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ABSTRACT
Current personal computers provide exceptional computing capabilities to engineer-
ing students that can greatly improve speed and accuracy during sophisticated prob-
lem solving. The need to actually create programs for mathematical problem solving
has been reduced if not eliminated by available mathematical software packages.
This paper summarizes a collection of ten typical problems from throughout the
chemical engineering curriculum that requires numerical solutions. These problems
involve most of the standard numerical methods familiar to undergraduate engineer-
ing students. Complete problem solution sets have been generated by experienced
users in six of the leading mathematical software packages. These detailed solutions
including a write up and the electronic files for each package are available through
the INTERNET at www.che.utexas.edu/cache and via FTP from ftp.engr.uconn.edu/
pub/ASEE/. The written materials illustrate the differences in these mathematical
software packages. The electronic files allow hands-on experience with the packages
during execution of the actual software packages. This paper and the provided
resources should be of considerable value during mathematical problem solving and/
or the selection of a package for classroom or personal use.
iNTRODUCTION
Session 12 of the Chemical Engineering Summer School* at Snowbird, Utah on
* The Ch. E. Summer School was sponsored by the Chemical Engineering Division of the American
Society for Engineering Education.
Page 1
Page 2 A COLLECTION OF TEN NUMERICAL PROBLEMS
August 13, 1997 was concerned with “The Use of Mathematical Software in Chemical Engineering.”
This session provided a major overview of three major mathematical software packages (MathCAD,
Mathematica, and POLYMATH), and a set of ten problems was distributed that utilizes the basic
numerical methods in problems that are appropriate to a variety of chemical engineering subject
areas. The problems are titled according to the chemical engineering principles that are used, and the
numerical methods required by the mathematical modeling effort are identified. This problem set is
summarized in Table 1.
MATHEMATICAL
SUBJECT AREA PROBLEM TITLE MODEL PROBLEM
MATLAB - Joseph Brule, John Widmann, Tae Han, and Bruce Finlayson, Department of Chemi-
cal Engineering, University of Washington
The complete problem set has now been solved with the following mathematical software pack-
ages: Excel*, Maple†, MathCAD‡, MATLAB•, Mathematica#, and Polymath¶. As a service to the aca-
demic community, the CACHE Corporation** provides this problem set as well as the individual
package writeups and problem solution files for downloading on the WWW at http://
www.che.utexas.edu/cache/. The problem set and details of the various solutions (about 300 pages) are
given in separate documents as Adobe PDF files. The problem solution files can be executed with the
particular mathematical software package. Alternately, all of these materials can also be obtained
from an FTP site at the University of Connecticut: ftp.engr.uconn.edu/pub/ASEE/
APPENDIX
(Note to Reviewers - The Appendix which follows can either be printed with the article or provided
by the authors as a Acrobat PDF file for the disk which normally accompanies the CAEE Journal. File
size for the PDF document is about 135 Kb.)
A COLLECTION OF TEN NUMERICAL PROBLEMS Page 5
1. MOLAR VOLUME AND COMPRESSIBILITY FACTOR FROM VAN DER WAALS EQUATION
P + ------
a
- ( V – b ) = RT (1)
2
V
where
2 2
27 R T c
a = ------ -------------- (2)
64 P c
and
RT c
b = ----------- (3)
8P c
(a) Calculate the molar volume and compressibility factor for gaseous ammonia at a pressure
P = 56 atm and a temperature T = 450 K using the van der Waals equation of state.
(b) Repeat the calculations for the following reduced pressures: Pr = 1, 2, 4, 10, and 20.
(c) How does the compressibility factor vary as a function of Pr.?
A COLLECTION OF TEN NUMERICAL PROBLEMS Page 7
18% Xylene
15% Xylene
25% Styrene
#1
B1
{ 24% Styrene
42% Toluene
16% Benzene
40% Toluene
15% Xylene
{
20% Benzene D2 10% Styrene
54% Toluene
F=70 mol/min 21% Benzene
#3
B
24% Xylene
B2
{ 65% Styrene
10% Toluene
1% Benzene
Figure 1 Separation Train
Page 8 A COLLECTION OF TEN NUMERICAL PROBLEMS
Material balances on individual components on the overall separation train yield the equation set
Xylene: 0.07D 1 + 0.18B 1 + 0.15D 2 + 0.24B 2 = 0.15 × 70
Styrene: 0.04D 1 + 0.24B 1 + 0.10D 2 + 0.65B 2 = 0.25 × 70
(6)
Toluene: 0.54D 1 + 0.42B 1 + 0.54D 2 + 0.10B 2 = 0.40 × 70
Benzene: 0.35D 1 + 0.16B 1 + 0.21D 2 + 0.01B 2 = 0.20 × 70
Overall balances and individual component balances on column #2 can be used to determine the
molar flow rate and mole fractions from the equation of stream D from
Molar Flow Rates: D = D1 + B1
where XDx = mole fraction of Xylene, XDs = mole fraction of Styrene, XDt = mole fraction of Toluene,
and XDb = mole fraction of Benzene.
Similarly, overall balances and individual component balances on column #3 can be used to
determine the molar flow rate and mole fractions of stream B from the equation set
Molar Flow Rates: B = D2 + B2
(a) Calculate the molar flow rates of streams D1, D2, B1 and B2.
(b) Determine the molar flow rates and compositions of streams B and D.
A COLLECTION OF TEN NUMERICAL PROBLEMS Page 9
Temperature, T Pressure, P
(oC) (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
require these data to be accurately correlated by various algebraic expressions which provide P in
mmHg as a function of T in °C.
A simple polynomial is often used as an empirical modeling equation. This can be written in gen-
eral form for this problem as
P = a 0 + a 1 T + a 2 T 2 + a 3 T 3 + ...+a n T n (9)
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 represen-
Page 10 A COLLECTION OF TEN NUMERICAL PROBLEMS
(a) Regress the data with polynomials having the form of Equation (9). Determine the degree of
polynomial which best represents the data.
(b) Regress the data using linear regression on Equation (10), the Clausius-Clapeyron equation.
(c) Regress the data using nonlinear regression on Equation (11), the Antoine equation.
A COLLECTION OF TEN NUMERICAL PROBLEMS Page 11
Solve this system of equations when CA0 = CB0 = 1.5, K C1 = 1.06 , K C2 = 2.63 and K C3 = 5
starting from four sets of initial estimates.
(a) C D = C X = C Z = 0
(b) C D = C X = C Z = 1
(c) C D = C X = C Z = 10
Page 12 A COLLECTION OF TEN NUMERICAL PROBLEMS
where v t is the terminal velocity in m/s, g is the acceleration of gravity given by g = 9.80665 m/s2, ρ p
is the particles density in kg/m3, ρ is the fluid density in kg/m3, D p 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).
24
C D = ------- for Re < 0.1 (14)
Re
24 0.7
C D = ------- ( 1 + 0.14 Re ) for 0.1 ≤ Re ≤ 1000 (15)
Re
4
C D = 0.19 – 8 ×10 ⁄ Re for 350000 < Re (17)
(a) Calculate the terminal velocity for particles of coal with ρp = 1800 kg/m3 and D p =
0.208×10-3 m falling in water at T = 298.15 K where ρ = 994.6 kg/m3 and µ = 8.931×10−4 kg/
m⋅s.
(b) Estimate the terminal velocity of the coal particles in water within a centrifugal separator
where the acceleration is 30.0 g.
A COLLECTION OF TEN NUMERICAL PROBLEMS Page 13
where UA = 10 kJ/min·°C is the product of the heat transfer coefficient and the area of the coil for
each tank, T = temperature of the oil in the tank in °C , and Q = rate of heat transferred in kJ/min.
T0=20oC T1 T2 T3
W1=100 kg/min T1 T2 T3
Energy balances can be made on each of the individual tanks. In these balances, the mass flow
rate to each tank will remain at the same fixed value. Thus W = W1 = W2 = W3. The mass in each tank
will be assumed constant as the tank volume and oil density are assumed to be constant. Thus M =
M1 = M2 = M3. For the first tank, the energy balance can be expressed by
Accumulation = Input - Output
dT 1
MC p ----------- = W C p T 0 + UA ( T steam – T 1 ) – W C p T 1 (19)
dt
Note that the unsteady state mass balance is not needed for tank 1 or any other tanks since the mass
Page 14 A COLLECTION OF TEN NUMERICAL PROBLEMS
in each tank does not change with time. The above differential equation can be rearranged and explic-
itly solved for the derivative which is the usual format for numerical solution.
dT 1
----------- = [ W C p ( T 0 – T 1 ) + UA ( T steam – T 1 ) ] ⁄ ( MC p ) (20)
dt
Similarly for the second tank
dT 2
----------- = [ W C p ( T 1 – T 2 ) + UA ( T steam – T 2 ) ] ⁄ ( MC p ) (21)
dt
For the third tank
dT 3
----------- = [ W C p ( T 2 – T 3 ) + UA ( T steam – T 3 ) ] ⁄ ( MC p ) (22)
dt
Determine the steady state temperatures in all three tanks. What time interval will be required
for T3 to reach 99% of this steady state value during startup?
A COLLECTION OF TEN NUMERICAL PROBLEMS Page 15
where CA is the concentration of reactant A (kg mol/m3), z is the distance variable (m), k is the homo-
geneous reaction rate constant (s-1) and DAB is the binary diffusion coefficient (m2/s). A typical geom-
etry for Equation (23) is that of a one dimension layer which has its surface exposed to a known
concentration and allows no diffusion across its bottom surface. Thus the initial and boundary condi-
tions are
C A = C A0 for z = 0 (24)
dC A
= 0 for z = L (25)
dz
where CA0 is the constant concentration at the surface (z = 0) and there is no transport across the bot-
tom surface (z = L) so the derivative is zero.
This differential equation has an analytical solution given by
cosh [ L ( k ⁄ D AB ) ( 1 – z ⁄ L ) ]
C A = C A0 ----------------------------------------------------------------------------- (26)
cosh ( L k ⁄ D AB )
Page 16 A COLLECTION OF TEN NUMERICAL PROBLEMS
(a) Numerically solve Equation (23) with the boundary conditions of (24) and (25) for the case
where CA0 = 0.2 kg mol/m3, k = 10-3 s-1, DAB = 1.2 10-9 m2/s, and L = 10-3 m. This solution
should utilized an ODE solver with a shooting technique and employ Newton’s method or
some other technique for converging on the boundary condition given by Equation (25).
(b) Compare the concentration profiles over the thickness as predicted by the numerical solu-
tion of (a) with the analytical solution of Equation (26).
A COLLECTION OF TEN NUMERICAL PROBLEMS Page 17
where k2 is the vapor liquid equilibrium ratio for component 2. If the system may be considered ideal,
the vapor liquid equilibrium ratio can be calculated from k i = P i ⁄ P where Pi is the vapor pressure of
component i and P is the total pressure.
A common vapor pressure model is the Antoine equation which utilizes three parameters A, B,
and C for component i as given below where T is the temperature in °C.
A – --------------
B
-
T + C
P i = 10 (28)
The temperature in the batch still follow the bubble point curve. The bubble point temperature
is defined by the implicit algebraic equation which can be written using the vapor liquid equilibrium
ratios as
k1 x1 + k2 x2 = 1 (29)
The batch distillation of benzene (component 1) and toluene (component 2) mixture is being car-
ried out at a pressure of 1.2 atm. Initially, there are 100 moles of liquid in the still, comprised of
60% benzene and 40% toluene (mole fraction basis). Calculate the amount of liquid remaining in
the still when concentration of toluene reaches 80%.
Page 18 A COLLECTION OF TEN NUMERICAL PROBLEMS
q
Ta
FA0 X
T0 T
Ta
q
The various parameters values for this reactor design problem are summarized in Table (3).
(a) Plot the conversion (X), reduced pressure (y) and temperature (T ×10-3) along the reactor
from W = 0 kg up to W = 20 kg.
(b) Around 16 kg of catalyst you will observe a “knee” in the conversion profile. Explain why this
knee occurs and what parameters affect the knee.
(c) Plot the concentration profiles for reactant A and product C from W = 0 kg up to W = 20 kg.
Addition Information
The notation used here and the following equations and relationships for this particular problem are
adapted from the textbook by Fogler.2 The problem is to be worked assuming plug flow with no radial
gradients of concentrations and temperature at any location within the catalyst bed. The reactor
design will use the conversion of A designated by X and the temperature T which are both functions of
location within the catalyst bed specified by the catalyst weight W.
The general reactor design expression for a catalytic reaction in terms of conversion is a mole
balance on reactant A given by
dX
F A0 --------- = – r' A (30)
dW
The simple catalytic reaction rate expression for this reversible reaction is
CC
– r' A = k C 2A – -------- (31)
KC
where the rate constant is based on reactant A and follows the Arrhenius expression
EA 1 1
k = k ( @T=450°K ) exp -------- --------- – ---- (32)
R 450 T
and the equilibrium constant variation with temperature can be determined from van’t Hoff’s equa-
˜ = 0
tion with ∆C P
∆H R 1 1
K C = K C ( @T=450°K ) exp ------------- --------- – ---- (33)
R 450 T
The stoichiometry for 2 A C and the stoichiometric table for a gas allow the concentrations to
be expressed as a function of conversion and temperature while allowing for volumetric changes due
to decrease in moles during the reaction. Therefore
1 – X P T0 T0
C A = C A0 ----------------- ------ ------ = C A0 ---------------------- y ------
1–X
(34)
1 + εX P 0 T 1 – 0.5 X T
and
P
y = ------
P0
(35)
0.5C A0 X T 0
CC = ------------------------ y ------
1 – 0.5 X T
Page 20 A COLLECTION OF TEN NUMERICAL PROBLEMS
The pressure drop can be expressed as a differential equation (see Fogler2 for details)
d ------
P
P 0 – α ( 1 + εX ) P 0 T
---------------- = ----------------------------- ------ ------ (36)
dW 2 P T0
or
dy – α ( 1 – 0.5 X ) T
--------- = ---------------------------------- ------ (37)
dW 2y T0
dT U a ( T a – T ) + r' A ( ∆ H R )
--------- = --------------------------------------------------------------- (38)
dW
∑
F A0 ( θ i C Pi + X ∆C ˜ )
P
dT U a ( T a – T ) + r' A ( ∆ H R )
--------- = --------------------------------------------------------------- (39)
dW F A0 ( C PA )
A COLLECTION OF TEN NUMERICAL PROBLEMS Page 21
PI
controller
Feed
W, Ti, ρ, Cp
q
Measured
Tm
V, T
W, T0, ρ, Cp
Thermocouple
dT W C p(T i – T ) + q
-------- = --------------------------------------------- (40)
dt ρV C p
with initial condition T = Tr at t = 0 which corresponds to steady state operation at the set point tem-
perature Tr..
The thermocouple for temperature sensing in the outlet stream is described by a first order sys-
tem plus the dead time τd which is the time for the output flow to reach the measurement point. The
dead time expression is given by
T 0 ( t ) = T ( t – τd ) (41)
The effect of dead time may be calculated for this situation by the Padé approximation which is a first
order differential equation for the measured temperature.
dT 0 τ d dT 2
----------- = T – T 0 – ----- -------- ----- I. C. T0 = Tr at t = 0 (steady state) (42)
dt 2 dt τ d
The above equation is used to generated the temperature input to the thermocouple, T0.
The thermocouple shielding and electronics are modeled by a first order system for the input
temperature T0 given by
dT m T0 – Tm
------------ = --------------------- I. C. Tm = Tr at t = 0 (steady state) (43)
dt τm
where Kc is the proportional gain of the controller, τI is the integral time constant or reset time. The qs
in the above equation is the energy input required at steady state for the design conditions as calcu-
lated by
q s = W C p ( T r – T is ) (45)
The integral in Equation (44) can be conveniently be calculated by defining a new variable as
d
( errsum ) = T r – T m I. C. errsum = 0 at t = 0 (steady state) (46)
dt
Thus Equation (44) becomes
Kc
q = q s + K c ( T r – T m ) + ------- ( errsum ) (47)
τI
Let us consider some of the interesting aspects of this system as it responds to a variety of parameter
Page 23 A COLLECTION OF TEN NUMERICAL PROBLEMS
and operational changes.The numerical values of the system and control parameters in Table (4) will
be considered as leading to baseline steady state operation.
Tis = 60 °C Tr = 80 °C
τd = 1 min τm = 5 min
Kc = 50 kJ/min⋅°C τI = 2 min
(a) Demonstrate the open loop performance (set Kc = 0) of this system when the system is ini-
tially operating at design steady state at a temperature of 80°C, and inlet temperature Ti is sud-
denly changed to 40°C at time t = 10 min. Plot the temperatures T, T0, and Tm to steady state,
and verify that Padé approximation for 1 min of dead time given in Equation (42) is working
properly.
(b) Demonstrate the closed loop performance of the system for the conditions of part (a) and the
baseline parameters from Table (4). Plot temperatures T, T0, and Tm to steady state.
(c) Repeat part (b) with Kc = 500 kJ/min⋅°C.
(d) Repeat part (c) for proportional only control action by setting the term Kc/τI = 0.
(e) Implement limits on q (as per Equation (47)) so that the maximum is 2.6 times the baseline
steady state value and the minimum is zero. Demonstrate the system response from baseline
steady state for a proportional only controller when the set point is changed from 80°C to 90°C at
t = 10 min. Kc = 5000 kJ/min⋅°C. Plot q and qlim versus time to steady state to demonstrate the lim-
its. Also plot the temperatures T, T0, and Tm to steady state to indicate controller performance
Page 24 A COLLECTION OF TEN NUMERICAL PROBLEMS
REFERENCES
INTRODUCTION
This document contains Mathcad solutions for a set of chemical engineering problems developed
for the Use of Mathematical Software Packages in Chemical Engineering Education Session at the
ASEE Chemical Engineering Summer School held in Snowbird, Utah on August 13, 1997. The
problems chosen are representative of numerical problems that are typically found in most
chemical engineering undergraduate courses.
a .( V
P b ) R .T
2
V
atm .liter
R 0.08206 .
mole .K
2.
R .T c
2
27 . R T c atm .liter
2
liter
a a = 4.197 b b = 0.037
64 Pc mole
2 8 .P c mole
a .( V
P b ) R .T Equation to be solved
2
V
liter
V Find( V ) V = 0.575 End of Solve Block
mole
P.V
Z Z = 0.872
R .T
In the Find statement above, Mathcad solves for the value of the unknown variable but does
not change the value of the variable (V). Therefore, the value of the solution of the equation is
assigned to the variable (V) so that it can be used in subsequent calculations (e.g., calculation
of the compressibility factor (Z).
Page MC-3 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
b) Reformulate solution in terms of Pr. One powerful feature of Mathcad is the ability to define a
function using a solve block. The argument of the function is one of the variables in the equation
being solved and the value of the function is the solution of the equation. In this case the molar
volume is defined as a function of the reduced pressure. The structure of the solve block is
essentially the same as in part a).
liter
Initial guess for volume: V 0.6 .
mole
Given
a .
P r .P c (V b ) R .T
2
V
P r . P c .V P r
V Pr Find( V ) Z Pr
R .T
i 1 .. 5 The variable i here is called a range variable and takes on a range of values, in
this case 1, 2, ..., 5. This is similar to an index variable in a counted loop. Pr is
an array of values specified in the problem statement.
Pr V Pr
i i
Z Pr
liter .mole
1 i
1
0.704
2 0.234
0.466
4 0.077
0.731
10 0.061
1.533
20 0.051
2.783
0.046
c) The reduced pressure can be defined as a range variable and the molar volume can then be
plotted as a function of reduced pressure.
Pr 0.1 , 0.2 .. 50
8
7
6
5
Z Pr 4
3
2
1
0
0 5 10 15 20 25 30 35 40 45 50
Pr
Page MC-4 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
There are two approaches to solving this problem in Mathcad. The first is to simply include
all of the equations in a Solve Block and solve for the unknown variables. This simplifies the
formulation of the numerical problem because the problem does not need to be rewritten in
matrix form. In the second method, the problem is broken up into a problem requiring the
solution of 4 simultaneous linear equations followed by a series of simple algebraic equations.
F D D
Guess values of flow rates D D1 B1
and mole fractions: 2 2 2
F B B
B D2 B2
2 2 2
Given
Component balances over entire system
D
B
D1
B1
D2
B2
x DX
x DS Find D , B , D 1 , B 1 , D 2 , B 2 , x DX , x DS , x DT , x DB , x BX , x BS , x BT , x BB
x DXT
x DXB
x BX
x BS
x BT
x BB
Page MC-6 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Answer
D 1 = 26.25
D = 43.75 x DX = 0.114 x DS = 0.12 x DT = 0.25 x DB = 0.25
B 1 = 17.5
D 2 = 8.75
B = 26.25 x BX = 0.21 x BS = 0.467 x BT = 0.247 x BB = 0.077
B 2 = 17.5
The second method starts with the solution the component balances over the entire process.
This yields a system of four linear equations in four unknowns. The problem is formulated in
matrix form and is solved by matrix inversion.
The remaining total and component balances yield a series of simple algebraic equations.
B D2 B2
D D1 B1
x D2X . D 2 x B2X . B 2
x D1X . D 1 x B1X . B 1 x BX
x DX B
D
x D2S .D 2 x B2S . B 2
x D1S .D 1 x B1S .B 1 x BS
x DS B
D
x D2T .D 2 x B2T .B 2
x D1T .D 1 x B1T .B 1 x BT
x DT B
D
x D2B .D 2 x B2B .B 2
x D1B .D 1 x B1B .B 1 x BB
x DB B
D
Answer
D 1 = 26.25
D = 43.75 x DX = 0.114 x DS = 0.12 x DT = 0.492 x DB = 0.274
B 1 = 17.5
D 2 = 8.75
B = 26.25 x BX = 0.21 x BS = 0.467 x BT = 0.247 x BB = 0.077
B 2 = 17.5
Page MC-7 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
There are a variety of ways to solve this problem in Mathcad. To fit a polynomial, the
Mathcad function, linfit, can be used to fit any linear combination of arbitrary functions in the
form y = a0 + a1*f 1(x) + a2*f 2(x) + ... + an*fn(x). Mathcad gives as the result the vector a, the
coefficients of the linear combination.
Both the Clausius-Clapeyron and Antoine equations can be rewritten in a form so that linear
regression can be used. Otherwise, a non-linear least-squares technique could be applied.
a) To fit an nth order polynomial, an vector containing the n+1 functions is used in the linfit
function. The function also requires the vectors containing the data. To calculate the
variance of the error, the Mathcad function var is used. This example shows the calculation
for the polynomial that gave the smallest variance. The variance for other polynomials is
shown in a table below.
36.7 1
Define vectors T and P containing the data:
19.6 5
11.5 10
Define the vector of functions, F(x), to be fit:
2.6 20
1
7.6 40
x T P
15.4 60
2
x
26.1 100
F( x ) 3
x 42.2 200
4
x 60.6 400
5 80.1 760
x
Use the last function to count the number of data points, ndata, and the number of terms in
the function array. Note that Mathcad starts vectors and matrices with index 0 as the default.
The last function actually gives the index of the last term in the vector.
ndata last( T ) i 0 .. ndata n last( F( 1 ) )
24.754264
Results:
1.609017
c linfit( T , P , F ) 0.035605 Order Variance
1 11,859
c= 4 2 852
4.129782 10
3 20
6 4 0.199
4.226066 10
5 0.1944
9 6 0.1210
2.505099 10
n
Calculate the errors
c. T
j
errori P var( error ) = 0.194361
and then the variance i j i
j=0
Page MC-8 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
800
600
P
i
n
j 400
c. T
j i
j= 0
200
0
40 20 0 20 40 60 80 100
T
i
For the Clausius-Clapeyron and Antoine equations the equations can be rearranged into a form
so that linear regression can be used. By multiplying by the denominator of the second term on
the right hand side and rearranging algebraically, the following equations are obtained:
For the Clausius-Clapeyron equation linear regression can be used by setting y = log(P) and
x = 1/(T+273.15). The slope = -B and the intercept = A. Mathcad has slope and intercept
functions for linear regression.
For the Antoine equation, least squares is used using a psuedo-inverse calculation.
A intercept( x , y ) A = 8.75201
3
B slope ( x , y ) B = 2.035 10
B 3
Calculate the errors errori log Pi A var( error ) = 6.073244 10
and then the variance Ti 273.15
Page MC-9 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
P
i
B 500
A
T 273.15
i
10
0
220 240 260 280 300 320 340 360
T 273.15
i
Mi , 0 Ti Mi , 1 log Pi Mi , 2 1
B
Calculate the errors errori log Pi A 4
Ti C var( error ) = 2.26 10
and then the variance
P
i
B 500
A
T C
i
10
0
40 20 0 20 40 60 80 100
T
i
Page MC-10 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
This problem can be solved directly using a Mathcad Solve Block. The Solve Block includes
the equilibrium equations as well as the equations describing the stoichiometry. An initial
guess must be made for the concentrations. Initial guesses will be used as given.
Given initial concentrations and equilibrium constants: C A0 1.5 C B0 1.5
K C1 1.06 K C2 2.63 K C3 5
C A0 C B0 C A0
CA CB CC CY 0
2 2 2
Given
K C1 . C A .C B C C .C D K C2 . C B .C C C X .C Y K C3 . C A .C X CZ
C A C A0 CD CZ C B C B0 CD CY CC CD CY CY CX CZ
0.4207
0.2429
0.1536
Find C A , C B , C C , C D , C X , C Y , C Z = 0.7053
0.1778
0.5518
0.374
K C1 . C A .C B C C .C D K C2 . C B .C C C X .C Y K C3 . C A .C X CZ
C A C A0 CD CZ C B C B0 CD CY CC CD CY CY CX CZ
0.4207
0.2429
0.1536
Find C A , C B , C C , C D , C X , C Y , C Z = 0.7053
0.1778
0.5518
0.374
Page MC-11 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
K C1 . C A .C B C C .C D K C2 . C B .C C C X .C Y K C3 . C A .C X CZ
C A C A0 CD CZ C B C B0 CD CY CC CD CY CY CX CZ
0.4207
0.2429
0.1536
Find C A , C B , C C , C D , C X , C Y , C Z = 0.7053
0.1778
0.5518
0.374
Mathcad gives the same results for all sets of starting values.
Page MC-12 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Define the drag coefficient, CD, based on the value of the Reynolds number.
8 .10
4
24 24 .
0.14 .Re
0.7
C D ( Re ) if Re < 0.1 , , if Re < 1000 , 1 , if Re < 350000 , 0.44 , 0.19
Re Re Re
kg
0.208 .10 .m 1800 .
3
Particle diameter and density Dp ρp
3
m
4 kg kg
Fluid viscosity and density µ 8.931 .10 . ρ 994.6 .
m . sec m
3
m
vt 1.
Guess a starting value of the terminal velocity: sec
Given
4 . g. ρ p ρ . D p
vt
3 . C D Re v t .ρ
vt Find v t
m
Answer: v t = 0.016 Re v t = 3.656
sec
Note that units have been included for all of the variables. The answer can be expressed in
any set of units desired. Some examples are given below.
ft mi mm in
v t = 0.052 v t = 0.035 v t = 15.782 v t = 37.279
sec hr sec min
Page MC-13 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
b) Mathcad has the gravitational acceleration predefined. For this case, g is redefined as 30g.
m
g 30 .g Guess: vt 1.
sec
Given
4 . g. ρ p ρ . D p
vt
3 . C D Re v t .ρ
vt Find v t
m
Answer: v t = 0.206 Re v t = 47.723
sec
Page MC-14 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Calculate the steady state temperature by setting derivatives to zero and solving remaining
equations using a Mathcad Solve Block.
Given
For the solution of multiple ODEs Mathcad requires that the functions of the right hand side be
defined in a vector of functions. The initial conditions are assigned to the vector variable to be
solved for.
20 W .C p . T 0 T1 UA . T steam T1
Initial conditions: T 20 M .C p
20 W .C p . T1 T2 UA . T steam T2
D( t , T )
Function vector: M .C p
W .C p . T2 T3 UA . T steam T3
M .C p
Set initial time, final time and size of time step in minutes. Calculate number of points calculated.
t final t0
t0 0 t final 100 ∆t 1 npoints 1
∆t
Solve the differential equations using the function Rkadapt.
Z Rkadapt T , 0 , t final , npoints , D
The solution is stored in an array. The first column represents the time at each step. The
remaining columns represent the solution vectors.
Assign columns of the solution array to vectors for clarity
64
99 .% .T3ss
50
T1
n
T2
n 40
T3n
30
20
0 20 40 60 80 100
time
n
99% of steady state value: 99 .% .T3ss = 50.804 Calculate value at 64 minutes: T3 64 = 50.777
∆t
The solution to this problem will use Mathcad's ability to solve two point boundary value
problems. The solution method has two parts. In the first part, Mathcad estimates the missing
boundary conditions at the first point. These estimated values are then used in the standard ODE
solvers to find the solution between the two boindary points. Check the Mathcad help files for
more details on using this method.
Assign values to the pysical properties and dimensions for the problem
1.2 . 10
9 3
Diffusivity D AB Reaction rate constant k 10
3
Initial concnetration: C A0 0.2 Slab depth: L 10
L
Set position of first and second point and step size: z1 0 z2 L ∆z
100
Mathcad uses the load and score functions in estimating the missing initial conditions
Initial guess for vector of unknown initial conditions: v0 1
C A0
Initial conditions (including guess vector): load( z1, v )
v0
Vector of functions representing the right hand side of the differential equations:
C1
D( z , C ) k .C
0
D AB
Score function is a measure of the difference between the computed and given values at the end
point.
score ( z2 , C ) C1
Function sbval calculates the missing initial conditions:
Now solve the differential equation using the estimated value of the inital conditions.
C0 C A0
L
z0 0 z end L npoints 1
∆z
Y Rkadapt C , z 0 , z end , npoints , D
Page MC-17 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
n 0 .. npoints zn Yn , 0 CA Yn, 1 dC A Yn , 2
n n
0.2
0.19
0.18
CA
n
z 0.17
cosh L . . 1
k n
D AB L
C A0 .
cosh L .
k 0.16
D AB
0.15
0.14
0.13
0 2 10 4 4 10 4 z 6 10 4 8 10 4
n
The differential equation that describes the unsteady state material balance includes the
k-value of component 2, k2. k2 depends implicitly on the mole fraction of component 2, x2. A
solve block will be used to define k2 as a function of x2. The first step in doing this is to write
the equilibrium temperature, Teq, as a function of x2. The vapor mole fraction can then be
defined as a function of x2 assuming the liquid behaves as an ideal solution and the vapor as
an ideal gas. k2 can then be defined as the ratio y2/x2.
atm
mole 1 mmHg C K
Coefficients for Antoine equation 760
B1 B2
A1 A2
T C1 T C2
P 1( T ) 10 . mmHg P 2( T ) 10 . mmHg
Given
1 x 2 .P 1( T ) x 2 .P 2( T ) P
Teq x 2 Find( T )
x 2 .P 2 Teq x 2
Define vapor mole fraction assuming ideal gas: y2 x2
P
y2 x2
Definition of k-value: k2 x2
x2
Page MC-19 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Now solve the unsteady state material balance equation using the adaptive Runge-Kutta method
Define the function on the right hand side of the differential equation:
L
D x 2, L
x 2. k 2 x 2 1
x 2f x 2i
Set initial and final values x 2i 0.4 x 2f 0.8 ∆x 2 0.01 npoints 1
∆x 2
i 0 .. npoints Li Zi , 1 x2 Zi , 0
i
80
60
L
i
40
20
0
0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75
x2
i
Page MC-20 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
J J
Heat of reaction: ∆H R 40000 . Activation energy: EA 41800 .
mole mole. K
6
dm
k 450 0.5 .
Arrhenius constant at 450 K: kg. min. mole
3
dm
Equilibrium constant at 450 K: K C450 25000 .
mole
J
Heat transfer coefficient: UA 0.8 . Coolant temperature: Ta 500. K
kg. min. K
mole mole
Initial flow rate, concentration and pressure: F A0 5.0 . C A0 0.271. P0 10. atm
min 3
dm
y A0 1.0
Initial temperature and gas mole fraction of A: T0 450. K
1
Constant used in calculating pressure drop: α 0.015. kg
EA
Kinetic rate expression: k( T ) k 450. exp . 1 1
R T0 T
∆H R
Equilibrium expression: K C( T ) K C450. exp . 1 1
R T0 T
1 X . .T 0 0.5 . X . . T 0
C A( X , y, T ) C A0. y C C ( X , y, T ) C A0. y
1 0.5 . X T 1 0.5 . X T
Page MC-21 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Reaction rate expressed as a function of conversion, vapor mole fraction and temperature
2
C C( X , y , T )
r A( X , y , T ) k( T ) . C A( X , y , T )
K C( T )
Mathcad requires the unknown variables to be expressed as a vector. We will define the variables
as follows: X = x0, y = x1 and T = x2
Express the right hand side of the three differential equations as a vector of functions
r A x0 , x1 , x2. T 0
F A0
1 0.5 . x0 x2. T 0
D( W , x ) α. .
2 . x1 T0
0
Initial conditions: x 1
1
Wf W0
Initial and final weight of catalyst: W0 0 Wf 20 ∆W 0.1 npoints 1
∆W
i 0 .. npoints Wi Zi , 0 Xi Zi , 1 yi Zi , 2 Ti Zi , 3. T 0
Page MC-22 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
1.5
X 1 y
i i
y
i
Ti Ti /(1000K) Xi
1000. K 0.5
0
0 2 4 6 8 10 12 14 16 18 20
W
i
b) The "knee" in the curve represents the acceleration in reaction rate due to the rapid increase in
temperature for the exothermic reaction.
c) Evaluate the concentration profiles using the calculated values of conversion, vapor mole
fraction and temperature
0.3
0.25
C A X ,y ,T CA
i i i 0.2
mole
3
dm
0.15
C C X ,y ,T
i i i
mole
3 0.1
dm
0.05
0
0 5 10 15 20
W
i
Page MC-23 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
KC
Define the heat input calculated by the controller: q T m, e .e
qs K C. T r Tm
τI
Mathcad requires the unknown variables to be expressed as a vector. We will define the variables
as follows: T = x0, T0 = x1, Tm = x2, and errsum = x3
The step change in inlet temperature is represented in Mathcad by defining the inlet temperature as
a function of time using an if function.
Ti( t ) if t < 10 , T is , T is 20
Define the vector of functions representing the right hand side of the ODEs
WC p . Ti( t ) x0 q x2 , x3
ρVC p
τ d WC p . Ti( t ) x0 q x2 , x3
x0 x1 . .2
D( t , x ) 2 ρVC p τd
x1 x2
τm
Tr x2
Page MC-24 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Tr Final time: tf 60
x
Tr Time step: ∆t 0.1
tf t0
0 npoints 1 i 1 .. npoints
∆t
Z Rkadapt x , t 0 , t f , npoints , D
ti Zi , 0 Ti Zi , 1 T0 Zi , 2 Tm Zi , 3 errsumi Zi , 4
i i
85
80
T
i 75
T0
i
T m 70
i
65
60
0 10 20 30 40 50 60
t
i
Page MC-25 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Define the vector of functions representing the right hand side of the ODEs
WC p . Ti( t ) x0 q x2 , x3
ρVC p
τ d WC p . Ti( t ) x0 q x2 , x3
x0 x1 . .2
D( t , x ) 2 ρVC p τd
x1 x2
τm
Tr x2
85
T 80
i
T0
i
75
Tm
i
Tr 70
65
0 20 40 60 80 100 120 140 160 180 200
t
i
Page MC-26 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Define the vector of functions representing the right hand side of the ODEs
WC p . Ti( t ) x0 q x2 , x3
ρVC p
τ d WC p . Ti( t ) x0 q x2 , x3
x0 x1 . .2
D( t , x ) 2 ρVC p τd
x1 x2
τm
Tr x2
100
T
i
T0
i
80
Tm
i
Tr
60
0 20 40 60 80 100 120 140 160 180 200
t
i
Page MC-27 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
Define the vector of functions representing the right hand side of the ODEs
WC p . Ti( t ) x0 q x2 , x3
ρVC p
τ d WC p . Ti( t ) x0 q x2 , x3
x0 x1 . .2
D( t , x ) 2 ρVC p τd
x1 x2
τm
Tr x2
Tr Final time: tf 60
x
Tr Time step: ∆t 0.1
tf t0
0 1 npoints i 1 .. npoints
∆t
Solve the system of ODEs using the adaptive Runge-Kutta method
Z Rkadapt x , t 0 , t f , npoints , D
85
T 80
i
T0
i
75
Tm
i
Tr 70
65
0 10 20 30 40 50 60
t
i
Page MC-28 MATHEMATICAL SOFTWARE PACKAGES IN CHEMICAL ENGINEERING
KC 5000 τI 2000000
Define the step increase in set point at time 10 using Mathcad if function.
Ti( t ) T is T r( t ) if t < 10 , T r0 , T r0 10
Define the limiting behavior of the heater using nested Mathcad if functions.
KC
q 0 T m, e, t qs K C. T r( t ) Tm .e
τI
Define the vector of functions representing the right hand side of the ODEs
WC p . T is x0 q x2 , x3 , t
ρVC p
τ d WC p . T is x0 q x2 , x3 , t
x0 x1 . .2
D( t , x ) 2 ρVC p τd
x1 x2
τm
T r( t ) x2
Solve the system of ODEs using the fixed interval Runge-Kutta method. The adaptive method was
too slow!
Z rkfixed x, t 0 , t f , npoints , D
100
95
Ti
90
T0
i
Tm
i
85
Tr t
i
80
75
0 20 40 60 80 100 120 140 160 180 200
t
i
8 104
4
6 10
0
4
q 0 T m , errsum , t 4 10
i i i
q T m , errsum i , ti
i
2 104
2.6 . q s
2 104
0 50 100 150 200
t
i