Microsoft Excel For Chemical Engineers Notes (By Moataz and Mohammed) PDF

CAIRO UNIVERSITY
FACULTY OF ENGINEERING
CHEMICAL ENGINEERING DEPARTMENT
INTRODUCTION TO
MICROSOFT EXCEL
WITH APPLICATIONS IN CHEMICAL
ENGINEERING
Eng. Moataz Bellah Mahmoud Mousa

Eng. Mohammed Gamal Abdel Nasser
July 2009
Table of Contents
Microsoft Excel 2007 Basics .................................................................................................................... 1
Inserting Charts ...................................................................................................................................................... 1
Data fitting using least square method ......................................................................................................... 5
Array calculations .................................................................................................................................................. 9
Matrices ................................................................................................................................................................... 10
Thermodynamics ..................................................................................................................................... 14
Equations of state ................................................................................................................................................ 14
Solving equations of state using excel ........................................................................................................ 16
Vapor Pressure Data Representation Using Equations ........................................................................ 17

Chemical Reaction Engineering........................................................................................................... 21
Batch reactor yield optimization ................................................................................................................... 21
Chemical reaction equilibrium ....................................................................................................................... 23
Example Using Excel........................................................................................................................................... 24
Regressing rate constants in rate equation from experimental data .............................................. 26
Multiple regression using Excel.................................................................................................................... 26
Non linear regression ....................................................................................................................................... 30
Nonlinear Regression Using Excel .............................................................................................................. 30

Fundamentals of Chemical Engineering ........................................................................................... 33
Material Balance................................................................................................................................................... 33
Material balance for non-reactive system .................................................................................................. 35
Material balance for a reactive system without recycle ......................................................................... 37
Material balance for a reactive system with recycle ............................................................................... 39
Energy Balance ..................................................................................................................................................... 43
Energy balance on a non-reactive system .................................................................................................. 50
Energy balance on a reactive system ........................................................................................................... 53

Fluid Mechanics ........................................................................................................................................ 59
Terminal Velocity of Falling Particles .......................................................................................................... 59
Emptying Tank...................................................................................................................................................... 62
Runge-Kutta method .......................................................................................................................................... 62
Pipeline optimization ......................................................................................................................................... 64

PHASE EQUILIBRIA AND MASS TRANSFER .................................................................................. 68
Introduction ........................................................................................................................................................... 68
Bubble point Calculations................................................................................................................................. 70
Dew point Calculations ...................................................................................................................................... 71
Flash Calculations ................................................................................................................................................ 71
Performing flash calculations using Microsoft Excel......................................................................... 72

Microsoft Excel 2007 Basics
Inserting Charts
Microsoft Office Excel 2007 supports many types of charts to help you display data in ways that are
meaningful to you. There are many types of charts available in Microsoft excel, and here we will try to
show the most commonly used ones in the engineering applications:
Line charts
Data that is arranged in columns or rows on a worksheet can be plotted in a line chart. Line charts can
display continuous data over time, set against a common scale, and are therefore ideal for showing
trends in data at equal intervals. In a line chart, category data is distributed evenly along the horizontal
axis, and all value data is distributed evenly along the vertical axis.
Pie charts
Data that is arranged in one column or row only on a worksheet can be plotted in a pie chart. Pie charts
show the size of items in one data series, proportional to the sum of the items. The data points in a pie
chart are displayed as a percentage of the whole pie.
Consider using a pie chart when:

You only have one data series that you want to plot.
None of the values that you want to plot are negative.
Exercise: Search the Microsoft Excel help to find out more information about bar charts and how to
use it to draw a Gantt chart
XY (scatter) charts (most used in chemical engineering applications)
Data that is arranged in columns and rows on a worksheet can be plotted in an xy (scatter) chart. Scatter
charts show the relationships among the numeric values in several data series, or plots two groups of
numbers as one series of xy coordinates.
A scatter chart has two value axes, showing one set of numeric data along the horizontal axis (x-axis)
and another along the vertical axis (y-axis). Scatter charts are typically used for displaying and
comparing numeric values, such as scientific, statistical, and engineering data.
Consider using a scatter chart when:
You want to change the scale of the horizontal axis.
You want to make that axis a logarithmic scale.
There are many data points on the horizontal axis.
You want to effectively display worksheet data that includes pairs or grouped sets of values and
adjust the independent scales of a scatter chart to reveal more information about the grouped
values.
You want to show similarities between large sets of data instead of differences between data
points.
You want to compare many data points.
Some of Microsoft Excel charts (unstacked, 2-D, area, bar, column, line, stock, xy (scatter), or bubble
chart) provide an easy means of fitting data and getting the equation that fits the data plotted on the
graph using a method called Regression.
Fitting data is performed by an option called Add Trendline
Choosing the right trendline type for your data
When you want to add a trendline to a chart in Microsoft Office Excel, you can choose any one of these
six different trend or regression types:
linear trendlines power trendlines
logarithmic trendlines exponential trendlines
polynomial trendlines moving average trendlines
Linear trendlines
A linear trendline is a best-fit straight line that is used with simple linear data sets. Your data is linear if
the pattern in its data points resembles a line. A linear trendline usually shows that something is
increasing or decreasing at a steady rate.
Logarithmic trendlines
A logarithmic trendline is a best-fit curved line that is used when the rate of change in the data
increases or decreases quickly and then levels out. A logarithmic trendline can use both negative and
positive values.
Polynomial trendlines
A polynomial trendline is a curved line that is used when data fluctuates. The order of the polynomial
can be determined by the number of fluctuations in the data or by how many bends (hills and valleys)
appear in the curve. An Order 2 polynomial trendline generally has only one hill or valley. Order 3
generally has one or two hills or valleys. Order 4 generally has up to three hills or valleys.
Power trendlines
A power trendline is a curved line that is used with data sets that compare measurements that increase
at a specific rate. You cannot create a power trendline if your data contains zero or negative values.
Exponential trendlines
An exponential trendline is a curved line that is used when data values rise or fall at constantly
increasing rates. You cannot create an exponential trendline if your data contains zero or negative
values.
Moving average trendlines

A moving average trendline smoothes out fluctuations in data to show a pattern or trend more clearly.
A moving average uses a specific number of data points (set by the Period option), averages them, and
uses the average value as a point in the line. For example, if Period is set to 2, the average of the first
two data points is used as the first point in the moving average trendline. The average of the second and
third data points is used as the second point in the trendline, etc..
NOTE: Choosing the type of trendline in many cases depends on the case whose data is being fitted,
i.e. you may know that your data must fit linear or logarithmic or whatever trendline before
they are plotted.
A trendline is most accurate when its R-squared value is at or near 1. When you fit a trendline to your
data, Excel automatically calculates its R-squared value. If you want to, you can display this value on
your chart.
The table below summarizes the types of trendlines and the final forms of equations:
Use this type To create
Linear A linear trendline by using the following equation to calculate the least squares
fit for a line:
where m is the slope and b is the intercept.

Logarithmic A logarithmic trendline by using the following equation to calculate the
least squares fit through points:
where c and b are constants, and ln is the natural logarithm function.

Polynomial A polynomial or curvilinear trendline by using the following equation to
calculate the least squares fit through points:
where b and are constants.

Power A power trendline by using the following equation to calculate the least
squares fit through points:
where c and b are constants.

This option is not available when your data includes negative or zero values.
Exponential An exponential trendline by using the following equation to calculate the least
squares fit through points:
where c and b are constants, and e is the base of the natural logarithm.
This option is not available when your data includes negative or zero values.
Moving A moving average trendline by using the following equation:
average
Data fitting using least square method
Microsoft Excel proved to be very effective in curve fitting, but it does so for five forms of equations
which were mentioned previously. If the equation that you need to fit your data to is not one of these
five forms then Microsoft Excel will not be able to fit your data automatically using the Trendline
option.
In these cases the user must be able to fit his data to the form he needs by himself. There are many
methods to do so, the most common and easy to use is what so called Least square method.
To understand this method lets see the next example:
Consider the following experimental data relating any two variables (say x and y)
X 3.4 7.1 16.1 20.0 23.1 34.4 40.0 44.7 65.9 78.9 96.8 115.4 120.0
9.59 5.29 3.63 3.42 3.46 3.06 3.25 3.31 3.50 3.86 4.24 4.62 4.67
Y
And that from your knowledge about your experiment you know that the relation must take the form:
Y=aX+b/X+c
And you now need to fit these data to that equation to get the values of a, b and c, also to calculate the
R-squared.
This method is based on a simple idea, which is assuming values for the variables a, b and c, then
calculating values of Ys based on the assumed values, then comparing the calculated and the real
values of Ys, and finally changing the values of assumed a, b and c till the difference between the real
and calculated vales of Ys is minimum.
This is simply done by building a simple table, two columns for the experimental data available (Xs
and Ys ), another column for the calculated values of Ys ( based on the values of X ).
Remember to add the dollar signs on typing the names of cells containing assumed vales of a, b and c
before dragging. After dragging the table will be in the form shown below:
Now its now required to minimize the difference between the calculated and the real values. So a new
column is introduced to calculate the difference between the calculated and the real values.
Now its required to minimize all the values in the last column by varying the values of the variables a,
b and c. Microsoft Excel has a tool that performs this form of iterations which is Solver. Its available
under the Data toolbar in the analysis tab.
On clicking the solver tab a window will appear having the shape:
This tool can change the value of multiple cells to set the value of ONLY ONE cell to a maximum,
minimum or a specific value.
And we need now to change the value of the three cells (a, b and c) to set the values of 13 cells to zero,
which is not available using this tool.
A trick can be done to avoid this problem. If the sum of the differences is calculated and then is set to
the value of zero then consequently the values of all the 13 cells will be minimized, so a cell for the
sum values in the last column is set and calculated. And is now the cell that will be set to zero.
But remains a small problem, you may notice that some of the values in the last column are positive
and some are negative, so the summation may be zero but the entire cells in the column may not be
zeros. So a new column is added where the SQUARES of the values of the difference column are
calculated, so all the values will be positive and this problem is no more present. And thats why this
method is called Least Square Method.
Finally the table will have the form:
Now we are now ready to use the solver.

By clicking solve the final results appear:
Its now clear that the values in columns D and E are minimized. Now to ensure the accuracy of this
fitting the R-squared value must be calculated.
R-squared value is calculated from the following relation:
Then finally the shape of the table will be as follows:
And the R-squared value is found to be 0.9967 which is a very good fit.
Array calculations
An array formula is a formula that can perform multiple calculations on one or more of the items in an
array. Array formulas can return either multiple results or a single result. For example, you can place an
array formula in a range of cells and use the array formula to calculate a column or row of subtotals.
You can also place an array formula in a single cell and then calculate a single amount.
To understand the concept on arrays well, lets consider the least square method example discussed
previously.
On calculating the value of the sum of square of the differences between the calculated and the real
values we had to add a column to calculate the differences then another column to calculate the square
of the differences, and finally a cell to calculate the summation of the squares.
Array calculations provide a quicker means to do these 3 or 4 steps in only one step.
In any cell type the following formula =SUM(C2:C14-B2:B14) then press Ctrl+Shift+Enter and
compare it with the value in cell D17, you will find that they both have the same value, this means that
this formula calculated the difference between the values in two columns and got the sum of these
values.
On typing the following formula: =SUM((C2:C14-B2:B14)^2) you will be able to calculate directly
the sum of squares of the differences.
Matrices
Matrix calculation is a special type of array calculations, as Microsoft Excel deals with matrices as
arrays. Microsoft Excel can perform many matrices operations such as adding, subtracting, multiplying
matrices, also getting the inverse of a matrix and the value of its determinant.
Before discussing how these operations are performed using Microsoft Excel, its recommended to
revise quickly the matrix operations and calculations.
Consider a system of linear equations like :
a1X+b1Y+c1Z=L
a2X+b2Y+c2Z=M
a3X+b3Y+c3Z=N
where X,Y and Z are variables
a1,b1,., b3,c3 are their coefficients ( constants )
L,M and N are constants
And its required to solve these equations to get the values of X,Y and Z.
One of the methods of solving this system of equations is using Matrices.
This can be simply performed by putting the system of equations in the form of matrix as follows
a1 b1 c1 X L
a2 b2 c2 Y = M
a3 b3 c3 Z N
Which takes the general form: AX=B

Before solving such a system, we must check first if its solvable or not, which can be verified by
calculating the value of the determinant of the matrix A. If its value 0 then its solvable, if its
value=0 then its not solvable.
After performing this check the system has to be solved. This was done by performing the following
steps:
AX=B
A AX=A-1B
-1
X=A-1B
So getting the final solution requires first getting the inverse of the matrix A, then multiplying it by
matrix B to get the final solution.
NOTE:on multiplying two matrices, the number of columns of the first matrix has to be equal to the
number of rows of the second one.
Now, consider a set of linear equations that we have to solve using Microsoft Excel, like:
X-Y-Z+3 L=1
2X+4 Y+3 Z+L=2
2.25 X+Y+2 Z+2 L=3
X+1.5 Y+Z+2 L=4
This will take the matrix form as follows:
1 -1 -1 3 X 1
2 4 3 1 Y 2
=
2.25 1 2 2 Z 3
1 1.5 1 2 L 4
This is introduced to Microsoft Excel as an array:
Then we have to check if the determinant A equals zero or not, Microsoft Excel can calculate the
value of the determinant of a matrix using the function MDETERM
Entering the following formula MDETERM(array region) then as in any array calculation- pressing
Ctrl+Alt+Enter calculates the value of the determinant.
Now its verified that the system of equations is solvable. Now we need to get the inverse of the matrix
A, this is calculated using the function MINVERSE
Entering the following formula MINVERSE(array region) after highlighting the array of the inverse
matrixthen pressing Ctrl+Alt+Enter, calculates and shows the inverse of the matrix.
Finally to get the solution we have to multiply A-1 by B
To do this use the function MMULT, Entering the following formula MMULT(array1,array2)
after highlighting the array of the product then pressing Ctrl+Alt+Enter, calculates and shows the
matrix X, which is the solution.
Other matrix operations can be easily performed using excel such as addition subtraction of matrices,
multiplying matrix by a constant, ... etc.
Thermodynamics
This chapter introduces the ideal gas equation of state, then describes how computer programs such
as Excel, use modified equations of state to easily and accurately solve problems involving gaseous
mixtures.
Also in this chapter the vapor pressure data representation is discussed, then the use of Excel to
determine constants of different equations, relating vapor pressure to temperature, is illustrated for
optimum representation to the experimental data.
Equations of state
Solving equations of state allows us to find the specific volume of a gaseous mixture of chemicals
at a specified temperature and pressure. Without using equations of state, it would be virtually
impossible to design a chemical plant. By knowing this specific volume, you can determine the size
and thus cost of the plant, including the diameter of pipes, the horsepower of compressors and
pumps, and the diameter of distillation towers and chemical reactors.
The ideal gas equation of state, which relates the pressure, temperature, and specific volume, is a
familiar equation:
The term p is the absolute pressure, V is the volume, n is the number of moles, R is the gas
constant, and T is the absolute temperature. The units of R have to be appropriate for the units
chosen for the other variables. This equation is quite adequate when the pressure is low (such as one
atmosphere). However, many chemical processes take place at very high pressure. For example,
ammonia is made at pressures of 220 atmospheres or more. Under these conditions, the ideal gas
equation of state may not be a valid representation of reality. Other equations of states have been
developed, usually in conjunction with process simulators, to address chemical processes at high
pressure.
There are two key features:

(1) the equation can represent the real pVT behavior; and
(2) the parameters must be easily found, including for mixtures. This last criterion is no small
requirement. There are more than 25 million chemicals, leading to an infinite number of different
mixtures.
Obviously, you cannot look up the properties of all those mixtures on the Web.
The first generalization of the ideal gas law was the van der Waals equation of state:
15 INTRODUCTION TO
MICROSOFT
EXCELermodynamics
In this equation, the b accounts for the excluded volume (a second molecule cannot use the same
space already used by the first molecule), and the a accounts for the interaction force between two
molecules. This extension is just a first step, however, because it will not be a good approximation
at extremely high pressures.
The RedlichKwong equation of state is a modification of van der Waals equation of state:
Where,
In these equations, Tc is the critical temperature (in absolute terms), Pc is the critical pressure.
The RedlichKwong equation of state was modified further by Soave to give the RedlichKwong
Soave equation of state, which is a common one in process simulators:
Now the parameter a is given by a different formula,
The is the acentric factor, which is a tabulated quantity for many substances. Thus, the value of
can be computed for each chemical and reduced temperature.
The PengRobinson equaton is another variation:
All these equations can be rearranged into a cubic function of specific volume. The form of the
RedlichKwong and RedlichKwongSoave equation of state is
When given the temperature and pressure of a gaseous mixture, and the parameters a and b, then to
find the specific volume you would have to solve the cubic equation of state for specific
volume . This represents one algebraic equation in one unknown, the specific volume.
For a pure component, the parameters a and b are determined from the critical temperature and
critical pressure, and possibly the acentric factor. These are all tabulated quantities, and there are
even correlations for them in terms of vapor pressure and normal boiling point, for example. For
mixtures it is necessary to combine the values of a and b for each component according to the
16 INTRODUCTION TO
MICROSOFT
EXCELermodynamics
composition of the gaseous mixture. Common mixing rules are shown in next equations, in which
the ys are the mole fraction of each chemical in the vapor phase:
where
for Redlich-Kwong
or
for Redlich-Kwong-Soave
Thus, the only difference between the problem for a pure component and that for a mixture is in the
evaluation of the parameters a and b.
Here is the mathematical problem need to be solved:
Given a set of chemicals, temperature and pressure, find the specific volume of the mixture. To do
this, you must find the critical temperature and pressure of each chemical. Once you have the
parameters, you must solve the cubic equation, which is a nonlinear equation in one variable.
Excel allows us to easily solve for the specific volumes. However, one advantage of process
simulators is that the physical properties of many components are saved in a database that users can
access. The next section illustrates how to use Excel to solve equations of state.
Solving equations of state using excel

Problem
Calculate the molar volume and compressibility factor for gaseous ammonia at a pressure P = 40
atm and a temperature T = 400 K using the van der Waals and Redleich-Kwong equations of state.
Step 1 You must first find the critical temperature and pressure; Perrys Chemical Engineers
Handbook gives Tc = 405.4 K and Pc = 111.3 atm for ammonia
Step 2 Calculate values of a and b for Redlich-Kwong using the following equations:
Van der Waals parameters are

a= 0.4233 J.m3/mol2, b= 3.737E-5 m3/mol
17 INTRODUCTION TO
MICROSOFT
EXCELermodynamics
Step 3 Prepare the spreadsheet shown in next figure. The title, name, and data will be useful when
you come back to the problem at a future date
Step 4 You enter the parameters in the parameter box. The cells containing the critical parameters
and the temperature and pressure can be named Tc, Pc, T, and P, respectively.
That way, the equation for f (v) will be easier to understand
Step 5 The lower box gives the equations actually used as well as the results. Use the Goal Seek
command to make f (v) (cell B15) equal to zero by changing (cell B16)
Step 6 For reference, the result for an ideal gas is also shown
Exercise
a) Repeat the calculations for the following reduced pressures: Pr = 1, 2, 4, 10, and 20.
Vapor Pressure Data Representation Using Equations

Vapor pressure is the pressure of a vapor in equilibrium with its non-vapor phases. All liquids have
a tendency to evaporate to a gaseous form, and all gases have a tendency to condense back into their
original form. At any given temperature, for a particular substance, there is a pressure at which the
gas of that substance is in dynamic equilibrium with its liquid form. This is the vapor pressure of
that substance at that temperature. The equilibrium vapor pressure is an indication of a liquid's
evaporation rate. It relates to the tendency of molecules and atoms to escape from a liquid or a
solid. A substance with a high vapor pressure at normal temperatures is often referred to as volatile.
The atmospheric pressure boiling point of a liquid is the temperature where the vapor pressure
equals the ambient atmospheric pressure. The higher the vapor pressure of a liquid at a given
temperature, the lower the normal boiling point (i.e., the boiling point at atmospheric pressure) of
the liquid.
18 INTRODUCTION TO
MICROSOFT
EXCELermodynamics
The vapor pressure of any substance increases non-linearly with temperature and is independent of
the applied pressure. Also it differs from one substance to another thus it can be a considered a
characteristic physical property for substances.
There is a large number of saturation vapor pressure equations used to calculate the pressure of
water vapor over a surface of liquid water. The two most commonly used equations are
1) Clausius-Clapeyron
where P is the vapor pressure in mmHg and T is the temperature in C. Note that the
denominator is just the absolute temperature in K. Both A and B are the parameters of the
equation which are typically determined from experimental data.
2) Antoine equation
where typically P is the vapor pressure in mmHg and T is the temperature in C. Note that
this equation has parameters A, B, and C which must be determined by experimental data.
Also a simple polynomial can be used to relate vapor pressure with temperature. This can be
written in general form for this problem as
Where a0... an are the parameters (coefficients) to be determined by regression and n is the
degree of the polynomial. Typically the degree of the polynomial is selected which gives the
best data representation when using a least-squares objective function.
So the main task to be done here is to find a good values for the equation constants
(whatever it was Antoine, clausius-clapeyron or a simple polynomial equation) from a set of
experimental results. After determining the constants you have to compare the equation
results with the experimental data to assess the equation reliability.
19 INTRODUCTION TO
MICROSOFT
Problem
EXCELermodynamics
Next table presents data of vapor pressure versus temperature for benzene. Some design
calculations require these data to be accurately correlated by various algebraic expressions which
provide P in mmHg as a function of T in C.
Vapor Pressure of Benzene

Temperature, T, (0C) Pressure, P, (mm.Hg)
-36.7 1
-19.6 5
-11.5 10
-2.6 20
7.6 40
15.4 60
26.1 100
42.2 200
60.6 400
80.1 760
(a) Determine the constants for best fit of the experimental data using a polynomial equation. Also
Determine the degree of polynomial which best represents the data.
(b) Determine the constants for best fit of the data using Clausius-Clapeyron equation.
(c) Determine the constants for best fit of the data using Antoine equation.
Step 1 The spreadsheet was set up with the data for temperature and pressure entered in the
indicated columns
Step 2 Columns for temperature in K and Log P were developed
Step 3 Columns were then added for each of the curve fits that were to be carried out along with
the parameters that would be manipulated to generate the calculated curves. These are shown above
the calculated columns as parameters.
Step 4 A row of sum of squares cells were added along the bottom. The contents were set up as
array formulas and entered with Crtl+Shift+Enter. For example for the calculated Clasius-
Clapeyron column: in the sum of squares cell the following was entered:
SUM ((E16:E25-D16:D25) ^2) followed by Crtl+Shift+Enter. The function will be written
between brackets { }
Step 5 The Solver program was then utilized for each of the curve fits. For example for the
Clausius-Clapeyron fit E5 and E6 (A and B) were manipulated until E27 (the sum of squares) was
minimized.
20 INTRODUCTION TO
MICROSOFT
EXCELermodynamics
Exercise
The vapor pressure of a pure liquid as a function of the absolute temperature can be expressed as:
log (P0) = )
The total vapor pressure of a three component mixture is given by:
P= x1P01+x2P02+x3P03
Where xi is the mole fraction of component i. Set up a worksheet to use with solver to find the
normal boiling point (the temperature at which P= 760mm.Hg) of a three component mixture. Use
the following data
a b x
Benzene 7.8413 1750 0.5
Toluene 8.0884 1985 0.3
Ethyl benzene 8.114 2129 0.2
Chemical Reaction Engineering
Batch reactor yield optimization
A chemical plant uses the following process in its production:
A volume V m3 of solution of compound A having a concentration of a0 gmoles/m3 is allowed
to react for tr hours; the reactor is then emptied, cleaned and recharged for another cycle. The
reaction occurring is a first order reaction with rate constant of 1.
It is required to find the optimum reacting time tr for maximum reactor product at different
combinations of solution volume, concentration and cleaning time as shown in the next table.
(1) (2) (3) (4)
V (m3) 5 5 10 10
3
a0 (gmol/m ) 0.1 0.2 0.1 0.1
tc (hrs) 0.5 0.5 0.5 1
Step1 You must first develop an equation for the reaction yield to be optimized.
In general for first order reaction,
But,
and the amount of product formed is the difference between initial and final moles of A
For optimization purposes it is better to optimize the product yield per unit process time, thus
22 Chemical Reaction Engineering
Step 2 Enter the values in the table as shown in the next figure
Step 3 In yield row the yield equation need to be optimized must be written. The equation entered
in cell B8 is shown in row 9 as appears in the next figure.
The presence of dollar sign on the left of cell numbers is to allow dragging of the function to other
cells in the same row without changing the cells numbers in the functions.
Step 4 Now, initial guesses for tr must be entered in other cells then solver is used to find the
optimum values. For example in the first case, Solver will try to find optimum value for cell B8 by
changing B10. The final sheet form is shown in the next figure.
Chemical reaction equilibrium

aA+bB cC+dD
This is a reversible reaction. When the forward reaction happens at the same rate as the backward
reaction, the reaction progress stops and the reaction reaches equilibrium.
If the reaction is elementary, then the concentration of reactants and products are related to each
other according to:
The number KC is called the equilibrium constant and is a function of temperature. a ,b,c and d are
the stoichiometric coefficients.
There is another useful definition of the equilibrium constant based on pressure rather than
concentration and is used when dealing with gases since the pressure is usually more convenient to
measure than concentration.
Under conditions of low pressure (~10atm.) the gas can be considered to behave ideally and follows
the ideal gas low
PV=nRT
Here P is the total pressure. In the cases of several components, each has a partial pressure, all of
which sum up to the total pressure.
P=PA+PB+PC+PD
For each component, we can write the ideal gas law as follows:
If we plug in the partial pressures in the definition of KC above we get:
Using the realtion pi=yiPT

Gibbs free energy is related to KP by the relation:
N.B.: Of course, the reaction rate may not be infinitely high, and you may use a catalyst to speed up
the reaction. However, even if the reaction rate is increased, you can never go beyond the
composition determined by chemical reaction equilibrium. Here is how to set up that problem
mathematically.
Example Using Excel

When the carbon monoxide and hydrogen enter the reactor in a 1:2 ratio, use Excel to find
the equilibrium conversion when the pressure is 50 atm and KP=0.0016.
Consider the methanol formation reaction
CO + 2H2 CH3OH
At equilibrium:
Thermodynamic data give the value of KP=0.0016 atm-4 at reaction conditions and 50atm pressure.
If you start with a stoichiometric mixture of carbon monoxide and hydrogen, what will the
equilibrium composition be?
Step 1: We will start by making a quick material balance by writing 3 component material balance
equations

Step 2: You can solve for the equilibrium using Excel, by putting the equilibrium equation in one
cell, a guess of r in another cell, and use the Goal Seek to make the former cell zero by changing
r. The final results are shown in next figure.
Second column is the initial moles of each species. The third column is computed according to the
equations displayed in the column beside it. The equilibrium equation is calculated in C10,
according to the formula displayed in cell D10. Goal seek is used to make cell C10 zero by varying
cell C9.
Now once you have prepared the spreadsheet, it is easy to change the conditions, either the
equilibrium constant or the starting moles of various species.
Exercise
Find the molar flow rates of all species out of an equilibrium reactor used in ammonia production
when the inlet moles ratio of nitrogen, hydrogen and ammonia are 1.1, 3, and 0.2 respectively. The
equilibrium constant is 0.05atm-4 at 589 K. The reactor is operated at 220 atm.
Regressing rate constants in rate equation from experimental data
Engineers often need to express experimental data in terms of an equation. They must decide on the
equation and then determine the parameters that provide the best fit to the data. The problem is
simplest if the equation is linear. The mission will a little bit harder if the best fit equation is
polynomial one. Although this later case can be considered easy, as long as the equation relates 2
variables only. In this part we will discuss how to fit any set of functions of more than 2 parameters
either appearing linearly (multiple linear regression), or nonlinearly (multiple non-linear
regression).
Multiple regression using Excel

Early in the introduction of the course it was shown how to fit a polynomial to data. The same thing
can be done when the functions are not simple powers, but are more complicated functions.
However, to keep the problem linear, the unknown coefficients must be coefficients of those
functions; that is, the functions are completely specified. Multiple regression simply determines
how much of each one is needed. Thus, the form of the equation is
The goal is to find the best M values of ai, given the M functions fi (x) and data yi = y
(xi), i =1,. . ., N.
In Excel, you put the x values in a column and create additional columns, with each column being a
function, evaluated for the x value in that row. The example used here is to find the constants in a
reaction rate formula. The expected expression is
and the goal is to find the values of k, n, and m that give the best fit of the rate for various partial
pressures of substances A and B. This form is not linear, which is a requirement of multiple
regression, but a transformation can make it linear. Take the logarithm of both sides of the equation.
This equation has the following form:
where the dependence upon two or more variables is clear. The data is entered into the spreadsheet,
and the various terms are transformed as shown in next table. Columns A and B are the
partial pressures of the two chemicals for which the rate is measured, as indicated in column C.
Step 1 Obtain columns D, E, and F by taking the logarithm of columns A, B, and C, respectively.
Do this in the first cell (D2), copy it across the E and F rows, and copy down the three rows (D2,
E2, and F2).
Step 2 Proceed with parameter estimation by choosing Data/Data Analysis, and then choosing
Regression. If Data Analysis does not appear in your menu under Data you will have to add it
from Add-Ins. Enter F2:F13 for the y values and D2:E13 for the x values. This tells the computer
that you want the best line representing ln(rate) depending linearly upon ln pa and ln pb.
Step 3 There are several other options; choose residuals, residual plots, and line fit plots. These are
all useful for evaluating the results. You can place the results on another sheet in the same
Workbook or on the same sheet by specifying a location. Next table shows part of the output. The
best fit is for
The curve fit is then
You might think at this point the correlation is complete. It is not, though, because the data were
transformed to make the parameter estimation problem linear. Thus, the statistics are in terms of the
transformed problem. It is always a good idea to calculate the curve fit using the original variables.
Non linear regression

Nonlinear regression is a curve fit in which the unknown parameters enter into the problem in a
nonlinear way. Nonlinear regression is much more difficult (for the computer), so it is best to
always try to manipulate your model into a form that is linear. Sometimes that is not possible, and
then nonlinear regression must be used. You need to be aware, though, that the methods described
here do not always work. Nonlinear regression uses techniques borrowed from the field of
optimization, and it is difficult to construct a method that works every single time for every
problem.
For nonlinear curve fits it is necessary to use functions such as Solver in Excel. This is
demonstrated using the same example given above for multiple regression.
Nonlinear Regression Using Excel

Step 1 Place the data on a new sheet as shown in next figure
Step 2 Enter arbitrary values for the parameters k, n, and m.

Step 3 In column D, calculate the value of rate using the parameters in C16:C18, the data in
columns A and B, and the formula, Eq.
Step 4 Make column E the difference between columns C and D, and then square the result and put
it in column F.
Step 5 Sum Column F, divide by the number entries [COUNT (F2:F13)] to obtain the (sum of
squares)/N, Eq. (E.3).
Step 6 The goal is to minimize F17 by choosing values C16:C18. To do that, choose
Tools/Solver. You might have to add it to the Excel program if that was not done when the
program was installed. A screen appears in which you insert F17 as the quantity to be affected, and
choose Min as the option. Then insert C16:C18 as the cells to be changed, and click Solve. The
results are shown in next figure.
The best correlation is
These numbers are slightly different from those obtained using multiple regression. Multiple
regression and nonlinear regression obtained the solution by minimizing two different objective
functions.
Fundamentals of Chemical Engineering
Material Balance
Generally the material balance calculation was simply governed by the equation:
In=out + r
Where In and out are the flow rates of the component in the inlet and outlet streams to the unit around
which material balance in established, is the stoichiometric coefficients (-ve for reactants and
+ve for products ) if there is a chemical reaction involved in the unit .
Generally this equation can be applied to a single unit or group of units.
To be able to know if the available information about the unit are sufficient to solve this unit or there
are some information needed we calculate the degrees of freedom of this unit as follows:
DOF= number of variables- number of equations- number of given variables-number of

additional relations
The system will be solvable if the DOF=Zero, if the DOF is negative then the system is said to be over
specified i.e. more information are given, if the DOF is positive then the system is said to be under
specified i.e. more information are needed to solve this unit.
For a flow sheet where a number of units are operating depending on each other, a DOF table should be
constructed to ensure that the system can be solved using the available data.
Unit I Unit II ---------- Unit N Process Overall

No. of variables
No. of equations
No. of
given variables
No. of
additional relations
DOF
The system will be solvable if the DOF of process equals zero (gray cell) even if the DOF of all units
are not Zeroes.
Note: The degrees of freedom table not only indicates if the system is solvable or not, but also
determines what so called Strategy of solution or the way by which the system will be solved
and the sequence of units solved.
34 Fundamentals of Chemical Engineering
The solution is not usually straight forward, so there are some techniques that are usually used to be
able to solve such a system. The main two of them are tearing and carrying over.
Tearing: a method where a stream is assumed ( components flow rates ) and recalculated again, then
comparing the assumed with the calculated values, and so on till both are equal.
Carrying over: a method where all equations of all units are written and the uncalculated values
remain unknown till the calculations lead to getting their values, sometimes the equations are put in a
matrix form.
The most common way used in simulation programs is the tearing method.
In practical cases material balance and energy balance are both performed simultaneously, and this of
course- will result in more accurate results, however, more calculations and harder iterations will be
needed.
But in some cases when the effect of pressures and temperatures on material balance is not significant,
or when some equipment lack such information material balance calculations can be performed alone.
Microsoft Excel can be used successfully in solving material balance problems, its main advantage is
that the user builds the program by himself not like the other simulation programs where the user
only is inputing the data and this gives a good chance to understand the principals well and know the
source of error in calculations if exists.
Material balance for non-reactive system

Separation Train D1
7% Xylene
4% Styrene
Xylene, styrene, toluene and benzene are to 54% Toluene
35% Benzene
be separated with the array of distillation
D
columns that is shown below where F, D, B, #2
D1, B1, D2 and B2 are the molar flow rates in

18% Xylene
mol/min. 24% Styrene
B1 42% Toluene
F is the feed flow rate of 70 mol/min 16% Benzene
F
a- Its required to calculate the flow #1
rates of the top and bottom products 15% Xylene
25% Styrene 15% Xylene
of the second and third distillation 40% Toluene
D2 10% Styrene
20% Benzene 54% Toluene
columns. 21% Benzene
b- Also its required to calculate the
B
molar flow rates of the four #3
components in both streams B and
D. 24% Xylene
65% Styrene
10% Toluene
B2 1% Benzene
Part a :
Solution of such a system can be performed by solving a set of algebraic equations simultaneously,
these equations are material balance equations for each component.
Material balance equations on the overall of the three columns will yield:
0.1570=0.07D1+0.18B1+0.15D2+0.24B2
0.2570=0.04D1+0.24B1+0.10D2+0.65B2
0.4070=0.54D1+0.42B1+0.54D2+0.10B2
0.2070=0.35D1+0.16B1+0.21D2+0.01B2
This can be shown in the form of a matrix:

AX=B
Its solution is as follows
X=A-1B
So the inverse of the matrix A must be calculated, by using Microsoft excel, a function called
MINVERSE is used to calculate the inverse of a matrix.
Then the inverse is multiplied by matrix b using the function MMULT.
The calculated matrix is then the solution to the above system of equations and required flow rates are
calculated.
Part b :
The two streams B and D can be got from material balance equations around both towers
number 2 and 3, For tower 2:
D=D1+B1
For tower 3:
B=D2+B2
Material balance for a reactive system without recycle

Get started
The following flow diagram represents a part of methanol production process, its produced by the
reaction of synthesis gas ( CO and H2 ) according to the following reaction:
CO
H2
CH4
3 CH3OH
Catalytic Reactor
1 2
Flash
CO Separator
CO
H2
H2
CH4
CH4
CH3OH
4 CO
H2
CH4
CH3OH
Fresh feed of 1000 Kgmol/hr containing 33% CO, 66.5% H2 and 0.5% CH4 (all in mole %) is
introduced to the reactor, this reaction is catalytic and only 40% conversion of CO is achieved. The
product is then fed to a separator where methanol is separated from the unreactants, it was reported that
the bottom product contains 3% of CO2, 2% of H2, 4% of CH4 and 96% of methanol reactor effluent.
You are now required to solve this system to get the flow rates of all components in all streams in
addition to the rate of the reaction, once by solving a system of equations (using matrix) and once by
unit-to-unit calculations.
For the unit-to-unit calculations method:

Its common to arrange the variables in the form of table where the columns represent the streams and
the rows represent the components in each stream as shown:
1 2 3 4
CO
H2
CH4
CH3OH
Total
So each cell represents the flow rate of a component in a stream.

The solution requires filling the cells with the material balance equations of the units involved and the
additional relations (note that the size of matrix equals the number of variables in the process column).
Note that there must be an external cell for the rate of reaction.
For example consider the table will be in the next form:
Then the inserted formulas will be as follows:
Material balance equation In cell Formula

Feed
CO)1=0.33Stream (1) B2 =0.33*E8
H)1=0.665Stream (1) B3 =0.62*E8
CH4)1=0.005Stream (1) B4 =0.05*E8
Reactor
CO)2=CO)1-r C2 =B2-B8
H)2=H)1-2r C3 =B3-2*B8
CH4)2= CH4)1 C4 =B4
CH3OH)2= CH3OH)1+r C5 =B5+B8
r=0.4 CO)1 B8 =0.4*B2
And so on for the separation unit.

Finally the results appear in all streams. This method has the advantage that you neednt build a matrix
of a big size especially for systems containing may units and many components. Also it makes the user
able to know the location of error ( if exists ) and so easiness in correction and modification.
The final results will be:
Material balance for a reactive system with recycle

For the above example, its clear that nearly half the reactants only reacted and the other half was
introduced to the separator, separated from the product. Practically in such processes the unreacted
reactants are recycled and mixed with the fresh feed to make use of them, also in such systems where
there are some inerts in the feed (like Methane) some of the recycle stream is purged before mixing
with the fresh feed to prevent accumulation of inerts in the system.
On applying such a concept in the above case we will realise that the flow diagram will be as follows:
7 6 CO
CO H2
H2 CH4
4 CH3OH
CH4
CH3OH
Catalytic Reactor
1 2 3
Flash
CO CO CO Separator
H2 H2 H2
CH4 CH4 CH4
CH3OH CH3OH
5 CO
H2
CH4
CH3OH
First, the degrees of freedom table must be constructed, itll be as follows:
Mixer Reactor Flash Splitter Process

No of var 11 9 12 12 28
No of Eq 4 4 4 4 16
No of rel 0 1 4 4 9
No of G.V 3 0 0 0 3
No of DOF 4 4 4 4 0
Its clear that the system is solvable as the degrees of freedom of process is zero, so either a matrix is
constructed and a system of equations is solved (28 equations, i.e. square matrix 2828) and itll be so
time consuming, or the easier method unit-to-unit calculations.
But note that the solution will no be straight forward as there is no unit that has zero degrees of
freedom, so tearing technique can be applied. It should be clear first that a number of variables will be
assumed and recalculated again, the assumed variables will be determined based on the degrees of
freedom table, as the assumed variables must solve a unit and introduce new information to the next
unit and so on till the recycle stream is calculated and the assumed variables are recalculated again.
So lets assume the flow rates of the components in stream 2 (feed to the reactor), then the sequence of
solution will be as follows:
7
1 3 4
Mixer Reactor Separator Splitter
2 2
calculated assumed
5 6
Now, stream 2 can be totally assumed (flow rates of all four components) then four information are
added to the reactor and then can be solved, then stream 3 is specified which will allow the solution of
the separator, which in turn will add four information (stream 7) to the mixer and as a result the mixer
can be solved and stream 2 can be recalculated. Then the calculated values are compared with the
assumed ones, if the difference is in the range of allowable error then its Ok, else the calculated values
are used as the assumed ones till the values of the assumed and the calculated flow rates are equal (or
the difference between them is nearly zero).
To achieve this, a table must be constructed (like that constructed in the previous example) but the only
difference is that there will be two columns for the same stream 2 (assumed one) one will be for the
assumed value and the other for the calculated one. And the aim is to equalize the terms in both
columns. Note that the cells of the assumed flow rates will not contain formulas; itll contain the
assumed values, while the cells of the calculated flow rates will contain the formulas.
The formulas will be inserted in the same way as the previous example; the table will be as follows:
These formulas will result in the following flow rates:
1 2 assum 3 4 5 6 7 2 Calc
CO 330 600 360 349.2 10.8 34.92 314.28 644.28
H2 620 800 320 313.6 6.4 31.36 282.24 902.24
CH4 50 100 100 96 4 9.6 86.4 136.4
CH3OH 0 10 250 10 240 1 9 9
Total 1000 1510 1030 768.8 261.2 76.88 691.92 1691.92
r 240 Feed 1000 Kgmol/hr
Its now clear that the flow rates of column 2 assumed are not equal to those of column 2 calc so if
we can change the flow rates of column 2 assumed (as they contain values not formulas) so that they
are equal to column 2 calc then these flow rates are the final ones and all the other cells will be
automatically calculated.
To achieve this we can insert another column in which the square the difference between the assumed
and the calculated values is calculated (Why Square Of The Difference???), and the sum of the squares
will be calculated below, then the table will be in the form shown:
This will yield the following values:
1 2 assum 3 4 5 6 7 2 Calc square Diff

CO 330 600 360 349.2 10.8 34.92 314.28 644.28 1960.7184
H2 620 800 320 313.6 6.4 31.36 282.24 902.24 10453.0176
CH4 50 100 100 96 4 9.6 86.4 136.4 1324.96
CH3OH 0 10 250 10 240 1 9 9 1
Total 1000 1510 1030 768.8 261.2 76.88 691.92 1691.92 188779246
r 240 Feed 1000 Kgmol/hr
Now we can say that setting the cell J6 to the value of zero means that the difference between the
assumed and the calculated values is zero, or they are equal. The final step is to use the solver to
change the assumed values in order to set the cell J6 to the value of zero.
Finally, the solver solution will yield the following results:
1 2 assum 3 4 5 6 7 2 Calc square Diff

CO 330 692.985693 415.791416 403.317673 12.4737425 40.3317673 362.985906 692.985906 0.01460138
H2 620 1110.25734 555.868781 544.751406 11.1173756 54.4751406 490.276265 1110.27627 0.13758542
CH4 50 367.668119 367.668119 352.961394 14.7067248 35.2961394 317.665255 367.665255 0.05351814
CH3OH 0 10.3516531 287.54593 11.5018372 276.044093 1.15018372 10.3516535 10.3516535 0.00063926
Total 1000 2181.2628 1626.87425 1312.53231 314.341936 131.253231 1181.27908 2181.27908 0.20634421
r 277.194277 Feed 1000 Kgmol/hr
Now compare the values of the cells in column 2 assum and column 2 calc. Its clear that assumed
and calculated values are the same.
Now all flow rates are available in the table.
Energy Balance
The basic Closed-system energy balance equation (for non reactive systems)
Where Hi, Hj are the specific enthalpies of the stream i (outlet stream) and stream j (inlet stream)
[KJ/Kg]
Zi, Zj are the elevations of streams i and j
i, j are the velocities of streams i and j
Q is the heat input to the system
W is the work done by the system
Magnitude of potential and kinetic energies are relatively small in chemical process applications
Except pumps, turbines and compressors most chemical process units do not involve work
If this is the case, the energy balance will reduce to:
Now, its important to know how the enthalpy term is calculated.
Enthalpy:
Specific Enthalpy term represents the energy of the stream, and its calculated from:
Its known that calculating enthalpy requires setting a reference temperature, i.e. the value of
enthalpy varies according to the reference temperature.
So, the above equation must be in the following form
For a mixture the specific enthalpy takes the form:
For non-ideal mixtures a term of heat of mixing must be added.
Heat capacities are always function of temperature, the general form of the heat capacity is:
Cp=C1+C2T+C3T2+C4T3+C5T4
So after integration H will have the form (For a single component stream):
The values of constants C1, C2, C3, C4 and C5 vary according to the component, these values are
available in many references, the most popular are:
- Coulson and Richardson, Chemical Engineering, Volume 6, Appendix D.
- Robert H. Perry, Chemical Engineers Handbook, Chapter 2.
So for a single component stream, say liquid Benzene, to calculate its enthalpy at any temperature
we have to get the values of the constants, which will be :
C1=1.2944E+05
C2=-1.6950E+02
C3=6.4781E-01
C4=0
C5=0
Where T in Kelvin, Cp in J/Kmol.K (these values are got from chapter 2 in Perry).
Then, taking reference temperature 25oC (298oK), the value of the enthalpy of this stream will be
calculated as follows:
Substituting the temperature by 70oC (343oK) the solution will be

H=6.3795E6 J/Kmol
Now, lets consider such a stream but with two components, say toluene and o-xylene (500 Kmol/hr
each), and we need to calculate the mixture enthalpy at temperature of 80oC taking reference
temperature of 298oK, so first the constants of both must be got and they were found to be:
Toluene Xylene
C1 1.4014E+05 3.36500E+04
C2 -1.5230E+02 1.0175E+03
C3 6.9500E-01 -2.6300E+00
C4 0 3.0200E-03
C5 0 0
Then the enthalpy of the stream will be the sum of the enthalpies of both components, so each one
will be separately calculated then added to each other.
The specific enthalpy of Toluene will be 7327606.7 J/Kmol
The specific enthalpy of Xylene will be 8508358.9 J/Kmol
And the total enthalpy of the stream =5007327606.7+5008508358.9=7.918E+09 J/hr
=7.918E+06 KJ/hr
The same can be applied for three or more components
Note: Try to check the values of the constants from Perry to make sure that you are able to get the
right values.
Calculating Enthalpy of streams using Microsoft Excel:

Consider the first case of pure Benzene stream:
First: the values of the constants must be entered in the worksheet:
Second: Enter the values of the reference temperature and the operating temperature, enter the
values in Celsius and calculate their values in Kelvin.
Third: Start writing the equation of enthalpy calculation as a function of temperature.
Fourth: If the stream flow rate is 100 Kmol/hr, then the total enthalpy of the stream can be
calculated.
For a case of a multicomponent stream, say the second example (toluene and o-xylene):
First: Introducing the constants for both components
Second: Entering the values of operating temperature and reference temperature, in oC and oK.
Third: Entering the formulas of specific enthalpies for both components, you may save time by
entering the formula for the first component and put dollar signs at the cells containing temperature,
then drag this formula to the next component, this will be so useful and time saving if there is a big
number of components.
Dragging this formula will yield the following results:
Fourth: Entering the flow rates of both streams to calculate the Enthalpy of each component.
Finally: The total enthalpy is calculated as the sum of both enthalpies of toluene and xylene. The
final result will be 9.836E9 J/hr
Energy balance on a non-reactive system

In many cases there are many units in which information are available about the flow rates and the
inlet temperatures, and its required to get the outlet temperature, or cases where there is a stream
that has to be at specific conditions of temperature and pressure, so other related streams must be
adjusted to keep that stream at its required conditions.
In such cases the conditions are adjusted by performing energy balance calculations on such a
stream.
Example:
In a process air is required to be heated to a temperature of 100oC. If the available heat source
provides 1.8E+06 KJ/sec. The feed flow rate is 1000 gmol/sec (790 gmol N2/sec and 210 gmol
H2/sec), what will be the temperature of the feed?
T 100oC
N2 N2
O2 O2
On applying the energy balance equation on this system, the equation will be:
Taking Tref=25oC=298oK, and Tout=100+273=337oK
Note that the units have to be homogeneous, i.e. the units of LHS must be KJ/sec as that of Q or the
RHS must be J/hr as that of Enthalpies.
Its now clear that all the parameters of the above equation are known except the inlet temperature,
and that this temperature must be adjusted so that the LHS=RHS, so a value will be assumed and
then the actual value is got by trial and error (let the assumed value 30oC).
Lets see how this is performed using Microsoft Excel.
First each term has to be calculated alone, i.e. Feed Enthalpy is first calculated, then product
Enthalpy.
Feed Enthalpy will be easily calculated as what was done in the previous examples based on any
assumed value (let it 30oC as mentioned above).
The same step is done for the product stream

Now only remains to place the Q term in the excel sheet
The calculated value of Q based on the assumed feed temperature of 30oC will be 2.05E+06 J/sec.
This value is required to be 1.8E+06 J/sec by changing the value of the inlet feed temperature.
Using the solver this can be done in only one step.
By clicking solve, the value of the feed temperature will be adjusted so that Q will be 1.8E+08 J/sec
and the feed temperature is now 311.56 oK which is 38.56oC
Energy balance on a reactive system

For a reactive system the energy balance equation is the same but only one term is added to the
equation which is the heat of reaction term. The equation takes the form:
Where r is the rate of reaction, Hr is the heat of reaction at the reaction temperature.
Note that Hr is negative for exothermic reactions and positive for endothermic reactions.
The heat of reaction can be calculated from the heat of formation of products and reactants at the
standard temperature (25oC) according to the relation:
Calculate the standard heat of reaction for the oxidation of Pentane:

C5H12 + 8O2 5CO2 + 6H2O
Given: Hf,C5H10 = - 146.54 KJ/mol
o
Hf,O2 o = 0.0 ( because its an element)

Hf,CO2 o = - 393.77 KJ/mol
Hf, H2O o = - 242 KJ/mol
So Hro = (5-393.77+6-242) - ( -146.54+80 ) = -3274.31 KJ/mol
Performing such a step using Microsoft Excel is easy as its only adding and subtracting as shown
To get the heat of reaction at any other temperature, some more calculations must be done. These
calculations are based on the next diagram:
Reactants (at Reaction temp.) Trxn Products (at Reaction temp.)
298oK
Reactants (at 298oK) Products (at 298oK)
Example:
Calculate the heat of reaction of oxidation of Pentane at 100oC
To do so we will need the constants for the Cps for all components, and Hr at reference
temperature (298oK)
Each term of the last equation will be calculated alone and finally they all will be added.
First the reactants term :
The same step is done for the third term in the equation
Finally the three terms are added to get the heat of reaction at 100oC
The heat of reaction at 100oC is -1223.17 KJ/mol

Example:
Pentane at 100oC and 1 bar is fed to a heater at a flow rate of 100 mol/sec where complete
combustion (reaction with oxygen) occurs according to the reaction:
C5H12+8O2 5CO2 + 6H2O
Air enters so that the oxygen molar flow rate is eight times that of pentane, and Nitrogen is four
times the oxygen. Calculate the temperature of the gases leaving the heater assuming no heat losses
from the heater.
100oC
C5H12 N2
O2 CO2
N2 H2O
To get the temperature of the exit stream the energy balance equation has to be solved.
As the previous example, each term is calculated separately, taking reference temperature 298 oK.
Note that the term Q=0 as there is no heat added or removed from the system.
First : Calculate the enthalpy of feed as past examples, note that the flow rate of Pentane is
100Kmol/hr, flow rate of Oxygen is 8100=800 mol/sec and the flow rate of
Nitrogen=4800=3200Kmol/hr.
Second : Heat of reaction term needs the rate of reaction and it equals the number of moles of
reactant converted to product per unit time, which in this case- is the feed flow rate 100 Kmol/hr.
And the heat of reaction was calculated in the previous example.
Third: Calculate the Enthalpy of product stream based on an assumed temperature (say 120oC)
Note that the product flow rates will be calculated based on MB calculations:
CO2)out=CO2)in+5r=500 Kmol/hr
H2O)out= H2O)in+6r=600 Kmol/hr
N2)out= N2)in=3200 Kmol/hr
Both Pentane and Oxygen are totally consumed.
Fourth: the Energy balance equation is now written
Finally use the solver to change the value of the product temperature to make the Energy balance
equation =0
Fluid Mechanics
Terminal Velocity of Falling Particles
A simple force balance on a spherical particle reaching terminal velocity in a fluid is given by
Where Vt is the terminal velocity in m/s, g is the acceleration of gravity given by g = 9.80665 m/s2,
is the particles density in kg/m3, r is the fluid density in kg/m3, DP is the diameter of the
spherical particle in m and CD is a dimensionless drag coefficient.
The drag coefficient on a spherical particle at terminal velocity varies with the Reynolds number
(Re) as follows (pp. 5-63, 5-64 in Perry3).
for Re<0.1
for 0.1Re1000
for 1000<Re350000
for 350000< Re
Where and m is the viscosity in Pa.s or kg/m.s.
It is required to calculate the terminal velocity for particles of coal with and
falling in water at T = 298.15K where and
Step 1 Enter particles and fluid properties at the top of the sheet.
Step 2 Enter equation in cell B9 for calculating Reynolds no. since choosing appropriate drag
coefficient equations depends in which range lies this value.
Step 3 Now you have to calculate the drag coefficient based on the calculated value of Reynolds
no. To do so we will use the If function.
60 Fluid Mechanics
The IF function returns one value if a condition you specify evaluates to TRUE, and
another value if that condition evaluates to FALSE. For example, the formula
=IF(A1>10,"Over 10","10 or less") returns "Over 10" if A1 is greater than 10, and "10
or less" if A1 is less than or equal to 10.
Syntax
IF(logical_test, value_if_true, [value_if_false])
The IF function syntax has the following arguments:
logical_test Required. Any value or expression that can be evaluated to

TRUE or FALSE. For example, A10=100 is a logical expression; if the value
in cell A10 is equal to 100, the expression evaluates to TRUE. Otherwise, the
expression evaluates to FALSE. This argument can use any comparison
calculation operator.
value_if_true Required. The value that you want to be returned if the
logical_test argument evaluates to TRUE. For example, if the value of this
argument is the text string "Passed" and the logical_test argument evaluates
to TRUE, the IF function returns the text "Passed If logical_test evaluates to
TRUE and the value_if_true argument is omitted (that is, there is only a
comma following the logical_test argument), the IF function returns 0 (zero).
To display the word TRUE, use the logical value TRUE for the value_if_true
argument.
value_if_false Optional. The value that you want to be returned if the
logical_test argument evaluates to FALSE. For example, if the value of this
argument is the text string "Refused" and the logical_test argument evaluates
to FALSE, the IF function returns the text "Refused" If logical_test evaluates
to FALSE and the value_if_false argument is omitted, (that is, there is no
comma following the value_if_true argument), the IF function returns the
logical value FALSE. If logical_test evaluates to FALSE and the value of the
value_if_false argument is omitted (that is, in the IF function, there is no
comma following the value_if_true argument), the IF function returns the
value 0 (zero).
The next figure shows the form of the sheet after adding the If condition for calculating the drag
coefficient. The used If nested loop is shown below the CD cell.
61 Fluid Mechanics
Step 4 Enter the terminal velocity function and an initial guess for the terminal velocity to get the
accurate terminal velocity using Goal seek or Solver.
62 Fluid Mechanics
Emptying Tank
In this Exercise we are going to solve a simple differential equation using the Runge-Kutta
method. A cylindrical tank of diameter D has a short pipe of diameter d at the bottom. The tank is
initially filled with water to a height h. We wish to examine how changing the diameter of the pipe
alters the rate of discharge of the tank. The problem chosen has an analytical solution. You may
wish to find it and compare the results from it with those found using the Runge-Kutta
approximation.
For a short pipe, we may assume the rate of change of his:
Runge-Kutta method
is an algorithm used to solve differential equations. Runge-Kutta method finds an approximation for y
based on the previous value.
The iterative formula for forth order Runge-Kutta method is as follows:-
Step1 Enter a value of 0.1 for h and 0.05 for R where R is the ratio between pipe and tank
diameters.
Step 2 In cell A8 enter the value of 5 and 0 in cell B8. This is the initial condition h(0)=5 (the
initial elevation is 5m).
Step 3 Enter a range of values for t, from 0 to 15 with an increment of h=0.1.
Step 4 Enter these formulas to compute the k parameters:
C8: =$B$4*(-($B$5^2)*(SQRT(2*9.81*B8)))
D8: =$B$4*(-($B$5^2)*(SQRT(2*9.81*(B8+(C8/2)))))
E8: =$B$4*(-($B$5^2)*(SQRT(2*9.81*(B8+(D8/2)))))
F8: =$B$4*(-($B$5^2)*(SQRT(2*9.81*(B8+E8))))
Step 5 In B9 enter =B8+((1/6)*(C8+2*D8+2*E8+F8)) to compute the first approximation.
63 Fluid Mechanics
Step 6 Copy the cells C8:F8 to C158:F158 then copy B9 to B158. This computes the successive y
approximations.
Step 7 Create a summary table for the results by copying the height values every minute in a
separate table as shown in next figure,
64 Fluid Mechanics
Pipeline optimization
Problem
We are in the design phase of constructing a new, grass-roots, 200,000 ton/year, dimethyl ether
(DME) plant. This will be part of a larger facility that also produces diethyl ether (DEE).
The PFD (Process Flow Diagram) for the feed and reaction sections is given in next figure. Feed to
the process consisting of liquid methanol, is mixed with recycle liquid methanol.
Stream 1 is liquid methanol at 110kpa, 250C, while stream 10 is recycled methanol saturated at
1200kpa.
There is a pump(s) P-1401 from tank storage to V-201. P-1401 is not shown on the PFD but it will
be near to tanks TK-1401 and TK-1402. For further details about plant layout and P-1401 location
refer to the plot plan in the next figure.
65 Fluid Mechanics
400m
5m
m
66 Fluid Mechanics
As you can see, the DME facility is part of a larger facility that also produces DEE. You are to size
the new pump(s), P-1401. You are to determine the optimum pipe size for the piping from tank
storage to V-201. The objective function for the optimization is the Equivalent Annual Operating
Cost (EAOC) of the piping system including the pump (EGP/y). The EAOC is defined as:
CAP includes only the installed cost of pipes and pumps, and operating costs include the electricity
to run the pump.
Place the pumps, P-1401, on the ground at a location you choose. All elbows are 90, and you
should place these as needed. Pipes from the tanks to the process must follow the indicated pipe
racks. We would like the flexibility for 25% scale-up in the future.
Step 1 Enter flow properties as shown in cells A10:G11 and DME physical properties as shown in
cells A14:B16.
Step 2 Enter pipe line specifications and costs as shown in cells A18:F20. Note that pipe and pump
prices are entered in different uncommon ways. The pipe prices are calculated using equation which
depends on pipe diameter. This equation varies with diameters, thus was the use of IF condition.
For pump price, it is function of required power and the correlation is shown in cell G20.
Step 3 Enter a first estimate pipe diameter in cell A5 (2) then calculate the equivalent SI diameter
in the next cell.
Step 4 Calculate the velocity for this pipe diameter from the flow rate using the following
equation:-
Step 5 Calculate Reynolds no. and /D in cells D5 and E5

Step 6 Calculate moody friction factor in cell F5 using Churchill equation as written in Perrys
N.B.:- Do not forget to multiply the Churchill equation result by 4 to get moody friction factor.
Step 7 the rest of equations for calculating total losses (minor and major losses), pump head, pump
power and total cost are as shown in the next lines:-
Minor losses equivalent length: =8*((0.81*(C5^2))/(2*9.81)) (for 8 900 elbows)
Total losses: =(F5*($B$19+G5)*(C5^2))/(2*9.81*B5)
Pump head: =(($E$12-$E$11)/(B15*9.81))+($H$12-$H$11)+H5
Pump power: =(B15*9.81*B13*I5)/1000
Total Cost: =((E19*$B$19)+($E$20*8))+((9.81*$B$12*I5)*8000*0.3)
67 Fluid Mechanics
Step 8 the target now is to reach the minimum total cost by changing the pipe diameter. This can
be easily done using minimization option of the solver tool.
The final sheet form is shown in the next figure:-
Exercise
Specify the liquid level to be maintained in the storage tanks to avoid cavitation of P-1401.
PHASE EQUILIBRIA AND MASS TRANSFER
Introduction
Phase equilibria is one of the main sciences that have many applications in chemical engineering, especially
in separation techniques. And according to the industrial practice, it rarely happens to find any chemical
plant that dont contain systems involving liquid-vapour contact, these equipment are like distillation
columns, absorbers, strippers, flash separators and many others.
Thats why its so important to understand the vapour liquid equilibria well, and to understand the equations
governing such systems.
From the important fundamental equations for gas liquid systems:

Daltons law: to calculate partial pressure of a component in the gas phase
Where yi is the mole fraction in the gas phase and equals ni/nT
Raults law: to calculate partial pressure of a component on the surface of a liquid phase
Where xi is the mole fraction in the liquid phase and Pio is the vapour pressure of component i
Antoins law: Empirical equation to calculate the vapour pressure of a component as a function of
temperature
Where T is temperature in Kelvin, Pio is the vapour pressure in mmHg, A, B and C are
constants for each component ( available in appendix D, Coulson and Richardsons Chemical
Engineering, Volume 6)
This part of the course will be considering three points: Determining bubble point, dew point and doing the
flash calculations for a mixture of two or more components in a mixture.
But first of all its important to note that the calculations that will be done are considering IDEAL SYSTEMS,
and that for non-ideal systems these calculations will not be so accurate as there are some thermodynamic
properties must be included such as fugacity, activity coefficients and others. That is why for non ideal
systems its preferred to use simulation programs like Hysys, Aspen, Pro II, . . But it still important to
understand the scientific background of such systems that are common in a big variety of industries.
Liquid-Vapour Equilibria:
According to mass transfer principals, for any two phases contacting each other there will be mass transfer
for the components of the two phases as well as the system has not reached the Equilibrium composition.
Equilibrium composition means that there is no driving force to permit further mass transfer. Generally,
69 Phase Equilibria and Mass Transfer
Equilibrium relation is a relation that relates the concentrations of a specific component in two phases in
contact with each other. There are many forms of equilibrium relations for vapour-liquid systems, its just a
relation between x and y.
The most common relation is whats called K value relation, its based on the assumption that at equilibrium
the difference between partial pressure of the component in gas phase and the partial pressure of the same
component on the surface of the liquid is zero, or they are equal, then:
This relation is the one thats used to get the bubble points, dew points, plotting the phase diagrams for
vapour-liquid systems, and doing the Flash calculations.
Bubble point Calculations

Bubble point represents the temperature at which the liquid starts
evaporation, i.e. the first bubble of vapour appears, this point is
shown in the phase diagram as the liquidous curve. Dew
To know how to determine the bubble point of a system under
Temperature
point
certain pressure we will assume that at this point only very small
amount of the liquid evaporates and that this small amount is in
equilibrium with the liquid that has the same initial concentration
( because the very small amount of vapour didnt cause any change
in liquid concentration ), so we want to calculate the temperature at Bubble
which the vapour will be in equilibrium with the liquid of point
concentration of feed at the operating pressure.
So using the equilibrium relation:
And 100% A 0% A
0% B Composition 100% B
Those two equations will be performed for all the components involved in such a system, to know
which temperature will be the bubble point there is a condition that must be fulfilled which is
yi=1, that cant be verified directly but by trial and error. A temperature must be assumed and yi
is calculated and another temperature is assumed till yi=1.
Dew point calculations:

Dew point represents the temperature at which the liquid starts condensation, i.e. the first droplet of
liquid appears, this point is shown in the phase diagram as the vapourous curve.
The dew point calculations are so similar to bubble point calculations, we will assume that at this
point only very small amount of the vapour condenses and that this small amount is in equilibrium
with the vapour that has the same initial concentration ( because the very small amount of liquid
didnt cause any change in vapour concentration ), so we want to calculate the temperature at which
the liquid will be in equilibrium with the vapour of concentration of feed at the operating pressure.
So using the equilibrium relation:
And Antoine equation, trial and error on temperature will be done to verify that xi=1.
Calculating Bubble and Dew points using Microsoft Excel:

Bubble point
First the Antoine constants for the components involved in the system must be available.
A cell for the temperature is set.
From the Antoine equation, the vapour pressures of all components can be calculated.
Using the feed composition as xis we can now calculate yis.
Summation of yis is calculated, if the summation equals 1 then the assumed temperature is true,
else we will go to the next step.
Using the solver or goal seek, set the cell of y to the value of 1 by changing the cell containing
the assumed temperature.
Then the temperature thats finally got is the bubble point.
Dew point Calculations

A cell for the temperature is set.
Using the feed composition as yis we can now calculate xis.
Summation of xis is calculated, if the summation equals 1 then the assumed temperature is true,
else use the solver or goal seek, set the cell of x to the value of 1 by changing the cell
containing the assumed temperature.
Then the temperature thats finally got is the Dew point.
Exercise
Try drawing the phase diagram of any binary system using the above calculations, for say
Benzene toluene system, calculate bubble and dew points of the system under atmospheric pressure
for different feed compositions (say 10%B, 20%B, 30%B, 90%B, 100%B) and then youll get
the final data in a table like this
Composition Bubble Point Dew Point
Plot these values of temperature vs composition, you will find it the phase diagram of a binary
system.
Flash Calculations
Flash separation is one of the most widely used methods of gas liquid
separation, its very cheap, simple piece of equipment, and performs
separation effectively.
y
Temperature
Flash separation is performed by changing the conditions of the system

(either temperature or pressure) so that the system will lie in the wet
region between the liquidous and vapourous curves, accordingly the
system will split into liquid and vapour phases in equilibrium with each
other (from tie line).
So simply the equations governing such a process are simply material x
balance equations and equilibrium relations, as will be discussed below.
But note that Flash calculations are performed at certain temperature
and pressure, so to know the region of operation bubble point and dew
point have to be specified first.
100% A xf 0% A
let the feed F and the composition of feed , the vapour product V and 0% B Composition 100% B
its composition yi , liquid product L and its composition xi.
From material balance
F=L+V (1) V
(2) y
From (1) and (2) F
(3) xf
From equilibrium relation

(4)
L
x
From (3) and (4)
And
Now there are two conditions that have to be fulfilled to know the final concentrations and flow
rates, these are xi=1 and yi=1. Such systems are solved by trial and error, some variables are
known (ki and ) but there are two variables that have to be determined, and it will be difficult to
change two variables to solve such equations. So some mathematical manipulation of the equations
can simplify the solution and make it only changing of a single variable.
Divide numerator and denominator of xi and yi by V, so we get:
And
So instead of changing L and V we will change only L/V.
Performing flash calculations using Microsoft Excel

First, the Antoine constants for the components involved in the system must be available.
A cell for the temperature is set, also a cell of pressure is set.
The K values of all components can be now calculated.
Feed compositions are entered to the sheet.
Set a cell for L/V, and assume its value.
Values of xi and yi for each component can be now calculated based on the assumed value of
L/V.
Summations of xis and yis are calculated, if each of them equals 1 then the assumed L/V is true,
else we will go to the next step.
Using the solver or goal seek, set the cell of y (or x) to the value of 1 by changing the cell
containing the assumed L/V.
Make sure that BOTH y and x equal 1, not only one of them.
Then the ratio thats finally got is the true one, and the final composition of both the liquid and
vapour phases are calculated.
From material balance

F=L+V
And now L/V is known, say L/V=a
Then L=aV
So F=(1+a)V
Or V=F/(1+a)
Generally, there is no problem with these equations, but generally using this method of performing
the flash calculations may lead to inaccurate results especially in very non ideal mixtures. This
results from the method of calculating the Ks. The general law of calculating K is:
Where i is the activity coefficient, foi is the fugacity of the pure chemical, i is the fugacity
coefficient in the vapour phase, and p is the total pressure. Most of these quantities can be
calculated using thermodynamics. Thats why in such cases performing such calculations manually
will result in inaccurate results, and it becomes easier to perform such calculations using any
simulation software such as Hysy, Pro II, Aspen, VMG, or any other software.
In some cases, especially in hydrocarbons, where separation occurs under high pressures there are
charts from which the values of Ks can be got directly without performing the thermodynamic
calculations.
The charts will be provided later.
An exercise about using these charts will be sent through email, try solving it yourself.

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CAIRO UNIVERSITY

Eng. Moataz Bellah Mahmoud Mousa

Inserting Charts ...................................................................................................................................................... 1

Data fitting using least square method ......................................................................................................... 5

Array calculations .................................................................................................................................................. 9

Equations of state ................................................................................................................................................ 14

Solving equations of state using excel ........................................................................................................ 16

Vapor Pressure Data Representation Using Equations ........................................................................ 17

Batch reactor yield optimization ................................................................................................................... 21

Chemical reaction equilibrium ....................................................................................................................... 23

Example Using Excel........................................................................................................................................... 24

Regressing rate constants in rate equation from experimental data .............................................. 26

Multiple regression using Excel.................................................................................................................... 26

Non linear regression ....................................................................................................................................... 30

Nonlinear Regression Using Excel .............................................................................................................. 30

Material balance for non-reactive system .................................................................................................. 35

Material balance for a reactive system without recycle ......................................................................... 37

Material balance for a reactive system with recycle ............................................................................... 39

Energy Balance ..................................................................................................................................................... 43

Energy balance on a non-reactive system .................................................................................................. 50

Energy balance on a reactive system ........................................................................................................... 53

Terminal Velocity of Falling Particles .......................................................................................................... 59

Runge-Kutta method .......................................................................................................................................... 62

Pipeline optimization ......................................................................................................................................... 64

Bubble point Calculations................................................................................................................................. 70

Dew point Calculations ...................................................................................................................................... 71

Flash Calculations ................................................................................................................................................ 71

Performing flash calculations using Microsoft Excel......................................................................... 72

Consider using a pie chart when:

Moving average trendlines

where m is the slope and b is the intercept.

where c and b are constants, and ln is the natural logarithm function.

where b and are constants.

where c and b are constants.

Now we are now ready to use the solver.

Then finally the shape of the table will be as follows:

Which takes the general form: AX=B

This is introduced to Microsoft Excel as an array:

There are two key features:

Now the parameter a is given by a different formula,

Solving equations of state using excel

Van der Waals parameters are

Vapor Pressure Data Representation Using Equations

Vapor Pressure of Benzene

Chemical reaction equilibrium

If we plug in the partial pressures in the definition of KC above we get:

Using the realtion pi=yiPT

Gibbs free energy is related to KP by the relation:

Example Using Excel

Regressing rate constants in rate equation from experimental data

Multiple regression using Excel

This equation has the following form:

The curve fit is then

Non linear regression

Nonlinear Regression Using Excel

Step 2 Enter arbitrary values for the parameters k, n, and m.

The best correlation is

DOF= number of variables- number of equations- number of given variables-number of

Unit I Unit II ---------- Unit N Process Overall

Material balance for non-reactive system

D1, B1, D2 and B2 are the molar flow rates in

This can be shown in the form of a matrix:

Its solution is as follows