Chemical Process Calculations

21/34
Purposes of the Course
Determination of the Values of Stream Variables
Temperature, Pressure, Flow Rate of Each Component
Determination of the Energy Requirements of Process Equipments (Q+W)
Relations between Stream Variables
Material Balance Equations, Energy Balance Equations,
Thermodynamic Relations, Process Specifications

Cooler
R/G
Recycle Compressor Receiver
Feed
Stream 1 Reactor Product
Stream
Distillation
Feed Separator Tower
Stream 2
Heater Reboiler
Recycle

Waste water Waste Oil

Textbook: Richard M. Felder and Ronald W. Rousseau,

"Elementary Principles of Chemical Processes", 3rd ed., John Wiley &
Sons, Inc. (2000).

Reference: David M. Himmelblau,

"Basic Principles and Calculations in Chemical Engineering", 6th ed.,
Prentice Hall (1996).
 Chapter 1. Introduction

1.1 Three Types of Missions for Process Engineers

(1) Calculations of Outlet Stream Variables with

Given Inlet Stream Variables for Existing
Processes

(2) Calculations of Inlet Stream Variables and Process

Conditions to Produce Outlet Streams of Given Stream
Variables
(3) Calculations of Process Conditions for Given Inlet and
Outlet Stream Variables
1.2 What will we learn?

Dimensions and Units for Process Variables

Concentrations, T, P, Force, Energy, Power

Dimensional Equations for Efficient Calculations of Variables

- Mathematical Calculations
- Unit Conversions

Relations among ProcessVariables

- Gas Equations
Relations between T and P for ideal and real gases.

- Raoults and Henrys Laws for Vapor-Liquid Equilibrium

Equations between the concentrations in a
vapor phase and a liquid phase at equilibrium.

Material Balance Equations

Energy Balance Equations

Degree of Freedom Analysis for System Specification

Chapter 2. Introduction to Engineering Calculations

2.1 Units and Dimensions

Numerical values are always followed by a space + units:

2 meters, 1/3 second, 4.29 kg, 400 oC

Exception: % --> 50% (no space between number and %)

Dimensions

a property that can be measured (length, time, mass, temperature, ...) or

calculated by multiplying or dividing other dimensions
[velocity (length/time), volume (length3), density (mass/length3), ...].

Units are methods to represent dimensions

length - cm, m, ft
time - second
mass - gram

The numerical values of two quantities can be added or subtracted

only when the units are the same.

(ex) 3 cm 2 cm 1 cm
3 cm 1 s ?

Numerical values and their corresponding units may always be

combined together by multiplication or division.

(ex) 3 N 4 m 12 N m
5.0 km/2.0 h 2.5 km/h
Electrochemical Experiments. Electrochemical experiments were
conducted in a water-jacketed electrochemical cell in acetate
buffer (150 mM sodium acetate, adjusted to pH 5.2) at 37 oC
unless otherwise noted. The electrolyte volume was 30 mL for all
experiments. Glucose concentrations were obtained by adding
aliquots of 1 M glucose solution that had been allowed to
mutarotate for at least 24 h. A saturated nitrogen atmosphere was
obtained by purging the solution with nitrogen for 20 min before
the start of an experiment unless stated otherwise.
Source: Langmuir 2010, 26(8), 60196027

Reaction 12 used the same conditions as reaction 11 (9:1

H2SO4/H3PO4 65 C for 2 h) but increased the amount of
KMnO4 to 8x. This was performed to monitor the oxidation
of the GONRs with increasing oxidizing agent. The product
appeared to be more highly oxidized than that of reaction
11; while the isolated weight gain and C:O ratios were
comparable, more weightwas lost in the TGA (82% versus
58% at 950 C) and the UV _max of the product of reaction
12 is blue-shifted further than any other sample studied
(227 nm). Most striking, however, was the light brown color
of the product of reaction 12; while all samples thus far
classified as highly oxidized were a brown-black color, the
color of the product of reaction 12 was a significantly lighter
brown (similar to peanut butter) than the others.
Source: www.acsnano.org VOL. 4 NO. 4 20592069

2010
< Examples of Uses of Numbers and Their Units>
2.2 Conversion of Units

Conversion Factors: A ratio between two units of a same dimension

(ex) 1 cm 10 mm
1 cm 10 mm
10 mm 1 cm
2
10 mm 100 mm 2

1 cm 1 cm 2

Unit Conversions
(ex) Convert 36 mg to its equivalent in grams

1g 36 mg 1g
36 mg 0.036 g or 0.036 g
1000 mg 1000 mg

Make sure that old units cancel, leaving the desired unit
The second form is called "Dimensional Equation" and is more useful in
the conversion of units.

(Example 2.2-1) Conversion of Units

Convert an acceleration of 1 cm/s 2 to its equivalent in km/yr 2 .

[Solution] Using Dimensional Equation

1 cm 3600 2 s 2 24 2 h 2 365 2 day 2 1m 1 km

2 2 2 2 2 3
9.95 10 9 km/yr 2
s h day yr 10 cm 10 m
2.3 Systems of Units

Three Classes of Units:

Base units
Multiple Units
Derived Units

(1) Base Units

Base Units
Dimension SI Unit CGS system American engineering
system (fps)
Length meter (m) centimeter (cm) foot (ft)
Mass kilogram (kg) gram (g) pound-mass (lbm)
Time second (s) second (s) second (s)
Moles gram-mole (mol) gram-mole (mol) gram-mole (mol)
Temperature kelvin (K) kelvin (K) kelvin (K)
Electric current ampere (A) ampere (A) ampere (A)
Light Intensity candela (cd) candela (cd) candela (cd)

(2) Multiple Units

Multiple Units
Dimension American Engineering
SI
System (fps)

km, cm, mm,

Length mile, inch (in), yard (yd)
m...
(metric) ton, g,
Mass ton, ounce (oz)
mg, g...
yr, month, day, year (yr), month, day, hour
Time
hr, min, ms... (hr), min, ms...
Multiple unit prefixes

Factor Prefix Symbol Factor Prefix Symbol

10 12 Tera T 10 1 deci d

10 9 Giga G 10 2 centi c

10 6 Mega M 10 3 milli m

10 3 Kilo k 10 6 micro

10 2 Hecto h 10 9 nano n

10 1 Deca da 10 12 pico p

Frequently used multiple units

Factor Profix Length Mass Time

10 3
kilo km kg
1 m g s

10 1 deci dm

10 2 centi cm

10 3 milli mm mg ms

10 6 micro m g s

10 9 nano nm ng ns

angstrom
-10
10
()
 (3) Derived Units

Compound units

(ex) cm 2 , ft/min, kg m/s 2

Defined equivalents of compound units

(ex) 1 erg = 1 g cm2/s2, 1 lbf = 32.174 lbm ft/s2

1 N = 1 kg m/s2

Derived
Quantity Dimension Symbol Compound Unit
Unit
Volume L3 Liter L 10-3 m3
Force ML/t2 Newton N 1 kgm/s2
Pressure M/Lt2 Pascal Pa 1 N/m2 = 1 kg/ms2
Energy ML2/t2 Joule J 1 Nm=1 kgm2/s2

Power ML2/t3 Watt W 1 J/s=1 kgm2/s3

Greek Alphabet

Alpha , Zeta , Lambda , Pi , Phi ,

Beta , Eta , Mu , Rho , Chi ,
Gamma , Theta , Nu , Sigma , Psi ,
Delta , Iota , Xi , Tau , Omega ,
Epsilon , Kappa , Omicron , Upsilon ,
(Example 2.3-1) Conversion Between Systems of Units

2 2
Convert 23 lb m ft/min to kg cm/s .

[Solution]

23 lb m ft 0.454 kg 30.48 cm 1 min 2 23 0.454 30.48 kg cm

min 2
1 lb m 1 ft 2
60 s 2
60 2 s2
2.4 Force and Weight

Newton's second law of motion : F = ma

Derived Units for Force

SI 1 newton (N) 1 kg m/s 2

CGS 1 dyne 1 g cm/s2

fps 1 lb f 32.174 lb m ft/s 2

Other unit of force:

1 kgf = 9.8 kgm/ s2 = 9.8 N

A pound-force (lbf) is defined as the product of a unit mass ( 1 lb m )

and the acceleration of gravity at sea level and 45 latitude

( 32.174 ft/s 2 = 9.8 m/s2)

A kilogram-force (kgf) is defined as the product of a unit mass (1 kg)

and the acceleration of gravity at sea level and 45 latitude (9.8 m/s2)

(Example) Calculate the force (weight) of 10 kg mass on Earth in

N, kgf, and lbf.

W = mg = 10 kg x 9.8 m/s2 = 98 kgm / s2 = 98 N

= kgf
= lbf
 Conversion factors between derived units and natural units

g c (1 / C )

kg m/s 2 g cm/s 2 lb ft/s 2

gc 1 1 32.174 m
N dyne lb f

F ma / g c .

Weight of an object is the force exerted on the object by

gravitational acceleration. W mg / g c

(Example 2.4-1) Weight and Mass

3 3
Density of water = 62.4 lb m /ft . Calculate the weight of 2.000 ft of water.

(a) at sea level and 45 latitude and

2
(b) in Denver, Colorado, where the altitude is 5374 ft and g = 32.139 ft/s .

[Solution]

The mass of water: m V (62.4 lb m /ft 3 ) (2 ft 3 ) 124.8 lb m

32.174 ft/s 2
(a) W mg / g c 124.8 lb m 124.8 lb f
lb m ft/s 2
32.174
lb f
32.139 ft/s 2
(b) W mg / g c 124.8 lb m 124.7 lb f
lb m ft/s 2
32.174
lb f
 Energy

Dimension of energy = ML2/t2

Units of Energy: J (Joule), 1 J = 1 Nm = 1 kgm2/s2
Other Units of Energy: 1 cal = 4.184 J, 1 Btu = 1055 J

Power (Energy/time)

Dimension of power = ML2/t3

Units of power: W (Watt), 1 W = 1 J/sec = 1 kgm2/s3
Other Unit of power: 1 hp = 745.7 J/s (W)
Conversion Factors

Quantity SI fps SI vs fps

1 m = 109 nm 1 ft = 12 in
1 m = 3.281 ft
Length = 1010 1 yd = 3 ft
1 ft = 0.305 m
1 km = 1000 m = 36 in
1 kg = 1000 g 1 lbm = 16 oz 1 kg = 2.205 lbm
Mass
1 metric ton = 1000 kg 1 ton = 2000 lbm 1 lbm = 0.454 kg
1 m3 = 35.31 ft3
Volume 1 m3 = 1000 L 1 ft3 = 7.48 gal
1 ft3 = 0.0283 m3
1 N = 1 kgm/s2
1 dyne = 1 gcm/s2
1 N = 0.225 lbf
Force 1 N = 105 dynes 1 lbf = 32.174 lbmft/s2
2 1 lbf = 4.45 N
1 kgf = 9.8 kgm/s = 9.8
N
1 Pa = 1 N/m2
1 atm = 1.013x105 Pa 1 atm = 14.7 psi
Pressure 1 psi = 1 lbf/in2
1 bar = 105 Pa 1 psi = 0.068 atm
1 atm = 1.013 bar
1 J = 1 Nm
1 erg = 1 dynecm 1 J = 9.48x10-4 Btu
Energy 1 J = 107 ergs 1 Btu = 778 ftlbf 1 Btu = 1055 J
1 J = 0.239 cal = 252 cal
1 cal = 4.184 J
1 W = 0.738 ftlbf/s
Power 1 W = 1 J/s 1 hp = 550 ftlbf/s = 1.341x10-3 hp
1 hp = 745.7 W

A calorie (cal): the amount of energy needed to heat 1 gram of water by 1 C.

A British thermal unit (Btu): the amount of energy needed to heat 1 lbm of water by
1 F.

hp: horsepower
2.5 Numerical Calculation and Estimation

2.5a Scientific Notation, Significant Figures, and Precision

(1) Scientific notation: Convenient to represent very large and very small numbers.

123000000 1.23 10 8
0.000028 2.8 10 5

(2) Significant Figures

In the presence of a decimal point

From the 1st nonzero digit on the left to the last zero or nonzero digit

2300. or 2.300 103 4 SF

2300.0 or 2.3000 103 5 SF

0.035 or 3.5 10 2 2 SF

0.03500 or 3.500 10 2 4 SF

In the absence of a decimal point

From the 1st nonzero digit on the left to the last nonzero digit

2300 or 2.3 10 3 2 SF

23040 or 2.304 10 4 4 SF
(3) The number of significant figure indicates the precision: The more significant
figures, the more precise is the value.

8.3 g : 2 SF 8.25 g ~ 8.35 g

8.300 g : 4 SF 8.2995 g ~ 8.3005 g

(4) Rules in the calculation of the measured numbers with significant figures.

Multiplication/Division

The number of significant figures in the calculated result equals the lowest
number of significant figures of any of the multiplicands or divisors.

# SF: (3) (4) (7) (3)

3.57 4.286 15.30102 15.3

Addition/Subtraction

The last significant figure farthest to the left of the numbers before
addition/subtraction is the position of the last permissible significant figure of
the sum or difference.

1530
2.56
1527.44 1530

1.0000 0.036 0.22 1.2560 1.26

2.75 106 3.400 10 4 (2.75 0.03400) 106
2.78400 106 2.78 106

(5) A rule of rounding off numbers

Always make the last digit of the rounded-off number even.

1.35 1.4
1.25 1.2
(6) General procedure in the calculation of the numbers with significant
figures.

For any mathematical operations such as Addition, Multiplication,

Division, Complex Functions (sin, cos, log, ...)

Calculate the result

Calculate the maximum result

Calculate the minimum result

Determine the error = (maximum result - minimum result)/2

Determine the number of significant figures of the result in

(Examples) log 3.54

sin 160

exp (2.5)

2.3 log (5.35 /1.2)

2.5b Validating Results

How do I get a solution?

How do I know my solution is right?

(1) Back substitution: Substitute your solution back into the equations and
make sure it works.

Q: Solve two equations to obtain the values of x and y

xy=2 (1)
x+y=6 (2)

Solution by Back-substitution:

Step 1: Solve the question: 2x = 8, x = 4, y = 2

Step 2: Validation: 4-2 = 2 (1) 4 + 2 = 6 (2)

(2) Order of magnitude estimation:

Come up with a crude and easy-to-obtain approximation of the answer.

(3) Applying the test of reasonableness:

Verify that the solution makes sense.

For any calculation of T, for example, if you get T of 10,000C, you should
notice that this result never makes sense.
 2.5c Sample Mean

2.5d Sample Variance of Scattered Data

Sample Range: Xmax Xmin

2 2
Sample Variance: S X = (Xi - Xave) /(N-1)

2
Sample Standard Deviation: SX = S X

Two-thirds of all measured values fall within one standard deviation of the mean.
About 95% fall within two standard deviations.
About 99% fall within three standard deviations.

X = 15, sd =3

99% data 15-9 ~ 15+9 : 6 to 24

95% data 15-6 ~ 15+6 : 9 to 21
66% data 15-3 ~ 15+3 : 12 to 18
2.6 DIMENSIONAL HOMOGENEITY AND DIMENSIONLESS QUANTITIES

All additive terms on both sides of the equation

must have the same dimensions.

For the equation

V V0 gt

V ( m/s ) V0 ( m/s ) g ( m/s 2 ) t (s)

Each term has the same dimension and unit of m/s .

For a dimensionally homogeneous equation;

V ( m/s ) V0 ( m/s ) g ( m/s 2 ) t (min) ( 60s / min) V0 60 gt

where each term has the same unit of m/s with t in min.

(Example 2.6-1) Dimensional Homogeneity

Consider the equation D (ft ) 3 t (s) 4

(1) What are the dimensions of the constants 3 and 4?

(2) What are the units of 3 and 4?
(3) Derive an equation for distance in meters in terms of time in minutes.

[Solution]

(1) For dimensional homogeneity, the constant 3 must have the dimension
length/time and 4 length.
(2) For consistency, the constants must be 3 ft/s and 4 ft.
(3) With newly defined variables D( m) and t(min) ;
 D (m) 3.2808 ft
D (ft ) 3.28 D
1m
t (min ) 60 s
t (s ) 60 t
1 min

3.28 D 3(60t ) 4
D 55t 1.22

Dimensionless Quantity

A pure number or a multiplicative combination of variables with no net

dimensions:

M (g ) (g/cm 3 )u (cm/s) D(cm)

(ex) ,
M 0 (g ) (g/cm s)

Dimensionless Quantities as Follows.

Exponents in exponential functions (2 and y in x2 , 3y )

Transcendental functions (log, exp, sin )

Arguments of transcendental functions: exponential, logarithm, trigonometric

(x in ln x, sin x, e x )

Y (meter) = 3 log x

3 meter, log x, x : dimensionless

Y (meter) = 4 exp(x)

Exp x and x are dimensionless

(Example 2.6-2) Dimensional Homogeneity and Dimensionless Groups

Dependence of k on T:

mol 20000
k 3 1.2 10 5 exp
cm s 1.987T

The unit of 20000 is cal/mol , T in K (Kelvin).

What are the units of 1.2 10 5 and 1.987 ?

[Solution]

5
Since exp is dimensionless quantity. the unit of 1.2 10 is the same as the unit
mol
of k : 3 .
cm s

The argument of exp is a dimensionless quantity, therefore,

cal 1
1
mol K [1.987]

cal
Unit of 1.987 is
mol K
2.7 PROCESS DATA PRESENTATION AND ANALYSIS

Process Variables: Temperature, Pressure, Flow Rates, Concentrations and so on.

Usually, indirect techniques are used to measure the process variables.

Calibration experiment

(ex) A variable y is measured for several values of another variable x.

x 1.0 2.0 3.0 4.0

y 0.3 0.7 1.2 1.8

Objective of calibration: Estimation of the value of y for a value of x between

tabulated points (interpolation) or outside the range of the table data ( extrapolation)

2.7a Two-Point Linear Interpolation

The equation of the line through ( x1 , y1 ) and ( x 2 , y 2 ) on a plot of y versus x is

x x1
y y1 ( y 2 y1 )
x 2 x1

(Test yourself )

1. Values of f at several times (t)

f 1 4 8
t 1 2 3

Find the values of (a) f (t 1.3) and (b) t ( f 5)

t t1
f f1 ( f 2 f1 )
t 2 t1

2.
2.7b Fitting a Straight Line

Equation for a straight line: y ax b

For two points ( x1 , y1 ) and ( x 2 , y 2 ) on the line,
y 2 y1
Slope : a
x 2 x1

b y1 ax1
Intercept :
y 2 ax 2
 (Example 2.7-1) Fitting a Straight Line to Flowmeter Calibration Data

[Solution]
2.7c Fitting Nonlinear Data

Examples of plots that yield straight lines:

y 2 ax 3 b y2 versus x3

y = ax2 + b y versus x2
y2 = a/x + b Y y2 versus 1/x
1/y = a(x+3) b 1/y versus (x+3)
sin y = a(x -4) sin y versus (x2-4)
2

Examples of nonlinear correlations

Excel program is used to optimal fit the corresponding linearized equations.

(Example 2.7-2) Linear Curve-Fitting of Nonlinear Data

m = a'T + b' m = aT1/2 + b

60 60

40 40 y = 4.100x + 1.798
R = 1
20 20
y = 0.329x + 12.93
0 0
R = 0.981
0 50 100 0 5 10
Problem 2.36

Nonlinear equation: PVk = C

Linearized equation: ln P = -k lnV + ln C, y = ax + b
where y = ln P, x = ln V, a = -k, b = ln C

What are the dimensions and units of k and C ?

V(cm3) P(mm Hg) Pcal Error

48.3 760 762.7 -2.7 Nonlinear plot
37.4 1140 1140.4 -0.4 4000
3500
31.3 1520 1509.0 11.0 3000
P(mm Hg)

24.1 2280 2276.5 3.5 2500

2000
20 3040 3052.5 -12.5 1500
1000
500
0
10 20 30 40 50
V (cm3)
17.4 3800 3800.1 -0.1

x = ln V y = ln P
3.8774 6.6333
Linearized plot
8.5
3.6217 7.0388
8.0
3.4436 7.3265
7.5
y=ln P

3.1822 7.7319
7.0
2.9957 8.0196
6.5
2.8565 8.2428 6.0
2.5 3.0 3.5 4.0
x=ln V
19.9771 44.9929

Final answers: a = -1.573 k = 1.573

b = 12.736 C = 3.4x105
Problem 2.45

Nonlinear equation: D = Do exp (-E/RT)

Linearized equation: ln D = ln Do -E/RT, where y = ln D, x = 1/T,
a = -E/R, b = ln Do

What are the dimensions and units of D, Do, E, ln D, ln Do ?

T(K) D(cm2/s) x 106

25.00
347.0 1.34
20.00
374.2 2.50
15.00
396.2 4.55 D 10.00
420.7 8.52
5.00
447.7 14.07 0.00
300.0 350.0 400.0 450.0 500.0
471.2 19.99

x = 1/T y = ln D
3.5
0.002882 0.293 3
y = -3666x + 10.8
0.002672 0.916 2.5

2
0.002524 1.515
1.5
0.002377 2.142
1
0.002234 2.644 0.5

0
0.002 0.0022 0.0024 0.0026 0.0028 0.003
0.002122 2.996

Final answers: a = -E/R = 3666 K

E = 3666 K x R = 3666 Kx8.314 J/(mol K) = 30.5 kJ/mol

b = ln Do = 10.8
Do = e10.8 = 49,041 x 10-6 cm2/s
 Example A.1-1

Nonlinear equation: P = 1/(m t0.5 + r)

Linearized equation: 1/P = mt0.5+r, where x = t0.5, y = 1/P, a = m, b = r

What are the dimensions of m and r ?

t P
1.0 0.279

2.0 0.194

3.0 0.168

5.0 0.12

10.0 0.083

x = t 0.5 y = 1/P 15
y = 3.944x - 0.515
1 3.584229
10 R = 0.996
1.414214 5.154639
1.732051 5.952381 5
2.236068 8.333333
0
0 1 2 3 4
3.162278 12.04819