +
Note:

1. Since no product stream mole fractions are known, subsequent calculations are easier if individual component amounts rather than a total amount and mole fractions are labeled. 2. Known information about the composition of air has been used to label the incoming N2 79 stream 3.76 = . 21 3. If the ethane reacted completely, q1 would be omitted. 4. Since excess air is supplied, O2 must appear in the product stream.
Theoretical O2
100 mol C 2 H 6 3.50 mol O 2 = 350 mol 1 mol C 2 H 6

O2 Fed

Q = (1.5)(350 ) =

525 mol O 2 fed

N2 Fed

(3.76)(525) = 1974 mol N2 fed

36

C2H6 Reacted C2H6 Balance

(0.90)(100) = 90 mol C2H6 reacted

Output = input - consumption ==> q1 = 100 - 90 = 10 mol


N2 Balance

Input = output ==> 1974 mol N2 = q3


CO Balance q4 =

Output = generation 0.25 x 90 mol C 2 H 6 react to form CO 2 mol CO formed 1 mol C 2 H 6 reacted

q4 = 45 mol CO
Atomic C Balance

Input = Output C2H 6 100 mol C 2 H 6

CO

CO 2

6 7 8 6 7 8 6 7 8 2 mol C = (q1 )(2 ) + (q4 )(1) + (q4 )(1) 1 mol C 2 H 6 q1 = 10 q4 = 45

q5 = 135 mol CO 2 Atomic H Balance

Input = Output 100 mol C 2 H 6 6 mol H 10 mol C 2 H 6 6 mol H = 1 mol C 2 H 6 1 mol C 2 H 6


+

q 6 (mol H 2O)

2 mol H 1 mol H 2O

q6 = 270 mol H 2O

37

Atomic O Balance

Input = Output 525 mol O 2 2 mol O 45 mol C O 1 mol O q ( mol O 2 ) 2 mol O = 2 + 1 mol O 2 1 mol O 2 1 mol CO
+ +

135 mol CO 2 270 mol H 2O

2 mol O 1 mol CO 2 1 mol O 1 mol H 2O

q2 = 232 mol O 2

The analysis of the stack gas is now complete. Summarizing:


q1 = 10 mol C 2 H 6 q2 = 232 mol O 2 q3 = 1974 mol N 2 q4 = 45 mol CO q5 = 135 mol CO 2 2396 mol dry gas + q6 = 270 mol H 2O 2666 mol total

Hence the flue gas composition on a dry basis is 10 mol C 2 H 6 mol C 2 H 6 = 0.00417 2396 mol dry gas mol 232 mol O 2 mol O 2 = 0.0970 2396 mol dry gas mol 1974 mol N 2 mol N 2 = 0.824 2396 mol dry gas mol 45 mol CO mol CO = 0.019 2396 mol dry gas mol 135 mol CO 2 mol CO 2 = 0.0563 2396 mol dry gas mol

y1 = y2 = y3 = y4 = y5 =

38

and the mole ratio of water to dry flue gas is 270 mol H 2O mol H 2O = 0.113 2396 mol dry flue gas mol dry flue gas

EXAMPLE: Combustion of a Natural Gas


A natural gas of an unknown composition is burned with air. An analysis of the product gas yields the following results 0.130 mole H2O/mole wet gas Orsat analysis of flue gas: 1.5% CO 6.0% CO2 8.2% O2 84.3% N2

Calculate the ratio of hydrogen to carbon in the gas, and speculate on what the gas might be.

Solution
Basis: 100 mol Dry Flue Gas Since the composition of the fuel is unknown, label it as though carbon and hydrogen were entering separately.

qH mol H
qC mol C

qO2 mol O2 3.76 qO2 mol N2

100 mol dry gas 0.015 mol CO / mol 0.060 mol CO 2 / mol 0.082 mol O / mol 2 0.843 mol N 2 / mol
Qw mol H2O

From the given mole fraction of water,

Qw =

100 mol dry gas 0.130 mol H 2O = 14.9 mol H 2O 0.870 mol dry gas

39

Atomic Carbon Balance


qc =
100 mol flue gas 0.015 mol CO 1 mol C mol flue gas 1 mol CO
C in CO 2 64 4 744 8 + (100 )(0.06 )(1) = 7.5 mol C

Atomic H Balance

qH =

Q w (mol H 2 O) 2 mol H = 2 14.9 = 29.8 mol H mol H 2 O

from which

qH 29.8 mol H mol H = = 3.97 qC 7.5 mol C mol C


The natural gas may therefore be written with the formula (CH3.97)n. Since there is only one hydrocarbon for which the ratio of H to C is close to 3.97 - that is, CH4 - we may conclude in this case that the natural gas is essentially pure methane, with perhaps trace amounts of other hydrocarbons. [If we had obtained, say, qH/qC 2, we could have gone no further than to write the fuel as (CH2)n: from the information given, there would have been no way to distinguish between C2H4, C3H6, a mixture of CH4 and C2H2, etc].

40

References
1. 2. 3. 4. Felder, R. and Rousseau, R. W., Elementary Principles of Chemical Processes, 2nd ed., John Wily & Sons, 1986. Himmelblau, D. M., Basic Principles and Calculations in Chemical Engineering, 4th ed., Prentice Hall, New Jersey, 1982. Perry, R. H. and Green, D., Perrys Chemical Engineering Handbook, 6th ed., McGraw Hill, New York, 1984. Al-Amer, M. J., Session 1 of a Short Course on Introduction to Chemical Engineering for Non-Chemical Engineers, KFUPM, Dhahran, 1998.

41

Chapter 5 PVT CORRELATIONS

PVT CORRELATIONS

1. Ideal Gas
To solve most problems that involve gases, an expression is needed that relates specific volume to temperature and pressure so that if any two of three properties are known, the third can be calculated. An equation that relates the quantities (mass or moles) and volume of a gas to its pressure and temperature is call Equation of State. The simplest and most widely used equation of state is the ideal gas law which is adequate for many engineering calculations over a wide range of conditions. At high pressures and low temperatures, however, all gases deviate from ideal behavior and more complex equations of state are needed to describe PVT relations.

1.1. Ideal Gas Law


The ideal gas law can be derived from the kinetic theory of gases by assuming that gas molecules have negligible volume, exert no force on one another and collide elastically with walls of their container. This law can be expressed as:

PV = n R T
where, P V n R T = = = = = Absolute pressure of the gas Volume of the gas Number of moles of the gas The gas constant Absolute temperature of the gas

(1)

The above equation can be written for one mole of the gas, as

Pv = RT
1

(2)

The gas constant, R, has the units of (Pressure)(volume)/(mole)(temperature). Since the product of pressure and volume has units of energy, R may also be expressed as (energy)/(mole)(temperature). The units of R are listed on the last page of Felder and Rousseau in various system of units.

1.2. Standard Conditions


The reference temperature of 0C (273 K, 492 R) and a pressure of one atmosphere (1 atm) are commonly referred to as standard temperature and pressure. The gas law gives,

Ps Vs = ns R Ts
P V R = s s Ts ns
Vs liters ft 3 STP . = 22 4 = 359 ( ) ( STP) mol lbmol ns

(3)

or,

(4)

however,

The value of gas constant R can therefore be calculated from equation (4).

1.3. Ideal Gas Mixtures


Let us consider a mixture of ideal gases and assume that the mixture itself can be considered an ideal gas. Let us further assume that the mixture consists of components A and B and that initially the components are separated and exist at temperature and pressure of the mixture as shown schematically in the figure below.
2

T Gas A Volume VA

T Gas B Volume VB

Gases A + B Volume V

Figure 3. The Amagats rule We can then write the equation of state for the individual component on a molal basis as follows:

P VA = nA R T PVB = nB R T

(5) (6)

At the same temperature and pressure, if the components are mixed together in one container, then

PV = n R T
It therefore follows that

(1)

VA n = A = yA V n

(7)

This equation simply means that volume fraction (VA/V) is equation to mole fraction. Further,

n = n A + nB
or

(8)

PV PVA PVB = + RT RTA RTB

(9)

i.e.

V = VA + VB

(10)

This leads to the Amagats rule of additive volumes which states that the volume of the mixture is equal to the sum of the volumes of individual constituents at the temperature and pressure of the mixture. An alternate approach in the analysis of ideal gas mixture is to consider that each component occupies the entire volume. The pressure of the component under these conditions is referred to as partial pressure. This is shown schematically in Figure 4.

T Gas A Volume V

T Gas B Volume V

Gases A + B Volume V

Figure 4. The Daltons model

The equation of state of each component of the mixture:

PA V = n A R T PB V = nB R T
PV = n R T

(11)

(12)

(1)

PA n = A = yA P n

(13)

Therefore, the ratio of partial pressure of the component to the total pressure is equal to the mole fraction.
4

Further,

n = nA + nB
PV PAV PB V = + RT RT RT

(8)

(14)

i.e.

P = PA + PB

(15)

where each partial pressure is evaluated at the temperature and volume of the mixture. The above equation is called Daltons law of Partial Pressure.

2. Real Gas
As the temperature of the gas decreases and the pressure increases, the ideal gas law discussed earlier provides increasingly poor description of the gas behavior. It becomes essential to turn to other equations of state which may satisfactorily represent the PVT behavior.

One approach to represent the PVT behavior of real gases is to use equations of state that contain number of constants whose value differ for different gases. Another approach is to correct the deviation from ideal behavior by including a term called the compressibility factor in the ideal gas law. The resulting equation is called the compressibility factor equation of state.

2.1. Compressibility Factor Equation of State


An equation of state that retains the simplicity of ideal gas law but describes the PVT behavior of real gases over a much wider rage of conditions is of the following form:

PV = Z n R T Pv = Z RT

(16)

(17)

The coefficient Z is called the compressibility factor and the equation is called the compressibility equation of state. A value of Z = 1 corresponds to ideal gas behavior. The compressibility factor depends on the gas temperature and pressure and differs for different gases at a given T and P.

2.2. Estimation of Compressibility Factors


2.2.1 Law of Corresponding States

It is possible to construct a single universal chart for the estimation of compressibility factors for all gases if independent variables other than P and T are used. Figure 5 (Figure 5.4 in Felder and Rousseau)) shows such a plot called generalized compressibility chart. The variables P and T and replaced by Pr = (P/Pc), and Tr = (T/Tc) where Pc and Tc are critical pressure and temperature respectively of the gas. The basis for the generalized compressibility chart is the experimentally observed fact that the value of certain physical properties of gases, such as compressibility depend on a greater extent on how near the gas is to its critical state. This suggests that a plot of Z versus reduced temperature (Tr) and reduced pressure (Pr) should be approximately be the same for all substances which indeed is the case. This assertion is known as law of corresponding states.
6

2.3. Real Gas Mixtures


The techniques that is both simple and reasonably accurate is Kays Rule which uses the compressibility factor equation of state:

PV = Zm n R T

(18)

P v = Zm R T
with Zm as the mean compressibility factor.

(19)

In order to determine Zm for the mixture of gases, A, B, C with the composition of mole fraction yA, yB, yC the pseudocritical constants of the mixture as average values of critical constants of the mixture components are calculated as follows:

Pseudocritical Temperature

Tc' = y A TcA + yB TcB + yC TcC + LLL

(20)

Pseudocritical pressure

Pc' = y A PcA + yB PcB + yC PcC + LLL

(21)

If the temperature and pressure of the mixture are known, pseudo reduced temperature

Tr' =

T P ' and pseudo reduced pressure P = are calculated and used to obtain r Tc' Pc'

the value of Zm for the mixture using the generalized compressibility charts. This value of Zm can be used to calculate V or v as desired from Eq. (18) or (19).

4. Selected Instruments For Process Variable Measurement


4.1. Fluid Pressure Measurement
Several mechanical devices are used for the measurement of fluid pressure. The most common of these devices is a Bourdon Gauge which is a hollow tube closed at one end and bent into a C congifuration. The open end of the tube is exposed to the fluid whose pressure is to be measured. As the pressure increases, the tube tends to straighten, causing a pointer attached to the tube to rotate. The position of the pointer on the calibrated dial gives the gauge pressure of the fluid. Figure 6 shows the schematic diagram of the Bourdon gauge.

P (psi)

Figure 6. Bourdon Gauge

A manometer is a U-shaped tube partially filled with a liquid of known density. When the ends of the tube are exposed to different pressures the fluid levels drops in the high pressure arm and rises in the low pressure arm. The difference between the pressures can be calculated from the measured difference between the liquid level in each arm. Manometers are used in different ways as shown in Figure 7 (Figure 3.4-4 in Felder and Rousseau). In each arm P1 and greater than P2.

Figure 7a shows an open ended manometer. One end is exposed to the fluid whose pressure is to be measured and the other end to the atmosphere. Figure 7b shows a differential manometer, used to measure the pressure difference between two points in a process line. Figure 7c shows a sealed end manometer which has a vacuum enclosed at one end. If the open end of the sealed-end manometer is exposed to the atmosphere (P1 = Patm) the device functions like a barometer.

4.2. Temperature Measurement


The temperature of a substance in a particular state of aggregation (solid, liquid or gas) is a measure of the average kinetic energy possessed by the substance molecules. Since the energy cannot be measured directly, the temperature must be determined indirectly by measuring some physical property of the substance whose value depends on the temperature in a known manner. Such properties and the temperature measuring devices based on them include electrical resistance of the conductor (Resistance Thermometer) voltage at the junction of two dissimilar metals (Thermocouple), spectra of emitted radiation (Pyrometer), and volume of fixed mass of fluid (Thermometer).

4.3. Flow Rate Measurement


9

A flow meter is a device mounted in a process line that provides a continuous reading of flow rate in the line. Two commonly used flow meters - The Rotameter and the Orifice meter are shown in Figure 8 (Figure 3.2-1 in Felder and Rousseau). The rotameter is a tapered vertical tube containing float, the larger the flow rate, the higher the float rises in the tube. The orifice meter is an obstruction in flow channel with a narrow opening through which the fluid passes. The fluid pressure drops from the upstream side of the orifice to the downstream side. The pressure drop varies with the flow rate; the greater the flow rate the larger is the pressure drop.

10