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Lecture 2

Processes and Process Variables

● 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

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

• 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

60F

SG

60F

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 20C 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)

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/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

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

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. 6.021023 molecules

of that species.

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 3.4 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

115

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

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

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

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. .

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 25C. 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)

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 13.61000 kg/m3 = 13,600 kg/m3.

P = Po + gh

Ph

i.e.

force

P fluid gPh (head of fluid )

area

127

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,

129

3.4b Atmospheric Pressure, Absolute

The abbreviation “psia” and “psig” mean absolute pressure

pressure, gauge pressure.

and gauge pressure in lbf/in2, respectively

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

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

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

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

134 135

136 137

General Manometer Eqn.

P1 1 gd 1 P2 2 gd 2 f gh

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

142 143

144 145

Temperature equivalent Example 3.16 Temperature Conversion

(a)

(b)

(c)

or

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.

(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?

(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),

(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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