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Main contents

Lecture 2
Processes and Process Variables

● Mass and volume ● Pressure


● Flow rate ● Temperature
94 ● Chemical composition 95

Objectives
3.1 Mass and Volume
• Understand the mass, volume and molar flow rates Density: mass per unit volume of the substance
• Given the composition of the mixture expressed in terms of mass and Densities of pure liquids and solids are independent of pressure
mole fractions and vary relatively slightly with temperature
• Determine the average molecular weight of the mixture mass m
  density = 
• Explain the difference between absolute pressure and gauge pressure volume V
• Convert a pressure expressed as a head of a fluid to the equivalent
The reference most commonly used for solids and liquids is water at 4.0 oC.
pressure
• Convert among temperatures expressed in various scales H O l  4 o C   1. 000 g / cm 3
2

=1000. kg/m3
=62.43 lbm/ft3
total mass of solids
 B  bulk density = For bed of particles
with void spaces
total empty bed volume
96 97
3.1 Mass and Volume
Specific volume: the volume occupied by a unit
mass of the substance; it is the inverse of density
^ volume V
V  specific volume = 
mass m

Specific gravity: the ratio of the density of the


substance to the density of a reference substance
SG   / ref
•The notation 20 o
SG  0 . 6
4o
total mass of solids
 B  bulk density = For bed of particles
with void spaces
total empty bed volume means the specific gravity of a substance at 20 oC with ref.to water at 4oC is 0.699
98

Special density units


• SG of selected liquids and solids are given in Table B1
(Felder and Rousseau, 2005) such as degrees Baumé (Bé)
Acetone SG = 0.791
Water SG = 1.00 For liquids denser than water: SG = 145/(145 - Baumé)
For liquids less dense than water: SG = 140/(Baumé + 130)
• Coefficients of linear and cubic thermal expansion of selected
liqs and solids are given as empirical polynomial functions of degrees API (API)
temp. in Perry’s, such as 141.5
API   131.5
60F
SG
60F

degrees Twaddell (Tw)


where V(T) is the volume of a mass of mercury at T (C)
V0 is the volume of the same mass of mercury at 0 C Tw  200 SG  1

100 101
Example 3.1 Mass, Volume, and Density Example 3.3 Application of Specific Gravity to Calculate Mass and Moles
In the production of a drug having a molecular weight of 192, the exit stream from the
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. reactor flows at a rate of 10.5 L/min, The drug concentration is 41.2% (in water), and the
specific gravity of the solution is 1.024. Calculate the concentration of the drug (in kg/L)
SOLUTION
in the exit stream, and the flow rate of the drug in kg mol/min.
The specific gravity of mercury at 20C as 13.546. Therefore, SOLUTION Basis: 1.000 kg solution

102
Felder and Rousseau, 2005 (example 3.1-1) Himmelblau and Riggs, 2004 (example103
2.5)

3.2 Flow rate


To get the flow rate, take a different basis, namely 1 minute

Basis: 1 min = 10.5 L solution 3.2a Mass, Volumetric and Molar Flow Rate
•Flow rate: the rate at which a material is transported through a
Convert the volume to mass and then to moles using the information previously process line.
calculated.

Mass flow rate Volumetric flow rate Molar flow rate


  
(mass/time; m) (volume/time, V ) (Mole/time; n )


n (moles fluid/s)

104 105
Rotameter: a tapered vertical tube containing a float
•The density of a fluid can be used to convert a known
volumetric flow rate of a process stream to the mass flow rate The lager the flow rate, the higher the float rises in the tube
of that stream or vice versa
m m
 
V V

3.2b Flow Rate Measurement


Mass flow controllers & Monitors (Kofloc®)
Flowmeter: a device mounted in a process line
 MFC specification
that provides a continuous reading of the flow
 Flow range 0-100 l/min
rate in the line  Signal 0-5 Vdc
Rotameter  Local operator interface (LOI)

Orifice meter
106 107

Orifice meter: an obstruction in the flow channel with a narrow


opening thru which the fluid passes

-the fluid pressure drops from the upstream side of the orifice to
the downstream side
-the pressure drop varies with the flow rate
i.e. the greater the flow rate, the larger the pressure drop
 Cooling tower and Pump specification
• Capacity 104 L/min
(Load designed 3 times for operating condition)
• Motor 1/6 hp (Single phase)
• SS316 Pump 750 watt, Head 25 m, Flow 50 L/min
• Temperature decreasing 35 to 30 0C
• Measuring flow by Arkon® band
• Adjusting valve by Belimo® control valve

108 109
3.3 Chemical Composition 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 MW.
- Mixtures of various compositions are commonly found in
chemical process system Other types of moles are similarly defined eg. kg-moles, lb-
moles, ton-moles
- The physical properties of a mixture depend on the mixture
composition 1 g-mole of any species contains approx. 6.021023 molecules
of that species.

3.3a Moles and Molecular weight Example:


1 mole of CO contains 28 g.
1 lb-mole of CO contains 28 lbm.
Atomic weight? Molecular weight? 1 ton-mole of CO contains 28 tons.

110 111

Example 3.5 Conversion Between Mass and Moles


Example 3.4 convert the mass flow rate to molar flow rate How many of each of the following are contained in 100.0 g of CO2 (MW = 44.01)?
(1) mol CO2; (2) lb moles CO2 ; (3) mol C; (4) mol O2;
SOLUTION
1.

2.
100 kg CO2 1 kmol CO2 kmol CO2 Each molecule of CO2 contains one atom of C, one molecule of O2, or two atoms
= 2.27 of O. Therefore, each 6.02 x 1023 molecules of CO2 (1mol) contains 1mol C, 1mol O2,
h 44.0 kg CO2 or 2mol O. Thus,
h
3.

4.

5.
112 Felder and Rousseau, 2005 (example 3.3-1)
113
Example 3.6 Conversion from a Composition by Mass to a Molar Composition

3.3b Mass and Mole Fractions and Average MW. A mixture of gases has the following composition by mass:
O2 16%
CO 4.0%
CO2 17 %
Mass fraction: xA = mass of A ( kg A ; g A ; lbm A ) N2 63 %
total mass kg total g total lbm total What is the molar composition?
SOLUTION Basis: 100 g of the mixture
A convenient way to perform the calculations is to set them up in tabular form
moles of A ( kmol A ; mol A ; lbm moles A ) Component Mass Fraction Mass (g) Molecular Moles Mole Fraction
Mole fraction: yA =
total moles kmol total mol total lbm moles total i xi (gi/g) mi = ximtotal Weight ni = mi/Mi yi= ni / ntotal
Mi(g/mol)
O2 0.16 16 32 0.500 0.150
The percent by mass of A is 100xA CO 0.04 4 28 0.143 0.044
CO2 0.17 17 44 0.386 0.120
The mole percent of A is 100yA N2 0.63 63 28 2.250 0.690
Total 1.00 100 3.279 1.000

114 Felder and Rousseau, 2005 (example 3.3-3)


115

Example 3.7 Nitrogen Requirements Used for the Growth of Cells


In normal living cells, the nitrogen requirement for the cells is provided from
protein metabolism (i.e., consumption of the protein in the cells), When individual
cells are commercially grown, (NH4)2SO4is usually used as the source of nitrogen. Average molecular weight, MW
Determine the amount of (NH4 ) 2 SO4 consumed in a fermentation medium in
which the final cell concentration is 35 g/L in a 500 L volume of the fermentation MW=y1MW1 +y2 MW2 +...=  yi MWi
medium. Assume that the cells contain 9 wt. % N, and that (NH 4)2SO4is the only allcomponent

1 x x xi
SOLUTION Basis: 500 L solution containing 35 g/L
= 1 + 2 +...= 
MW MW1 MW2 allcomponent MWi

yi is the mole fraction of the i th component of the


mixture
xi is the mass fraction of the i th component of the
mixture
MWi is the molecular weight of the i th component
Himmelblau and Riggs, 2004 (example116
2.7) 117
=
Example 3.8 Calculation of an Average Molecular Weight
Calculate the average molecular weight of air (1) from its approximate molar 3.3c Concentration
composition of 79% N2, 21% O2 and (2) from its approximate composition by mass
•The mass concentration of a component of a mixture or
of 76.7% N2, 23.3% O2. solution is the mass of this component per unit volume of
the mixture
SOLUTION

1. •The molar concentration of a component


is the number of moles of the component per unit volume
of the mixture
=
= •The molarity of a solution is the value of the molar
concentration of the solute expressed in g-moles solute /
2.
liter solution

Felder and Rousseau, 2005 (example 3.3-4)


118 119

Example 3.9 Conversion Between Mass, Molar, and Volumetric Flow Rates of a Solution
3. The mass fraction of H2 SO4 equals the ratio of the mass flow rate of H 2 SO4 —which we
know to the total mass flow rate, which can be calculated from the total volumetric flow
A 0.50 molar aqueous solution of sulfuric acid flows into a process unit at a rate of 1.25
rate and the solution density.
m3 /min. The specific gravity of the solution is 1.03. Calculate (1) the mass concentration of
H2SO4in kg/m3,(2) the mass flow rate of H2SO4 in kg/s, and (3) the mass fraction of H2SO4.

SOLUTION

1.

2. .

Felder and Rousseau, 2005 (example 3.3-5)


120 121
Example 3.10 Calculation of Mole Fraction and ppm from a Concentration in g/L
3.3d Parts per million (ppm) and Parts per billion (ppb)
A solution of HNO3 in water has a specific gravity of 1.10 at 25C. The concentration of
how many parts(grams, moles) of the species are the HNO3 is 15 g/L of solution. What is the
present per million or billion parts (grams, moles) of the a. Mole fraction of HNO3 in the solution?
b. ppm of HNO3 in the solution?
mixture.
SOLUTION Basis: 1 L of solution
ppmi = y i  106
ppbi = yi  109 Basis: 100 g solution
a. The mass of water in the solution is: 100 - 0.0134 = 99.986 g H2O.
where yi is the fraction of component i
g MW g mol mol fraction
Parts per million by volume and Parts per billion by volume HNO3 0.01364 63.02 2.164 x 10-4 3.90 x 10-5
ppmvi = v i  106 H2O 99.986 18.016 5.550 1.00
Total 5.550 1.00
ppbvi = vi  109
b.
where vi is the volume fraction of component i 122 Himmelblau and Riggs, 2004 (example123
2.9)

Fluid pressure The fluid pressure may be


3.4 Pressure defined as the ratio F/A, where
A(m2) F is the minimum force that
3.4a Fluid Pressure and Hydrostatic Head
would have to be exerted on a
F(N) frictionless plug in the hole to
A pressure is the ratio of a force to the area on which the force acts keep the fluid from emerging.
P(N/m2)
Pressure units are force units divided by area units e.g.
Hydrostatic pressure
N/m2 (= Pa, pascal), lbf/in2 (= psi) Hydrostatic pressure, P is the
force F exerted on the base
divided by the base area A.
•F =force on the top surface +
the wt of the fluid in the
column.

P=Po+gh
124 125
Example 3.11 Calculation of a Pressure as a Head of Fluid
•Pressure may be expressed as a head of a particular fluid—
that is, as the height of a hypothetical column of this fluid that Express a pressure of 2.00 ×105 Pa in terms of mm Hg.
would exert the given pressure at its base if the pressure at the
top were zero. SOLUTION Solve for Ph(mm Hg), assuming that g = 9.807 m/s2 and noting that
=0 the density of mercury is 13.61000 kg/m3 = 13,600 kg/m3.

P = Po + gh
Ph
i.e.

 force 
P   fluid gPh (head of fluid )
 area 

126 Felder and Rousseau, 2005 (example 3.4-1)


127

Example 3.12 Pressure Below the Surface of a Fluid


The relationship between the pressure at the base of a column of fluid of height h and
the pressure at the top is particularly simple if these pressures are expressed as heads What is the pressure 30.0 m below the surface of a lake? Atmospheric pressure (the pressure
of the given fluid: if the column is mercury, for example, then At the surface) is 10.4 m H2O, and the density of water is 1000.0 kg/m3. Assume that g is 9.807
m/s2.
SOLUTION First, the hard way,

Any other length unit and chemical species may be substituted for mm Hg in this equation.

The conversion table on the inside front cover of this book lists values of a pressure
expressed in several common force/area units and as heads of mercury and water.
The use of this table for pressure unit conversion is illustrated by the conversion
of 20.0 psi to cm Hg:
Next, the easy way,

Ph = 10.4 m H2O + 30.0 m H2O = 40.4 m H2O

(Verify that the two calculated pressures are equivalent)

128 Felder and Rousseau, 2005 (example 3.4-2)


129
3.4b Atmospheric Pressure, Absolute
 The abbreviation “psia” and “psig” mean absolute pressure
pressure, gauge pressure.
and gauge pressure in lbf/in2, respectively

 It is common to refer to negative gauge pressures (absolute


Pabsolute = Pgauge + Patm pressures less than atmospheric) as positive amounts of
vacuum:
 The fluid pressures referred to so far are all absolute Ex. a gauge pressure of –1 cm Hg (75.0 cm Hg absolute if
pressures. atmospheric pressure is 76.0 cm Hg) may also be called 1 cm of
 Pabsolute = 0 means a perfect vacuum. vacuum.
 Many pressure measuring devices give the gauge pressure
of a fluid, or the pressure rel.to atmospheric pressure.

130 131

Example 3.13 Pressure Conversion


The pressure gauge on a tank of CO2 used to fill soda-water bottles reads 51.0 psi. At the same
time the barometer reads 28.0 in. Hg. What is the absolute pressure in the tank in psia

SOLUTION
The calculation is

Atmospheric pressure

The absolute pressure in the tank is

51.0 psig + 13.76 psia = 64.8 psia

Himmelblau and Riggs, 2004 (example 5.2)


132 133
Example 3.14 Vacuum Pressure Reading
Small animals such as mice can live (although not comfortably) at reduced air pressures
3.4c Fluid Pressure Measurement
down to 20 kPa absolute. In a test, a mercury manometer attached to a tank, reads 64.5 cm Hg
and the barometer reads 100 kPa. Will the mice survive?
Pressure measurement devices are categorised as

1. Elastic-element methods—Bourdon tubes, bellows or


diaphragms
2. Liquid-column methods– barometer, manometers
SOLUTION 3. Electrical methods—strain gauges, piezoresistive
transducers, and piezoelectirc transducers.
The absolute pressure in the tank is

The mice probably will not survive

Himmelblau and Riggs, 2004 (example 5.3)


134 135

136 137
General Manometer Eqn.

P1  1 gd 1  P2  2 gd 2  f gh

• In a differential manometer, fluid 1 and 2, are


the same, then 1  2  

P1  1 gd 1  P2  2 gd 2  f gh
P1  gd 1  P2  gd 2  f gh
P1  P2   gd 1  gd 2  f gh
P1  P2   gh  f gh

P1  P2  f   gh
138 139

• If either fluid 1 or 2 is a gas at a moderate pressure, the density of Example 3.15 Pressure Measurement with Manometers
this fluid is 100 to 1000 times lower than the density of the 1. A differential manometer is used to measure the drop in pressure between two points
manometer fluid, so that the corresponding gd term in Eqn 3.4-5 In a process line containing water. The specific gravity of the manometer fluid is 1.05.
may be neglected. The measured levels in each arm are shown below. Calculate the pressure drop between
points 1 and 2 in dynes/cm2.
P1  1 gd 1  P2  2 gd 2  f gh
•If both fluids are gases

P1  P2  f gh 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
•If both P1 and P2 are expressed in inches of mercury? What is the absolute pressure if Patm= 30 in. Hg?
as heads of the manometer fluid

P1  P2  h
If P2 is atmospheric pressure, then the gauge pressure at point 1
Felder and Rousseau, 2005 (example 141
3.4-3)
is simply the difference in the levels of the manometer fluid. 140
SOLUTION
3.5 Temperature
1. h = (382 - 374) mm = 8 mm
Temperature is a measure of the average kinetic energy possessed
by the substance molecules

 Based on a relative scale

degree Fahrenheit (F) and degree Celsius (C)

2. From the definition of a gauge pressure,  Based on an absolute scale

degree Rankine (R) and Kelvin (K)

142 143

Temperature measurement devices are categorised as

1. Electrical resistance of a conductor—resistance thermometer

2. Voltage at the junction of two dissimilar metals–thermocouple

3. Spectra of emitted radiation–pyrometer

4. Volume of a fixed mass of fluid–thermometer

144 145
Temperature equivalent Example 3.16 Temperature Conversion

Convert 100°C to (a) K, (b) °F, and (c) °R

• Temperature difference • Temperature conversion SOLUTION

(a)

(b)

(c)

or

146 Himmelblau and Riggs, 2004 (example147


4.1)

Problems
Example 3.17 Temperature Conversion 3.1 The specific gravity of gasoline is approximately 0.70.
(a) Determine the mass (kg) of 50.0 liters of gasoline.
The heat capacity of sulfuric acid has the units J/(g mol)(°C), and is given by the relation (b) The mass flow rate of gasoline exiting a refinery tank is 1150 kg/min. Estimate the
volumetric Row rate in liters/s.
Heat capacity = 139.1 + 1.56 × 10-1 T (c) Estimate the average mass flow rate (lbm/min) delivered by a gasoline pump.
(d) Gasoline and kerosene (specific gravity = 0.82) are blended to obtain a mixture with a
where T is expressed in °C. Modify the formula so that the resulting expression has the specific gravity of 0.78. Calculate the volumetric ratio (volume of gasoline/volume of
associated units of Btu/(lb mol) (°R) and T is in °R. kerosene) of the two compounds in the mixture, assuming Vblend= Vgasoline + Vkerosene.
3.2 Liquid benzene and liquid n-hexane are blended to form a stream flowing at a rate of 700
SOLUTION lbm/h. An on-line densitometer (an instrument used to determine density) indicates that the
stream has a density of 0.850 g/mL. Using specific gravities from Table B.1, estimate the mass
and volumetric feed rates of the two hydrocarbons to the mixing vessel (in American
engineering units). State at least two assumptions required to obtain the estimate from the
recommended data.
3.3 Limestone (calcium carbonate) particles are stored in 50-L bags. The void fraction of the
particulate matter is 0.30 (liter of void space per liter of total volume) and the specific gravity
of solid calcium carbonate is 2.93.
(a) Estimate the bulk density of the bag contents (kg CaCO3/Iiter of total volume).
(b) Estimate the weight (W) of the filled bags. State what you are neglecting in your estimate,
(c) The contents of three bags are fed to a ball mill, a device something like a rotating clothes
dryer containing steel balls. The tumbling action of the balls crushes the limestone
particles and turns them into a powder. The limestone coming out of the mill is put back
into 50-L bags. Would the limestone (i) just fill three bags, (ii) fall short of filling three
Himmelblau and Riggs, 2004 (example148
4.2) bags, or (iii) fill more than three bags? Briefly explain your answer. 149
3.4 Aqueous solutions of the amino acid L-isoleucine (Ile) are prepared by putting 100.0 grams of 3.6 A as stream contains 18.0 mole% hexane and the remainder nitrogen, The stream flows to
pure water into each of six flasks and adding different precisely weighed quantities of lie to each denser while its temperature is reduced and some of the hexane is liquefied. The hexane mole
flask The densities of the solutions at 50.0±0.05 oC are then measured with a precision densitometer fraction m the gas stream leaving the condenser is 0.0500. Liquid hexane condensate is recovered at
with the following results: a rate of 1.50 L/min.

r (g Ile/100 g H2O) 0.0000 0.8821 1.7683 2.6412 3.4093 4.2064


 (g solution/cm3 ) 0.98803 0.98984 0.99148 0.99297 0.99439 0.99580

(a) Plot a calibration curve showing the mass ratio, r. as a function of solution density, , and fit a
straight line to the data to obtain an equation of the form r = a + b.
(b) The volumetric flow rate of an aqueous lie solution at a temperature of 50°C is 150 L/h. The (a) What is the Row rate of the gas stream leaving the condenser in mol/min? (Hint: First calculate
density of a sample of the stream is measured at 50° C and found to be 0.9940 g/cm3. Use the the molar flow rate of the condensate and note that the rates at which C6H14 and N2 enter the unit
calibration equation to estimate the mass flow rate of lie in the stream (kg Ile/h). must equal the total rates at which they leave in the two exit streams.)
(c) It has just been discovered that the thermocouple used to measure the stream temperature was (b) What percentage of the hexane entering the condenser is recovered as a liquid ?
poorly calibrated and the temperature was actually 47°C Would the lie mass flow rate calculated
in part (b) be too high or too low? State any assumption you make and briefly explain your 3.7 Three different liquids are used in the manometer shown here.
reasoning.

3.5 A mixture is 10.0 mole% ethyl alcohol, 75.0 mole% ethyl acetate (C4H8O2), and 15.0 mole%
acetic acid. Calculate the mass fractions of each compound. What is the average molecular weight of
the mixture? What would be the mass (kg) of a sample containing 25.0 kmol of ethyl acetate?

(a) Derive an expression for P1 – P2 in terms of A, B, h1 and h2.


(b) Suppose fluid A is methanol, B is water, and C is a manometer fluid with a specific gravity of
1.37; pressure P2 = 121.0 kPa; h1 = 30.0 cm; and h2 = 24.0 cm. Calculate P1 (kPa).
150 151

3.8 A fluid of unknown density is used in two manometers—one sealed-end, the other across an
orifice in a water pipeline, The readings shown here are obtained on a day when barometric pressure 3.10 As will be discussed in detail in Chapter 5, the ideal gas equation of state relates absolute
is 756 mm Hg. pressure, P (atm); gas volume, V (liters); number of moles of gas, n(mol); and absolute temperature,
What is the pressure drop (mm Hg) from point (a) to point (6)? T(K):

PV = 0.08206nT

(a) Convert the equation to one relating P (psig), V(ft3), n(Lb-mole), and T(°F)
(b) A 30.0 mole% CO and 70.0 mole% N2 gas mixture is stored in a cylinder with a volume of 3.5
3.9 A temperature scale that never quite caught on was formulated by the Austrian chemist Johann ft3 at a temperature of 85°F, The reading on a Bourdon gauge attached to the cylinder is 500 psi.
Sebastian Farblunget. The reference points on this scale were 0°FB, the temperature below which Calculate the total amount of gas (lb-mole) and the mass of CO (lbm) in the tank.
Farblunget's postnasal drip began to bother him, and 1000°FB, the boiling point of beer. Conversions (c) Approximately to what temperature (°F) would the cylinder have to be heated to increase the gas
between OC and °FB can be accomplished with the expression pressure to 3000 psig, the rated safety limit of the cylinder? (The estimate would only be
T(OC) = 0.0940T(°FB) + 4.00 approximate because the ideal gas equation of state would not be accurate at pressures this high.)

Louis Louis. Farblunget's French nephew, attempted to follow in his uncle's footsteps by
formulating his own temperature scale. He defined the degree Louie using as reference conditions
the optimum serving temperature of marinated snails (100°L corresponding to 15°C) and the
temperature at which the elastic in his briefs began to relax (1000°L corresponding to 43°C),

(a) At what temperature in °F does beer boil?


(b) What is the temperature interval of 10.0 Farblunget degrees equivalent to in °C, K, °F, and °R?
(c) Derive equations for r(°C) in terms of 7(°L) (see Example 3.5-1) and r(°L) in terms of T(°FB).
(d) What is the boiling point of ethane at 1 atm (Table B.1) in °F, K, °R, °FB, and °L?
(e) What is a temperature interval of 50.0 Louie degrees equivalent to in Celsius degrees, Kelvin
degrees, Fahrenheit degrees, Rankine degrees, and Farblunget degrees? 152 153

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