Chemical Engineering Department

CHAPTER 3
Processes and Process Variables

COURSE CODE: KMÜ 241

COURSE TITLE: MATERIAL AND ENERGY BALANCES I

COURSE TEXTBOOK: Felder, R. M. and R. W. Rousseau, "Elementary Principles of

Chemical Processes", 3rd Edition, John Wiley&Sons, Inc., New York, 2000.
3. Processes and Process Variables
A process is any operation or series of operations that causes a
physical or chemical change in a substance or a mixture of
substances.
The material that enters a process is referred to as the input or
feed to the process, and that which leaves is called the output or
product.
A process unit is an apparatus in which one of the operations
that constitute a process is carried out. Each process unit has
associated with it a set of input and output process streams,
which consist of the materials that enter and leave the unit.
As a chemical engineer, you might be called on to design
individual process units, supervise the operation of a
process, or modify a process design to accommodate a
change in the feed or in the desired product characteristics.
As a rule, to do any of these things you must know the
amounts, compositions, and conditions of the materials that
enter and leave each process unit.
3.1 Mass and Volume
The density of a substance is the ratio of its mass to its volume o
the substance (kg/m3, g/cm3, lbm/ft3, etc).

The specific volume of a substance is the volume occupied by a

unit mass of the substance; it is the inverse of density. Densities
of pure solids and liquids are essentially independent of pressure
and vary relatively slightly with temperature.

The temperature variation may be in either direction: the density

of liquid water, for example, increases from 0.999868 g/cm3 at
0oC to 1.00000 g/cm3 at 3.98oC, and then decreases to 0.95838
g/cm3 at 100oC. Densities of many pure compounds, solutions,
and mixtures may be found in standard references
The density of a substance can be used as a conversion factor
to relate the mass and the volume of a quantity of the
substance. For example, the density of carbon tetrachloride is
1.595 g/cm3; the mass of 20.0 cm3 of CCl4 is therefore

and the volume of 6.20 lbm of CCl4 is

The specific gravity of a substance is the ratio of the density
of the substance to the density of a reference substance at a
specific condition:
!
SG =
!!"#
The reference most commonly used for solids and liquids is water at 4.0oC, which
has the following density:

The density of a liquid or solid in g/cm3 is numerically equal to

the specific gravity of that substance. The notation
signifies that the specific gravity of a substance at 20oC with
reference to water at 4oC is 0.6.
Example 3.1-1 Calculate the density of mercury in lbm /ft3 from
a tabulated specific gravity, and calculate the volume in ft3
occupied by 215 kg of mercury.
The specific gravity of mercury at 20oC as 13.546 (Table B1)

𝝆𝑯𝒈=(13.546)(62.43 lbm/ft3) = 845.7 lbm/ft3

3.2 Flow Rate
3.2a Mass and Volmetric Flow Rate
The rate at which a material is transported through a process line is
the flow rate of that material.
The flow rate of a process stream may be expressed as a mass flow
rate (mass/time) or as a volumetric flow rate (volume/time).
Suppose a fluid flows in the cylindrical pipe, where the
shaded area represents a section perpendicular to the
direction of flow. If the mass flow rate of the fluid is 𝑚(kg/s)
̇ ,
then every second m kilograms of the fluid pass through the
cross section.

If the volumetric flow rate of the fluid at the given cross section is 𝑉̇ (m3/s), then every
second V cubic meters of the fluid pass through the cross section. However, the mass m
and the volume V of a fluid—in this case, the fluid that passes through the cross section
each second—are not independent quantities but are related through the fluid density,
̇ 𝑉̇
𝜌=m/V = 𝑚/
3.2b Flow Rate Measurement A flowmeter is a device mounted
in a process line that provides a continuous reading of the flow
rate in the line.
the rotameter and the orifice meter

The orifice meter is an obstruction in the flow channel

The rotameter is a tapered with a narrow opening through which the fluid passes.
vertical tube containing a The fluid pressure drops (decreases) from the
float; the larger the flow upstream side of the orifice to the downstream side;
rate, the higher the float the pressure drop varies with the flow rate—the
rises in the tube. greater the flow rate, the larger the pressure drop.
3.3 Chemical Composition
3.3a Moles and Molecular Weight
The atomic weight of an element is the mass of an atom of
that element on a scale that assigns 12C a mass of exactly 12.

The molecular weight of a compound is the sum of the

atomic weights of the atoms that constitue a molecule of that
compound.
Atomic oxygen (O), for example, has an atomic weight of
approximately 16, and therefore molecular oxygen (O2) has a
molecular weight of approximately 32.

A gram-mole (g-mole, or mol in SI units) of a species is

the amount of that species whose mass in grams is
numerically equal to its molecular weight.
Other types of moles (e.g., kg-moles or kmol, lb-moles,
ton-moles) are similarly defined.
For example,
Carbon monoxide (CO), has a molecular weight of 28;
1 mol of CO contains 28 g,
l lb-mole contains 28 lbm,
1 ton-mole contains 28 tons,
and so on.
If the molecular weight of a substance is M, then there are M
kg/kmol, M g/mol, and M lbm/lb-mole of this substance. The
molecular weight may thus be used as a conversion factor that
relates the mass and the number of moles of a quantity of the
substance.
For example, 34 kg of ammonia (NH3: M=17) is equivalent to

and 4.0 lb-moles of ammonia is equivalent to

Example 3.3-1
How many of each of the following are contained in 100.0 g of
CO2 (M = 44.01)?

mol CO2;

lb-moles CO2;

mol C;

mol O;
mol O2;

g O;

g O2;

molecules of CO2

One gram-mole of any species contains

6.02x1023 (Avagadro’s number) molecules of that species
The molecular weight of a species can be used to relate the mass
flow rate of a continuous stream of this species to the
corresponding molar flow rate. For example, if carbon dioxide
(CO2 : M=44.0) flows through a pipeline at a rate of 100 kg/h, the
molar flow rate of the CO2 is

If the output stream from a chemical reactor contains CO2

flowing at a rate of 850 lb-moles/min, the corresponding mass
flow rate is
3.3b Mass and Mole Fractions and Average Molecular Weight

Mass fraction: The mass fraction of a component in a mixture is the

ratio of the mass of the component to the total mass of the mixture.

Mole fraction: The mole fraction of a component in a mixture is the

ratio of the moles of the component to the total mole of the mixture.

The percent by mass of A is 100xA,

and the mole percent of A is 100yA.
Example 3.3-2

A solution contains 15% A by mass (xA=0.15) and 20 mole% B(yB=0.20)

1. Calculate the mass of A in 175 kg of the solution.

2. Calculate the mass flow rate of A in a stream of solution flowing at

a rate of 53 lbm/h.
3. Calculate the molar flow rate of B in a stream flowing at a rate
of 1000 mol/min.

4. Calculate the total solution flow rate that corresponds to a

molar flow rate of 28 kmol B/s.

5. Calculate the mass of the solution that contains 300 lbm of A.

Example 3.3-3
A mixture of gases has the following composition by mass:

𝑥%$ = 0.16 g O2/g total

What is the molar composition?

Basis: 100 g of the mixture.
Calculate how many moles of each substance are present
&.() * %$ ( /,. %$
𝑛%$ = 100 g total * +,+-. 01.& * %$
= 0.500 mol O2
&.&3 * 2% ( /,. 2,
𝑛2% = 100 g total * +,+-. 14 * 2%
= 0.143 mol CO ntotal=
&.(5 * 2%$ ( /,. 2%$ 3.279 mol
𝑛2%$ = 100 g total * +,+-. 33.& * 2% = 0.386 mol CO2
$
&.)0 * 6$ ( /,. 6$
𝑛6$ = 100 g total * +,+-. 14.& * 6$
= 2.250 mol N2
𝑦%$ = 𝑛%$ /nt = 0.500/3.279 = 0.15 mol 𝑂2/mol total
𝑦2% = 𝑛2% /nt = 0.143/3.279 = 0.044 mol CO/mol total
∑ 𝑦𝑖 =1.000
𝑦2%$ = 𝑛2%$ /nt = 0.386/3.279 = 0.12 mol 𝐶𝑂2/mol total

𝑦6$ = 𝑛6$ /nt = 2.250/3.279 = 0.69 mol N2/mol total

The average molecular weight (or mean molecular weight) of a
mixture, M (kg/kmol, lbm/lb-mole, etc.), is the ratio of the mass
of a sample of the mixture (mt) to the number of moles of all
species (nt) in the sample. If yi is the mole fraction of the ith
component of the mixture and Mi is the molecular weight of this
component, then

If xi is the mass fraction of the ith component, then

Example 3.3-4
Calculate the average molecular weight of air
1) from its approximate molar composition of 79% N2, 21% O2 and
2) from its approximate composition by mass of 76.7% N2, 23.3% O2.
1)

2)
3.3c Concentration
The mass concentration of a component of a mixture or
solution is the mass of this component per unit volume of
the mixture (g/cm, lbm/ft, kg/in.,..).
The molar concentration of a component is the number of
moles of the component per unit volume of the mixture
(kmol/m3, lb-moles/ft3,..).
The molarity of a solution is the value of the molar
concentration of the solute expressed in gram-moles
solute/liter solution (e.g., a 2-molar solution of A contains
2 mol A/liter solution).
The concentration of a substance in a mixture or solution can
be used as a conversion factor to relate the mass (or moles) of
a component in a sample of the mixture to the sample
volume, or to relate the mass (or molar) flow rate of a
component of a continuous stream to the total volumetric
flow rate of the stream.
Consider, for example, a 0.02-molar solution of NaOH (i.e., a
solution containing 0.02 mol NaOH/L): 5 L of this solution
contains

and if a stream of this solution flows at a rate of 2 L/min,

the molar flow rate of NaOH is
Example 3.3-5
A 0.50-molar aqueous solution of sulfuric acid flows into a
process unit at a rate of 1.25 m3/min. The specific gravity of the
solution is 1.03. Calculate
1) the mass concentration of H2SO4 in kg/m3,
2) the mass flow rate of H2SO4 in kg/s, and
3) the mass fraction of H2SO4.
3) The mass fraction of H2SO4 equals the ratio of the mass
flow rate of H2SO4—which we know— to the total mass flow
rate, which can be calculated from the total volumetric flow
rate and the solution density.
3.3d Parts per Million and Parts per
Billion
The units parts per million (ppm) and parts per billion
(ppb)3 are used to express the concentrations of trace
species (species present in minute amounts) in mixtures of
gases or liquids.
The definitions may refer to mass ratios (usual for liquids)
or mole ratios (usual for gases) and signify how many parts
(grams, moles) of the species are present per million or
billion parts (grams, moles) of the mixture. If yi is the
fraction of component i, then by definition
For example, suppose air in the vicinity of a power plant is
said to contain 15 ppm SO2 (15 parts per million sulfur
dioxide). Assuming that a molar basis has been used
(customary for gases), this statement means that every
million moles of air contains 15 moles of SO2, or
equivalently, that the mole fraction of SO2 in the air is
15x10-6 .
Units such as ppm and ppb have become increasingly
common in recent years as public concern about potentially
hazardous trace species in the environment has grown.
3.4 Pressure
3.4a Fluid Pressure and Hydrostatic Head
A pressure is the ratio of a force to the area on which the force
acts. Accordingly, pressure units are force units divided by area
units (e.g., N/m2, dynes/cm2, and lbf/in2 or psi). The SI pressure
unit, N/m2, is called a pascal (Pa).
Consider a fluid (gas or liquid) contained in a closed vessel or
flowing through a pipe, and suppose that a hole of area A is
made in the wall of the containing vessel,
The fluid pressure may be defined as the ratio F/A,
where F is the minimum force that would have to be
exerted on a frictionless plug in the hole to keep the
fluid from emerging.
Suppose a vertical column of fluid is h(m) high and has
a uniform cross-sectional area A(m2). Further suppose
that the fluid has a density of r(kg/m3), and that a
pressure P0(N/m2) is exerted on the upper surface of
the column. The pressure P of the fluid at the base of
the column—called the hydrostatic pressure of the
fluid is, by definition, the force F exerted on the base
divided by the base area A. F thus equals the force on
the top surface plus the weight of the fluid in the
column.
In addition to being expressible as a force per unit area, a
pressure may be expressed as a head of a particular
fluid—that is, as the height of a hypothetical column of
this fluid that would exert the given pressure at its base if
the pressure at the top were zero. You can thus speak of a
pressure of 14.7 psi or equivalently of a pressure (or
head) of 33.9 ft of water (33.9 ft H2O) or 76 cm of mercury
(76 cmHg). The equivalence between a pressure P
(force/area) and the corresponding head Ph (height of a
fluid) is given by Equation

with P0=0
Example 3.4-1
Express a pressure of 2.00 x 105 Pa in terms of mm Hg.

7 2.00x105 N
Ph = = m2
!%& *
Example 3.4-1
What is the pressure 30.0 m below the surface of a lake?
Atmospheric pressure (the pressure at the surface) is 10.4 m
H2O, and the density of water is 1000.0 kg/m . Assume that g is
9.807 m/s2 .

Ph =
3.4b Atmospheric Pressure, Absolute
Pressure, and Gauge Pressure
A typical value of the atmospheric pressure at sea level, 760.0
mm Hg, has been designated as a standard pressure of 1
atmosphere.
The fluid pressures referred to so far are all absolute pressures,
in that a pressure of zero corresponds to a perfect vacuum.
Many pressure-measuring devices give the gauge pressure of a
fluid, or the pressure relative to atmospheric pressure. A gauge
pressure of zero indicates that the absolute pressure of the fluid
is equal to atmospheric pressure. The relationship for converting
between absolute and gauge pressure is
• This result gives rise to two ways of expressing
fluid pressure:
as force per unit area (e.g., P 14.7 lbf/in2.) or
as an equivalent pressure head,
Ph = P/rg (e.g., Ph = 760 mm Hg)
the height of a column of the specified fluid with
zero pressure at the top that would exert the
specified pressure at the bottom.
• The earth’s atmosphere ca be considered a
column of fluid with zero pressure at the top.
The fluid pressure at the base of this column is
atmospheric pressure or barometric pressure,
Patm.
• The absolute pressure of a fluid is the
pressure relative to a perfect vacuum (P = 0).
• The gauge pressure is the pressure relative to
atmospheric pressure: Pgauge = Pabs - Patm.
3.4c Fluid Pressure Measurement
The most common mechanical device used for pressure
measurement is a Bourdon gauge, which is a hollow tube closed
at one end and bent into a C configuration. The open end of the
tube is exposed to the fluid whose pressure is to be measured.
As the pressure increases, the tube tends to straighten, causing a
pointer attached to the tube to rotate. The position of the
pointer on a calibrated dial gives the gauge pressure of the fluid.

Bourdon gauges are used to

measure fluid pressures from nearly
perfect vacuums to about 7000 atm.
More accurate measurements of
pressures below about 3 atm are
provided by manometers.
A manometer is a U-shaped tube partially filled with a fluid of
known density (the manometer fluid). When the ends of the
tube are exposed to different pressures, the field level drops in
the high-pressure arm and rises in the low-pressure arm. The
difference between the pressures can be calculated from the
measured difference between the liquid levels in each arm.
General Manometer equation
P1 + r1gd1 = P2 + r2gd2 + rfgh
Differential Manometer equation
P1 - P2 = (rf -r)gh
Manometer formula for gases
P1 - P2 = gh
Example 3.4-3
1. A differential manometer is used to measure the drop in
pressure between two points in a process line containing water.
The specific gravity of the manometer fluid is 1.05. The
measured levels in each arm are shown below. Calculate the
pressure drop between points 1 and 2 in 2 dynes/cm .
2. The pressure of gas being pulled though a line by a vacuum
pump is measured with an open- end mercury manometer. A
reading of -2 in. is obtained. What is the gas gauge pressure in
inches of mercury? What is the absolute pressure if Patm =30 in. Hg?
3.5 Temperature
The temperature of a substance in a particular state of
aggregation (solid, liquid, or gas) is a measure of the
average kinetic energy possessed by the substance
molecules. Since this energy cannot be measured directly,
the temperature must be determined indirectly by
measuring some physical property of the substance whose
value depends on temperature in a known manner. Such
properties and the temperature measuring devices based
on them include electrical resistance of a conductor
(resistance thermometer), voltage at the junction of two
dissimilar metals (thermocouple), spectra of emitted
radiation (pyrometer), and volume of a fixed mass of fluid
(thermometer).
Temperature scales can be defined in terms of any of these
properties, or in terms of physical phenomena, such as freezing
and boiling, that take place at fixed temperatures and pres- sures.
You might refer, for example, to “the temperature at which the
resistivity of a copper wire is 1.92 x 10-6 ohms/cm3” or to “the
temperature two-thirds of the way from the boiling point of water
at 1 atm to the melting point of NaCl.”
The two most common temperature scales are defined using the
freezing point (Tf) and boiling point (Tb) of water at a pressure of 1
atm.
Celsius (or centigrade) scale: Tf is assigned a value of 00C, and Tb is
assigned a value of 1000C. Absolute zero (theoretically the lowest
temperature attainable in nature) on this scale falls at -273.150C.
Fahrenheit scale: Tf is assigned a value of 320F, and Tb is assigned a
value of 2120F. Absolute zero falls at -459.670F.
The Kelvin and Rankine scales are defined such that absolute zero
has a value of 0 and the size of a degree is the same as a Celsius
degree (Kelvin scale) or a Fahrenheit degree (Rankine scale).
Temperature scales are obtained by assigning numerical values
to two experimentally reproducible temperatures. The four
most common temperature scales are Celcius (°C), Fahrenheit
(°F), and the absolute temperature scales Kelvin (K) and
Rankine (°R).
T(K) = T(°C) + 273.15
T(°R) = T(°F) + 459.67
T(°R) = 1.8 T(K)
T(°F) = 1.8 T(°C) + 32
Temperatures should not be confused with temperature
intervals.
For example, a temperature of 10°C is equivalent to a
temperature of 50°F, but a temperature interval of 10°C is
equivalent to a temperature interval of 18°F.
For example,
to find the number of Celcius degrees between 32 °F and 212 °F

∆𝑇 (°C) =
Example 3.5-1
Derive Equation T (°F) = 1.8T (°C) + 32
for T(°F) in terms of T(°C). Use T1=0°C (32°F) and T2=100°C (212°F).
Example 3.5.2
Consider the interval from 20 °F to 80 °F.
1. Calculate the equivalent temperatures in °C and the interval
between them.
2. Calculate directly the interval in °C between the temperatures.
Example 3.5-3
The heat capacity of ammonia, defined as the amount of heat
required to raise the temperature of a unit mass of ammonia by
precisely 1° at a constant pressure, is, over a limited
temperature range, given by the expression

Determine the expression for Cp in J/(g.oC) in terms of T (oC).