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Student Pocket Handbook

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Pocket Handbook

The AIChE Pocket Handbook

Thomas R. Hanley, Editor

American Institute of Chemical Engineers 3 Park Ave. 19th Floor New York, New York 10016

The AIChE Pocket Handbook is a publication of AIChE and its Student Chapters Committee.

Reprinted, 1988, 1990, 1992, 1993, 2001, 2004, 2005

Copyright © 1985 by the American Institute of Chemical Engineers ISBN 0-8169-0342-5

TABLE OF CONTENTS

Inorganic Chemistry ...................................................... 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

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!

AIChE would like to thank Professors David Murhammer, Chuck Coronella, Galen Suppes, and Joseph F. Louvar for their work on this Handbook.

INORGANIC CHEMISTRY
I. COMMON DEFINITIONS

Atomic number—the number of protons in the nucleus of an atom. Avogadro’s number—the 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)

where reaction is in the gas phase, Kp pc pd C D pa pb A B (p partial pressure)

Gram equivalent weight— 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

Mass number—the number of protons plus the number 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). Oxidation—the loss of electrons by an atom or group of atoms. pH—the negative logarithm ( base 10) of the hydrogen ion concentration in gram ions per liter; pH log10[H ]

Reduction—the 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 temperature a constant at a given

II.

PROPERTIES OF CHEMICAL ELEMENTS

Name Actinium Aluminum Americium Antimony

Symbol Ac Al Am Sb

Atomic Number 89 13 95 51 2

Atomic Weight (227) 26.9815 (243) 121.75

Common Valence 3 3 6,5,4,3 3,5

Name 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

Symbol 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

Atomic Number 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 3

Atomic Weight 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

Common Valence 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

Name 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

Symbol 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

Atomic Number 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

Atomic Weight 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)

Common Valence 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

4

Name Protactinium Radium Radon Rhenium 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

Symbol Pa Ra Rn Re 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

Atomic Number 91 88 86 75 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

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

5

III. COMMON ANIONS

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 Hydroxide Hypochlorite Iodide Iodate Molybdate Nitrate Nitrite Oxalate Perchlorate Peroxide Permanganate Phosphate Sulfate Sulfide Sulfite Thiocyanate Thiosulfate

Symbol OH OCl I IO3 MoO4 NO3 NO2 C2O4 ClO4 O2 MnO4 PO4 SO4 S SO3 CNS S2O3

ORGANIC CHEMISTRY

Note: For conciseness the following symbols are used: R R X n H atom or saturated hydrocarbon group hydrocarbon group only halogen an integer

I. GENERAL CLASSES OF COMPOUNDS

A. The straight and branched chain types of compounds
6

Type or Name 1. Alkane or paraffin (also saturated hydrocarbons) 2. Alkene or olefin (unsaturated hydrocarbons) 3. Alkyne

General Formula

4. Alcohol

5. Ether 6. Aldehyde

7. Ketone

8. Carboxylic Acid

9. Grignard reagent

10. Acyl halide

7

Type or Name

General Formula

11. Anhydride

12. Ester

13. Amide

14. Amine (base)

15. Nitrile

B. Cyclic Compounds

1. Cycloparaffin

8

Type or Name

General Formula

2. Cycloalkene

3. Aromatic

4. Naphthalenic

II.

PERTINENT NOTES

A. Markovnikov’s (Markownikoff’s) Rule for the addition of acids to acids to olefins: the negative group of the acid adds to the carbon atom having the fewest hydrogen atoms.
9

B. Mechanisms 1. Free radical (unshared electron) (no charge) 2. Carbonium ion (deficient in electrons) ( positive charge) (carbon with six electrons) 3. Carbanion (excess of electrons) (negative charge) (carbon with eight electrons)

PHYSICAL CHEMISTRY

1. Amagat’s Law of Partial Volumes—The volume 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 Kb where Hv Kb m Ma Kbm R(Tbp)2Ma Hv(1000)

molal heat of vaporization molal boiling point elevation stant molality solvent molecular weight
10

con-

R Tbp

ideal-gas constant solvent boiling point, absolute temperature

3. Clausius Equation dp dT where p T Hm V v Hm (V v) T

pressure absolute temperature molal heat of vaporization molar vapor volume molal liquid volume

4. Clausius-Clapeyron Equation—Where the volume of liquid can be ignored (or v 0) and where the ideal-gas law holds (or V RT p) the Clausius equation becomes d( ln p) dT and with Hm ln p2 p1 1 dp p dT Hm RT 2

constant, integration yields Hm T2 T1 c d T1T2

R

The symbols are the same as in sections 2 and 3 above. 5. Dalton’s Law of Partial Pressures—The 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

6. Faraday’s 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 where Hf Kf m Ma R Tf p Kf m R (Tf p)2Ma Hf (1000)

molal heat of fusion of solvent molal freezing point lowering constant molality solvent molecular weight ideal-gas constant solvent freezing point, absolute temperature

8. Gibbs Phase Rule—At 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

of the phase rule applies to non-reactive systems. 9. Graham’s Law of Diffusion—The rate of diffusion of a gas is inversely proportional to the square root of its density. 10. Henry’s Law—At 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. Raoult’s Law pa where pa xa Pa xa Pa

partial pressure of component A in vapor mole fraction of A in liquid solution vapor pressure of pure liquid A

12. van’t Hoff Reaction Isochore d ( ln K ) dT where 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, ln a K2 K1 b H T2 T1 c d T1T2

R

13. Molar Humidity—moles vapor/mole vaporfree gas Y ya 1 ya P pa pa

13

Humidity—pounds vapor/pound vapor-free gas Y Y Ma Mb

Relative Saturation—ratio of partial pressure of vapor to partial pressure of vapor at saturation (vapor pressure) Hr 100 pa Pa

Percentage of Saturation—ratio of vapor concentration to vapor concentration at saturation (ratio of molar humidity to saturated molar humidity) Hp where pa Pa P Ma Mb ya 100 Y Ysat 100 pa (P Pa (P Pa) pa)

partial pressure of component A in gas vapor pressure of pure liquid A total pressure molecular weight of A molecular weight of B mole fraction of a gas

FLUID FLOW
I. DEFINITIONS AND GENERAL EQUATIONS

Mass velocity G V
14

Simple manometer equation Pa Pb Rm g gc (
b)

a

Hagen-Poiseuille equation (laminar flow in long horizontal tube) Pa Average velocity, V V q, volumetric flow rate s, cross-sectional area Pb 32 L V gc D 2

Reynolds number, NRe NRe DV DV

Mechanical energy balance Pa
a

g gc

Za

V2 a 2gc
a

Ws

Pb
b

g gc

Zb

V2 b 2gc 4,000) 2,100)
b

Hf

where

1 for turbulent flow (NRe 0.5 for laminar flow (NRe

Hydraulic radius rH s, cross-sectional area Lp, the wetted perimeter

Equivalent diameter, De De 4 (hydraulic radius, rH)
15

II.

FRICTION

Skin friction Hfs 2 f LV 2 Dgc

Fanning friction factor, f (flow in smooth pipes) laminar turbulent f 1 f. .5 16 DV 16 NRe 0.4

4.0 log (NRe f. .5)

Friction of valves and fittings (Add to length of pipe to get total equivalent length.)
Equivalent resistance, pipe diameters 15 32 60 75 60 90 Negligible Negligible 7 300 170

Fittings and Valves 45-degree elbows 90-degree elbows (standard radius) 90-degree square elbows 180-degree close return bends T’s (used as elbow, entering run) T’s (used as elbow, entering branch) Couplings Unions Gate valves (open) Globe valves (open) Angle valves (open)

Friction loss from sudden expansion of cross section Hfe V2 a 2 gc a1 sa sb b
2

16

Friction loss from sudden contraction of cross section Hfc KcV 2 b 2 gc

Values of K c are given on page 6-18, Perry’s Chemical Engineers’ Handbook, 7th ed., Don W. Green, ed., McGraw-Hill Book Co., New York, NY, 1997.
III. MEASUREMENT OF FLOWING FLUIDS

Venturi meter 2V s b V2 a Cv 2gc ( pa B pb) (b is at throat of meter) 20,000) pb)

Orifice meter, design equation (NRe Vo 0.61 21
4

2gc ( pa B P) P)

Pilot tube (manometer measures ps V Cp 2gc ( ps B

IV. SYMBOLS USED

Cu , Cp D g gc Hf Hfs Hfc

coefficients of velocity diameter acceleration of gravity 32.2 ft /s 2 9.81 m/s2 Newton’s conversion factor 32.2 ft-lbm /(lbf -s2) 1 m-kg/(N-s 2 ) head loss due to friction head loss due to skin friction head loss due to contraction of cross section
17

Hfe Ke Kc L P Pa Pb pa, pb ps Rm s V V Va Vb Ws Z

a b

head loss due to expansion of cross section expansion loss coefficient contraction loss coefficient length of pipe pressure upstream pressure downstream pressure pressure in arms of manometer static pressure manometer reading cross-sectional area velocity average velocity upstream velocity downstream velocity shaft work done by pump elevation kinetic energy correction factor ratio of diameter of orifice to diameter of pipe fluid density, lbm /ft 3 density of manometer fluid density of fluid above manometer kinematic viscosity viscosity
HEAT TRANSFER

I.

CONDUCTION

Fourier’s Law (constant k) steady state q kA T x
18

T R

unsteady state T t Resistance in Series q T xA kA A RA xB kB A RB T RC xC kC A
2 k T x 2 Cp x

Radial Heat Flow Through a Cylinder q where Am rm rm
II.

k(2 rm) L T (ro ri )

k Am T r

logarithmic mean area normal to heat flow logarithmic mean radius (ro ri) ln [ro ri]

CONVECTION

q where h k x

hA T

k x , heat transfer coefficient thermal conductivity of the fluid thickness of the laminar film

III. COMBINED CONDUCTION AND CONVECTION

q where U T

UAavg ( T )

overall heat transfer coefficient overall temperature difference
19

1 U

Ar UAr

hi

1 Ai Ar Ar

km

xm Am Ar

ho

1 Ao Ar

hFi

1 Ai Ar

hFo

1 Ao Ar

where

hFi , hFo

reference area, usually the area of the solid through which heat is being conducted inside and outside fouling factors

IV.

RADIATION

q12 where q12 T1, T2 A

AF (T 4 1

T 4) 2

F

net radiation between surfaces 1 and 2, Btu/hr absolute temperature of surfaces 1, 2, R. area of either surface, sq ft Stefan-Boltzman Constant 1.712 10 9 Btu/hr-sq ft- R 4 geometric view factor

V. EMPIRICAL, DIMENSIONLESS CORRELATION

Turbulent Flow in Clean Smooth Pipes hiD k where 0.023(NRe)0.8(NPr)0.33( NRe NPr
0.14 [1 w)

(D L)0.7]

the Reynolds Number DG the Prandtl Number Cp k

Laminar Flow in Clean Smooth Pipes hiD k 1.86(NRe)0.33(NPr)0.33(
20
0.14 (D w)

L)0.33

where the Reynolds and Prandtl Numbers are as defined for turbulence

VI. HEAT TRANSFER TO AND FROM FLUIDS FLOWING NORMAL TO A SINGLE TUBE

ho Do kf where NRe

0.35

0.56(NRe)0.52 DoG
f

the Reynolds Number

The subscript f calls attention to the fact that the correlation is based on the mean film temperature, Tf , which is defined as the arithmetic mean of the average fluid temperature and the wall temperature.

VII. HEAT TRANSFER TO AND FROM FLUIDS FLOWING PERPENDICULAR TO TUBE BANKS

havg Do kf where NRe

b(NRe)n (b and n depend on geometry) the Reynolds Number DGmax
f

VIII. HEAT TRANSFER FROM CONDENSING VAPORS

Vertical Tubes havg Horizontal Tubes havg 0.725 c k3 f
2 fg f

1.13 c

k3 f

2 fg f

To L

d

0.25

To Do

d

0.25

21

IX.

NOTATION

A b Cp D G Gmax g h k L q R r T t U x

area, sq. ft. empirical constant specific heat at constant pressure, Btu/lb- F diameter, ft mass velocity, lbm /sq ft-sec mass velocity through minimum cross section in tube bundle acceleration of gravity, 32.2 ft/sec2 heat transfer coefficient, Btu/sq ft-hr- F thermal conductivity, Btu/sq ft-( F/ft)-hr length of tube or cylinder, ft heat flow per unit of time, Btu/hr resistance radius, ft temperature, F time, hr over-all heat transfer coefficient, Btu/sq fthr F distance in direction of heat flow; thickness of layer, ft latent heat of condensation or vaporization, Btu/lbm viscosity,lbm /ft-sec density, lbm /ft 3

Subscripts avg f i o r average film inside outside reference
22

w m

wall mean or log mean

DISTILLATION
I. FLASH (OR EQUILIBRIUM) DISTILLATION

FzF yV xL F V L
II.

(component material balance) (over-all material balance)

DIFFERENTIAL (SIMPLE OR RAYLEIGH) DISTILLATION

ln

W Wo

x

dx y x x

xo

When the relative volatility is constant y [1 ( 1)x] can be substituted to give ln W Wo 1 ( 1) ln c x(1 xo(1 xo) x) d ln c 1 1 xo x d

For binary system following Raoult’s Law (y x)a (y x)b where pi pa pb

partial pressure of component i

III. CONTINUOUS DISTILLATION (BINARY SYSTEM) WHERE CONSTANT MOLAL OVERFLOW IS ASSUMED

Total Material Balance F FzF D DxD
23

B BxB

Operating Lines 1. Rectifying Section Total material: Vn 1 Ln D Component A: Vn 1 yn 1 Ln xn yn Ln
1

DxD

Ln

D

xn

DxD Ln D

2. Stripping Section Total material: Lm Vm 1 B Component A: Lm 1 xm Vm 1 ym ym Lm
1

1

BxB

Lm

B

xm

BxB Lm B

3. Reflux Ratio Ratio of reflux to overhead product RD 4. Feed Condition Line
Type of Feed Superheated vapor Saturated vapor Liquid and vapor Saturated liquid Cold liquid Slope of feed line (downward to left) 0 (horizontal) (upward to left) (vertical) (upward to right)

L D

V D

D

5. Murphree Plate Efficiency EME yn y* n
24

yn yn

1 1

where

yn yn
1

y* n

concentration of vapor above plate n concentration of vapor entering from plate below n concentration of vapor in equilibrium with liquid leaving plate n

IV.

NOTATION

B D F L RD V W x y zD

relative volatility moles of bottoms product moles of overhead product moles of feed molar liquid downflow ratio of reflux to overhead product molar vapor upflow weight in still pot mole fraction of the more volatile component in the liquid phase mole fraction of the more volatile component in the vapor phase mole fraction of the more volatile component in the feed

Subscripts B D F m 1 n 1 o bottoms product overhead product feed any plate in stripping section of column plate below plate m any plate in stripping section of column plate below plate n original charge in still pot
25

m n

MASS TRANSFER
I. DIFFUSION

1. Molecular Diffusion NA A pA NA c P A NB A d D pA RT z

2. Unidirectional Diffusion of a Gas A Through a Second Stagnant Gas B (NB 0) NA A DP RT ( pB)lm ( pA2 x2 pA1) x1

in which ( pB )lm is the log mean of pB2 and pB1 3. Equimolar Countercurrent Diffusion (NB (gases) NA A D RT ( pA2 z2 pA1) z1 NA)

4. Unsteady State Diffusion pA t
2

D

pA

z2

II.

CONVECTION

1. Two-Film Theory NA A

kG ( pAG kG ( pAG

pAi) pA)
26

kL (CAi kL (CA

CAL ) CAL)

2. Overall Coefficients 1 KG 1 KL 3. Transfer Unit HTU—height of a transfer unit HTG HTL G KG a L KL a 1 kG 1 HkG H kL 1 kL

NTU—number of transfer units
y2

NTG
y1 x2

dy y* y

1 1 ln 2 1 1 1 ln 2 1

y2 y1 x1 x2

NTL
x1

x

dx x*

For dilute solutions (straight operating and equilibrium line) NTG Z NTG HTG y1 (y NTL HTL y2 y*)lm tower height

4. Dimensionless Group Equation (Sherwood) (NSh) 0.023 (NRe)0.8(NSc)1
27
3

III. MOMENTUM, HEAT, AND MASS TRANSFER ANALOGY

0.5 f where f

jH

jD

Fanning friction factor jH jM h Cp 0.667 c c d CpG k kc G (NSc)0.667
w

d

0.14

IV.

NOTATION

A a C d D G H h k K L N p P R NRe NSc NSh t T u

area perpendicular to direction of diffusion interfacial area per unit volume concentration in liquid phase tube diameter molecular diffusivity gas mass velocity, mass/(time)(area) Henry’s Law constant, pi HCi heat transfer coefficient film coefficient of mass transfer overall coefficient of mass transfer liquid mass velocity, mass/(time)(area) moles of a substance per unit time partial pressure total pressure gas constant Reynolds number du Schmidt number D Sherwood number kd D time absolute temperature velocity
28

lm

logarithm mean average

Greek Letters density viscosity Subscripts A, B G L i x y z * components of mixture gas phase liquid phase interface mole fraction of liquid mole fraction of gas length in direction of travel equilibrium concentration

THERMODYNAMICS
I. DEFINITIONS

System—an arbitrarily chosen portion of space which is under consideration. A. Closed system—one in which matter does not pass through its boundaries. B. Open system—one in which matter flows across its boundaries. C. Isolated system—one in which there is no interchange of energy or matter with the surroundings. Boundaries—the envelope separating the system from the surroundings. Universe—a system and its surroundings.
29

Total energy, E—the sum of the various forms of energy of the system: e.g., U, internal energy; Ek , kinetic energy; Ep, potential energy; Hence, E
II. FIRST LAW

U

Ep

Ek

In an isolated system In a closed system In an open system E E

E Q

E2 W

E1

0

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
III. SECOND LAW

Ek

Ep

Q

W

For any real process the total entropy of the universe always increases Ssystem Ssurroundings 0

IV. THERMODYNAMIC FUNCTIONS: DEFINITIONS AND RELATIONSHIPS

Definition of entropy S dQrev T

From First and Second Laws, with changes in Ek,
30

Ep , and composition negligible, dU Also dH dG dA Cp dU dH dU d(PV) d(TS) d(TS) ( U TdS SdT SdT T )v; VdP VdP PdV (Cp Cv) dQrev PdV TdS PdV

( H T )p; Cv

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

For any path:

H
T1 T2

Cp dT or ( H P)T

0

For any path:

U
T1

Cv dT or ( U V )T 2.5 R and Cv

0 1.5 R

For monoatomic gas: Cp For diatomic gas: Cp

3.5 R and Cv

2.5 R

Adiabatic (Q 0) and reversible path for system with Ep Ek 0. (P2 P1) Wnonflow U Wflow (V1 V2) RT1 1 H ca P2 P1 b
(

(T2 T1)
1)

(

1)

1 d (per mole)

[Wnonflow] ( per mole)

Isothermal path, flow or nonflow P2 P1
31

V1 V2

W

RT ln

V2 V1

RT ln

P1 P2

( per mole)

VI. CRITERIA FOR EQUILIBRIUM CHANGE

For system and surroundings: dSuniverse For system alone: dG dA 0 when P, T 0 when V, T

0 constant constant

VII. CHEMICAL THERMODYNAMICS

A. Fugacity ( f ) and Activity (a)
2

G

RT ln ( f2 f1)
1

VdP ( per mole) (constant-temperature path)

and the limit of f P as P approaches 0 a B. Equilibrium f f0

1.00

Standard free energy at temperature T for the reaction aA G rGR RT ln C. Cells At standard conditions G nF
32

bB ∆ rR sGS ar as R S aa ab A B

sS bGB

aGA

RT ln Ka

RT ln Ka

At actual conditions G nF nF RT ln ar as R S aa ab A B

VIII.

NOTATION

A a C E Ek Ep F f G gc H h K Ka Kf Kp n P Q R S T

U TS, Helmholtz work function activity heat capacity total energy of the system kinetic energy of the system potential energy of the system reversible voltage of cell faradays per equivalent fugacity H TS, Gibbs free energy Newton’s conversion factor U PV, enthalpy enthalpy per pound equilibrium constant for the reaction as written equilibrium constant in terms of activity equilibrium constant in terms of fugacity equilibrium constant in terms of partial pressure number of equivalents for the reaction as written pressure heat, defined as positive when absorbed by system gas constant entropy absolute temperature
33

U u V v W

internal energy of the system velocity volume specific volume work, defined as positive when done by system on surroundings final state minus initial state (Cp Cv)

Superscript standard state

KINETICS AND REACTOR DESIGN
I. RATE OR REACTION

The rate of reaction of any component A based on unit volume of fluid is rA 1 dNa V dt

and where density remains unchanged rA dCA dt

Frequently, the rate can be described as a temperaturedependent term times a concentration-dependent term, or rA k (T) f (CA, CB . . .)

A. Order, Molecularity, Elementary Reactions Where the rate can be expressed as
34

rA

kC a C b . . . A B

the reaction is ath order with respect to A and nth order overall; n a b NOTE: a, b, . . . are empirically observed and are not necessarily equal to the stoichiometric coefficients. In the special case where a, b, . . . are the stoichiometric coefficients, 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 Arrhenius’s Law the variation with temperature is k koe
E RT

or ln

k2 k1

1 c R T1 E

1 T2

d

where E is the activation energy of the reaction
II. HOMOGENEOUS, CONSTANT FLUID DENSITY, BATCH KINETICS

A. Irreversible First-order Reaction For the reaction A S products, with rate dCA dt kCA or dXA dt k(1 XA)

the integrated form is ln CA CA0 ln (1
35

XA)

kt

B. Irreversible Second-order Reaction For the reaction A B S products, with rate dCA dt When M ln C B0 CA0 ln M M(1 kCACB

1, the integrated form is XA XA) (CB0 CA0) kt

CB CA0 CB0 CA

When CA0

CB0 , the integrated form is 1 CA 1 CA0 XA 1 CA0 1 XA kt

C. Irreversible nth-order Reaction For the reaction with rate dCA dt the integrated form for n C1 n A C1 n A0 kC n A 1 is (n 1) kt

D. Reversible First-order Reaction 1 For the reaction A ∆ R, K 2 dCA dt dCR dt k1 k2 with rate

k1CA

k2CR

the integrated form is ln XAe XAe XA ln CA CA0
36

CAe CAe

(k1

k2)t

E. Integration of Rate in General For the reaction with rate rA
XA

dCA dt dXA ( rA )

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

t

CA0
0

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

CA0

which is to be solved analytically or graphically.

III. BATCH REACTION WITH CHANGING FLUID DENSITY

Where density change is proportional to the fractional conversion of any reactant A (isothermal systems), CA CA0 where VXA
A
1

1 1

XA
A XA

VXA
0

0

VXA

The rate for any reactant A is then ra 1 dNA V dt (1 CA0
A XA)

dXA dt

k f (CA, CB , . . .)

Integrating in the general case
XA

t

CA0
0

dXA (1
37
A XA)(

rA)

IV. FLOW REACTORS

A. Capacity Measures Space time: time required to process one reactor volume of entering feed mean residence time V v VCA0 FA0 (units of time)

B. Design Equation for Plug Flow (Ideal Tubular) Reactor In general
XA

CA0
0

dXA ( rA)

or

V FA0

XA

dXA ( rA)

0

For irreversible first-order reactions (isothermal) k (1
A)

ln (1

XA)

A XA

1 For reversible first-order reactions A ∆ rR 2 (isothermal) k1 where N C. Design Equation 1 for k2 k2 (1
A) A XA

N N2

A

N

ln (1

NXA)

Back-Mix

(Ideal

Stirred

38

Tank) Reactor CA0 XA ( rA) V FA0 XA ( rA)

or

For a first-order reaction in j equal-sized backmix reactors in series CA entering CA leaving D. NOTATION A, B, R, etc. a, b, . . . CA CA0 FA0 K k n NA rA T t V substance A, etc. exponents on concentration term of empirical rate expression concentration of A, moles A/volume initial concentration of A, moles A/ volume feed rate of A or flow rate of A entering the reactor, moles A/time equilibrium constant reaction rate constant, (conc1 n)(time 1) order of reaction moles of A rate of reaction of any comoponent A, moles A formed/time-volume temperature time volume of fluid in batch reactor, volume of fluid in a flow reactor, or reactor volume

(1

k per reactor) j

39

v XA

volumetric feed rate, volume of feed/ time 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 2.778 10 4 rev/s2 0.001745 rad/s2 0.01667 rev/min-s

1 rev/min2

Density 1 lbm /ft3 16.02 kg/m3 5.787 10 4 lbm /in3 0.01602 g/cc

Flow 1 ft3/min 4.719 10 4 m3/s 0.1247 gal/s
40

0.4720 liter/s 472 cc/s Length 1 ft 0.3048 m 1.894 10 4 mile 1 3 yd 12 in 30.48 cm 3.05 105 microns ( ) 10 10 m 10 8 cm 1 10 4 microns ( )

Angle 1 rad 1 2 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 10 4 long ton 5 10 4 short ton 4.536 10 4 metric ton 0.4536 kg 453.6 g 0.0311 slug

Pressure 1 lbf /in2 abs 6.895 6.895 103 N/m2 103 Pascal
41

0.06805 atm 0.07031 kg/cm2 2.036 in Hg @ 32 F 2.307 ft H2O @ 39 F 70.307 g/cm2 51.72 mm Hg @ 32 F 51.72 torr Power 1 ft-lb/min. 0.0226 W 2.26 10 5 kW 3.03 10 5 hp 3.24 10 4 kg-cal/min 0.001285 Btu/min

Temperature F K R Time 1 nanosecond 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 0.1047 rad/s 6 deg/s
42

1.8( C) 32 C 273 F 459

1

10

9

s

1 rev/min

Viscosity 1 centipoise 0.001 Pa-s 0.001 N-s/m2 0.01 g/cm-s 6.72 10 4 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 10 4 kW-hr 3.93 10 4 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
43

Mole fraction (x) to mass fraction (w) wA xA MA xA MA xB MB

Mass fraction (w) to mole fraction (x) xA where Mi wA MA wA MA wB MB

molecular weight of i

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

Avogadro’s number N 6.023 1023 molecules/g-mole

Boltzmann’s constant K 1.3805 10
16

erg/molecule-K

Newton’s conversion constant gc 32.17 lbm-ft /lb f -s 2 1.000 kg-m/N-s 2

44

Planck’s constant h 6.624 10
27

erg-s

Stefan-Boltzmann constant 1.355 1.712 Velocity of light c 186,000 miles/s 3 1010 cm /s 10 10
12 9

cal/s-cm2-K4 Btu /hr-sq ft- R4

Velocity of sound in dry air, 0 C and 1 atm 33,136 cm /s 1,089 ft /s

Heat of fusion of water at 1 atm, 0 C 79.7 cal /g 144 Btu /lbm

Heat of vaporization of water at 1 atm, 100 C 540 cal /g Ton of refrigeration 972 Btu/lbm

12,000 Btu /hr

1 lbm-mole of perfect gas occupies 359 ft 3 at standard conditions (32 F, 14.7 psi abs) 1 g-mole of perfect gas occupies 22.4 liters at 0 C and 760 mm Hg Thermochemistry F joules coulombs 96,500 coulombs/gram equivalent volts coulombs seconds

amperes

45

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 pgcd 2L V 2 (h cpG)(Cp k)2 3 (kc G)( D)2 3 V 2 gL wcp kL L3 2 g T 2 hd k LV cp k Pgc n3d5 cp k LV D Kc L D

Notation cp D d G g gc h k kc L n P p T V specific heat, Btu/lbm- F molecular diffusivity, sq ft/hr diameter, ft mass velocity, lbm /sq ft-hr acceleration of gravity, 32.2 ft/s2 conversion factor 32.2 ft-lbm /(lbf-s 2 ) 1 m-kg/(N-s2) heat transfer coefficient, Btu/sq ft-hr- F thermal conductivity, Btu/sq ft-( F/ft)-hr mass transfer coefficient, ft/hr characteristic dimension, ft rate of rotation, s 1 power to agitator, ft-lbf /s pressure drop, lbf /sq ft temperature, F fluid velocity, ft /s
46

w

mass flow rate, lbm /s coefficient of bulk expansion, F density, lbm /ft 3 viscosity lbm /ft-hr

1

Abbreviations atm Btu cal cm cu ft g hp hr in kg km kW lbm lbf m min ml pt qt quad R rad rev s yd atmosphere British thermal unit calorie centimeter cubic foot, feet gram horsepower hour inch kilogram kilometer kilowatt pound-mass pound-force meter minute milliliter pint quart quadrant degrees Rankine radian revolution second yard micron
47

GREEK ALPHABET

, , , , , , , , , , , ,

alpha beta gamma delta epsilon zeta nu xi omicron pi rho sigma

, , , , , M, , , , , , ,

eta theta iota kappa lambda mu tau upsilon phi chi psi omega

MATHEMATICS

a a

2 3

b b

2 3

(a (a (a c

b)(a b)(a
2

b) ab ab b b2) b2) 2b2 2a 4ac

a3 ax 2

b3 bx

b)(a2 0 x r2

Area of circle

Circumference of circle Surface of sphere Volume of sphere 4 r2

2 r

(4 3) r 3 1 3 (base area)(height)

Volume of cone or pyramid dax dx n adx nx n
1

dx
48

d(u d(uv) u dc d v deax dax d sin x

v)

du

dv vdu udv

udv vdu v2 aeax dx

ax logea dx cos x dx sin x dx sec 2 x dx v) dx uv xn loge x eax a
1

d cos x d tan x (u udv x n dx dx x eax dx

udx vdu (n ln x

vdx

1) for n

1

Binomial series (x xn Taylor series f (x) f (a) f (a) x 1!
49
2

y)n y2

xn

n x n 1y (y 2 x 2)

n(n 2!

1)

a

f (a)

(x 2!

a)2

MacLaurin series f (x) f (0) f (0) x 1! f (0) x2 2!

Exponential series ex 3.1416, e log10 x Arithmetic mean a 2 Geometric mean 2ab Harmonic mean 2ab a b Logarithmic mean a b ln a b Solution of dy dx Py Q b 1 x x2 2! x3 3! 2 1, i2 1, i4 1

2.71828, i

0.4343 ln x, ln x

2.303 log10 x

where P, Q are constants or functions of x Integrating factor Solution y IF e
Pdx

IF Q)dx C

(IF
50

CHEMICAL PROCESS SAFETY
Contributed by Joe Louvar I. COMMON DEFINITIONS: GENERAL CONCEPTS

Chemical Process Safety—The application of technology and management practices a) to prevent accidents in plants, and/or b) to reduce the potential for accidents. Process Safety Management—An 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 Technology—Design features and control features to reduce the potential for accidents. Safety Design Features—a) Inerting to control the concentration of a flammable gas to below the LFL, b) grounding and bonding to prevent static electricity charging and discharging (spark) and potential fire, 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 Features—a) 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.
51

II.

COMMON DEFINITIONS: TERMS

Auto Ignition Temperature (AIT)—A fixed temperature above which a flammable 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). Deflagration—An explosion with a flame front moving in the unburned gas at a speed below the speed of sound (1250 ft /s). Detonation—An 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 flammable limit (LFL). The mixture is also not combustible when the composition is above the upper flammability limit (UFL). Flammability Limits of Mixtures—They are computed with the following equations: LFLMIXTURE 1 yi a a LFL b
i

UFLMIXTURE

1 yi a a UFL b
i

52

Lower Flammability Limit in the Presence of Mists— LFLMISTS 0.1 LFL THEORETICAL Mechanical Explosion—An 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 b

Overpressure—The pressure on an object as a result of an impacting shock wave. Relief Valve—A device that relieves the pressure within a vessel when the pressure approaches the maximum allowable working pressure (MAWP). All vessels have reliefs. Risk—This is the product of the frequency and the consequence of an accident scenario.
BIOCHEMICAL ENGINEERING
Contributed by David Murhammer I. COMMON DEFINITIONS: GENERAL CONCEPTS

Aerobes—Organisms whose growth requires the presence of air or oxygen. Anabolism—Metabolism involved with the biosynthesis of cellular components. Anaerobes—Organisms that grow in the absence of air or oxygen. Biochemical Engineering—The extension of chemical engineering principles to biological systems with the goal of producing useful products.
53

Bioreactor—A vessel used for biological processes. Examples include growing microorganisms and animal cells for the production of useful products. Biotechnology—The 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. Catabolism—Metabolism involved with the breakdown of materials for the production of intermediates and energy. Enzyme—A catalytic protein (and in some cases RNA) produced by living cells. Eukaryote—A cell or organism with a membrane-bound nucleus and well-developed organelles. Examples include yeast, animals, and plants. Prokaryote—A cell lacking a true nucleus. Examples include bacteria and blue-green algae. Virus—A noncellular entity that consists minimally of protein and DNA or RNA and that can replicate only after entry into specific types of living cells.

II.

COMMON DEFINITIONS: TERMS

Antibiotics—Substances of microbial origin that in very small amounts have antimicrobial activity. Antibodies—Glycoprotein molecules produced by Blymphocytes in higher organisms in response to the introduction of a foreign material (antigen). These molecules react with antigens with great specificity. Attachment Dependent—Cells whose growth requires attachment to a surface. Also referred to as AnchorageDependent. Batch Culture—A culture that once supplied with raw materials is run to completion.
54

Chemostat—A bioreactor in which the continuous addition of fresh medium and removal of effluent results in constant nutrient, product, and cell concentrations when operated under steady state conditions. Death Phase—The portion of the growth curve in culture in which there is a net decline in the number of viable (live) cells. Exponential (Log) Growth Phase—A 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 dt X,

where X cell number (cells /mL) or cell biomass (mg/mL), t is time, and is the specific growth rate (h 1). Fed-Batch Culture—A culture to which nutrients are periodically added during the operation of the culture. Growth Yield—Yield of biomass based on substrate (e.g., glucose or oxygen) utilization: YX/S dX , dS

where YX S is the yield coefficient of biomass (X) based 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 a—Volumetric mass transfer coefficient usually measured in h 1 and often used to compare the efficiencies of bioreactors in supplying oxygen. The resulting oxygen transfer rate is then given by dCL dt KLa(C *
55

CL),

where CL is the dissolved oxygen concentration within the bioreactor, t in time, and C* is the equilibrium dissolved oxygen concentration (i.e., solubility) under the specified conditions. Lag Phase—The portion of the growth curve between inoculation and the beginning of cell growth. Media Sterilization—Removal of undesired microorganisms from the media through filtration or heat to prevent their growth during the course of a bioreactor run. Michaelis-Menton Kinetics—Common type of enzyme kinetics given by vmax[S] KM [S]

v

,

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 1⁄2 vmax , and [S] is the substrate concentration. Perfusion Culture—A 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 specific growth rate ( ) by ln(2)

PDT

.

Power Number (Np)—A dimensionless number commonly used to determine the amount of power introduced to the bioreactor as a result of agitation. The
56

Power Number is given by 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 Equation—An equation commonly used to model the effect of the rate-limiting substrate concentration on the specific growth rate. This equation is given by
m[S]

Ks

[S]

,

where is the specific growth rate, m is the maximum specific 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 1 concentration when ⁄2 m. Stationary Phase—Phase in growth curve following the exponential growth phase in which there is no net growth. This phase is commonly associated with nutrient depletion.

57

American Institute of Chemical Engineers 3 Park Avenue New York, NY 10016-5991 212.591.8100 www.aiche.org

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