Introduction to Chemical Engineering Calculations

Lecture 3.

Fundamental Process Variables

Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
3 Fundamental Process Variables in Chemical Engineering

What is a process?

General:

“An action or event which causes changes.”

Chemical Engineering:

“A process is a series of operations involving the

physical, chemical, or biological transformation of
an input material for the purpose of achieving a
desired product material.”

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Types of Chemical Processes – Batch Process

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Types of Chemical Processes – Continuous Process

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3 Fundamental Process Variables in Chemical Engineering

Types of Chemical Processes – Semicontinuous (Semibatch) Process

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3 Fundamental Process Variables in Chemical Engineering

What is a (chemical) process variable?

Any measurement used to characterize or describe a

chemical process.

The fundamental process variables

1. Measurements to quantify a material or specify a

chemical composition.

Mass, Volume, and Mole

2. Measurements used to specify process conditions.

Pressure and Temperature

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Mass and Volume: Conservation Principles

Conservation Law for Mass:

“Matter is neither created nor destroyed”

mA + mB = mT or mA + mB = mC + mD

For volume, there is no generalized conservation law.

1. For gases, VA + VB  VT

2. For liquids, VA + VB = VT
(if volume change is negligible)

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Mass and Volume: Density and Specific Gravity

Density ()
Ratio of mass per unit volume. Used as a factor for inter-
conversion of mass and volume.

mass  m g kg lbm 
ρ=  3, , 3, 3 
volume  L ml m ft 

1. Densities of gases depend on pressure and temperature.

2. Densities of solids and liquids do not change

significantly with pressure at ordinary conditions with
pressure but change with temperature.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Mass and Volume: Density and Specific Gravity

Specific Gravity (sp gr)

Ratio of two densities – that of the substance of interest to that of
a reference substance.

sp gr =
ρA
=
 kg / m
 g / ml A
=
3
 A =
 lbm / ft 3
 A
ρref  g / ml ref  kg / m3   lbm / ft 3
ref
ref

The specific gravity of gases frequently is referred to air, but may

be referred to other gases. The reference substance for liquids
and solids is normally water at 40C:

g kg lbm
ρH 2O at 40C = 1.000 = 1000 3 = 62.43 3
ml m ft

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Mass and Volume: Density and Specific Gravity

Specific Gravity (sp gr)

When referring to specific gravity, the temperature at which

each density is measured. Thus,

200
sp gr = 0.73 0
4
This can be interpreted as the specific gravity when the
substance of interest is at 200C and the reference substance
(water) is at 40C.

If temperatures are not stated, assume ambient

temperature and 40C, respectively.

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3 Fundamental Process Variables in Chemical Engineering

The Mole Unit

Refers to a certain number of molecules, atoms, or sub-

atomic particles.

“The amount of substance that contains as many

elementary entities as there are atoms in 0.012 kg of
carbon 12” – 1969 International Committee on Weights and
Measures

Contains Avogadro’s number of entities (molecule, atom,

or any particles) – 6.02 x 1023

Amount of a chemical species whose mass is equal to its

molecular weight.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

The Mole Unit

A gmol is the standard unit for mole and contains 6.02 x

1023 molecules or atoms. But the following units can also be
used for mole:

1 kmol = 1000 gmol

1 lbmol = 454.54 gmol

In fact, any equivalent unit for mole can be used by

defining an analogous unit to mass and using the same
conversion used for mass.

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3 Fundamental Process Variables in Chemical Engineering

The Mole Unit

To convert the number of moles to mass, we make use of

the molecular weight (MW):

mass  m g kg lbm 
Molecular Weight = , , ,
mole  n gmol kmol lbmol 

If the molecular weight of H2O is 18, then:

1 gmol contains 18 g of H2O (MW = 18 g/gmol)

1 kmol contains 18 kg of H2O (MW = 18 kg/kmol)
1 lbmol contains 18 lbm of H2O (MW = 18 lbm/lbmol)

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3 Fundamental Process Variables in Chemical Engineering

Quantifying Materials in a Continuous Chemical Process

For continuous process, it is best to use flow rates to

measure the amount of materials flowing through the
process:

 •  
1. Mass Flowrate  m ,m  m = mass/time (m/)
 
 •  
2. Volume Flowrate  V , V 
 
V = volume/time L3 /θ  
 •  
3. Molar Flowrate  n , n  n = moles/time (n/)
 

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Chemical Composition

In a mixture of two or more components, the composition

may be expressed as:

massof component i  mi 
1. Mass Fraction xi =
total massof mixture  mT 

molesof component i  n i 
2. Mole Fraction yi =
total molesof mixture  n T 

For liquids and solids, it will always be assumed that the

composition is on a weight basis unless otherwise stated.

For gases, it will be assumed to be in molar basis.

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3 Fundamental Process Variables in Chemical Engineering

Chemical Composition

Other methods of expressing concentration include:

1. Molarity (mol/L) and normality (equivalents/L).

2. Parts per million (ppm) and parts per billion (ppb)

– normally used for expressing concentration of
extremely dilute solutions.

3. Partial pressure – a method to express the

concentration of a gas mixture.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.1 – Mass and Volume Calculations

The specific gravity of gasoline is approximately 0.70.

a. Determine the mass (kg) of 50.0 liters of gasoline.

b. If the mass flow rate of gasoline delivered by a gasoline

pump is 1150 kg/min, what is the corresponding
volumetric flow rate in liters/s.

c. Gasoline and kerosene (specific gravity = 0.82) are

blended to obtain a mixture with a specific gravity of
0.78. Calculate the volumetric ratio (volume of
gasoline/volume of kerosene) of the two compounds in
the mixture, assuming the law of additive volume is
applicable.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.1 – Mass and Volume Calculations

Solution for (a):

mG = ρG VG = sp grG  ρref VG

 kg   1 m3 
mG =  0.70 1000 3  50.0 L    = 35.0 kg

 m   1000 L 

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.1 – Mass and Volume Calculations

Solution for (b):

 
 mG mG
VG = 
G sp grG  ρref
 kg  m3  m3
VG = 1150    1.643
min  0.70  1000kg  min

 m3  1min   1000L  L
VG = 1.643     27.38
min  60s   m3  s

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.1 – Mass and Volume Calculations

Solution for (c):

mmix
mix   sp grmix  ref  
Vmix

 mG  mK   VGG  VK K 
sp grmix  ref   
 VG  VK   VG  VK 

 VG sp grG  ref  VK sp grK  ref 

sp grmix  ref  
 VG  VK 

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.1 – Mass and Volume Calculations

Eliminating ref in the equation,

ref VG  sp grG   VK sp grK  

sp grmix  ref  
 VG  VK 

VG sp grG   VK sp grK 

sp grmix  
 VG  VK 
VG  0.70   VK  0.82
0.78 
VG  VK

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.1 – Mass and Volume Calculations

Rearranging the equation,

0.78VG  0.78VK  0.70VG  0.82VK

0.78  0.70 VG  0.82  0.78 VK

Solving for the volume ratio,

VG 0.82  0.78 0.04 L gasoline

   0.50
VK 0.78  0.70 0.08 L kerosene

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.2 – Mass and Volume Calculations

At 250C, an aqueous solution containing 35% H2SO4 has a

specific gravity of 1.2563.

a. Calculate the volume of the solution that will contain

195.5 kg of H2SO4.

b. Re-calculate the volume of the solution if pure-

component specific gravities of H2SO4 (SG = 1.8255) and
water had been used for the calculation. Assume
additive volume is applicable.

c. Estimate the percent error in volume calculation.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.2 – Mass and Volume Calculations

Solution for (a):

Solve for msol using the weight fraction of H2SO4:

 1 kg solution 
msol =195.5kg H2SO4    558.57 kg
 0.35 kg H2SO4 

Solve for Vsol using the specific gravity of mixture:

 m3   1000 L 
Vsol =558.57 kg sol   444.6 L
 1.2563  1000 kg   1 m3 
  

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.2 – Mass and Volume Calculations

Solution for (b):

If additive volume is applicable:

Vsol = Vwater + Vacid

Solve for the volume of acid:

 m3   1000 L 
Vacid =195.5kg H2SO4   107.09 L
 1.8255  1000 kg   1 m3 
  

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.2 – Mass and Volume Calculations

Solve for the volume of water:

 0.65kg H2O   1m3   1000 L 

Vwater =195.5kg H2SO4      3 
 0.35kg H2SO 4  1000 kg  1m 
Vwater  363.07 L

Solving for the total volume of solution:

Vsol = 363.07 L + 107.09 L

Vsol = 470.16 L

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.2 – Mass and Volume Calculations

Solution for (c):

measured value  true value

% error   100
true value

470.16 L  444.6 L
% error   100
444.6 L

% error  5.5%

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.3 – Calculations Involving the Mole Unit

A mixture contains:

10.0 mole% ethyl alcohol (C2H5OH)

75.0 mole % ethyl acetate (C4H8O2)
15.0 mole% acetic acid (CH3COOH)

a. Calculate the mass fractions of each component in the

mixture.

b. What is the average molecular weight of the mixture?

c. What would be the mass (kg) of a sample containing

25.0 kmol of ethyl acetate?

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.3 – Calculations Involving the Mole Unit

Solution for (a):

Consider 100.0 gmol of mixture.

Component Moles MW Mass Mass

i (gmol) (g/gmol) (g) Fraction

C2H5OH 10.0 46 460 0.0578

C4H8O2 75.0 88 6600 0.8291

CH3COOH 15.0 60 900 0.1131

Total 100.0 --- 7960 1.0000

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.3 – Calculations Involving the Mole Unit

Solution for (b):

total mass 7960g g

Ave.MW    79.6
total moles 100.0gmol gmol

Solution for (c):

 1kmol mixt.   79.6 kg mixt. 

msample  25kmol C4H8O2   
 0.75kmol C H O
4 8 2  kmol mixt. 
msample  2,653.3kg mixture

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Relative and Absolute Temperature Scales

Temperature: The average kinetic energy possessed by the

substance.

Relative Temperature Scale – Celsius and Fahrenheit

The zero value is preset at some arbitrarily defined level.

T(0F) = 1.8T(0C) + 32
T(0C) = (1/1.8)[T(0F) – 32]

Absolute Temperature Scale – Kelvin and Rankine

A temperature scale on which a reading of zero coincides with the
theoretical absolute zero (zero entropy configuration)

T(K) = T(0C) + 273.15

T(0R) = T(0F) + 459.67

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Unit Temperature Difference

When temperature is used as a unit difference, then the

following relationship is used:

0C = K
 0F =  0R

0C = 1.80F
K = 1.80R

Whether temperature is used as a unit temperature

difference must be interpreted from the context of the
equation or sentence being examined.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.4 – Temperature and Unit Temperature Difference

The thermal conductivity (k) of aluminum at 320F is:

k = 117 Btu/(hr)(ft2)(0F/ft)

Find the equivalent value in terms of Btu/(hr)(ft2)(K/ft).

Btu  1.8Δ 0 F   1Δ 0 C  Btu

117 × ×
   =221
 hr   ft 2  0
 0
Δ F/ft  1Δ C   1ΔK   
 hr  ft 2  ΔK/ft 

It is not correct to do the following conversion:

Btu
117
 1.8 0 C  32 
 hr   ft 2   
 ft 

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example – Temperature and Unit Temperature Difference

The heat capacity of sulfuric acid has the units of

J/(gmol)(0C) and is given by the relation

CP = 139.1 + (1.56  10-1)T(0C)

where T is expressed in 0C. Modify the formula so that the

heat capacity has a unit of Btu/(lbmol)(0R) and T is in 0R.

In the given relation, the T is used as a specific temperature

value and not a unit temperature difference.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.4 – Temperature and Unit Temperature Difference

Establish the relation between T(0R) and T(0C).

T(0C) = (1/1.8)  [T(0R) – 460 – 32]

Using this equivalence in the given relation.

 1  1  J
CP  139.1  1.56  10 
 1.8
T(0 R)  460  32     gmol  0 C

2 0 J
CP  215.852  8.67 10 T( R)
gmol  0 C

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.5 – Temperature and Unit Temperature Difference

Converting the resulting unit for heat capacity:

 2 0 J 
C P   215.852  8.67  10 T( R) 0 
 gmol  C 
 1Btu   454 gmol   1  0C 
   1lbmol   0 
 1055 J    1.8  R 

Btu
C P  23.06  2.07 102 T(0 R)
lbmol  0 R

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Pressure – General Definition

Pressure is defined as normal force per unit area.

Force (F)

Area (A)

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3 Fundamental Process Variables in Chemical Engineering

Absolute and Relative Pressures

Absolute Pressure (PA)

Pressure measured relative to a fixed reference point of
zero pressure (vacuum).

Gauge Pressure (PG)

Pressure measured relative to the atmosphere pressure
(relative pressure). Many pressure measurement devices
measure only gauge pressure.

Pabs = PG + Patmospheric

Note:
When using English units, absolute pressure and gauge
pressure are designated as psia and psig, respectively.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

The Atmospheric (Barometric) Pressure

Can vary with location, weather conditions and other

factors. Usually determined from a barometer (barometric
pressure).

The Standard Atmospheric Pressure:

Patm = 1.000 atm

= 760.0 mmHg
= 101.3 kPa
= 29.92 in Hg
= 33.91 ft H2O
= 14.7 psi (lbf/in2)

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Hydrostatic Pressure

Hydrostatic pressure is the pressure at the bottom of a

static (non-moving) column of water.
P0 Relationship between pressure on top
(P0) and pressure at the bottom (P)

P = P0 + gh
Fluid Density where
()

h P = pressure at the bottom of the fluid

P P0 = pressure at the top of the column
 = density of the fluid
h = height of the fluid
g = acceleration due to gravity

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.7 – Hydrostatic Pressure Calculation

The great Boston molasses flood occurred on January 15,

1919. In it, 2.3 million gallons of crude molasses flowed
from a 30-foot high storage tank that ruptured, killing 21
people and injuring 150.

The estimated specific gravity of crude molasses is 1.4.

What were the mass of molasses in the tank in lbm and the
pressure at the bottom of the tank in lbf/in.2?

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.7 – Hydrostatic Pressure Calculation

Calculation for mass (in lbm):

m M  M VM  SG M ref VM
 3 
 lbm  1ft
mM 6

 1.4  62.43 3  2.3  10 gal 
 ft  7.481gal
 
 
m M  2.69 107 lbm

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.7 – Hydrostatic Pressure Calculation

Calculation for pressure at the tank bottom (in lbf/in.2):

Applying the formula for hydrostatic pressure:

P = P0 + Mgh = P0 + SGMrefgh

What is the pressure at the top (P0)?

P0 = Patm

In the absence of any information, assume standard

atmospheric pressure:

P0 = Patm = 14.7 lbf/in.2

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.7 – Hydrostatic Pressure Calculation

Substituting actual values in the formula:

 lbf   lbm   ft 
P  14.7 2   1.4  62.43 3   32.174 2   30 ft 
 in.   ft   s 
lbf lbm  ft  1lbf 
P  14.7 2  84,362.16 2 2  2
in. ft  s  32.174 lbm  ft / s 
lbf lbf  1ft 2  lbf
P  14.7 2  2, 622.06 2  2
 14.7  18.1 2
in. ft  144in.  in.
lbf
P  32.91 2
 or psia 
in.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Pressure Measure Device – The Manometer

Used for measurement of pressures

below 3 atm.

U-shaped tube partially filled with

a fluid of known density
(manometer fluid).

Both ends of the tube are exposed

to different pressures causing
differences in the level of the
manometer fluid in both arms.

The differences between pressures

can be calculated from the
measured difference between the
liquid levels of each arm.

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Manometer Pressure Calculations

Based on the principle that the fluid pressure must be the same at
any two points at the same height in a continuous fluid.

P = P1 – P2 = (f –  )gh

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3 Fundamental Process Variables in Chemical Engineering

Types of Manometer

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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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3 Fundamental Process Variables in Chemical Engineering

Example 3.8 – Manometer Pressure Calculation

The pressure difference between two gas tanks A and B is

measured by a U-tube manometer, with mercury as the
manometer liquid. The barometric pressure is 700 mmHg.
What are the gauge and absolute pressures in tank A in
mmHg?

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
48
3 Fundamental Process Variables in Chemical Engineering

Example 3.8 – Manometer Pressure Calculation

Using the pressure difference formula for a manometer:

P = PA – PB = (Hg –  )gh1

Since the tanks contain gases, the density of the gas () can
be neglected in the calculation:

PA – PB = Hggh1

Solving for PA:

PA = PB + Hggh1

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
49
3 Fundamental Process Variables in Chemical Engineering

Example 3.8 – Manometer Pressure Calculation

First, calculate for PB:

PB – (0) = Hggh2

Substituting the equivalent expression for PB in the last

equation for PA:

PA = Hggh2 + Hggh1

PA = Hgg(h2 – h1)

How do we get the density of mercury (Hg)?

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
50
3 Fundamental Process Variables in Chemical Engineering

Example 3.8 – Manometer Pressure Calculation

Knowing the density of mercury is not necessary if mmHg

is used as unit for pressure, such that:

PA = h2 – h1
PA = (860 – 20) mm Hg
PA = 840 mm Hg

Is this pressure in tank A absolute or gauge?

The calculated PA is an absolute pressure since it was

measured relative to a vacuum. To determine the gauge
pressure:

PA (gauge) = (840 – 700) mm Hg = 140 mm Hg

SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
51