Chapter 3

PROCESS VARIABLES
 PROCESS VARIABLES

1. Liquid and Solid Densities

Density is the ratio of mass per unit volume, for example, kg / m3, g / cm3, lbm/ft3. It
has both numerical values and units. To determine the density of a substance, you
must find both its mass and its volume. If the substance is solid, the common method
to determine its volume is to displace a measured quantity of inert liquid. For
example, a known weight of a material can be placed into a container of liquid of
known weight and volume, and the final weight and volume of the combination be
measured. The density (or specific gravity) of a liquid is commonly measured with a
hydrometer which consists of a body of known weight and volume which is dropped
into a liquid and the depth to which it penetrates into the liquid is noted.

Specific gravity is a dimensionless ratio of two densities - that of substance (A) of

interest to that of a reference substance.

 lbm   g   
 3
 ft  A  cm3  A  kg m3  A
Specific gravity = = = (1)
 lbm   g   kg 
 3  cm3  ref  m3  ref
 ft  ref

The reference substance of liquids and solids is normally water.

Gas densities are quite difficult to measure; one device used is the Edwards Balance
which compares the weight of a bulb filled with air to the same bulb filled with the
unknown gas. The specific gravity of a gas is frequently referred to air but may be
referred to other gases.

In petroleum industry the specific gravity of petroleum products is usually reported in

terms of hydrometer called °API, defined as,

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o 141. 5
API = − 1315
. (2)
60o
SpGr o
60
or

60o 141. 5
SpGr o = o (3)
60 API + 1315
.

The density of liquids and solids does not change very much with pressure. For
common substances data is reported in literature. When a liquid or solid is heated, it
normally expands (i.e. its density decreases). In most process applications, however, it
can usually be assumed with little error that solid and liquid densities are independent
of temperature, provided that no phase change occur. Similarly changes in pressure
don not cause significant changes in the liquid or solid densities; these substances are
therefore termed incompressible.

2. Flow Rate

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.

m (kg fluid /sec)

v (m3 fluid /sec)

Figure1. Flow of a fluid in a pipe

If the mass flow rate of the fluid is ‘m’ (kg/sec), then every second m kilograms of
fluid pass through the cross section. If the volumetric flow rate of the fluid at the
given cross-section is ‘v’ (m3 /sec), then every second, v cubic meters of fluid pass

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through the cross-section. However, the mass flow rate m and volumetric flow rate v
are not independent quantities but are related through density.

3. Chemical Composition

3.1. Moles and Molecular Weight

The atomic weight of an element is the mass of an atom on a scale that assigns 12C (the
isotope of carbon whose nucleus contains six protons and six neutrons) a mass of
exactly 12. The molecular weight of a compound is the sum of atomic weights of the
atoms that constitute a molecule of the compound.

A gram-mole( gmole or mole in SI units system) 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-mole or kmol, lb-mole, ton-mole etc.) are similarly defined. Carbon
monoxide (CO), for example, has a molecular weight of 28. One mole of CO therefore
contains 28 grams; 1 lb-mole contains 28 lbs.; 1 ton-mol contains 28 tons).

The molecular weight of a substance, M, can be expressed as M kg/kmol, M g/gmol.,

M lbs/lb-mol etc. The molecular weight may thus be used as a conversion factor that
relates mass and number of moles of the quantity of the substance. Therefore,
34 kg ammonia (NH3) are equivalent to:

 1 kmol NH3 
34 kg NH3   = 2 kmol NH3 (4)
 17 kg NH3 

3.2. Mass and Mole Fractions

Process streams occasionally contain one substance but more often consist of mixture
of liquids or gases or solutions of one or more solutes in liquid solvent. Following

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terms may be used to define the composition of a mixture of substances including a
species A.

Mass Fraction

mass of A  kg of A g of A lbm of A
xA =  , or  (5)
Total mass  total kg total g total lbm 

Mole Fraction

moles of A  kmol of A mol of A lb − mol of A 

yA =  , or  (6)
Total moles  total kmol total mol total lb − moles 

For example, if a solution contains 15% A by mass (xA = 0.15) and 20% B (xB =
0.20), calculation of the mass of A in 175 kg of solution:

 015
. kg A 
175 kg solution   = 26 kg A (7)
 kg of sol .

similarly, the mass flow rate of A in a stream of solution flowing at the rate of 53 lbm/
hr is given as,

lbm  015
. lbm A lb A
Flow rate of A = 53   = 8.0 m (8)
hr  lbm  hr

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3.3. Conversion from a Composition by Mass to Molar Composition

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

O2 = 16%, CO = 4%, CO2 = 17% N2 = 63%

Define the molar composition.

Solution:
Basis: 100 g of the mixture
 016
. g O2   1 mol O2 
nO2 = 100 g total    = 0.5 mol
 g total   32 g O2 
Similarly,

 1
nCO = 100 ( 0.04)  = 0143
. mol
 28

 1
nCO2 = 100 (017
. )  = 0.386 mol
 44 

 1
nN 2 = 100 (0.63)  = 2.25 mol
 28 
nT = nO2 + nCO + nCO2 + nN 2 = 3.279 mol
Therefore,
nO2 0.5 mol O2
yO2 = = = 015
.
nT 3.279 total mol
nCO 0143
. mol CO
yCO = = = 0.044
nT 3.279 total mol
nCO2 0.386 mol CO2
yCO2 = = = 012
.
nT 3.279 total mol
nN 2 2.25 mol N2
yN2 = = = 0.69
nT 3.279 total mol
Σ yi = 015
. + 0.044 + 012
. + 0.69 = 1.0

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3.4. Average Molecular Weight

The average molecular weight or mean molecular weight of a mixture, M (kg/kmol)

is the ratio of the mass of sample of the mixture (mtotal) to the moles (ntotal) of all the
species in the mixture, i.e.
mtotal
M = = y1 M1 + y2 M 2 + y3 M 4 + LLL (9)
ntotal
or
N
M = ∑ yi Mi
i =1 (10)
where N = total number of components
Also,
1 x x x N x
= 1 + 2 + 3 + LLL + ∑ i (11)
M M1 M 2 M 3 i =1 M i

3.5. 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/cm3, kg/m3, lbm/ft3). The concentration
can also be expressed as molar concentration which is the number of moles of the
component per unit volume of the mixture (gmol/cm3, kmol/m3, lbmol/ft3). The
molarity of the solution is the value of the molar concentration of the solute expressed
in gram moles of solute per liter of solution. The density of a mixture of liquids can be
estimated by assuming that component volumes are additive: e.g. if 2 ml of liquid A
and 3 ml of liquid B are mixed, the resulting volume would be assumed to be 5 ml.
This leads to a simple averaging formula for the mixture density (ρ);

1 x1 x2
= + (12)
ρ ρ1 ρ2

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where ρ1 and ρ2 are the densities of component A and B respectively while x1 and x2
are their mass fractions respectively.

4. Pressure
Pressure is the ratio of a force to the area on which it acts. Therefore, the pressure
units are force units divided by area units (N / m2, dynes / cm2, or lbf / ft2). The SI unit
of pressure is N / m2 and is known as Pascal.

In most investigations we are concerned with absolute pressure. Most pressure

measuring devices read the difference between absolute pressure and atmospheric
pressure existing at the gauge and this is referred to as gauge pressure. This is shown
graphically in the figure below:

Pressure above
Atmospheric Pressure
Ordinary Pressure
gauge reading

Ordinary vacuum gauge reads

difference between atmospheric
and absolute pressure
Atmospheric
Pressure

Absolute pressure that

is less than atmospheric
pressure
Zero
Pressure

Figure 2. Illustration of terms used in pressure measurement

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From the principles of hydrostatics, it is possible that pressure may be expressed as
head of a particular fluid - i.e. as a height of a hypothetical column of this fluid that
will exert the given pressure at its base if pressure at the top were zero. You can thus
speak of a pressure of 14.7 lbf /in2 as equivalent of 33.9 ft of water (33.9 ft of H2O) or
76 cm of mercury (76 cm Hg)

∆P = ρ g ∆h (13)
where,
ρ = density of fluid
g = acceleration due to gravity
∆h = head of the fluid.
If ∆P = 2.0 ×105 Pa, the corresponding head of mercury can be calculated using the
above equation:

N  m3   kg   103 mm
∆h = 2.0 × 105 2
   . × 103 mm
 = 15
m  13600 kg   9.807 N   m 

5. Temperature

The temperature is a measure of the degree of hotness or coldness of the body. There
are two commonly used scales for measuring temperature, namely the Fahrenheit and
Celsius scales. The Celsius scale was formerly called the Centigrade scale.

Until 1954 each of these scales was based on two fixed and easily duplicated points,
the ice point and the steam point. The temperature of the ice point is defined as the
temperature of a mixture of ice and water which is in equilibrium with saturated air at
the pressure of 1 atm. The temperature of the steam point is the temperature of water
and steam which are in equilibrium at the pressure of 1 atm. On the Fahrenheit scale,

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these two points are assigned the number 32 and 212 respectively. On the Celsius
scale the respective points are numbered 0 and 100. Letters °F and °C denote the
Fahrenheit and Celsius scales respectively.

In 1954 the Celsius scale was redefined in terms of a single fixed point and the
magnitude of the degree. The triple point of water (the state where the solid, liquid
and vapor phases of water exist together in equilibrium) assigned the value 0.01°C.
On the scale the steam point is experimentally found to be 100.0°C. Thus there is
essential agreement between the old and new temperature scales.

The absolute scale of temperature related to Celsius scale is referred to as the Kelvin
scale designated as K.

K = o C +27315
. (14)

The absolute scale related to the Fahrenheit scale is referred to as the Rankine scale
designated as R. The relation between the two scales is

R = o F +459.67 (15)

The following relationships may be used to convert a temperature expressed in one

defined scale unit to its equivalent in another:

T ( K ) = T ( o C ) + 27315
. (16)

T ( R ) = T ( o F ) + 459.67 (17)

. T (K)
T ( R ) = 18 (18)

( )
T o F = 18
. T ( C) + 32
o
(19)