CHAPTER TWO: PROCESSES AND PROCESS

VARIABLES
A PROCESS is any operation or series of operations by which a particular
objective
Here, we is accomplished.
address those operations that cause a physical or chemical change in a
substance or mixture of substances.
The material that enters a process is referred to as the INPUT or FEED, and that
which leaves is the OUTPUT or PRODUCT.
It is common for processes to consist of multiple steps, each of which is carried out
in a PROCESS UNIT, and each process unit has associated with it a set of input and
output PROCESS STREAMS.
As an applied chemist, you are likely to be called upon to DESIGN or
OPERATE a process.
DESIGN includes formulation of a process flowchart (layout) as well as specification
of individual process units (such as reactors, equipment to separate mixtures into
their constituents, heat exchangers, pumps, and compressors) and associated
process variables that specify the conditions at which the units are to be operated.
OPERATION involves the day-to-day performance of an existing process. The
process is expected to produce a product at a specified rate with specified
characteristics, and the chemist’s tasks may involve controlling the individual units
so that these objectives are met. SS01
In addition to carrying out those two activities, you may be called upon to perform
process ANALYSIS, with objectives that may vary from one process to another.
For example, a task might be to identify ways to reduce costs associated with raw
materials and energy consumption.
The methodology could involve controlled tests on the actual process or a scaled-
down version of it, or it may require developing a mathematical model to predict
process outcomes at different operating conditions.
Examination of an operating process should be ongoing, but there is a special need
when the process is functioning poorly and TROUBLESHOOTING is required to
identify the cause of the problem.
Sometimes an increase in market demand requires an increase in production rate,
and the required increase exceeds the capacity of the existing equipment.
Identifying and modifying a step in the process that is limiting the production rate
in order to obtain greater throughput is referred to as DEBOTTLENECKING.
When demand for the product falls, adjusting the process through TURNDOWN
becomes important.

SS02
The links among all of the activities and functions described in the preceding
discussion are the process streams connecting process units and forming the
process flowchart. Performance of the functions requires knowledge of the amounts,
compositions, and conditions of the process streams and materials within the
process units. You must be able to measure or calculate such information for existing
units or specify and calculate it for units being designed.
MASS AND
VOLUME
The DENSITY of a substance is the mass per unit volume of the substance (kg/m 3 or
g/cm3). 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 variation with temperature may be in either
direction: the density of liquid water, for example, increases from 0.999868 g/cm 3 at
0°C to 1.00000 g/cm3 at 3.98°C, and then decreases to 0.95838 g/cm3 at 100°C.
The specific gravity of a substance is the ratio of the density ρ of the substance to
the density ρref of a reference substance at a specific condition:
SG = ρ/ρref (1)

SS03
FLOW
RATE
MASS AND VOLUMETRIC FLOW
RATEprocesses involve the movement of material from one point to another,
Most
sometimes between process units, sometimes between a production facility and a
transportation depot. 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 (gas or liquid) flows in the cylindrical pipe, shown below, where the
shaded area represents a section perpendicular to the direction of flow.

SS04
If the mass flow rate of the fluid is (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 (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, ρ:
(2)
Thus, the density of a fluid can be used to convert a known volumetric flow rate of a
process stream to the mass flow rate of that stream or vice versa.
The mass flow rates of process streams must be known for many process
calculations, but it is frequently more convenient to measure volumetric flow rates.
A common procedure is therefore to measure and calculate from and the density
of the stream fluid.

SS05
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. Two commonly used flowmeters, the
ROTAMETER and the ORIFICE METER are shown schematically in Figure 1.

Figure 1 Flowmeters: (a) rotameter and (b)

orifice meter.
The rotameter is a tapered vertical tube containing a float; the larger the flow rate,
the higher the float rises in the tube.
The orifice meter measures the pressure drop across an orifice (a small opening) in
a thin plate restricting the flow in a conduit. Fluid flows through the orifice, and the
pressure decreases from the upstream side of the orifice to the downstream side.
SS06
The pressure difference, which varies with flow rate, may be measured with a
number of devices, including a differential manometer, which is discussed in the
next section. The greater the flow rate, the larger the pressure drop.

CHEMICAL
COMPOSITION
MOLES AND MOLECULAR
WEIGHT
The ATOMIC WEIGHT of an element is the mass of an atom on a scale that assigns
C (the isotope of carbon whose nucleus contains six protons and six neutrons) a
12

mass of exactly 12.

The MOLECULAR WEIGHT of a compound is the sum of the atomic weights of the
atoms that constitute a molecule of the 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.
Carbon monoxide (CO), for example, has a molecular weight of 28; 1 mol of CO
therefore contains 28 g.
If the molecular weight of a substance is M, then there are M kg/kmol or M g/mol
mole of this substance.
SS07
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

One gram-mole of any species contains approximately 6.02 × 1023 (Avogadro’s

number) molecules of that species.
EXAMPL
E
How many mol are contained in 100.0 g of CO2 (M = 44.01)? Hence number
of molecules
SOLUTIO
N

SS08
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

MASS AND MOLE FRACTIONS AND AVERAGE

MOLECULAR WEIGHT
Process streams occasionally contain one substance, but more often they consist
of mixtures of liquids or gases, or solutions of one or more solutes in a liquid
solvent.
The following terms may be used to define the composition of a mixture of
substances that includes a species A.
(3)

(4)

SS09
EXAMPL
E
A solution contains 15% A by mass (xA = 0.15) and 20 mole
% B (yB = 0.20).
(a) Calculate the mass of A in 175 kg of
the solution.
SOLUTIO
N

(b) Calculate the molar flow rate of B in a stream flowing at a rate of

1000 mol/min.
SOLUTIO
N

(c) Calculate the total solution flow rate that corresponds to a molar flow
rate of 28 kmol B/s.
SOLUTIO
N

SS01
EXAMPL
E
A mixture of gases has the following composition by mass:
O2, 16% (xO2 = 0.16 g O2/g total); CO, 4.0%; CO2, 17% and
N2, 63%
What is the molar composition?
SOLUTIO
N
Assume 100 g of the mixture. A convenient way to perform the calculations is to
set them up in tabular form.

SS01
CONCENTRATIO
N
The MASS CONCENTRATION of a component of a mixture or solution is the mass of
this component per unit volume of the mixture (g/cm3).
The MOLAR CONCENTRATION of a component is the number of moles of the
component per unit volume of the mixture (kmol/m3).
The MOLARITY of a solution is the value of the molar concentration of the solute
expressed in gram moles solute/litre solution (e.g., a 2-molar solution of A contains
2 mol A/litre 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

SS01
and if a stream of this solution flows at a rate of 2 L/min, the molar
flow rate of NaOH is

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
ppmi = yi × 106 (5)
(6)
ppbi = yi ×10 9

SS01
 A FEW PARTS PER BILLION MAY SEEM LIKE AN INSIGNIFICANT AMOUNT, BUT FOR
SOME CHEMICALS IT’S A LOT. FOR EXAMPLE, CHEMICALS CALLED AFLATOXINS ARE
POTENT CARCINOGENS WITH ACUTE TOXICOLOGICAL EFFECTS IN HUMANS. THEY
ARE OFTEN FOUND IN GRAINS AND PEANUT BUTTER, AND THE FDA RESTRICTS
THEIR PRESENCE IN MILK TO LESS THAN 0.5 PPB AND IN GRAIN FED TO DAIRY
CATTLE TO LESS THAN 20 PPB.

SS01
PRESSUR
E
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/m 2, dynes/cm2 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,
as in Figure 2. 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.

Figure 2 Fluid pressure in a tank and

a pipe. SS01
We introduce an additional definition of fluid pressure to explain the concept of
atmospheric pressure and to discuss common methods for measuring pressures of
fluids in tanks and pipes.
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 ρ(kg/m3)., and that a
pressure P0(N/m2) is exerted on the upper surface of the column (See Figure 3).

Figure 3 Pressure at the base of a

fluid column.

SS01
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. It is not difficult to show that:
P = P0 + ρgh (7)
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.
The equivalence between a pressure P (force/area) and the corresponding head Ph
(height of a fluid) is given by the equation, with P0 = 0.

(8)

SS01
EXAMPL
E
Express a pressure of 2.00 × 105 Pa in terms
of mm Hg.
SOLUTIO
N
Solve Equation 8 for Ph(mm Hg), assuming that g = 9.807 m/s2 and noting that the
density of mercury is 13.6 × 1000 kg/m3=13 600 kg/m3.

SS01
TEMPERATU
RE
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 molecules of
the substance. Since this energy cannot be measured directly, the temperature
must be determined indirectly by measuring some physical property of the
substance whoseand
Such properties value
thedepends on temperature indevices
temperature-measuring a known manner.
based on them include
electrical resistance of a conductor (RESISTANCE THERMOMETER), voltage at the
junction of two dissimilar metals (THERMOCOUPLE), spectrum of emitted radiation
(PYROMETER), and volume of a fixed mass of fluid (THERMOMETER).
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 0°C, and Tb is
assigned a value of 100°C. ABSOLUTE ZERO (theoretically the lowest temperature
attainable in nature) on this scale falls at 273.15°C.
FAHRENHEIT SCALE: Tf is assigned a value of 32°F, and Tb is assigned a value of
212°F. Absolute zero falls at -459.67°F.

SS01
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).
The following relationships may be used to convert a temperature expressed in one
defined scale unit to its equivalent in another:
T(K) = T(°C) + (9)
273.15 (10
T(°R) = T(°F) + )(11
459.67 )(12
T(°R) = 1.8T(K) )
EXAMPL T(°F) = 1.8T(°C) +
E 32 of T(°C). Use T1 = 0°C
Derive Equation 12 for T(°F) in terms (32°F) and T2
= 100°C (212°F).
SOLUTIO
N

SS02