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You are on page 1of 64

4/12/04

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Pocket

Handbook

Page 1

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12/5/05

2:17 PM

Page p1

The AIChE

Pocket Handbook

3 Park Ave. 19th Floor

New York, New York 10016

13282AICEtext

11/30/05

10:03 AM

Page 2

AIChE and its Student Chapters Committee.

American Institute of Chemical Engineers

ISBN 0-8169-0342-5

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Page p3

TABLE OF CONTENTS

Organic Chemistry.........................................................

Physical Chemistry ........................................................

Fluid Flow.......................................................................

Heat Transfer..................................................................

Distillation ......................................................................

Mass Transfer .................................................................

Thermodynamics ...........................................................

Kinetics and Reactor Design ........................................

Conversion Factors .......................................................

Physical Constants ........................................................

Greek Alphabet ..............................................................

Mathematics ...................................................................

Chemical Process Safety ..............................................

Biochemical Engineering..............................................

1

6

10

14

18

23

26

29

34

40

44

48

48

51

53

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Page p5

Foreword

The purpose of this handbook is to make readily available in a limited number of pages some of the more important chemical, biological, physical, safety, and mathematical data and concepts that are fundamental to the

practice of the chemical engineering profession.

With these principles you should be able to solve many

chemical engineering problems.

Good Luck!

Chuck Coronella, Galen Suppes, and Joseph F. Louvar for

their work on this Handbook.

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Page 1

INORGANIC CHEMISTRY

I. COMMON DEFINITIONS

of an atom.

Avogadros numberthe number of molecules

(6.023 1023) in one gram-mole of a substance.

Equilibrium constants for the reaction aA bB

cC dD

where reaction is in solution,

Kc

[C ]c[D]d

[A]a[B]b

([ ] refers to molarity)

Kp

p cC p dD

p aA p bB

( p partial pressure)

A. (nonredox reaction) the mass in grams of a

substance equivalent to 1 gram-atom of hydrogen,

0.5 gram-atom of oxygen, or 1 gram-ion of the

hydroxyl ion. It can be determined by dividing

the molecular weight by the number of hydrogen

atoms or hydroxyl ions (or their equivalent)

supplied or required by the molecule in a given

reaction.

B. (redox reaction) the molecular weight in grams

divided by the change in oxidation state.

Ion product of water (Kw)the product of the

hydrogen ion and hydroxyl ion concentrations in

gram-ions per liter;

Kw [H][OH]

1

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of neutrons in the nucleus of an atom.

Molality (m)(gram moles of solute)/(kilograms of

solvent).

Molarity (M)(gram moles of solute)/(liters of

solution).

Normality (N)(gram equivalents of solute)/(liters of

solution).

Oxidationthe loss of electrons by an atom or group

of atoms.

pHthe negative logarithm ( base 10) of the hydrogen

ion concentration in gram ions per liter;

pH log10[H]

Reductionthe gain of electrons by an atom or group

of atoms.

Solubility product (S.P. or Ksp)for the slightly soluble

solid, Aa Bb , dissolving

Aa Bb (solid) aA (aq) bB(aq)

where A is any cation and B is any

anion

S.P. or Ksp [A]a[B]b a constant at a given

temperature

II.

Name

Actinium

Aluminum

Americium

Antimony

Symbol

Atomic

Number

Atomic

Weight

Common

Valence

Ac

Al

Am

Sb

89

13

95

51

(227)

26.9815

(243)

121.75

3

3

6,5,4,3

3,5

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Name

Symbol

Atomic

Number

Atomic

Weight

Common

Valence

Ar

As

At

Ba

Bk

Be

Bi

B

Br

Cd

Ca

Cf

C

Ce

Cs

Cl

Cr

Co

Cu

Cm

Dy

Es

Er

Eu

Fm

F

Fr

Gd

Ga

Ge

Au

Hf

He

Ho

18

33

85

56

97

4

83

5

35

48

20

98

6

58

55

17

24

27

29

96

66

99

68

63

100

9

87

64

31

32

79

72

2

67

39.948

74.9216

(210)

137.34

(247)

9.0122

208.980

10.811

79.904

112.40

40.08

(249)

12.01115

140.12

132.905

35.453

51.996

58.9332

63.546

(247)

162.50

(254)

167.26

151.96

(253)

18.9984

(223)

157.25

69.72

72.59

196.967

178.49

4.0026

164.930

0

3,5

1,3,5,7

2

4,3

2

3,5

3

1,5

2

2

3

4,2

3,4

1

1,3,5,7

6,2,3

2,3

2,1

3

3

3

3,2

1

1

3

3

4

3,1

4

0

3

Argon

Arsenic

Astatine

Barium

Berkelium

Beryllium

Bismuth

Boron

Bromine

Cadmium

Calcium

Californium

Carbon

Cerium

Cesium

Chlorine

Chromium

Cobalt

Copper

Curium

Dysprosium

Einsteinium

Erbium

Europium

Fermium

Fluorine

Francium

Gadolinium

Gallium

Germanium

Gold

Hafnium

Helium

Holmium

12:20 PM

Page 3

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Name

Symbol

Atomic

Number

Atomic

Weight

Common

Valence

Hydrogen

Indium

Iodine

Iridium

Iron

Krypton

Lanthanum

Lawrencium

Lead

Lithium

Lutetium

Magnesium

Manganese

Mendelevium

Mercury

Molybdenum

Neodymium

Neon

Neptunium

Nickel

Niobium

Nitrogen

Nobelium

Osmium

Oxygen

Palladium

Phosphorus

Platinum

Plutonium

Polonium

Potassium

Praseodymium

Promethium

H

In

I

Ir

Fe

Kr

La

Lw

Pb

Li

Lu

Mg

Mn

Md

Hg

Mo

Nd

Ne

Np

Ni

Nb

N

No

Os

O

Pd

P

Pt

Pu

Po

K

Pr

Pm

1

49

53

77

26

36

57

103

82

3

71

12

25

101

80

42

60

10

93

28

41

7

102

76

8

46

15

78

94

84

19

59

61

1.00797

114.82

126.9044

192.2

55.847

83.80

138.91

(257)

207.19

6.939

174.97

24.312

54.9380

(256)

200.59

95.94

144.24

20.183

(237)

58.71

92.906

14.0067

(254)

190.2

15.9994

106.4

30.9738

195.09

(242)

(210)

39.102

140.907

(147)

1

3

1,5,7

2,3,4,6

2,3

0

3

4,2

1

3

2

7,6,4,2,3

2,1

6,5,4,3,2

3

0

6,5,4,3

2,3

5,3

3,5,4,2

2,3,4,6,8

2

2,4

3,5,4

2,4

6,5,4,3

2,4

1

3,4

3

Page 4

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Name

Symbol

Atomic

Number

Protactinium

Radium

Radon

Rhenium

Pa

Ra

Rn

Re

91

88

86

75

Rhodium

Rubidium

Ruthenium

Samarium

Scandium

Selenium

Silicon

Silver

Sodium

Strontium

Sulfur

Tantalum

Technetium

Tellurium

Terbium

Thallium

Thorium

Thulium

Tin

Titanium

Tungsten

Uranium

Vanadium

Xenon

Ytterbium

Yttrium

Zinc

Zirconium

Rh

Rb

Ru

Sm

Sc

Se

Si

Ag

Na

Sr

S

Ta

Tc

Te

Tb

Tl

Th

Tm

Sn

Ti

W

U

V

Xe

Yb

Y

Zn

Zr

45

37

44

62

21

34

14

47

11

38

16

73

43

52

65

81

90

69

50

22

74

92

23

54

70

39

30

40

Page 5

Atomic

Weight

(231)

(226)

(222)

186.2

102.905

85.47

101.07

150.35

44.956

78.96

28.086

107.870

22.9898

87.62

32.064

180.948

(98)

127.60

158.924

204.37

232.038

168.934

118.69

47.90

183.85

238.03

50.942

131.30

173.04

88.905

65.37

91.22

Common

Valence

5,4

2

7,6,4,

2,1

2,3,4

1

2,3,4,6,8

3,2

3

2,4,5

4

1

1

2

2,4,6

5

7

2,4,6

3,4

3,1

4

3,2

4,2

4,3

6,5,4,3,2

6,5,4,3

5,4,3,2

0

3,2

3

2

4

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Page 6

Name

Arsenite

Arsenate

Acetate

Bicarbonate

Bisulfate

Bromate

Bromide

Carbonate

Chlorate

Chloride

Chromate

Cyanamide

Cyanide

Dichromate

Dithionate

Ferricyanide

Ferrocyanide

Formate

Symbol

AsO3

AsO4

C2H3O2

HCO3

HSO4

BrO3

Br

CO3

ClO3

Cl

CrO4

CN2

CN

Cr2O7

S2O6

Fe(CN)6

Fe(CN)6

CHO2

Name

Symbol

Hydroxide

Hypochlorite

Iodide

Iodate

Molybdate

Nitrate

Nitrite

Oxalate

Perchlorate

Peroxide

Permanganate

Phosphate

Sulfate

Sulde

Sulte

Thiocyanate

Thiosulfate

OH

OCl

I

IO3

MoO4

NO3

NO2

C2O4

ClO4

O2

MnO4

PO4

SO4

S

SO3

CNS

S2O3

ORGANIC CHEMISTRY

used:

R H atom or saturated hydrocarbon group

R hydrocarbon group only

X halogen

n an integer

I. GENERAL CLASSES OF COMPOUNDS

6

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Type or Name

Page 7

General Formula

1. Alkane or parafn

(also saturated

hydrocarbons)

2. Alkene or olen

(unsaturated

hydrocarbons)

3. Alkyne

4. Alcohol

5. Ether

6. Aldehyde

7. Ketone

8. Carboxylic Acid

9. Grignard reagent

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Type or Name

Page 8

General Formula

11. Anhydride

12. Ester

13. Amide

15. Nitrile

B. Cyclic Compounds

1. Cycloparafn

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Type or Name

Page 9

General Formula

2. Cycloalkene

3. Aromatic

4. Naphthalenic

II.

PERTINENT NOTES

of acids to acids to olens: the negative group of

the acid adds to the carbon atom having the fewest

hydrogen atoms.

9

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B. Mechanisms

1. Free radical (unshared electron)

(no charge)

2. Carbonium ion (decient in electrons)

( positive charge)

(carbon with six electrons)

3. Carbanion

(excess of electrons)

(negative charge)

(carbon with eight electrons)

PHYSICAL CHEMISTRY

of a mixture of gases is equal to the sum of the partial volumes of each component gas. The partial

volume of a component gas is the volume which

that component would occupy at the same temperature and pressure.

2. Boiling Point Elevation (Tb)The following equations hold for a dilute solution of a nonionic nonvolatile solute.

Tb Kbm

Kb

where

R(Tbp)2Ma

Hv(1000)

Kb molal boiling point elevation

stant

m molality

Ma solvent molecular weight

10

con-

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R ideal-gas constant

Tbp solvent boiling point, absolute temperature

3. Clausius Equation

Hm

dp

dT

(V v) T

where

p pressure

T absolute temperature

Hm molal heat of vaporization

V molar vapor volume

v molal liquid volume

of liquid can be ignored (or v 0) and where the

ideal-gas law holds (or V RTp) the Clausius

equation becomes

d( ln p)

dT

Hm

1 dp

p dT

RT 2

ln

p2

p1

Hm T2 T1

c

d

R

T1T2

above.

5. Daltons Law of Partial PressuresThe pressure of a mixture of gases is equal to the sum of

the partial pressures of each component gas.

The partial pressure of a component gas is the

pressure which that component would exert if

it alone occupied the volume at the same temperature.

11

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6. Faradays Laws

First Law: The mass of a substance reacting

at the electrodes is directly proportional to the

quantity of electricity passed through the solution.

Second Law: The masses of different substances produced during electrolysis are directly

proportional to their equivalent weights; 96,496

coulombs of electricity 1 faraday electricity to

yield 1 gram equivalent of any substance.

7. Freezing Point Depression (Tf)The following equations hold for a dilute solution of a

nonionic solute in which the solid phase is pure

solvent.

Tf Kf m

Kf

R (Tf p)2Ma

Hf (1000)

Kf molal freezing point lowering constant

m molality

Ma solvent molecular weight

R ideal-gas constant

Tf p solvent freezing point, absolute temperature

8. Gibbs Phase RuleAt equilibrium the number

of independent variables (F ) required to specify the system is equal to the number of components (C ) minus the number of phases (P) plus

two, or symbolically F C P 2. This form

12

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9. Grahams Law of DiffusionThe rate of diffusion

of a gas is inversely proportional to the square root

of its density.

10. Henrys LawAt a constant temperature, the concentration of a gas dissolved in a liquid is directly

proportional to the partial pressure of the gas above

the liquid.

11. Raoults Law

pa xa Pa

where

vapor

xa mole fraction of A in liquid solution

Pa vapor pressure of pure liquid A

d ( ln K )

dT

H

RT 2

at constant pressure

H heat of reaction

K reaction equilibrium constant

R ideal-gas constant

T absolute temperature

If H is constant,

where

ln a

K2

K1

b

H T2 T1

c

d

R

T1T2

Y

ya

1 ya

13

pa

P pa

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Y Y

Ma

Mb

vapor to partial pressure of vapor at saturation

(vapor pressure)

Hr 100

pa

Pa

(ratio of molar humidity to saturated molar

humidity)

Hp 100

where

pa (P Pa)

Y

100

Ysat

Pa (P pa)

gas

Pa vapor pressure of pure liquid A

P total pressure

Ma molecular weight of A

Mb molecular weight of B

ya mole fraction of a gas

FLUID FLOW

I.

Mass velocity

G V

14

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Page 15

Pa Pb Rm

g

gc

( a b)

Pa Pb

32 L V

gc D 2

Average velocity, V

V

s, cross-sectional area

NRe

DV

DV

Pa

a

g

gc

Za

V 2a

2gc a

Ws

Pb

b

g

gc

Zb

V 2b

2gc b

0.5 for laminar ow (NRe 2,100)

Hydraulic radius

rH

s, cross-sectional area

Lp, the wetted perimeter

Equivalent diameter, De

De 4 (hydraulic radius, rH)

15

Hf

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II.

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Page 16

FRICTION

Skin friction

Hfs

2 f LV 2

Dgc

laminar

turbulent

f

1

f. .5

16

DV

16

NRe

get total equivalent length.)

Equivalent

resistance,

pipe diameters

45-degree elbows

90-degree elbows (standard radius)

90-degree square elbows

180-degree close return bends

Ts (used as elbow, entering run)

Ts (used as elbow, entering branch)

Couplings

Unions

Gate valves (open)

Globe valves (open)

Angle valves (open)

15

32

60

75

60

90

Negligible

Negligible

7

300

170

Hfe

V 2a

2 gc

a1

16

sa

sb

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Page 17

Hfc

KcV 2b

2 gc

Engineers Handbook, 7th ed., Don W. Green, ed.,

McGraw-Hill Book Co., New York, NY, 1997.

III.

Venturi meter

2V sb V 2a Cv

of meter)

Vo

2gc ( pa pb)

0.61

21 4 B

V Cp

2gc ( ps P)

B

Cu , Cp coefcients of velocity

D diameter

g acceleration of gravity 32.2 ft /s 2 9.81 m/s2

gc Newtons conversion factor 32.2 ft-lbm /(lbf -s2)

1 m-kg/(N-s 2 )

Hf head loss due to friction

Hfs head loss due to skin friction

Hfc head loss due to contraction of cross section

17

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Ke expansion loss coefcient

Kc contraction loss coefcient

L length of pipe

P pressure

Pa upstream pressure

Pb downstream pressure

pa, pb pressure in arms of manometer

ps static pressure

Rm manometer reading

s cross-sectional area

V velocity

V average velocity

Va upstream velocity

Vb downstream velocity

Ws shaft work done by pump

Z elevation

kinetic energy correction factor

ratio of diameter of orice to diameter of

pipe

uid density, lbm /ft 3

a density of manometer uid

b density of uid above manometer

kinematic viscosity

viscosity

HEAT TRANSFER

I.

CONDUCTION

steady state

q

kAT

T

x

R

18

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unsteady state

T

k

2T

x 2

t

Cp x

Resistance in Series

T

xC

xB

kA A kB A kC A

T

RA RB RC

q

xA

q

where

II.

(ro ri )

k AmT

r

ow

rm logarithmic mean radius

rm (ro ri)ln [ro ri]

CONVECTION

q hAT

where

k thermal conductivity of the uid

x thickness of the laminar lm

q UAavg (T )

where

T overall temperature difference

19

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Ar

1

U

UAr

hi

Ar

xm

Am

km

Ar

1

Ao

ho

Ar

Page 20

1

Ai

hFi

Ar

1

Ao

hFo

Ar

of the solid through which heat is

being conducted

hFi , hFo inside and outside fouling factors

where

IV.

1

Ai

12:20 PM

RADIATION

q12 AF (T 41 T 42)

q12 net radiation between surfaces 1 and

2, Btu/hr

T1, T2 absolute temperature of surfaces 1,

2, R.

A area of either surface, sq ft

Stefan-Boltzman Constant 1.712

109 Btu/hr-sq ft-R 4

F geometric view factor

where

hiD

k

0.023(NRe)0.8(NPr)0.33(w)0.14[1 (DL)0.7]

NRe the Reynolds Number DG

NPr the Prandtl Number Cp k

where

hiD

k

1.86(NRe)0.33(NPr)0.33( w)0.14(DL)0.33

20

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for turbulence

NORMAL TO A SINGLE TUBE

ho Do

kf

0.35 0.56(NRe)0.52

The subscript f calls attention to the fact that the

correlation is based on the mean lm temperature,

Tf , which is dened as the arithmetic mean of the

average uid temperature and the wall temperature.

PERPENDICULAR TO TUBE BANKS

havg Do

kf

Vertical Tubes

havg 1.13 c

k 3f 2f g

To L f

0.25

Horizontal Tubes

havg 0.725 c

k 3f 2f g

To Do f

21

0.25

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Page 22

NOTATION

b empirical constant

Cp specic heat at constant pressure, Btu/lb-F

D diameter, ft

G mass velocity, lbm /sq ft-sec

Gmax mass velocity through minimum cross section in

tube bundle

g acceleration of gravity, 32.2 ft/sec2

h heat transfer coefcient, Btu/sq ft-hr-F

k thermal conductivity, Btu/sq ft-(F/ft)-hr

L length of tube or cylinder, ft

q heat ow per unit of time, Btu/hr

R resistance

r radius, ft

T temperature, F

t time, hr

U over-all heat transfer coefcient, Btu/sq fthrF

x distance in direction of heat ow; thickness of

layer, ft

latent heat of condensation or vaporization,

Btu/lbm

viscosity,lbm /ft-sec

density, lbm /ft 3

Subscripts

avg average

f lm

i inside

o outside

r reference

22

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w wall

m mean or log mean

DISTILLATION

I.

FzF yV xL

FVL

II.

(over-all material balance)

ln

W

Wo

xo

dx

yx

[1 ( 1)x] can be substituted to give

ln

x(1 xo)

1 xo

W

1

ln c

d ln c

d

Wo

( 1)

xo(1 x)

1x

(yx)a

(yx)b

pa

pb

III. CONTINUOUS DISTILLATION (BINARY SYSTEM)

WHERE CONSTANT MOLAL OVERFLOW IS ASSUMED

FDB

FzF DxD BxB

23

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Page 24

Operating Lines

1. Rectifying Section

Total material: Vn1 Ln D

Component A: Vn1 yn1 Ln xn DxD

yn1

Ln

Ln D

xn

DxD

Ln D

2. Stripping Section

Total material: Lm Vm1 B

Component A: Lm1 xm Vm1 ym1 BxB

ym1

Lm

Lm B

xm

BxB

Lm B

3. Reux Ratio

Ratio of reux to overhead product

RD

L

VD

D

D

Type of Feed

Superheated vapor

Saturated vapor

Liquid and vapor

Saturated liquid

Cold liquid

(downward to left)

0 (horizontal)

(upward to left)

(vertical)

(upward to right)

EME

yn yn1

y*n yn1

24

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where

IV.

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Page 25

n

yn1 concentration of vapor entering from

plate below n

y*n concentration of vapor in equilibrium

with liquid leaving plate n

NOTATION

relative volatility

B moles of bottoms product

D moles of overhead product

F moles of feed

L molar liquid downow

RD ratio of reux to overhead product

V molar vapor upow

W weight in still pot

x mole fraction of the more volatile component in

the liquid phase

y mole fraction of the more volatile component in

the vapor phase

zD mole fraction of the more volatile component in

the feed

Subscripts

B bottoms product

D overhead product

F feed

m any plate in stripping section of column

m 1 plate below plate m

n any plate in stripping section of column

n 1 plate below plate n

o original charge in still pot

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MASS TRANSFER

I.

DIFFUSION

1. Molecular Diffusion

NA

A

pA NA

NB

D pA

c

d

P A

A

RT z

Stagnant Gas B (NB 0)

NA

A

( pA2 pA1)

DP

RT ( pB)lm

x2 x1

3. Equimolar Countercurrent Diffusion (NB NA)

(gases)

NA

A

( pA2 pA1)

D

RT

z2 z1

pA

t

II.

D

2pA

z 2

CONVECTION

1. Two-Film Theory

NA

A

kG ( pAG pA) kL (CA CAL)

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2. Overall Coefcients

1

1

H

KG

kG

kL

1

1

1

KL

HkG

kL

3. Transfer Unit

HTUheight of a transfer unit

HTG

G

KG a

HTL

L

KL a

NTG

y2

x2

y1

NTL

x1

dy

y* y

1 y2

1

ln

2

1 y1

1 x1

dx

1

ln

x x*

2

1 x2

NTG

y1 y2

(y y*)lm

4. Dimensionless Group Equation (Sherwood)

(NSh) 0.023 (NRe)0.8(NSc)13

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0.5 f jH jD

where f Fanning friction factor

jH

jM

IV.

h Cp 0.667 w 0.14

c

c

d

d

CpG k

kc

G

(NSc)0.667

NOTATION

a interfacial area per unit volume

C concentration in liquid phase

d tube diameter

D molecular diffusivity

G gas mass velocity, mass/(time)(area)

H Henrys Law constant, pi HCi

h heat transfer coefcient

k lm coefcient of mass transfer

K overall coefcient of mass transfer

L liquid mass velocity, mass/(time)(area)

N moles of a substance per unit time

p partial pressure

P total pressure

R gas constant

NRe Reynolds number du

NSc Schmidt number D

NSh Sherwood number kdD

t time

T absolute temperature

u velocity

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Greek Letters

density

viscosity

Subscripts

A, B components of mixture

G gas phase

L liquid phase

i interface

x mole fraction of liquid

y mole fraction of gas

z length in direction of travel

* equilibrium concentration

THERMODYNAMICS

I.

DEFINITIONS

under consideration.

A. Closed systemone in which matter does not pass

through its boundaries.

B. Open systemone in which matter ows across its

boundaries.

C. Isolated systemone in which there is no interchange

of energy or matter with the surroundings.

Boundariesthe envelope separating the system from

the surroundings.

Universea system and its surroundings.

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of the system: e.g., U, internal energy; Ek , kinetic energy; Ep, potential energy; Hence,

E U Ep Ek

II.

FIRST LAW

In an isolated system E E2 E1 0

In a closed system E Q W

In an open system E g(H Ep Ek) Q W

where the summed terms refer to leaving () and entering () streams

In a steady state open system

Esystem 0

Hence for the entering and leaving streams

H Ek Ep Q W

III.

SECOND LAW

always increases

Ssystem Ssurroundings 0

IV. THERMODYNAMIC FUNCTIONS: DEFINITIONS

AND RELATIONSHIPS

Denition of entropy

S

dQrev

T

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dU dQrev PdV TdS PdV

Also

dH dU d(PV)

TdS VdP

dA dU d(TS) SdT PdV

Cp (HT )p; Cv (UT )v; (CpCv)

P, V, T, S, U, H, G, A are state functions. Q and W are path

functions and have no total derivatives.

V. PERFECT-GAS RELATIONSHIPS

T2

T2

Cp dT or (HP)T 0

T1

Cv dT or (UV )T 0

T1

For diatomic gas: Cp 3.5 R and Cv 2.5 R

Adiabatic (Q 0) and reversible path for system with

Ep Ek 0.

(P2P1) (V1V2) (T2T1)(1)

Wnonflow U

RT1

1

ca

P2

P1

(1)

1 d (per mole)

Isothermal path, ow or nonow

P2

P1

31

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W RT ln

V2

V1

12:20 PM

P1

RT ln

P2

Page 32

( per mole)

For system alone: dG 0 when P, T constant

dA 0 when V, T constant

VII. CHEMICAL THERMODYNAMICS

G RT ln ( f2f1)

(constant-temperature path)

and the limit of fP as P approaches 0 1.00

a ff0

B. Equilibrium

Standard free energy at temperature T for the

reaction

aA bB rR sS

G rGR sGS aGA bGB

RT ln

a rR a sS

a aA a bB

RT ln Ka

C. Cells

At standard conditions

G nF RT ln Ka

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At actual conditions

G nF nF RT ln

VIII.

a rR a sS

a aA a bB

NOTATION

a activity

C heat capacity

E total energy of the system

Ek kinetic energy of the system

Ep potential energy of the system

reversible voltage of cell

F faradays per equivalent

f fugacity

G H TS, Gibbs free energy

gc Newtons conversion factor

H U PV, enthalpy

h enthalpy per pound

K equilibrium constant for the reaction as written

Ka equilibrium constant in terms of activity

Kf equilibrium constant in terms of fugacity

Kp equilibrium constant in terms of partial pressure

n number of equivalents for the reaction as

written

P pressure

Q heat, dened as positive when absorbed by

system

R gas constant

S entropy

T absolute temperature

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u velocity

V volume

v specic volume

W work, dened as positive when done by system

on surroundings

nal state minus initial state

(CpCv)

Superscript

standard state

I. RATE OR REACTION

volume of uid is

rA

1 dNa

V dt

rA

dCA

dt

term, or

rA k (T) f (CA, CB . . .)

A. Order, Molecularity, Elementary Reactions

Where the rate can be expressed as

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rA kC aA C bB . . .

the reaction is ath order with respect to A and

nth order overall; n a b

not necessarily equal to the stoichiometric coefcients. In the special case where a, b, . . . are the

stoichiometric coefcients, the reaction is elementary:

unimolecular (n 1), bimolecular (n 2), trimolecular

(n 3)

B. Rate Constant k and Temperature Dependency of a

Reaction

k (conc)1 n(time)1

From Arrheniuss Law the variation with temperature is

k koeERT or ln

k2

k1

1

1

c d

R T1

T2

E

II. HOMOGENEOUS, CONSTANT FLUID DENSITY,

BATCH KINETICS

For the reaction A S products, with rate

dCA

dt

kCA or

dXA

dt

k(1 XA)

ln

CA

CA0

ln (1 XA) kt

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For the reaction A B S products, with rate

dCA

kCACB

dt

ln

CB CA0

CB0 CA

ln

M XA

M(1 XA)

(CB0 CA0) kt

XA

1

1

1

kt

CA

CA0

CA0 1 XA

C. Irreversible nth-order Reaction

For the reaction with rate

dCA

dt

kC nA

C 1n

C 1n

A

A0 (n 1) kt

D. Reversible First-order Reaction

1

For the reaction A R, K k1k2 with rate

2

dCA

dt

dCR

dt

k1CA k2CR

ln

XAe XA

XAe

ln

CA CAe

CA0 CAe

36

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For the reaction with rate

rA

t CA0

XA

dCA

dt

k f (CA, CB , . . .),

dXA

(rA )

CA

CA0

dCA

k f (CA, CB , . . .)

Where density change is proportional to the fractional conversion of any reactant A (isothermal systems),

CA

CA0

1 XA

1 A XA

where

A

VXA 1 VXA 0

VXA 0

ra

1 dNA

V dt

CA0

dXA

(1 A XA) dt

k f (CA, CB , . . .)

t CA0

XA

dXA

(1 A XA)(rA)

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A. Capacity Measures

Space time: time required to process one reactor

volume of entering feed

mean residence time

VCA0

FA0

(units of time)

Reactor

In general

CA0

XA

dXA

(rA)

or

V

FA0

XA

dXA

(rA)

k (1 A) ln (1 XA) A XA

1

For reversible rst-order reactions A rR

2

(isothermal)

k1

A XA

N

N A

N2

ln (1 NXA)

where

N1

C. Design

Equation

for

k2

k2

(1 A)

Back-Mix

38

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Tank) Reactor

CA0 XA

(rA)

or

XA

V

FA0

(rA)

CA entering

CA leaving

(1 k per reactor) j

D. NOTATION

A, B, R, etc. substance A, etc.

a, b, . . . exponents on concentration term of

empirical rate expression

CA concentration of A, moles A/volume

CA0 initial concentration of A, moles A/

volume

FA0 feed rate of A or ow rate of A entering

the reactor, moles A/time

K equilibrium constant

k reaction rate constant, (conc1n)(time1)

n order of reaction

NA moles of A

rA rate of reaction of any comoponent A,

moles A formed/time-volume

T temperature

t time

V volume of uid in batch reactor, volume of uid in a ow reactor, or reactor

volume

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time

XA fraction of reactant A converted, dimensionless

Greek Symbols

A measure of density change with reaction, dimensionless

space time based on entering feed, time

Subscripts

e equilibrium value

CONVERSION FACTORS

Acceleration

1 ft/s2 0.3048 m/s2

0.6318 (mile/hr)/sec

1.097 km/hr-s

30.48 cm /s2

1 rev/min2 2.778 104 rev/s2

0.001745 rad/s2

0.01667 rev/min-s

Density

1 lbm /ft3 16.02 kg/m3

5.787 104 lbm /in3

0.01602 g/cc

Flow

1 ft3/min 4.719 104 m3/s

0.1247 gal/s

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0.4720 liter/s

472 cc/s

Length

1 ft 0.3048 m

1.894 104 mile

13 yd

12 in

30.48 cm

3.05 105 microns ()

1 1010 m

108 cm

1 104 microns ()

Angle

1 rad 12 circle

0.1592 rev

0.637 quad

57.3 deg

3,438 min

2.063 105 s

Mass

1 lbm 0.4536 kg

4.464 104 long ton

5 104 short ton

4.536 104 metric ton

0.4536 kg

453.6 g

0.0311 slug

Pressure

1 lbf /in2 abs 6.895 103 N/m2

6.895 103 Pascal

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0.06805 atm

0.07031 kg/cm2

2.036 in Hg @ 32F

2.307 ft H2O @ 39F

70.307 g/cm2

51.72 mm Hg @ 32F

51.72 torr

Power

1 ft-lb/min. 0.0226 W

2.26 105 kW

3.03 105 hp

3.24 104 kg-cal/min

0.001285 Btu/min

Temperature

F 1.8(C) 32

K C 273

R F 459

Time

1 nanosecond 1 109 s

Velocity

1 ft/s 0.3048 m/s

0.011364 mile/min

0.6818 mile/hr

1.0973 km./hr

18.29 m/min

30.48 cm/s

1 rev/min 0.1047 rad/s

6 deg/s

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Viscosity

1 centipoise 0.001 Pa-s

0.001 N-s/m2

0.01 g/cm-s

6.72 104 lbm /ft-s

2.42 lbm /ft-hr

Volume

1 ft3 0.02832 m3

0.03704 yd3

0.80357 bushel (U.S.)

7.481 gal (U.S.)

6.229 gal (British)

25.714 qt (dry, U.S.)

29.92 qt (liq., U.S.)

1.728 103 in3

28.32 liters

2.832 104 cm3

2.832 104 ml

59.8 pt (U.S. liq.)

Work and Energy

1 Btu 1054 J

2.93 104 kW-hr

3.93 104 hp-hr

0.252 kg cal

0.293 W-hr

10.41 liter-atm

252 g cal

778 ft-lb f

0.3676 ft3-atm

1.054 1010 ergs

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wA

xA MA

xA MA xB MB

xA

wAMA

wAMA wBMB

PHYSICAL CONSTANTS

Gas constants

R 0.0821 atm-liter/g-mole-K

1.987 g-cal/g-mole-K

1.987 Btu/lbm-mole-R

8.314 joules/g-mole-K

1.546 ft-lbf /lbm-mole-R

10.73 (psi)-ft 3/lbm-mole-R

0.7302 atm-ft 3/lbm-mole-R

Acceleration of gravity (standard)

g 32.17 ft/s2 980.7 cm /s2

Avogadros number

N 6.023 1023 molecules/g-mole

Boltzmanns constant

K 1.3805 1016 erg/molecule-K

Newtons conversion constant

gc 32.17 lbm-ft /lb f -s 2 1.000 kg-m/N-s 2

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Plancks constant

h 6.624 1027 erg-s

Stefan-Boltzmann constant

1.355 1012 cal/s-cm2-K4

1.712 109 Btu /hr-sq ft-R4

Velocity of light

c 186,000 miles/s 3 1010 cm /s

Velocity of sound in dry air, 0C and 1 atm

33,136 cm /s 1,089 ft /s

Heat of fusion of water at 1 atm, 0C

79.7 cal /g 144 Btu /lbm

Heat of vaporization of water at 1 atm, 100C

540 cal /g 972 Btu/lbm

Ton of refrigeration 12,000 Btu /hr

1 lbm-mole of perfect gas occupies 359 ft 3 at standard conditions (32F, 14.7 psi abs)

1 g-mole of perfect gas occupies 22.4 liters at 0C and

760 mm Hg

Thermochemistry

F 96,500 coulombs/gram equivalent

joules volts coulombs

coulombs amperes seconds

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Dimensionless Groups

Name

Fanning friction factor

Heat transfer factor

Mass transfer factor

Froude number

Graetz number

Grashof number

Nusselt number

Peclet number

Power number

Prandtl number

Reynolds number

Schmidt number

Sherwood number

Symbol

f

jH

jM

NFr

NGz

NGr

NNu

NPe

NPo

NPr

NRe

NSc

NSh

Formula

pgcd2LV 2

(hcpG)(Cpk)23

(kc G)(D)23

V 2gL

wcpkL

L32gT2

hdk

LV cpk

Pgcn3d5

cpk

LV

D

Kc LD

Notation

cp specic heat, Btu/lbm-F

D molecular diffusivity, sq ft/hr

d diameter, ft

G mass velocity, lbm /sq ft-hr

g acceleration of gravity, 32.2 ft/s2

gc conversion factor 32.2 ft-lbm /(lbf-s 2 )

1 m-kg/(N-s2)

h heat transfer coefcient, Btu/sq ft-hr-F

k thermal conductivity, Btu/sq ft-(F/ft)-hr

kc mass transfer coefcient, ft/hr

L characteristic dimension, ft

n rate of rotation, s1

P power to agitator, ft-lbf /s

p pressure drop, lbf /sq ft

T temperature, F

V uid velocity, ft /s

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coefcient of bulk expansion, F1

density, lbm /ft 3

viscosity lbm /ft-hr

Abbreviations

atm atmosphere

Btu British thermal unit

cal calorie

cm centimeter

cu cubic

ft foot, feet

g gram

hp horsepower

hr hour

in inch

kg kilogram

km kilometer

kW kilowatt

lbm pound-mass

lbf pound-force

m meter

min minute

ml milliliter

pt pint

qt quart

quad quadrant

R degrees Rankine

rad radian

rev revolution

s second

yd yard

micron

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GREEK ALPHABET

,

,

,

,

,

,

,

,

,

!,

#,

%,

,

,

,

,

,

M,

,

,

,

",

$,

&,

alpha

beta

gamma

delta

epsilon

zeta

nu

xi

omicron

pi

rho

sigma

eta

theta

iota

kappa

lambda

mu

tau

upsilon

phi

chi

psi

omega

MATHEMATICS

a b (a b)(a b)

2

a3 b3 (a b)(a2 ab b2)

a3 b3 (a b)(a2 ab b2)

a x 2 bx c 0 x

b 2b2 4ac

2a

Area of circle r 2

Circumference of circle 2r

Surface of sphere 4r 2

Volume of sphere (43) r 3

Volume of cone or pyramid 13 (base area)(height)

dax adx

dx n nx n1 dx

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d(u v) du dv

d(uv) udv vdu

dc

u

vdu udv

d

v

v2

deax aeax dx

dax ax logea dx

d sin x cos x dx

d cos x sin x dx

d tan x sec 2 x dx

(u v) dx udx vdx

udv uv vdu

x n dx x n1(n 1) for n 1

dx

loge x ln x

eax dx

eax

a

Binomial series

(x y)n x n n x n1y

n(n 1)

2!

x n2 y 2

(y 2 x 2)

Taylor series

(x a)

xa

f '(a)

1!

2!

2

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MacLaurin series

f (x) f (0) f (0)

x

x2

f '(0)

1!

2!

Exponential series

ex 1 x

x2

x3

2!

3!

log10 x 0.4343 ln x, ln x 2.303 log10 x

Arithmetic mean

ab

2

Geometric mean

2ab

Harmonic mean

2ab

ab

Logarithmic mean

ab

ln ab

Solution of

dy

dx

Py Q

Integrating factor e Pdx IF

Solution y IF (IF Q)dx C

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Contributed by Joe Louvar

I.

and management practices a) to prevent accidents in

plants, and/or b) to reduce the potential for accidents.

Process Safety ManagementAn OSHA regulation that

emphasizes the management of safety within plants.

This is an especially important and effective regulation

that has 14 elements: 1) Employee Participation,

2) Process Safety Information, 3) Operating Procedures,

4) Process Hazards Analysis, 5) Mechanical Integrity,

6) Management of Change, 7) Incident Investigation,

8) Hot Work Permits, 9) Employee Training 10) PreStartup Review, 11) Emergency Planning, 12) Contractors, 13) Audits, and 14) Trade Secretes.

Safety TechnologyDesign features and control features

to reduce the potential for accidents.

Safety Design Featuresa) Inerting to control the concentration of a ammable gas to below the LFL, b) grounding and bonding to prevent static electricity charging

and discharging (spark) and potential re, c) installing

relief valves to prevent vessel ruptures, d) installing

double block and bleeds to prevent the backup of reactive chemicals into a monomer storage tank, e) installing

an explosion suppression system to prevent dust explosions, f) installing containment systems to catch the release from relief valves, etc.

Safety Control Featuresa) Monitoring the temperature

and pressure to prevent abnormal conditions, b) adding

reactor safeguards to prevent runaway reactions,

c) adding redundant controls to decrease the frequency

of accidents, d) adding more reliable instruments to reduce the frequency of plant accidents, etc.

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above which a ammable mixture is capable of extracting enough energy from the environment to self-ignite.

Boiling Liquid Expanding Vapor Explosion (BLEVE)A

BLEVE occurs when a vessel ruptures which contains

a liquid at a temperature above its atmosphericpressure boiling point. It is the explosive vaporization

of a large fraction of the vessel contents; possibly followed by the combustion or explosion of the vaporized

cloud if it is combustible (similar to a rocket).

DeagrationAn explosion with a ame front moving in

the unburned gas at a speed below the speed of sound

(1250 ft /s).

DetonationAn explosion with a shock wave moving at

a speed greater than the speed of sound in the unreacted medium.

Flash Point (FP)The FP of a liquid is the lowest temperature at which it gives off enough vapor to form an

ignitable mixture with air.

Flammability Limits (LFL and UFL)A gas mixture will

not burn when the composition is lower than the lower

ammable limit (LFL). The mixture is also not combustible when the composition is above the upper ammability limit (UFL).

Flammability Limits of MixturesThey are computed

with the following equations:

LFLMIXTURE

1

yi

a a LFL b

i

UFLMIXTURE

1

yi

a a UFL b

i

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LFLMISTS 0.1 LFL THEORETICAL

Mechanical ExplosionAn explosion due to the sudden

failure of a vessel containing a nonreactive gas at a

high pressure.

Minimum Oxygen Concentration (MOC)A mixture of

gas will not burn if the oxygen concentration is below

the minimum oxygen concentration.

Minimum Oxygen Concentration (MOC)It is estimated

using the following equation:

MOC (LFL%) a

Moles

of

Oxygen

Moles

of

Fuel

an impacting shock wave.

Relief ValveA device that relieves the pressure within a

vessel when the pressure approaches the maximum

allowable working pressure (MAWP). All vessels have

reliefs.

RiskThis is the product of the frequency and the consequence of an accident scenario.

BIOCHEMICAL ENGINEERING

Contributed by David Murhammer

I.

AnabolismMetabolism involved with the biosynthesis

of cellular components.

AnaerobesOrganisms that grow in the absence of air or

oxygen.

Biochemical EngineeringThe extension of chemical

engineering principles to biological systems with the

goal of producing useful products.

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BioreactorA vessel used for biological processes. Examples include growing microorganisms and animal

cells for the production of useful products.

BiotechnologyThe use or development of methods of

direct genetic manipulation for a socially desirable

goal. Examples include the production of a particular

chemical, production of better plants or seeds, and

gene therapy.

CatabolismMetabolism involved with the breakdown of

materials for the production of intermediates and energy.

EnzymeA catalytic protein (and in some cases RNA)

produced by living cells.

EukaryoteA cell or organism with a membrane-bound

nucleus and well-developed organelles. Examples include yeast, animals, and plants.

ProkaryoteA cell lacking a true nucleus. Examples include bacteria and blue-green algae.

VirusA noncellular entity that consists minimally of

protein and DNA or RNA and that can replicate only after entry into specic types of living cells.

II.

small amounts have antimicrobial activity.

AntibodiesGlycoprotein molecules produced by Blymphocytes in higher organisms in response to the

introduction of a foreign material (antigen). These molecules react with antigens with great specicity.

Attachment DependentCells whose growth requires

attachment to a surface. Also referred to as AnchorageDependent.

Batch CultureA culture that once supplied with raw

materials is run to completion.

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ChemostatA bioreactor in which the continuous addition of fresh medium and removal of efuent results in

constant nutrient, product, and cell concentrations

when operated under steady state conditions.

Death PhaseThe portion of the growth curve in culture

in which there is a net decline in the number of viable

(live) cells.

Exponential (Log) Growth PhaseA period of growth in

a culture in which the number of cells or cell mass increases exponentially, i.e., the growth rate is proportional to the population density:

dX

X,

dt

where X cell number (cells /mL) or cell biomass

(mg/mL), t is time, and is the specic growth rate (h1).

Fed-Batch CultureA culture to which nutrients are periodically added during the operation of the culture.

Growth YieldYield of biomass based on substrate (e.g.,

glucose or oxygen) utilization:

YX/S

dX

,

dS

on Substrate (S) and is usually given in terms of either

(gm biomass/gm or mole substrate) or (cell number/gm

or mole substrate).

KL aVolumetric mass transfer coefcient usually measured in h1 and often used to compare the efciencies

of bioreactors in supplying oxygen. The resulting oxygen transfer rate is then given by

dCL

dt

KLa(C * CL),

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the bioreactor, t in time, and C* is the equilibrium dissolved oxygen concentration (i.e., solubility) under the

specied conditions.

Lag PhaseThe portion of the growth curve between inoculation and the beginning of cell growth.

Media SterilizationRemoval of undesired microorganisms from the media through ltration or heat to prevent their growth during the course of a bioreactor run.

Michaelis-Menton KineticsCommon type of enzyme kinetics given by

v

vmax[S]

KM [S]

where v is the reaction rate, vmax is the maximum reaction rate, KM is the Michaelis Constant and is equal to

the substrate concentration at v 12 vmax , and [S] is

the substrate concentration.

Perfusion CultureA bioreactor in which cells are

retained, medium is added continuously or semicontinuously, and spent medium containing toxic

metabolites is removed.

Population Doubling Time (PDT)The time required for

the viable cell population to double. This term is commonly used for animal cell cultures, and is related to

the specic growth rate () by

PDT

ln(2)

Power Number (Np)A dimensionless number commonly used to determine the amount of power introduced to the bioreactor as a result of agitation. The

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NP

P

N 3D 5

where P is the power input, is the density of the solution being agitated, N is the rotational speed of the impeller, and D is the impeller diameter.

Monod EquationAn equation commonly used to model

the effect of the rate-limiting substrate concentration

on the specic growth rate. This equation is given by

m[S]

Ks [S]

specic growth rate when [S ] W K s, [S ] is the substrate concentration, and Ks is the saturation constant

or half-velocity constant and is equal to the substrate

concentration when 12 m.

Stationary PhasePhase in growth curve following the

exponential growth phase in which there is no net

growth. This phase is commonly associated with nutrient depletion.

57

12/5/05

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Page 2

American Institute of

Chemical Engineers

3 Park Avenue

New York, NY

10016-5991

212.591.8100

www.aiche.org

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