Solving Basic Chemical

Engineering Problems
Using Spreadsheets

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 1
Problems Using Spreadsheets
  Molar volume and compressibility form Redlich-Kwong Equation
 Calculation of the flow rate in a pipeline

Topic Outline  Correlation of physical properties of ethane

 Complex chemical equilibrium by Gibbs minimization
 Comparison of friction factor correlations for turbulent pipe flow

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Concepts used
 Calculation of the analytical solution of the cubic Redlich-Kwong
(RK) equation for compressibility factor.
 Calculation of the molar volume at various reduced temperature and
Molar volume pressure values

and  Numerical methods applied

 Solving a set of explicit equations
compressibility  Excel Tools used
form Redlich-  Explicit solution involving definition of constants and arithmetic
formulas.
Kwong (RK)  Arithmetic functions
 Creating series
Equation  Absolute and relative addressing
 If statements and logical functions
 Two-input data tables
 XY (scatter) plots

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Problem Definition
 The R-K equation is usually written as:

Molar volume (2-1)

 Where
and (2-2)
compressibility  And
(2-3)

form Redlich- P = pressure in atm

Kwong (RK) V = molar volume in liters/g-mol
T = temperature in K
Equation R = gas constant (R = 0.08206 (L-atm/g-mol·K))
Tc = critical temperature in K
Pc = critical pressure in atm

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Compressibility factor is expressed as:
(2-4)
 Using algebra, equation 2-1 can be written as:
Molar volume (2-5)
and  Where:

compressibility (2-6)

form Redlich- (2-7)

(2-8)
Kwong (RK)
(2-9)
Equation In which:
= reduced pressure
= reduced temperature

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Equation (2-5) can be solved analytically for three roots. Some of
these roots are complex. Considering only the real roots, the
sequence of calculations involves the steps:
Molar volume (2-10)

and  Where:

compressibility (2-11)
(2-12)
form Redlich-  If there is one real solution for z given by:
Kwong (RK) (2-13)
Equation  Where:
(2-14)
(2-15)

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
Molar volume  If , there are three real solutions,

and where (2-16)

compressibility  Where:

form Redlich- (2-17)

 In the supercritical region when , two of these solutions are
Kwong (RK) negative, so the maximal zk is selected as the true
Equation compressibility factor.

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Example 2-1
a. (1) Calculate the volume of steam (critical temperature
is Tc = 647.4 K and critical pressure is Pc = 218.3 atm) at Tr = 1.0 and
Pr = 1.2. Compare your result with the value obtained from a
physical property data base (V = 0.052456 L/g-mol). (2) Also
complete the calculation for Tr = 3.0 and Pr = 10 (V = 0.0837 L/g-
mol). Carry out both calculations only if the parameter C > 0.
b. Calculate the compressibility factor and the molar volume of
steam using Excel for the reduced temperatures and reduced
Example 2-1 pressures listed in Table 2–1. Prepare a table and a plot of the
compressibility factor versus Pr and Tr as well as a table and a plot
Table 2-1. Reduced Pressures and Temperatures for Calculation
of the molar volume versus pressure and Tr. The pressure and the
volume should be in a logarithmic scale in the second plot.

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Solution
a-1)

Example 2-1

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 9
Problems Using Spreadsheets
 a-2)

Example 2-1

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
 b)

Compressibility Factor for

1.4 Steam
1.2

Compressibility factor (z)

0.8

Example 2-1 0.6

0.4

0.2

0
0 2 4 6 8 10
Reduced Pressure (Tr) in atm

Tr=1 Tr=1.2 Tr=1.5 Tr=2 Tr=3

Figure 2-1. Compressibility factor

of steam at various reduced
pressure and temperature

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 11
Problems Using Spreadsheets
 Molar Volume for Steam
10

Molar Volume (L/g-mol)

1

Example 2-1 0.1

0.01
10 100 1000 10000
Pressure (atm)

Tr=1 Tr=1.2 Tr=1.5 Tr=2 Tr=3

Figure 2-2. Molar volume of steam at

increasing pressures for various
reduced temperature

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Concepts used
 Mechanical energy balance for incompressible fluids
 Calculation of flow rate in a pipeline for various pipe diameter and
length
Calculation of  Numerical methods applied
the flow rate in  Solution of a single nonlinear algebraic equation
 Alternative solution using the successive substitution method
a pipeline  Excel Tools used
 Absolute and relative addressing,
 “Goal seek” tool
 Programming of the successive substitution technique

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Problem Definition
 Figure 2-3 shows a pipeline that delivers water at a constant
temperature from point 1 where the pressure is and the elevation is
ft to point 2 where the pressure is atmospheric and the elevation is
Calculation of  Density of water can be calculated by:
(2-18)
the flow rate in  Viscosity of water can be calculated by:
a pipeline (2-19)
 Where T is in , is in

Figure 2-3. Pipeline at steady state

Topic 2 - Solving Basic Chemical Engineering
Note: Equations and values for density and viscosity
ChE 315 - Computer Applications in Chemical Engineering of fluids can also be obtained from Perry’s Handbook 14
Problems Using Spreadsheets
  Equations and Numerical Data
 General Mechanical Energy Balance for Incompressible fluids
(2-20)
 Where
 v = flow velocity in ft/s
Calculation of 

g = acceleration of gravity given by
is the difference in elevation (ft)
the flow rate in 

= conversion factor (in English units )
is the difference in pressure )
a pipeline  fF = Fanning friction factor
 L = length of the pipe (ft)
 D = inside diameter of the pipe (ft)
 The use of the successive substitution method requires Equation (2-
20) to be solved for v as :
(2-21)

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Equations and Numerical Data
 The equation for calculation of the Fanning friction factor depends
on the Reynold's number, , where μ is the viscosity in .
 For laminar flow (Re < 2100), the Fanning friction factor can be
calculated from the equation:
Calculation of (2-22)
 For turbulent flow (Re > 2100), the Shacham equation can be used:
the flow rate in (2-23)

a pipeline  Where is the surface roughness of the pipe for commercial steel pipes).
 The flow velocity in the pipeline can be converted to flow rate by
multiplying it by the cross section are of the pipe, the density of
water (7.481 gal/ft3), and factor (60 s/min). Thus q has units of
(gal/min). The inside diameters (D) of nominal 4-, 5-, 6-, and 8-inch
schedule 40 commercial steel pipes can be obtained from Perry’s
Handbook.

Note: Equations for Fanning friction can also be

obtained from Perry’s Handbook
Topic 2 - Solving Basic Chemical Engineering
ChE 315 - Computer Applications in Chemical Engineering 16
Problems Using Spreadsheets
 a. Calculate the flow rate q (in gal/min) for a pipeline with effective
length of L = 1000 ft and made of nominal 8-inch diameter
schedule 40 commercial steel pipe. (Solution: v = 11.61 ft/s, gpm
= 1811 gal/min)
b. Calculate the flow velocities in ft/s and flow rates in gal/min for
pipelines at 60°F with effective lengths of L = 500, 1000, …
10,000 ft and made of nominal 4-, 5-, 6- and 8-inch schedule 40
Example 2-2 commercial steel pipe. Use the successive substitution method
for solving the equations for the various cases and present the
results in tabular form. Prepare plots of flow velocity v versus D
and L, and flow rate q versus D and L.
c. Repeat part (a) at temperatures T = 40, 60, and 100°F and
display the results in a table showing temperature, density,
viscosity, and flow rate.

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Solution
a. Using Goal Seek Tool

Example 2-2

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Problems Using Spreadsheets
  Solution
a. Using MOSS

Example 2-2

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ChE 315 - Computer Applications in Chemical Engineering 19
Problems Using Spreadsheets
  Solution
b.

Flow Velocity Plot versus Pipe Length and Diame-

ter
16
12 D=4"

Velocity (ft/s)
Example 2-2 8
4
D=5"
D=6"
D=8"
0
0 00 00 000 000 000 000 000 000 000 000
10 20 3 4 5 6 7 8 9 10
Pipe Length (ft)

Figure 2-4. Flow Velocity Plot versus

Pipe Length and Diameter

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Solution
b.

Flow Rate versus Pipe Length and Diameter

1400
1200

Flow Rate (gal/mimn)

1000
800
600

Example 2-2 400

200
0
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Pipe Length (ft)

Figure 2-4. Flow Rate versus Pipe

Length and Diameter

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Solution
c.

Example 2-2

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Problems Using Spreadsheets
  Concepts used
 Correlations for heat capacity, vapor pressure, and liquid viscosity
for an ideal gas.
.
Correlation of  Numerical Methods used
Physical  Polynomial, multiple linear, and nonlinear regression of data with
linearization and transformation functions.
Properties of  Excel Options and Functions Demonstrated
Ethane  Use of the Excel LINEST function for multiple linear and polynomial
regression.
 Use of the Excel Add-In “Solver” for nonlinear regression.

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Problem Statement
 Determine appropriate correlations for heat capacity, vapor
pressure, and liquid viscosity of ethane. The data files are given and
also the data are available in Appendix F (Cutlip). Compare those
correlations with the expressions suggested by the Design Institute
for Physical Properties (DIPPR)
a. Compare third-degree and fifth-degree polynomials for the
correlation of the heat capacity data (Table F–1 of Appendix F) using

Example 2-3 Excel by examining the respective variances, confidence intervals,

and residual plots.
b. Use Excel to compare the fifth-degree polynomial for the correlation
of the heat capacity data (Table F–2 of Appendix F) with the two
DIPPR recommended correlations for the appropriate temperature
intervals.
c. Utilize multiple linear regression in Excel to fit the Wagner equation
to the vapor pressure of ethane data found in Table F-3 of Appendix
F. Comment the applicability of the Wagner equation for correlating
these data. Compare the correlation obtained by the Wagner
equation with that of the Riedel equation recommended by DIPPR.

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 24
Problems Using Spreadsheets
  Solution
a. Temperature dependency of the heat capacities of gases is
commonly represented by simple polynomials in the form:
(2-24)
where Cp is the heat capacity in J/kg-mol·K, T is the temperature in K,
and a0, a1,... are the coefficients (parameters) of the correlation
determined by regression of experimental data. The degree of the
Example 2-3 polynomial which best represents the experimental data can be
determined based on the variance, the correlation coefficient (R2), the
confidence intervals of the parameters, and the residual plot.
The heat capacity data for ethane gas are given in Appendix F, Tables
F–1 and F–2. There are 19 data points in Table F–1 but they encompass
a wider temperature range (1450 K) than the 41 data points in Table F–
2 that have a much smaller range of temperature range (400 K)

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 25
Problems Using Spreadsheets
  Solution
a. For 3rd degree polynomial

Example 2-3

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 26
Problems Using Spreadsheets
 Third-Degree Polynomial Representation
for Heat Capacity of Ethane
160000.0
140000.0

Heat Capacity (J/kg-mol-K)

120000.0
100000.0
80000.0
60000.0
40000.0
20000.0
0.0

Example 2-3
0.0 200.0 400.0 600.0 800.0 1000.0 1200.0 1400.0 1600.0
T (K)

Residual Plot for Heat Capacity Represented by Third-Degree

Polynomial for Data Set A
3000.0
2000.0
1000.0
0.0

Residuals
-1000.0
-2000.0
-3000.0
-4000.0
30000.0 50000.0 70000.0 90000.0 110000.0 130000.0 150000.0
Expected Cp

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 27
Problems Using Spreadsheets
  Solution
a. For 5th degree polynomial (R2=0.9999) therefore 5th degree
polynomial adequately represents the heat capacity of ethane in
Table F-1

Example 2-3

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
 Residual Plot Created in Excel for Heat Capacity Represented by
Fifth-Degree Polynomial for the Data Set A

600

400

200

Residuals
0

Example 2-3 -200

-400

-600
30,000.00 50,000.00 70,000.00 90,000.00 110,000.00 130,000.00 150,000.00

Cp Calculated (J/kmol-K

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 29
Problems Using Spreadsheets
  Solution
b. DIPPR recommends the equation for heat capacity of ethane
(200K<T<1500K) as:
(2-25)
Where: ,,, , and .
For 50K<T<200K, DIPPR recommends using a second-degree
polynomial
Example 2-3 With the parameter values:
(2-26)

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Problems Using Spreadsheets
Example 2-3

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Problems Using Spreadsheets
 200.00

150.00

100.00

50.00

0.00

Residuals
Example 2-3
-50.00

-100.00

-150.00

-200.00

-250.00
30000.00 35000.00 40000.00 45000.00 50000.00 55000.00 60000.00 65000.00 70000.00 75000.00 80000.00

Cp expected

Cp_calc residuals CpD residuals

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 32
Problems Using Spreadsheets
  Solution
c. The Wagner equation is considered by many as the most
appropriate model to represent the vapor pressure data over the
full range between the triple point and critical point. The most
widely used form of the Wagner equation is:

Example 2-3 (2-27)

Where: is the reduced temperature, is the reduced pressure, and .
For ethane, , and the triple point temperature is 90.352 K. The data
from Table F-3 covers almost the full range between the triple point
and the critical point, thus, the Wagner equation can be used.

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Problems Using Spreadsheets
Example 2-3

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
 Residual Plot in Excel for Ethane Vapor Pressure Data Represented by
the Wagner Equation

0.0500

0.0400

0.0300

0.0200

Example 2-3
Residual
0.0100

0.0000

-0.0100

-0.0200

-0.0300
-16.0000 -14.0000 -12.0000 -10.0000 -8.0000 -6.0000 -4.0000 -2.0000 0.0000

ln(P/Pr)

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 35
Problems Using Spreadsheets
  Solution
c. The Riedel equation recommended by DIPPR for vapor pressure
data of ethane is given by
Example 2-3 (2-28)
with the parameters A = 51.857, B = –2600, C = –5.13, D = 1.49E-05 and
E = 2.

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 36
Problems Using Spreadsheets
Example 2-3

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 37
Problems Using Spreadsheets
  Concepts Used
 Formulation of a chemical equilibrium problem as a Gibbs energy
minimization problem with atom balance constraints.
Complex  Use of Lagrange multipliers to introduce the constraints into the
chemical objective function.
 Conversion of the minimization problem into a system of nonlinear
equilibrium by algebraic equations.

Gibbs  Numerical Methods Used

 Solution of a system of nonlinear algebraic equations with
minimization constraints.
 Excel Options and Functions Demonstrated
 Use of the Excel Add-In Solver for constrained minimization.

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 38
Problems Using Spreadsheets
  Ethane reacts with steam to form hydrogen over a cracking
catalyst at a temperature of T = 1000 K and pressure of P = 1 atm.
The feed contains 4 moles of H2O per mole of CH4. Balzisher et al.
suggest that only the compounds shown in the table below are
present in the equilibrium mixture (assuming that no carbon is
deposited). The Gibbs energies of formation of the various
compounds at the temperature of the reaction (1000K) are also
given in the table below. The equilibrium composition of the
effluent mixture is to be calculated using these data.
Table 1. Compounds Present in Effluent of Steam Cracking Reactor
Example 2-4

Topic 2 - Solving Basic Chemical Engineering

ChE 315 - Computer Applications in Chemical Engineering 39
Problems Using Spreadsheets
 a. Formulate the problem as a constrained minimization problem.
Introduce the constraints into the objective function using
Lagrange multipliers and differentiate this function to obtain a
system of nonlinear algebraic equations.
Example 2-4 b. Use Excel's “Solver” to solve the problem as a constrained
minimization problem without the use of Lagrange multipliers
and without differentiation of the objective functions.

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Problems Using Spreadsheets
  Solution
a. The objective function to be minimized is the total Gibbs energy
given by:
(2-29)
where ni is the number of moles of component i, c is the total number
of compounds, R is the gas constant, and Gi0 is the Gibbs energy of
pure component i at temperature T. The minimization of Equation (2-
27) must be carried out subject to atomic balance constraints:
Example 2-4
Oxygen Balance:
Hydrogen Balance:
Carbon Balance: .
These three constraints can be introduced into the objective functions
using Lagrange multipliers: λ1, λ2, and λ3. The extended objective
function is :
(2-30)

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Solution
a. The condition for minimum of this function at a particular point is that
all the partial derivatives of F with respect to ni and λj vanish at this
point. The partial derivative of F with respect to n1, for example, is:
(2-31)
The other partial derivatives with respect to ni can be obtained similarly. If
it is expected that the amount of a particular compound at equilibrium is
very close to zero, it is preferable to rewrite the equation in a form that
does not require calculation of the logarithm of a very small number.
Example 2-4 Rearranging Equation (2-31), for example, yields:
(2-32)
The partial derivatives of F with respect to λ1, λ2, and λ3 are g1, g2, and g3
respectively.

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
  Solution
b. It should be noted that the Solver Add-In cannot find the minimum
when Equation (2-29) is entered in its original form. Excel
execution stops with error messages indicating that there is an
attempt to calculate logarithm of a negative number. In order to
prevent calculation of logarithm of a negative number or logarithm
of zero, the expressions for calculating the partial Gibbs energy of
Example 2-4 some of the compounds have been changed according to:
(2-33)

where ε is a very small number (). This equation is used only for the
compounds which present in trace amounts in the effluent: O2, C2H2,
C2H4, and C2H6.

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
Example 2-4

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Problems Using Spreadsheets
  Concepts used
 Various correlations for calculating friction factors of turbulent fluid
flow in pipes.
 Numerical Methods Used
Comparison of  Solution of nonlinear algebraic equations.
friction factor  Problem Statement
correlations for  The Fanning friction factor can be used to calculate the friction loss
for isothermal liquid flow. This friction factor is dependent upon the
turbulent pipe Reynolds number and the surface roughness factor ε in m. The
Reynolds number is Re = Dvρ/μ, where ρ is the density of the fluid in
flow kg/m3 and μ is the viscosity in kg/m·s. A widely used chart gives
experimental values of the friction factor as a function of Re and ε.
(See, for example, Geankoplis or Perry et al.)

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Problems Using Spreadsheets
  There are also a number of implicit and explicit correlations for the
Comparison of friction factor in turbulent flow where Re > 3000. For hydraulically
friction factor smooth pipes where ε/D = 0, an implicit equation is:
(Nikuradse equation) (2-34)
correlations for  And an explicit equation is:
turbulent pipe (Blasius equation) (2-35)
flow

Topic 2 - Solving Basic Chemical Engineering

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Problems Using Spreadsheets
Comparison of  For rough pipes, where surface roughness characterized by ε/D
ratios is important, a widely used implicit equation is:
friction factor (Colebrook and White equation) (2-36)

correlations for  and explicit equations are given by:

turbulent pipe (Shacham equation) (2-37)

flow (Haaland Equation) (2-38)

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Problems Using Spreadsheets
 a. Summarize calculated friction factors from Equations (2-34)
through (2-38) at Re = 104 and 107 for smooth pipes where ε/D =
0. Comment on the differences between the implicit and
explicit equations.
b. Summarize calculated friction factors from Equations (2-34)
through (2-38) at Re = 104 and 107 for rough pipes where ε/D =
Example 2-5 0.0001 and 0.01. Comment on the differences between the
implicit and explicit equations.
c. Compare the results of (a) and (b) with the friction factors
obtained from a general graphical presentation of the Fanning
friction factor.

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Problems Using Spreadsheets
Example 2-5

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Problems Using Spreadsheets
Example 2-5

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Problems Using Spreadsheets