Reference

NBS

PUBLICATIONS

.^'^^r"^

NATL INST. OF STAND & TECH

AlllDb 3MD1D7

<5

\. 35

^''ffCAU O* "/ NBS TECHNICAL NOTE 1096

U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards

Basic Tables for Chemical

Analysis

Thomas J. Bruno

Paris D.N.Svoronos

QC

100 1

_ _

.U5753

#1096

1986

>"
NBSTechnical Publications

Periodical

Journal of Research—The Journal of Research of the National Bureau of Standards reports NBS research and development in those disciplines of the physical and engineering sciences in which the Bureau is active. These include physics, chemistry, engineering, mathematics, and computer sciences. Papers cover a broad

range of subjeas, with major emphasis on measurement methodology and the basic technology underiying

standardization. Also included from time to time are survey articles on topics closely related to the Bureau's

technical and scientific programs. Issued six times a year.

Nonperiodicals

Monographs—Major contributions to the technical literature on various subjects related to the Bureau's scientific and technical activities. Handbooks—Recommended codes of engineering and industrial practice (including safety codes) developed in cooperation with interested industries, professional organizations, and regulatory bodies.

Special Publications—Include proceedings of conferences sponsored by NBS, NBS annual reports, and other

special publications appropriate to this grouping such as wall charts, pocket cards, and bibliographies.

Applied Mathematics Series—Mathematical tables, manuals, and studies of sf)ecial interest to physicists,

engineers, chemists, biologists, mathematicians, computer programmers, and others engaged in scientific and

technical work.

National Standard Reference Data Series—Provides quantitative data on the physical and chemical properties

of materials, compiled from the world's literature and critically evaluated. Developed under a worldwide pro- gram coordinated by NBS under the authority of the National Standard Data Act (Public Law 90-396).

NOTE: The Journal of Physical and Chemical Reference Data (JPCRD) is published quarterly for NBS by

the American Chemical Society (ACS) and the American Institute of Physics (AIP). Subscriptions, reprints,

and supplements are available from ACS, 1155 Sixteenth St., NW, Washington, DC 2(X)56. Building Science Series—Disseminates technical information developed at the Bureau on building materials,

components, systems, and whole structures. The series presents research results, test methods, and perfor- mance criteria related to the structural and environmental functions and the durability and safety

characteristics of building elements and systems.

Technical Notes—Studies or reports which are complete in themselves but restrictive in their treatment of a

subject. Analogous to monographs but not so comprehensive in scope or definitive in treatment of the subject

area. Often serve as a vehicle for final reports of work performed at NBS under the sponsorship of other government agencies.

Voluntary Product Standards—Developed under procedures published by the Department of Commerce in Part 10, Title 15, of the Code of Federal Regulations. The standards establish nationally recognized re- quirements for products, and provide all concerned interests with a basis for common understanding of the

characteristics of the products. NBS administers this program as a supplement to the activities of the private

sector standardizing organizations.

Consumer Information Series—Practical information, based on NBS research and experience, covering areas of interest to the consumer. Easily understandable language and illustrations provide useful background

knowledge for shopping in today's technological marketplace.

Order (he above NBS publications from: Superintendent of Documents, Government Printing Office,

Washington, DC 20402. Order the following NBS publications—FIPS and NBSIR 's—from the National Technical Information Service, Springfield, VA 22161.

Federal Information Processing Standards Publications (FIPS PUB)—Publications in this series collectively constitute the Federal Information Processing Standards Register. The Register serves as the official source of

information in the Federal Government regarding standards issued by NBS pursuant to the Federal Property

and Administrative Services Act of 1949 as amended, Public Law 89-306 (79 Stat. 1127), and as implemented

by Executive Order 11717 (38 FR 12315, dated May 11, 1973) and Part 6 of Title 15 CFR (Code of Federal

Regulations). NBvS Interagency Reports (NBSIR)—A special series of interim or final reports on work performed by NBS

for outside sponsors (both government and non-government). In general, initial distribution is handled by the sponsor; public distribution is by the National Technical Information Service, Springfield, VA 22161, in paper copy or microfiche form.
i\!< RESEARCH NBS

3EAR( INFORMATION .^o CENTER

Basic Tables for Chemical Analysis ^^^

Thomas J. Bruno

Thermophysics Division

Center for Chemical Engineering

National Engineering Laboratory

National Bureau of Standards

Boulder, Colorado 80303

Paris D.N. Svoronos

Department of Chemistry

Queensborough Community College

City University of New York

Bayside, New York 11364

and

Department of Chemistry

Georgetown University

Washington, DC 20057

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrlge, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued April 1986
National Bureau of Standards Technical Note 1096

Natl. Bur. Stand. (U.S.), Tech Note 1096, 240 pages (Apr. 1986)

CODEN:NBTNAE

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON; 1986

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington. DC 20402
CONTENTS

Page

Abstract 1

Introduction 1

I. Tables for Gas Chromatography 5

Mesh Sizes and Particle Diameters 7 Gas Chromatographic Support Materials 9 Carrier Gas Properties 12

Properties of Some Liquid Phases 15

Stationary Phases for Packed Column Gas Chromatography 33

Silicone Liquid Phases 35

Adsorbents for Gas-Solid Chromatography 48

Porous Polymer Phases 51 Cryogens for Subambient Temperature Gas Chromatography 58

Some Useful Fluids for Supercritical Fluid Chromatography 60

II. Tables For Liquid Chromatography 61

Solvents for Liquid Chromatography 63

Modes of Liquid Chromatography 66

Reverse Phase Materials and Solvents 67

HPLC Column Packings 68

III. Tables for Ultraviolet Spectrophotometry 71

Solvents for Ultraviolet Spectrophotometry 73

Transmittance - Absorbance Conversion 76

Correlation Table for Ultraviolet Active Functionalities 80

IV. Tables for Infrared Spectrophotometry 85

Infrared Optics Materials 87

Wavelength - Wavenumber Conversion Table 91 Useful Solvents for Infrared Spectrophotometry 94

acetonitrile 95

benzene 96

bromoform 97

111
CONTENTS (cont.)

Page

carbon disulfide 98

carbon tetrachloride 99

chloroform 1 00

cyclohexane 1 01 dimethyl sulfoxide 1 02

1 , 4- dioxane 1 03

ethyl acetate 1 04

n-hexane 105

isopropanol 1 06

methyl ethyl ketone 107

n-octane 108

paraffin oil 1 09

tetrahydrof uran 110

toluene Ill

Polystyrene Wavenumber Calibration 112

IR Correlation Chart 113

Aromatic Substitution Bands 114

Infrared Absorptions of Major Chemical Far:ilies 115

Hydrocarbon Compounds 116

Organic Oxygen Compounds 122

Organic Nitrogen Compounds 137

Organic Sulfur Compounds 146

Organic Silicon Compounds 149

Organic Phosphorous Compounds 150

Organic Halogen Compounds 152

V. Tables for Nuclear Magnetic Resonance Spectroscopy 155

Tables for Nuclear Magnetic Resonance Spectroscopy 157

Magnetic Properties of Some Nuclei 158

NMR Correlation Chart 1 59

Proton NMR Absorptions of Major Chemical Families 1 60

Hydrocarbons 1 61 Organic Oxygen Compounds 162

Organic Nitrogen Compounds 166

IV
CONTENTS (cont.)

Page

Organic Sulfur Compounds 169

Some Useful ^H Coupling Constants 171

Solvent Positions of Residual (Impurity) Protons

in Incompletely Deuterated Solvents 172

^^C Chemical Shifts of Useful NMR Solvents 174

VI. Tables for Mass Spectrometry 1 77

Natural Abundance of Important Isotopes 179

Rules for Determination of Molelcular Formula I8l

Chlorine - Bromine Combination Isotope Intensities 183

Common Fragmentation Pattern of Families of Organic Compounds. .. 1 86

VII. Tables for Qualitative Analysis 193

Organic Group Qualitative Tests 195

Protocol for Chemical Tests 197

Inorganic Group Qualitative Tests 207

Acid (Anion) Tests 208

Metal (Cation) Tests 211

VIII. Miscellaneous Tables 21 7

Common Drying Agents for Organic Liquids 219

Flammability Hazards of Common Solvents 221

Properties of Hazardous Solids 225

Hazardous Material Log Sheet 229

Unit Conversions 230

BASIC TABLES FOR CHEMICAL ANALYSIS

THOMAS J. BRUNO

Thermophysics Division

Center for Chemical Engineering

National Bureau of Standards

Boulder, CO 80303

and

PARIS D.N. SVORONOS

Department of Chemistry

Queensborough Community College

City University of New York

Bayside, NY 11364

and

Department of Chemistry

Georgetown University

Washington, DC 20057

Tables of important data for use in the analytical

chemistry laboratory are provided. These tables contain

information for use in gas chromatography, liquid

chromatography, infrared and ultraviolet spectrophotometry,

mass spectrometry, and wet chemical techniques. Tables

relating to safe practice in the analytical laboratory

are also included.

Key words: chemical analysis; instrumental analysis.

Introduction

This set of tables is intended to serve as a handy reference for both the

practicing chemist and student. Included are data which are not easily

obtainable elsewhere, collected in a source which is intended to reduce the

need for consulting a bookshelf of reference works in the daily practice of

analytical chemistry.
This technical note grew out of a booklet of tables which accompanied a

series of lectures on analytical chemistry presented by one of the authors

(T.J.B) for the professional staff and students working at the National Bureau

of Standards Boulder Laboratories. That booklet has now been expanded and

augmented by the authors in this volume. The primary purpose of these tables

is to support the teaching and research activities of the authors, and it is

offered to the scientific community as a low-cost source of useful information

for the practicing scientist.

The topics covered in this volume include gas chromatography, liquid

chromatography, thin layer chromatography, infrared and ultraviolet

spectrophotometry, mass spectrometry , and "wet" chemical tests. Aspects of

safety in the analytical laboratory are also considered. Topics such as

atomic absorption, x-ray methods, and electroanalytical chemistry have not

been included in the present volume but will be included in a future edition.

While the authors have endeavored to include data and information which

they perceive to be most useful, there will undoubetdly be areas which have

been slighted. V/e therefore ask you, the reader, to assist us in this regard

and inform the corresponding author (T.J.B.) of any topics which should be

included in future editions. The authors have made every effort to provide

correct and up-to-date information in this volume. For the occasional mistake

which may have crept into these pages, however, each author blames the other.

The authors would like to acknov/ledge the assistance of Juli Schroeder in

the preparation of several of these tables. Terry Yenser, Barb Powers, and

Marlene Deutsch are to be thanked for the excellent word processing services.

The authors would like to acknowledge one of their teachers. Professor Charles
F. Hammer of Georgetwon University, who taught them much of what they know

about spectroscopy. One of the authors (T.J.B.) gratefully acknowledges the

financial support of the Gas Research Institute and the United States

Department of Energy, Office of Basic Energy Sciences.

DISCLAIMER

CERTAIN COMMERCIAL EQUIPMENT, INSTRUMENTS, OR MATERIALS ARE IDENTIFIED IN

THIS TECHNICAL NOTE IN ORDER TO PROVIDE AN ADEQUATE DESCRIPTION. SUCH

IDENTIFICATION DOES NOT IMPLY RECOMMENDATION OR ENDORSEMENT BY THE NATIONAL

BUREAU OF STANDARDS, NOR DOES IT IMPLY THAT THE MATERIALS OR EQUIPMENT

IDENTIFIED ARE NECESSARILY THE BEST AVAILABLE FOR THE PURPOSE.

Note

Occasional use is made of non-SI units in order to conform to standard and

accepted practice in modern analytical chemistry.

I. Tables for Gas

Chromatography

Mesh Sizes and Particle Diameters

The following tables give the relationship between particle size diameter

(in ym) and several standard sieve sizes. The standards are as follows:

United States Standard Sieve Series, ASTM E-11-61

Canadian Standard Sieve Series, 8-GP-16

British Standards Institution, London, BS-il10-62

Japanese Standard Specification, JI S-Z-8801

French Standard, AFNOR X-1 1-501

German Standard, DIN-41 88

Particle British Japanese Canadian

Size, U.S. Sieve Tyler Mesh Sieve Sieve Sieve

ym Size Size Size Size Size

4000 5 —

—— 2000 10 9 8 9.2 8

1680 12 10 — — —

1420 14 12 — — —

1190 16 14 — — —

1000 18 16 — — —

841 20 20 18 20 18

707 25 24 — — —

595 30 28 25 28 25

500 35 32 — — —

420 40 35 36 36 36

354 45 42 — — —

297 50 48 52 52 52

250 60 60 60 55 60

210 70 65 72 65 72

177 80 80 85 80 85

149 100 100 100 100 100

125 120 115 120 120 120

105 140 150 150 145 150

88 170 170 170 170 170

74 200 200 200 200 200

63 230 250 240 250 240

53 270 — 300 280 300

44 325 — 350 325 350

37 400 — — —
French and German

Sieve Sizes

Particle Sieve

size, ym size

2000 34

800 30

500 28

400 27

315 26

250 25

200 zn

160 23

125 22

100 21

80 20

63 19

50 18

40 17
Gas Chromatographic Support Materials

The following table lists the more common solid supports used in packed

column gas chromatography, along with relevant properties [1-M]. The

performance of several of these materials can be improved significantly by

acid washing and treatment with DMCS (dimethyldichlorosilane) to further

deactivate the surface. Most of the materials are available in several

particle size ranges. The use of standard sieves will help insure

reproducible packings from one column to the next.

REFERENCES

[1 ] Poole, C.F., Schuette, S.A., Contemporary Practice of Chromatography , Elsevier, Amsterdam, 1984.

[2] Gordon, A. J., Ford, R.A., The Chemist's Companion , John Wiley and Sons,

New York, 1972.

[3] Heftmann, E., ed., Chromatography; A Laboratory Handbook of Chromatographic and Electrophoretic Methods , 3i"d ed.. Van Nostrand Reinhold, New

York, 1975.

[4] Grant, D.W., Gas Liquid Chromatography , Van Nostrand Reinhold, London,

1971 .
CO

CD -Po2

most

useful

for

preparative

gas

chromatography;

high

strength;

high

liquid

phase

capacity;

low

surface

activity.

high

mechanical

strength;

low

surface

activity;

high

density.

high

mechanical

strength;

high

liquid

capacity;

moderate

surface

activity;

for

separations

of

moderately

polar

compounds.

lower

mechanical

strength

than

pink

supports;

very

low

surface

activity;

for

polar

compound

separation.

maximum

temperature

of

250

°C;

handling

is

difficult

due

to

static

charge;

tends

to

deform

when

compressed;

useful

for

analysis

of

high

polarity

compounds

.

i.O

r-i oo

c

i-i CX

JJ 4J

CO —1

>> x: o 3

c

CX

-p—

3

1

f-< x:3

Maximum liquid loading 6^

C\J in oCV-1

6^

LTi

Surface area mVg

ino

O O in

=

I^

LP. COLH CO

Density

(packed

)

g/mL COo

LOo o

C\J o

0^o

Density

(free

fall)

g/mL o o

COo

COo

CMo

Support type

J-)

•.-1 E

O

pi

CO

•r-l •o

diatomite

^

•r-l -.H E S- O Xi

P)

CO t.

(D p)•^E

O

jJ

CO

r-l a

-po <x> Cl E

CX CO D C

cyD

Chromosorb

A

Chromosorb

G

X5o

COo

E

O

s_ x:

CJ)

O

COo

Eo

L

x:o

Chromosorb

T

c

CDt,>,

x:

CDO

t.o

D

i-H

CO jJ

CD P)

>,

I—

O

CX

a.

10
CO p>o

2:

most

useful

for

preparative

gas

chromatography;

high

strength;

high

liquid

phase

capacity;

low

surface

activity.

high

mechanical

strength;

low

surface

activity;

high

density.

high

mechanical

strength;

high

liquid

capacity;

moderate

surface

activity;

for

separations

of

moderately

polar

compounds.

lower

mechanical

strength

than

pink

supports;

very

low

surface

activity;

for

polar

compound

separation.

maximum

temperature

of

250

°C;

handling

is

difficult

due

to

static

charge;

tends

to

deform

when

compressed;

useful

for

analysis

of

high

polarity

compounds.

O

<-\ oo

c

r-iCX

CO rH

>> x; O 3

c

CX

p>

rH

x;3

p>

rH

x:3

Maximum liquid loading LO

C\J in om

&S. in LPl

Surface area mVg C\J

ino

o

-3- o LTl C—

Q. 1^

in

CX)

LTi LOOO

Density

(packed) g/mL COo

c»

LOo O

CNJ o

CTn O

Density

(free

fall)

g/mL o

o o

CX) o

COo

CMO

Support type E

O

03 rHa

pirHE

O

4^

03 a

^

pi o M rH E L

O XI

pi

03 t,

'>-{ •t-\ CD Cm

•p

iHEo

pi

03

r-l a.

O

a. E

D. 03 3 C

00

XIO

COO

E

O

x;o

o

X)L

O

COi

x:o

X)O

COO

E

O

X

:3

X)

J-o

COo

Eok

o

XIo

COo

Eo

u

x;o

c

>,

x:

-po

o

3

rH

Cm

03 JP

-P

>,

I—

I

O

CX

H

a.

11
Carrier Gas Properties

The following table gives the properties of common gas chromatographic

carrier gases. These properties are those used most often in designing

separation and optimizing detector performance. The density values are

determined at 0°C and 0.101 MPa (760 Torr) [1]. The thermal conductivity

values are determined at 48.9°C (120°F) [1]. The viscosity values are

determined at the temperatures listed, and at 0.101 MPa (760 Torr) [1]. The

heat capacity (constant pressure) values are determined at 15°C and 0.101 MPa

(760 Torr) [2].

REFERENCES

[1 ] Weast, R. C, ed., Handbook of Chemistry and Physics , 63rd ed., CRC

Press, Boca Raton, 1983.

[2] Dal Nogare, S., Juvet, R. S. , Gas-Liquid Chromatography: Theory and

Practice, John Wiley and Sons ( Interscience )

, New York, 1962.

12
Molecular Weight O

CM

CY-l o

o o

o

o

CMOO

O

OO

CM

o

OO

CM

Heat

Capacity (J/kg-K)

1^ U3O

OO CM

CM

OO

CJ^ O

OOO

o

OOo

Viscosity (Pa's)

0.876

(20.7°C)

1.086

(129.

4°C)

1.381

(299.

0°C)

1.941

(20.0°C)

2.281

(100.

0°C)

2.672

(200.

0°C) O O O o o o O O LPi O O O

CM^^ ^ CM

t- ^ LO CO OO o

O OO ^D

O CJ O o o o

<— t^ O

CT^ t>- 1^ ^ CM C^

--^ ^ CM

CO OO i>- r- >X) t— o in o ...

CM CM CV-)

O O O o o o ^ CM I>-

l>- t- ^

CM CM CM ^ .- CM ^ ^ C3^ OO CT^ LTi C- >- LP, ^ CM CM

o o o o o o

l>- t^- o

^ vr> [^- CM CM CM

v-' — 0^

OO ro CO

LT^ CO ^

t>- ^ LO ^ CM CM

ivity

6X

(Ar) oo COOO

CO CJ>

. o

LTi COO o

al

Conduct

Difference SX

(NJ C7^

. CM

eno

o

o

1

1

OOo

o

1

Therm

6A

(He)

CO

1

1 o

O

CM

1

C7^ CO

Cv) 7

CJ^

CM

1

o

OO

1

Thermal Conductivity X

10-2

(W/m-K) 1^

LTi oo

LO OO

cm'

LOi

CM*

^o

1 CVJ

Density (kg/m^)

OO

CO

CTn COO

o

COO

o

OO

o

o

^3"

LPi

LPi O

LTi

o

o

LTi CM

Carrier Gas C

CD

faO o

>>

::!

r-H CD

CDC

CO x:

CDE

c

CD

faO >>X

o

nitrogen

carbon

monoxide

13
Molecular Weight o

o

on

ino

CO

C\J

O

^5-

^3-

on

O

CM

CO

LO

O

Heat

Capacity (J/kg.K)

o

1

1

1

1 CM

LPl

>-o CO

1

1

o

>> .^ in ^-^

CO 1 CO O O • O ^ 03 CO X a. •M —

>

O CJ> o o o o

C\J -^ CYI t- O O

^ O v-^ r- C\J ^ m cr O -^S" o

C3> >— .:T

CD ^ ^

o (l; o o o o O O O

COO CM O O -^ ^ CM

cc ^- ^

O LH ^

CM LTi

o o o o o o

<J^ .=r CY^

tr— O 0>

.— CTv

LO CJ^ ro

C3^ O LPi I>- O (\J o' ^ ^

O CLJ CJ o o o O O O

O O O

CM

-—- .^ CM

f- ir^ oo ^ C7^ CM

CM <D CM CM CM CO

o o o o o o O r- =r O CTi CM

CM cr> CO

O ^ ^

CO ^O CM ^ CO CM ^ ^ cm'

o

O

O

Oo

CM

O

in

.=3-

ivity

6X

(Ar) Ino ^

°

on

(3

1

1

C~- O

O

1

cx) o

o

1

CMO

1

al

Conduct

Difference 6\

(N^) o

1 O1

CMO

1

LTi COO

1

CM

CJN O

1

m

o

1

CM

1

Therm

6X

(He) o

r>~i no

1 ,_

1

CO

1

0^m

1

CM

CTn on

1

.3-

1

Thermal Conductivity X

10"'

(W/m-K) . C\J

o

en

CM ocm'

o

C7^ CO

CM CO CO

Density (kg/m^)

o

inm

o

o

C\J

O

vO

CT> O

O

CM

o

m

CO

O

CJ^

c

o

C7^

CM

OoO

O CM LO •—

r-l CO

t, CO

t. o

CO o

c

03 x:

4->

CDc

Q) SZ

4-3

0)c

03

Ci. O

Jco

bO

03

0) c -o O -rH £1 X

t, o

03 •-< o -a

C

03

1C

CD X3

•rH

D Ci-i <;-< 03

i-H X

3

CO -C

14
Properties of Some Liquid Phases

The following table lists some of the more common gas-chromatographic

liquid phases, along with some relevant data and notes [1,2], Most of these

have been largely superseded by silicone phases used in capillary columns, but

these liquid phases still find application in many instances. The minimum

temperatures, where reported, indicate the point at which some of the phases

approach solidification, or when the viscosity increases to the extent that

performance is adversely effected. The maximum working temperatures are

determined by vapor pressure (liquid phase bleeding) and chemical stability

considerations. The liquid phases are listed by their most commonly used

names. Where appropriate, chemical names or common generic names are provided

in the notes.

The McReynolds constants tabulated here are based on the retention

characteristics of the following test probe samples:

Constant Test probe

X benzene

Y 1-butanol

Z 3~pentanone

U 1 -nitroporpane

S pyridine

Compounds which are chemically similar to these probe solutes will show

similar retention characteristics. Thus, benzene can be thought of as

representing lower aromatic or olefinic compounds. Higher values of the

McReynolds constant usually will indicate a longer retention time (higher

retention volume) for a compound represented by that constant, for a given

liquid (stationary) phase.

15
Properties of Some Liquid Phases (cont.)

Solvents : Ace - acetone MeCl - methylene chloride

Chlor - chloroform Tol - toluene

Pent - pentane MeOH - methanol

DMP - dimethylpentane HjO - water

Polarity: N - nonpolar

P - polar

I - intermediate polarity

H. B. - hydrogen bonding

S - specific interaction

REFERENCES :

[1] McReynolds, W.O., J. Chroraatogr. Sci, 8, 685, 1970.

[2] McNair, H. ., Bonelli, E.J., Basic Gas Chromatography , Varian Aerograph,

Palo Alto, 1968.

16
COCDo

C

03

4-> 3

JDC

03>,

•Ha

1 50^

oxazoline,

weakly

cationic

2-

(8-Heptadecenyl

)-2-

imidazoline-1

-ethanol

low

vapor

pressure

hydrocarbon

oil

low

vapor

pressure

hydrocarbon

oil

low

vapor

pressure

hydrocarbon

oil

low

vapor

pressure

hydrocarbon

oil

low

vapor

pressure

hydrocarbon

oil

low

vapor

pressure

hydrocarbon

oil

low

vapor

pressure

hydrocarbon

oil

00

-

CM m CM LO

CM CO

LH LP

COc

oo

^

-=r ro

C7^ CM LO

CM

CC) 00

CMLO LP

LP

CO •aM

O

IS! CMCM 5 CO CM LO LPl CO

CM cn

C^ c

o

-

>H

CX3 CM C» in cn

CM

CM CMCM

LPl

CY-)

5: X

00

t^

LH COen

CMon ro

CO00

CMCO

CO

4-> c

rH00

CD rH

rH

x:

rH a: rH

x: E 2:

rH

x: s

rH

x:

rH

rH

x: S

rH

x: s

r-\

X: S

i. rH

rH

x: S

jr. rH

x:

>>

-P•H

S-03 -H

1—1 1—

1

HH M Cu 2: ;s 2 s 2; 2 2;

X

OSe

CM 00 LO

LO

CX) LO

CM 00 CY-) CM fv-1

+

CY-)

LP

CM

c

•HE

1 LTi CM LO C3> in LO s cn S LPl LPl LP

T3

•rH3

•rH J

CO

03 x:

'0 c c

Jj) -H

TD

03 C

03 rH X

>.c x:

1 -P Ln

- CM

03 -—

-P3

X2•H

J_ -PM -P >> 03 -P

-H

03

rH

•HL

H

C

CX H

73

03

c

03 - -P

E-<

1 03 Cn

bO t, C- 3

CO -P

03 C

::< -H

rH E

< 03

CM

CMc

•H<

c

N

rHCX

•r( CX

C

N

•HCX <

c

•H

Q. <

2

c

[Si •HCX

c

N

•H<

c

N

•r-i a. <

17
CO

CDo

24,2i|-diethyl-19,29-

dioctadecyl

heptatetracontane,

C-87

hydrocarbon

primary

aliphatic

amine

CDC

•rH s

COo

•rH -P

CO x:ex

•rH rH

CO>,U

CO acoo

CD

CO

CD rH

•rH

4->

•rH CO

•rH -P

CO x;

ex

•rH

r-H CO

Chlorinated

biphenyl

complex

mixture

of

aliphatic,

aromatic

and

heterocyclic

compounds

sorbitan

partial

fatty

acid

esters E3

•rHco

CO

f-H>,O

CD o

CO -POo

-a

CD

r-H -P

>, tH X c

.P o

CD J-J S C

•rH CD -o X>

CD

,-t

•rH -P

•rHCO

-P

CDO

CO rHC

CD x:

ex

00

LTi OO

COcoo

:3

CM

COo M

OO

>>

CD a:o

>H

O

s:

X

OO

CO 4Jo

GO

rHO

J-O

M

rH

O

x: CD

i-H

O

x: CD OS

r-H O o

rHx:o O

CD s:

O rH

r-H (J) x: CD

O r-l

r-H CJ> x: CD O 2 or-H x:

CJi o

,—{ x:o

rHo

X.o

CD

rHO2

CDO<

-p

•.H

cO 1—

o

Cu S

OO- CQ

(X

H

CQ

Oh

CQX

Oh Cu

M IS 1—

e-H 00M COM

CJ) oX

COS CO oo oo CM oo O LPi og oo

OO o O

00

O

LTi in

00

O ooC

•iHs o

OO o

OO

O

00

•a3

cr

CD

CO

CO x;

oo1CDC

CO

r-H o

ex

Q

OOc

(D

CDE Q

C\J C

CD

CDs O1c

CD

CDB

i-

•=i:

En:00c

CDCDS< Q

rH

CD

CDC<

.::r LO

00o

rHOo<

-p

CO x:ex

CO < oOO

•p

CD

4-i <

r-H O

4-> CD

CD oXoN

CO1exa

^3" oo1CDCO

.pc

CD CQ

CD T3

•rH C

COO

Nl

CD o2

=a;1 a

•HC

to>5oNC

CD XI

rHc

x:

ex rH

•a

rHc

XI

18
CO

0)

J-> os

>,

NlC

Q) jQOCOE

,—1 Oo

>,

bO

CDC

(D>^ (D £: s: 4J 4-> CD CD

CD x:-p

CD

r-H

Nlc

(D ID

•rH

00

C\J ooo

<5 S

4JCoo o

ooen ^^^ o

C\J

CY~1 o <3D O LTl

CO •o

r-l o

tsi cwO

OO OJ CX5

m

C\J CX5

CJD c

>.

CD DCo

>H

CMCO

C\J

incn o

c^

C7^ o

LO

LH 2 X

LO LH

O C\JOm

CO

4-) C

0)>

.—1 o

00

8mM O

x: <D

O rH

rH

O

x: CD

i.O rH

rH

O

x: CD o

CD

Xo

CD

CDO oCD rH o x: < o O rH

rH

O

X: CD

O rH

•-] o

X: CD

O

rH

x:o

>>

r-i

1—1 o

I—1

1—1 M IH HH

MM \—\

Cu CL, M ooXs o

LPl

g o

LPl LH o

LO

O

LTi o inCM

C\J

OO

OvJ oocB o o O

00

O o

cr

CO

0)C

tH

r—1 oc

crO

ISl C

0) X31 CO

[>-

CD>O

COo

r—1

rH

CD CJ

rH>^

toc

CD CO

CD x:

4-> CD rH

Klc

CD

rH>>

sz-U

>>Xo

4J3 (D ,Q -U 1 CC

C\J rH — 03 x:

CO JJ

•rH x:

X) en.

,—t >>

x:

4J

CD rH>.Xo

x:

4_) CD

(D -P 1 CO

Cvl ^

^^ CO x:

CO JJ

•^ x:

X2 ca

rH

>>

x:

4-J CDXo

x:

p>

0)1 -!-> C\J CO --- o

CO CO £l

.-( CD X3 00 1 '-- C CD

CO "O >> -rH O E 1 CO

cxj

B

--^

LO

CO Cn

•rH X3 .H 1 >, 2 ,C > P> 2 ci)

iH

>,

x:

4-> CD>>Xo

x:

CD1 CD

fVI -PQ.

CO -rH •M -a

J2) CO 5

CD>,Xo

x:

j-> CD1 a)

(\J 4^

--^ COCi

CO -rH rH -O

CD P>

CO rH ^

>, CO X x:

CD -P

x: x: rH ex

>, o

x: i., P o W rH 1 x: CM O ^ fO

CO 4J •H CD JD -P

CD -p

CO •Ho

CO

,-{ oH

T3

CDc

CO P

=5 X3 1

*> rr-t O CD rH 4J

-O CO

CDC

C -rH CO o P o D 3

X) CO

19
CD -po

tetraethylene

glycol

dimethylether polyethylene

glycol,

av.

mol.

wt. <

380 polyethylene

glycol,

av.

mol.

wt.

380-420 polyethylene

glycol,

av.

mol.

wt.

570-630

methoxy

polyethylene

glycol,

av.

mol.

wt.

715-785

.-H oE>

CO

rHOo

>^

r-H bO

0)

O

C LO

CD

O

rH r-

>^ 1 x: o

-P LO

CD C7^ rHO -P

CX 3 >

CO

f-H oo

>^ o

rH

O

bO vo1 CD O C O

CD LO

I-H>, . SZ -P

jJ 3

CD>. . I-H rH o o

D. E

polyethylene

glycol,

av.

mol.

wt.

1300-1600

polyethylene

glycol,

av.

mol.

wt.

3000-3700 o

•r-t r—

CO x:

-p

x:

D.

CD

J-CD 4J

x:

4-) H3

-o

CD -P

COC

•HE -a

t- -H

CD o

-P CO

CO

C3> 00

LO

CM

COco

:=) vX> OO

LO

CO rHO

tsi LOo

CM CO

CY-,

CO en

LO

^3-

OOen c

CD >H en

LO en

CO

LO o en

LO

LO s X

C>~1 OO

en

en

on OO en

CO jjc>

I-Ho

00 o

rH

SZO

.—1 o

CD

C_)CD

r-H Or-H o

r-H CJ

CD

O

CD

I-H O1 O

CD

rHo

CD

rHO

CD

r-H

CD

.-1

X o o

CD CD

Polarity 1—

0- CL. Cu Cu cu D- CU a. Q. a. Cu Q_ ooX

COE o

LP. oo

LO

C\J LOCM LO

C\J LO LO o

LO

LOOO

CM oo OO

CM

LO

OoCE

E- o ° O o

CM o

en

LO

CM o O o^3-

O

a

•r-( 3

CT

•I-H

CD

(0

CO x:CX

CD 1 x: >. jj X CD o

x: 1—1 4J I-H <D >, E x: 1 -p CM CD 1 >>

CO

X

I—

J o

CO x:

•rH 4-> X> CD oo

enX

to3o

CO O ooX

COB

CO O oO CD 3- j->CO X 0)

CO -H 3 O O 1 X2 O

i, c

CO

O

cj E O

LO

LOX

to3o

JD

JCO ooX

CO3O

JD

CO O o cu O -P KD CO X CO

CO CD 3 -tJ O CO £> O L c

CO

O

cj e O

LOC—X

CO3o

JD

i_

(0 O oooX

COg

CO o O

LO oO X

LO CO ^ 3o X £)

CO i- 3 CO o o

CO

O o ^^ o

LOX

CO3o

to o OoX

O

CO LO 3 OO O en

JZl

to

O

a.

E-oooX

CO3O

JZl S-CO O

20
CO

<vo2

polyethylene

glycol,

av.

mol.

wt.

6000-7500

polyethylene

glycol

av.

mol.

wt.

7000-8500

polyethylene

glycol,

av.

mol.

wt.

15,000-20,000 o

•H

r—1

CO x:jj

x:Q.

x:

4-3 •H3o

4J

COC

•He -ao

4-i CO

triglyceride

of

12-

hydroxysteric

acid

(hydrogenated

castor

oil)

chlorinated

parafin,

70^

(wt/wt)

CI ooO1 4J

CO

CO •H•H

Sh 4JH>

C/D ^3-

CM CvJ

LPl o o

CMin CM

CXD

^3- OO

ro

COcoo n >-

in

CMin

m CM

CM cr>

OO

C3>

^3" o

CO o

I—1 o

(SI C^m

C3^ m

C7> OO CO

moCO

CMCO rn co

>H o o vX) ro

CM

C3>

C7^

VX5 OOo ^ X

C\J OO

C\J

CM

CvJ CM

CMen

CMen

m

OOO

CT> CM

ro

cv^ CM

COc>

l—t 5

rHOs

f—1 o

CD o

x:o o ^^s o O<

i-O

.—1 x:o O

iH

JCO rHo

a.

Cu cu a. Cu CU cu Cu 1—I

Cu 1—1 2 ooX

COs o

CM

C\J oo

CM o

CM

O

LO

CvJ

O

in

CM oo

CM

O

CY-I LO LPl o

LPl

C\J

O ooc

•HB

E- o O

O o ov£5

g

O

CM oo

•H

cr •H

CD

CO

CO x:

a. ooO (D =r 4-> CO X s,

CO (D 3 P O CO £1 O ^ c

CO o O E OO

^DX

CO3o

XD

SCO CJ 8§X

CO3o

to o o

OJX

CO3o

XD

CO o <

CU1X

CO3O

Xi

CO o X

CO3O

4J

CO

CO o o

c-X

CO3oh

rH

x:o c

rH

CO x:

4JCXo

t^o

.—1

x:o1

COoo

CO

x:

4-)

COo C rH

CO

O

X c -P

CO 03 x: x: c O J_> -H

i-H

O

O S O

>. -H 3 O -O CO c

COo

•o1c 1>. P X CO o -^

x: CO p x:

4-> >, x: X (X o

s: ^^ P -H>> -^ x: •H 4J O

21
1 !

0)o

00

4-> coo .

CO o

rHo

c

>>

O)o

o

om

COON

CO

05 JJC

a)> 1 a- 1—

1

1 o

o i=C CO

I I

COon

onm

o

o

CM

CvJ

in

CM

on

v£3 o

C\J

CvJ

o

OO

vX5

ITi

O

roO

CO

o

D

o

inro

CO

OO

OOo

in

.3-

(D

OO

O

OO

OO

OvJ O

CMOO

ro

CO

LTi OO

o

O

icu

o

X

03SLTi O

O

OvJ O O o

o CM o o o

o

E

O

l7

OCO o

ro oC\J

>! 1 Xo tt) T-; 4-> 4-> r- (D 3 Cfl zt ra JD D.

' CO s ^ •rH

-.-4 x: M •o

_1 Du a rtl

E o -<

>, 0) >. X .tJ 4-J o 03 D

-U r-- .c D 03 1 x:) ^ c

-^^ 1j 1 •fH x: •.-* X3 Q. -o

0) -p

03m

x:x:ex

rH

•a

r—I

I

si

'-'

! >> c

73 Ol

J3 .-Hi •^ Sl\

I03

t4-)

0) 4J

03 .H

03 x:

-p

o

(i>

•rHl Ol

X

SI -!-> O 03

r-H .—

I

CJ 03 >> s: O -P —I SI o ex

o

o

>^

i-H o

c

,— CD

x: 03

(D —

t

.,H T3

T3 03

oo

c o

.—

I

03

SI 03 -P -P3

-a bo

oo

>,

r-H bO

(Uc

CD O

nH 4-3 >, 03 £ O

4-3 03 0) J2!

•nH CD -O CO

O

O

>,

r—

f

hO

o;C CD

CD 4-> ^ 03 >> C

x: —I

4J 'J CD O

•--I 3]

o

O

w

CDC

CD CD

r-- 4J

>, 03 s: ^

4-5 03

CD CD

•rH +J

X3 CO

I X

>, CD x: 4J

4-> 03

CJ

1 03 ro x:

-—' 4-> -' x: T3 CX

22
COo

j-> COCl

•n-l •o

CO -^

4-> Oo a

•rH O

COo

r-i

•-{ >,Xo

X3

Itoo

f-( am O o

00Q

CO inC\J CO

CO

LPl CO

CM o in

in

COo

CO

C7> in DVD

COcoo

:3

O

CO

CM

CTn LO OO

:3- o

CM

CO

CM

cv-i

CO

cv-i CO

O

cn

CM

CO oo M CM COo O o

CM

m

CO in o

in c

>>

CDo

>H 5

CO

C\J OO

CO

LTi c-^ oo cn

CJ^

CV, CO CO 2 X

CM

cv^ c—

CO s

•=r C7^ cn

CO

CO

C3^

COc>

r—1 o

00

0)O<

.-H o

1—1 o

CD 2 o o

CD CD rHo

E-H

CDo< o<

rH CD O OCDO o

rHO

rHO

CD

O

rHC< 3

CD rHo

ErHo

E-H

>>

4->

r-{

r—1 o

a.

Cu 1—1

00 CQ hH Q- cu t-H

M a, HH 1—1

a. Cu

M hH ooX

COE

EO

LTi

C\J

LPl

C\J LO

O

C\J

O

Ln

in o

ITi

O

in

in o

in

O in o

CO o

CO

O

in

O

in

OoC

•iHE O

cn1 o

CNJ1 OCM

O1 O

CTn o o o oCO1 oCO oCO o

CM1

•a

a0)

DX

cu x:

4-> CD 0) -P 1 CO CM D. — •,-(

-O CO

rH>.X

CD x:

x:+j -p

CD CO 1 o

(AJ CO ^- n o CO

CD

CO

t,CO

J_> s_

CO

4-)1 Q1 1—1

>.

SZ

4-> CD

•r-H X3

--I O

5-CDO

bO

-a

(D -P

CO rH

to x:p

x:D.

i-H>>

to rH

•H•o

CD

J-> COQ.

•rH •o

CO

r-H >,O

(D •oo

CO

•r-H •rH •a

CD

COCX

•rH o

CO rH

>,

-POoo

CO

r-i

•rH a

(D p

CO

r-H to x:p

x:a.

i-H>,O

CD oO

CO

•rH

•r-H

CD

4-J COo

CO JD

tD

CO rH>^

P>Oo

CO a

rH

s:

4J CD

tD c B CO

•rH rH a o 1 ti-H - 3

CO CO o

•rH E

•rH •o

J-) CO

•—t CO x:p

x:

a.

r-i

4-> ooo

CO ^

•o

CD -o

•rHE

toE

suo

ti-H

rH

.c

-p

<DEa

CD •o

•rHXo

Cl-H ,-{

CO

r—{>>

x:-p

CDE

•r-H a

CD

to

r-tCO .c

+J

x:a.

•-^>icoc

•rH -o

CD P

to

r-HCO -Cp

x:CX

rH>.oo

rH

23
CO

CD -Po

2:

aryloxy

polyethylene

oxyethanol

epichlorohydrin-bisphenol A

resin,

av.

mol.

wt=

900 1—1 oo

>,

rHXo

CDc

CD 1—1

>, CD x: -p

4-:> CO CD U

>> CO ^ CD O -P a CO o

•H

-p

CO x:aH

.-HCO •o

CO iH

>>Xo

x:

•p

CD CD >> C

:H -H O E a CO

CO cn

CM o^3-

:3- o cn

cn

(3> OO

cn

CM

CX) OOOO

COCoo

:=) CDCO

CT)

CJ^ on

in o

COcn

O

cn

in

in 5

OOoCT^

CO •o

I—1 o

ISl COo

C\J CM LPl CM

O

CM

CMCM

on

LP

CMOOO

v£5

CDo

>H LTi cn

CJ> OO

.=r

CMCOOO

C7^ cn VX5 oo

s:

X

CMo

CM COCM

C3^ OO

CMcn

cn

LP. cn

LPl

Solvents .—1 o O

O o o

r—1

x:o

rH

CJI -P

CD

O

5: x:

CJ -P

CD

O ^ x:

rHo

CD 5:

r—1

CJ> CD .HoCDO

rHo

CD

O +-> CD O s x:

Polarity I l-H cu

n CU 1—1

a.

a. a.M IH

D-IH IH 1 "o 111 X 1 O

n3 ' o E ^ OO C\J CM oo

CM

LPl CM CM

LPl CM

CM ooCM ooCM

LPl CM

CM ooCM ooCe o o1 o o O O oo Oo

-D

•r-J CD

COCO JC

D.

CD

4-) CO

c;> CO £)

CD

CO -^

1:^ o

0)E

03EO

c^

-H

>>c

CD

J"—

m

rH

CO -C

4-> r-CX

M

O

>, <U Q, O^

c_ x:

Q.

O 1 CO C !- ' 4-^

(I) 4J

CO .—1

CO sz

x:

Ci.

r—1 o

CD o

[>- CO1c3

J-O

a. oo^o

CMO

(0o

.c

-p c

<D

CDEO

.c

4J o

iH

b.0

CDC CD CD P>

,H CO >> CX

x: -H

jJ -o

(D to oo

>,

.H

bO CD <D -P C CO

CD ^

.H CO >. x: ^ -p -p x:

CD D- oo

>>

•—{ w

CD

CD -P C COC

rH -H

>>

O

x: o

-PD

CD rn

,HO

,HM

CD

CD -P C CO

5- ^ CO >> -P

x: 3

Jj rH oo

>>

.—1 w

CD CD

CD ca rH O

>, CO x: n

jJ (D

CD CO

24
CO

CD 4Jo2

CO 2:

&SC\J CO "

2:H 2

%«. fe«. 0-1 ^

CM in

Carbowax

20M

nitro

terephthalic

acid

ester

-PC

CO

j->

CO Cu

:_

:3COc

suCO

CD 0HS

CO

SCD

4-3 CO

r-i >>

x:

4-> CDe

•H

-0

CD •a•Hs

CO

CD rH

rH>>

x:4J

CDs

•H0

(D •He

CO

!-

x:a.

CO

x:

rH

x:

4J

CDE

COX

(D x:

CD 4J

CO

C2. •H

•0

CO rH

>,

rH

bO

CDC

CD rH

x:

4J

CD H

X3

00 CM

CY^ CM in

,—

^3"

m

CM COin

COCOo ^

CO

CNJ j3-

CO in

CM

CY1 CM

CV-) 00en

CM

CV^ in

COo

tsi COm

C7N

CNJ

C7N

CV-i

CY-) CO on vO

CDo

>H CO

in

en

C\J CO

in c»CM >- t^

CY-|

2:

X 00 CO

CO

CM

C7N CO

in

in CO

[>-

CV-)

CO

•4-> c>

CO

r—

5:

CD

M

i.

r-i x: CD CD 5:

=1;

1—

CD

.—1

CD x:

CD CD <CD <

rHx:

r-i x:

>1

4->

iCO 1—

Cu ' CO

00

cu 1—

CQ

MMM IH cu

cu

X

COs CNJ 00 in

CM in CM in in in

CM in

in

CM

CS

C\J S CM CM CO

CM in CM CM

•a

D"

•rH

<D

CO

CO

ST.

0) 1^

1—

CO ^ x:JJ

x: >^ a M

CD rH c s:

(D

(—1 CO >^ L

x: -p

4_> (D CD -i-i

>>bO

CDc

CD rH>.

CD

1—

a>

CJ -IJ >i CO M J-. bO -i-i •H

CDC

C

CD ^

rH CD >> >

x: <-i

4J> -H

CD CO

H

4->

CD 4J

(D

Cu<

CD -o•He

COH

i-

.—

CD

.HbO 1 CJ>

[x.

to

L.

.—

00T

•a•HE

•-^ rH

CO X 1 COT

-oHE

i-H rH

CO X

in

CM1c

CO

rH

CO X

CMinmc

CO

^^

CO X

><ONc

X)

CO

,—t CO X

CM

CYl Tc

Xi

SLh CO

CO X

;3- T1§

£1

CO

:-\ CO X <

cuX

CU<T

CmW1 •HX

25
CD r-H •p

Jj CO ^-v

CO 0) .>-^ JP I-H •—\ C -p (D -0 CO 4P P> CO -p >->

•rH ct3 •P c CO -p CO x: CO

a

,—{ c CO i-H c ^ C CO -p I-H r-i Cl CO rH CO x: CO t. c 3 •rH C 4-^ V c CO XI Q. x: ex m CO X3 CO 3 =5 '<-i X5 -p

x: 3 CO x: X3 CO 3 g CO CO x: >,

-U r-H CO -p CO CO CO •f-{ Q.

X

CO CD ^ r-H rH I-H r-H (U E r-H E I-H I-H rH I-H S- Jj •M >> •rH >, c -0 o 0 f—{ >> T3 >, -1 CO >, >. 2 bO >, ^ .-H a X >> I-H >5 >> x:

0) f—1

bO I-HW 1 -p rHM I-H I-H 1 c bO C >, ^^ bO w bO C\J

ct5 0)

C rH CO x: ^ > rH I-H

—

X 4J> CP >,X jp >i ,

0 -P >,

CD Cd rH

C J-> -P 1 CO

C 4P c c CO x: c >, (n c x: -p E -P c ^ C c H CO -M sz r-H CO CO CO c >, -^ I-H I-H I-H ^ ^ -p >. ex ^ Ci S_ Q. a. CO C Q >, G. >, >> CO tCD jr. —1 jj •rH -P x: i= x: -P

>>

D •rH jj >i -0 -o 3 X 3 4P 4P 4^ 3

CO -0 c CO jP CO c XI Q, CO

C CO

tm a^ t^

CO ,

vO c» CM , v-D ^3- CO t^

Jj

CO LH co CY^ C7^ c :=> in o> ^3- ro o v£) ^r CO CTN ^ o

CO 00

m ro

m CM

TD

N LH

m c:> ^^T CJ^

r-H ^=r ro LPl vD -=r oc

>> ^D ^ ,— t~- CM

>H tr— .=r LPl OD ^ CE LO .=r t- f- C- o

2: '

C\J ,c:> f- VD

[r- ^- C^ 00 CT)

Xm C\J =r in

m

CO 1 Jj> 1 C 1 s- ^ s_ i- S- t- S_ J_ J- i- s_ J- J- CD 1 X > 1 r-H ^ r-H ,—{ ^ .—1 ,-H I-H I-H rH I-H ,-H I-H .-H 1 SZ x: sz x: x; x; X x: x: x; x: x: X 1 CJ CJ c_) CJ s: 00 1

>> 1 Jj 1 rH 1 cl. a- a. Cu cu cu Cu Cl. Cu Cu Cu D- D_ CU L •. . •> ^ - - > - ^ ^ ^ -

CtS 1—1hh' I-H

n l-H I-H 1—1

t-t t—1

t—\

M hH hH i—f Cu 1 ^

a. 1 uX c LO

CC ^ uo O") LT. LT^ ro cv~) CO ^T CM E CM CM CM CM CM CM CM CM CM CM CM CM CM CM H 11 C• fH C\J LH LH C\J LP E ,

,

^~ , ^

T ^

1

I H 11111ii 11ii1t! 1 G- CO

a. CD G. Cl. O. CU cu Cu CL. CO C. cu Cl. a. 1 1 =1: CO CD m < < cE C2 X CiH ^

Q- 1 CO 1 C\J OD ,

C\J on CO CT- on. ;T CM C^ rg OvJ 1 1 1 1 1 1 1 1 1 1 7 1 1 1 1 ! a Cm '"(-( ^ C-H c^ C|_. Ci_< (t-, C^-i ^ Ct-i CtH CtH C|-H CO ! •iH 0) Ck-, '"-t-i <t-i £.-< <i-i <i-. '^-^ Ct- Q-j r^ ^ C^H Cm CtH C^-i 1 3 CO to uJ M uJ UJ IJJ td LJ tJ LJ U2 Ld ua X t. 1 cr m 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ex 1 ^ x: -rH rH •rH •r-^ •rH •rH •rH ^^-^ •rH •r.{ rH rH •rH 'f-^ >> J a. X H X 3: X X X X X rr" X X X X X

26
CO

CDo2

high

boiling

ester

of

pentaerythritol

and a

saturated

aliphatic

acid

J10m O

nonyl

phenoxypolyethyleneoxy

ethanol n=

30

nonylphenoxypoly

(ethyleneoxyethanol) n=

100

nonylphenoxy

poly

(ethylene

oxyethanol) n= 9

OO o(3^

-3- C7^ ^ CM

^3- OO OO OO OO

-p

COcoo n

CXD CM

"" CMC»

^3" o CMOOOO

OO

CM o O

CO •ao

ISI OO CO1 ro

LTi OO

LO

CM

C7^ CO ro

vX5

CO c

>,

CDO

>H C\J CO

^3- C^

CM

CM OOo OOOOCO l^- OO OO S X

CM CM

CM

OO

C3^ CM

CM00 o

CO

O

CO

COco

rHO

rHO

CD

-pc

CD Cu

4-> c

CD Oh oCD

O

CD

rHO -P

CD

O s x:

rHO -P

CD

O

O -P

CD

O s x:

3:: oCD

rH

CD

•r^

COO

a.

a.

Du 2 S 1—

2 MM HH h-\ HH

Cl- HH ooX

COS

E- o

in

O

O o in o

in

OO

CM 8CM oOOvJ oo

CO o O

in

OoC

•rHs

LTi

C\J o

CM

O

CM o

c»

OOO § oo o

•r-i 3

•HJ

(D

CO

CO x:

Cu 1 O

CO ^

•H o

:s; >,

COO

X 1 <D >i

x:

Xo ^ x: in CD - o ^ C '- « lO CD ro >> C - O CO CM 1 X - CM CD <- --' x:

O8X

CD

•—{ Cmoo

CD X.

CDC

COO

CD a

COX

CD x:1c

CDC

(DO

CD o

COX

CD x:

rHoc

COo

CD o

COX

CD x:1

CDc

CO -pcoo

•rH

•P

COX

CD x:

O

C»

CO1 oo<

cuo

hH

O

0^

CJ\1 OJ

<C

D-o

HH o

OO1 oO<

Cuo

HH

O

OOoo<

cuwo

HH o1 oo<

cuo

HH o1 o

(J) <

a.w

HH

•—{ r-{

-P

•rH CO

•rH Q.O

a.

•rH •ao 1 c

CO. •rH - e

CQ .rH

CD

•rH HOC

•rH D

CTO

CO

27
COO c

rH

CO

(U

S0)

COco

Jn3o

>.

.—

o

ex

rH

•rH oc

•HCm

CiH(0

COCX

complex

mixture

of

petroleum

liquids o

eg1

a,

Cu

CObOc

rH

LP

cnbOc

•H

(DE

rHo

CX

x:bO

•rH x:

00 COCO CMm

:3- t^- '-

CvJ mLO CM 1 en

C7^ eg

4-) mco

^3 o

en

en

in

^o o

CV-l

m

LPl

on

en

^3-

on

on

mao

IS]

C\J CM

CM CO

CM eg ^^ 1 coen

CO

CM

eg c

>>

0)

ce: o

>H LO

CM CO ^3-

in o

C>~l

LTl in

in oooo

LO

LPl en

on

en

eg s X mCM 1^

Cvj CMo^ o

CXD on

eg

egenLPl eg

COCO

COc

r—

O

00 s o o

rHo

1—

o

CD

1—

o

CD

.—

O

CD

pC

a.

piC

CD Oh

CDO< XO

CD rHo

rHo O

cd" o<rHo

ErH

JnJ

r-H O

CU

Du 1—

1—

1—

M s 2 CU Q.

M ^ (HM

CJ) o X

03s O!>-

C\J oo

C\J o

CM oCM

LTl

C\J

LPl C^ oo LTl o

CO

eg

O

LPl eg

LPl en o

LP

eg ooen

O oocs O

CM

CM o O

OinOin o

LPl o

en o LPl eg o oLP

•rH 3

cr

(DCO

ct3

C

COX

<x> o

-p

•rH cc

COE

rHOO

>,

rHhO

r-H>,

+J CD C -P

CD CIS D. CU. O -I

(D "O C CO

rHoo

>> CD rH -P hO CO M rH >^ CO -p x: C -P

CD

X o o

CD CO C -rH

i-H oo

>>

rHbO

rH

>> CD P -P C CO CD O

CX CO O J3

CD CD C CO

rHoo

rHW

rH CD >> -p P CO c c;

CD -H

CX o o o

CD 3 C CO o

•"—) 32

CDC

COo

(D -o

CO P>OO1c M-PHco

J- o

CDC

rHE

CO ^ CD O -P C CO rH CO C

>5 iz: •H C pi o

CD CD

O

x: -H 3

Q. -O CO

CDcE

•rH

CDC

CD rH

x:p

CD>.

rHo

CX

CDC

CD

<-t>!X

rH

>,c

CD x;E1>>

rHo

CX

CD x:

pi

CDc

CD x:

CX1EL

.HO

CX

CD x:pi

CD

rHc

CD x:a1E1 rHo

CX

CD x:pi

rHC

x:CX1E1>i

rHo

CX

28
CO

CD

4-> O2

COc

•rH ooo

CM

II J

rHOs>

CO o

•rH rHO

>.O

,—{ o

•rH "Oc

COCX 4P O CO

i- c

CX o

CM I, « CO ^ o

N,N,N'

,N'-tetrakis

(2-

hydroxypropyl )

ethylenediamine

poly(propylene

glycol

adipate)

poly

(propylene

glycol

sebacate)

CO c\; CM

CO

CM CM

CM

C7^ CO o

CY-l -Pcoo o

CM 5on CM

CM

l>- oCMon

CO o

1—1 o M LTl CM

CO <3^ o OO

cri CM co

>H

CM

LPl cnLPl CM

^3- LPl o

ro

s:

X

c»

CM CT> CMCM

CM o CM

LPl

CO -pc

CD>

1—1 o

CO

O

CD

O

CD oo

rHO o

rHo o o<

a:

i-o

,-i szO

rH2 o

-pc

Cu

-pc

cu

JP

•H

CO

i-H o

hH . 1—100

CUHH D- HH

g

CQ

n

M D- 2:

HH2" ooX

COS

EO

O

LTi LO

CM

CM

in

OO

CM

O in LO

CM

CM

O

LPl oo

CM

O

CM

O oo OoC

•-HS

E- oLPl

OOC\J o

CM

O

O o O

OO o O

O o

C\J

T3

•r-4

•f-H

CD

COCO (X

CD x:

-p

CD

rH

>>c

x:O, CD 1 c E CO 1 ^

>, CO rH 3 O cr CX CO

r-l oO

bO

CDC

rH

>,

CXO

CXO

CX

,-{OO

rH

bOC

rH>.

CXO -P

t, CO CX CJ >. CO rH J2I O

CX CO

rHOO

,—i bO

4->

C CO

S^ rH -P >^ -rH CX c o

CX

>. >

rH rH O -rH CX CO

C

•rH B

•r-\ C

rH>.

CXo

inCX

>.

rHO

CX

-P

COco

SL. COOc

•-\ >1ao

t.CX

CO

CO>!o

CX c

rH

O

>. -o C -rH •H rH > o

>^ S- rH L o >> CX CX

rHo

CD'

OX

r-{ CXo OOX

,-{ CXo

cc

rH

•rH

-P

•rH Coo

CO X3

CO c

CO rH

COcr

CO c

•-^ CO3

cr

CO

29
to

^.

—s Xo C

v._^ •iH

IS i-H E X o to

U] 4J •t-< O CO CDc

•iH

a > s: CD x: c ^ Q. Kl CD 4-3 o C t. >, .-H OT jc; CO CD r! !L >>

<D o r-l JD 4J CD x:

4-> o CO T—1 X to 4-> O r-H >, >. •r-H 4-) 2 CO .—1 o E C >.

n3 (D 1 0)

X o c o 4-:i O CI o

•^ CT3

O (D

C c -a SJ- •a 4-> CO CO CD o o o CO o 4J >, 4J >-. >1 •iH E C CO o O CO x:

x: o 3 O 1 CO to '-H CO

cti !- -I Cw 2 Cm c >>

L

X (D o ^ < J- 4J x: 4-) CD 4-> o =s Cu 3 4J

x: CO CO CO 00 00 4J> CD 4J

t^ CO

m ITi CT> I>- OO

00 CM UD ^ CJ^ vo LT. ro ^ C3> , vX) CM ir\ CM Ln CY^ CO CTn CO

jJ

CO

O \D CM CO ,— C7^ o CO ,— c ^ ,

,

LO !^ t^- CO C\J ^ o o vD CM vO cn ^ cn C7^ o OO o

CO fY-i

OO CT^

_ CO [^- on vO

•o

N ,

O t- .=r Lf> ^£5 LTi C- t>- CM

.—1

m ^q- ,

.3- CM •a- CM KD t— vr> oc

>. (M VD vO ro o O

O CM o CM

0) >H CO CO vO in CO f- CO CO ^ •=r Cd \r\ in CM m on \S\ m t~- CO CTi o

s:

C\i LO [>- in CM XT t~ <o t~-m

m -^ CTN on t^ -:a- cr^ CM ,

^ X C\l ro CT) ' CV-i ' in ^ ^

CO -Uc i. e <L t.

L s.

CD o o X

O

M o <-\ .—1 X

O o > r—1

r-i o ^ o 0) 1—1

O ^ o o <—{ r-H rH x: x: CD x: 0) o x: CD O (D CD x: x: o o o s: o s: a: o s: H S S o o

00

>>

jj^ Q- D. a. cn 1—1

Cu

:_ - » •. ^ •. CD - CQ

n3 Q_ h-1

o_ 1—1

1—1

D- a. a. DX I-H

X

i-fO

a.oo X o li^

O o o o LO LH o O

O o in

OJ LO Ln ^— LO o LTi r— ^- in I^- in o CM H ,

CM CM ^

CM CM ,

t

CO ^

CM , HOoC LH O O o O O o o o o O

•rH ,—

O CO CM C3> ^ CT) o <— E ^— X— f

E0) ^

CD 4-) CD

O

4J CO 4-)

O 1 n3 -l-> CO o o >. 4J 1 CD <x> 4-3 •nH •H .—1 c CO r—1 o CD c o bO CD tH

O

O CO J-3 o o to CX ^ '-- t

o CO to to •.-1 CD CD CO <-t 1 c X 4-5 to c o C C c_ >.

00 o (D CD <D 4-> o H CD CD 4-> x: a1 E x:

ra to oo 2 .—1

to

i-H CD 4-)

4-) r—1

CD c .—1 J_ rH x: x: x: 1 o O 4-> to o >1 (D o 4J 4-3 4-3 ^ c

X! 4_) CO -U 4_) CO JJ CO 4-> x: CD CD - to

•rH 0) r-l c •iH •W

O

D o rH LTl U2 Q. to to CD

m >. c Q

D CO JD Ou o £! X3 1. X3

L bO ro D_ CD S_ 1-C - o to to O" Cfl J- cC ex J- t. o o o i- 1 Ci] ;- 4-> J_) -rH CM 1 J^ u •-< x: o H 'r-^ O O D CO D <D O- o CD CD CD E - CM Zi X J D- CO 00 00 CO CO CO ••H CO H 2 E- 4-> 4-> 4-> CO ^ v_^ X5 E30
CO

(D

4-> O2

CD

4-3 CO szex

COo

x:

ex

r-l rHO

•rH

4-> o•iH o

COo

•rH rHo

X3

COo

•rH 4J

•»in O

rHoc

CO x:

+j

CD rH

x:

CD>>

<-\ o

Q.

>>Xoc

CD x:cx

4Joo

rHoC

CO .C

4->

r-\ >>

x:

4-> CD>>o

cx

>,Xoc

(D x:cx

>-> oo c

CO 4J

rH

X3o

CO CD >> 4J X CO o t, x: 3

4-3 CO

CD '-f >, o o o

cx e C

CO

4-) rHX5

t.o

CO>> OJ X +J o to x: (D 4J <-i CD O

>> o

rH

C o o

cx s

105^

polyethylene

glycol,

90^

propylene

glycol

00

C7N

CNJ

caD t—on

CMon o

C>~1 ^3- CYI o

eg

COcoo

HD

0)

CO on

CMC»

O

CvJ o

CO

CO

CO

=1-

m.:q- eg

en

1—1 o

IS] o

CO

•rH o

C\J

on CTN CO

rvj CO

on

OO

eg

CO

LO c

>>

cco X C\J CY^ C\J CO

cy\ on ^3- o

on

eg s X bO

^3- C7^

.=r o

eg

CM

CM

egeg

CO

COc

r-( o

CO o

CD 5:

O

CO

CDO< Xo

CD

Xo

CD

Xo

CD

Xo

s:

CDO< o

rH

x:o o

CD

CDO< O< Xo

CD

Xo

CD T. o

rH

x:o O

a. CU 1—1

I-H

X ' CU 1—1

a.

Cu Cu hH Du Du cu ooX

COE

E- oo o

C\J C\J oo oo

CNJ o

en LOC\J

O^3- o

C7N o

CM

O

ITi CM o

LO o oo

CM

Oc

•r-l e

E- o O

OvJ

O

C\J oen oCM o

CM o

CM

O

eg

O

eg o

eg

O

CM

O

cr

r-4

0)

COa

x:

CD

i-H

•rH

r-t CO

r-HCXO

cx

•rH 1 -a - o

CQ .^ - x: CQ JJ) c

•rH

CO

r-{

4-)

CDo

x:ex

JO

•H

S4-)

CD

fO sz

ex

COo

x:a. rH

>>

CO

CD

t-oH

4->

CDc

•Hs

CO rHOc

(0 x:

-(-> CD

•fH o

•r-i O

CO

0)e

•rH

4-5 1Oc

CO

CD 1 C

C\) CO ^^ cxo

CO s-

•-H cx i^1 >, ":§

<- CD

>>

ClH

CmO

-o a; >, 4-J x: CO CO x:

i- cx

CO 4-> CO

•rH CD o

!- 4-> x: 4J --^ cx

rH

x:

4-> CDoC CD

CO

C

>^ CO o x: 1 4->

CvJ CD ^ eo

CO S-. •rH 4J

i- -rH

OOTXco

4-J rH

LHOCY-) 1 Xco

4J

•rH

ECD

4-3 CO x:cx

COo

x:cx

rHo

•-{>,X

4J o

eg

O

OO

EX1 o

LTl

LP.1 CQJOO

:=>

31
CO

CDO2

305^

polyethylene

glycol,

70%

propylene

glycol

40^

polyethylene

glycol,

607o

propylene

glycol

5055

polyethylene

glycol,

50^

propylene

glycol cH

CO

CD

SLh

CD

•rH S

CO rHO

CX

•rHto

(D

CD o

•rH E

CO rHo

(D -P

CO

CD ^

rH

COoO3

rH

CD -P

COO

•C

CXE

COoooo

rH

COoo

rH

C|-l

807o

polyethylene

glycol,

}0%

propylene

glycol c

•rH CO

CD

•rHE

(0>,

iHO

CX

00

c^J o

en ro

inCO

CM

O

CM

CO

cu ^S

C^O

CM

CDCOO 3 CT)

CJ^ on

CM

LPi CM

CM

CM

CT^ l>- en

oo

CT^ o

i>- CM

CO T3

rHo

ISI c—

CM

C\J

CV-) CM

CX) CM o

CO

CO o

CMcn

C3^ in

CT^

CJ^ CU ^^ c

CDo

>H

CMon

j3- CJ^ m

CO CO

CT^ LO

CY^ o

C\J ooCM

CM OO

oo s X

t-t^

CMO

CM CM

CMCO

CJ^ OC^O CM

CU o

oo UD

LTi

LPi CU

CT^ O

COc

rHo

00

O

rHo b

szo

rHo

CD oCD

rH

(D

O

CD 2

rHorHO

CD

rHo

CD

'e

CD t- O CO < 2

rHO

CD

rH

CLJCD

>>

•rH

CU rHo

a.

(X Cu Cu hH Qh Cu hH 1—

hH hH Cu Cu ooXE oo

(AJ ooC\J

Oo

C\J oo

cu o

in

cu ooCM

LPi

Oo

CM ooCU

in

Oo

CU

O

LPl

OoC

rHs o o o

CM o

cu o LPi LTi oo o

CM

LPl o

•rHcr

•rH

CD

COro .Ca.

X1 o

CO

C\J1 To

LPl 2O

:3 ooo

cu1 m1 o

LTi Oo

:=3

O

CQ

3::1 o

LHO

CJ) ^3

inTa2O oo

CT^

CD

•rH E

CO

CO

i.

CD > O

C7^

CD a

•rHE

CO

CO

S^

CD >

CD 4J

CO

jc;Q.

COo

szCX

rHc

CD rH>,X

H

<-{ >>co

ISI

r-H COM

CD -p

CO

CO

CD

COoc

•rH

OO

CT^11 LPl o O

OO

C7^

CD •o

•rHE

CO

CO

S-CD >

32
stationary Phases for Packed Column Gas Chromatography

The following stationary phases have been shown to be useful in

separating the following classes of compounds, using coated packed columns.

The resolution obtained will probably be lower than that obtainable with

capillary columns. Alternative stationary phases are to be found in the

previous table.

Compounds Suggested Stationary Phase

- Alcohols

Ci - c. Hallcomid M-18 OL, Carbowax 600 - Carbowax 1540

r - c

* FFAP, Carbowax 20M

Di-Poly FFAP, QF-1, Porapak Q, Porapak QS

- Aldehydes

Ci - c. Ethofat

C 5 ~ Ci 8 Carbowax 20M

- Alkaloids QF-1, SE-30

- Amides Versamid 900, FFAP, Ethofat or Carbowax 600 (on

Chromosorb T)

- Amino Acid Derivatives DEGS/EGSS-X

- Amines Dowfax 9N9/KOH, Pennwalt 213, Chromosorb 103

- Boranes Apiezon L, Hexadecane, Octadecane, Squalane

- Essential Oils * ** FFAP, Carbowax 20M

- Esters DNP, Porapak Q

- Ethers Carbowax 1500 - 20M

- Glycols Porapak-Q, QF-1

- Halogen Compounds Carbowax 1500-20M, QF-1, FS-1265, FFAP Porapak

(for freons)

* - consider a capillary column

** - consider HPLC

33
stationary Phases for Packed Column Gas Chromatography (cont. )

Compounds Suggested Stationary Phase

- Hydrocarbons

Ci - C3 Carbowax 400 - Carbowax 1500, Proplyene Carbonate,

Tributylophosphate , Didecylphalate

c - c * Carbowax 20M, SE-30, Squalane

Aromatics Tetracyanoethylatedpentaerythritol, DNP, Liquid

Crystalline Phases (such as Cyanobiphenyls,

Cholesterics)

- Ketones Lexan, FFAP, Carbowax 20M

- Nitriles FFAP, XF-1150

- Organometallics** FFAP, SE-30 (lower temperatures)

- Phosphorous Compounds SE-30, STAP

- Silanes SF-96, STAP

- Sulfur Compounds Carbowax 20M, FFAP, DNP, Solid Absorbents

* - consider a capillary column

** - consider HPLC

34
Silicone Liquid Phases

The following table lists the chromatographic properties of some of the

more popular polysiloxane based liquid phases [1-8]. The polysiloxanes are

the most widely used stationary phases in gas chromatography, and are

especially applicable to capillary columns. The listing provided here is far

from exhaustive. Since it is impractical to present the structures of all

polysiloxane-based phases, the OV phases have been chosen as representatives

since their properties are among the most well characterized. The phases

which are listed in the notes as "similar phases" have thermal and

chromatographic properties which are similar to the phase described.

The McReynolds constants are indices with respect to the following test

probe compounds:

McReyno Ids Test

Consta nt Probe

1 benzene

2 1-butanol

3 2-pentanone

4 1-nitropropane

5 pyridine

6 2-methyl-2-pentanol

7 1-iodobutane

8 2-octyne

9 1 ,4-dioxane

10 cis-hydrindane

The use of these constants is described in the previous table

35
Solvents

Ace - acetone Chlor - chloroform

Tol - toluene

Note : denotes a phenyl group in a structure.

REFERENCES :

[1] Yancey, J.A. , J. Chromatogr. Sci., 23, 161, 1985.

[2] McReynolds, W.O., J. Chromatogr. Sci., 8, 685, 1970.

[3] Mann, J.R. , Preston, S.T., J. Chromatogr. Sci., 11, 216, 1973.

[4] Trash, C.R., J. Chromatogr. Sci., 11, 196, 1973.

[5] McNair, H.M. , Bonelli, E.J., Basic Gas Chromatography , Varian Aerograph.

Palo Alto, 1969.

[6] Heftmann, E., Chromatography: A Laboratory Handbook of Chromatographic

and Electrophoretic Methods , 3rd ed.. Van Nostrand Reinhold, New York,

1975.

[7] Grant, D.W., Gas Liquid Chromatography , Van Nostrand Reinhold, London,

1971.

[8] Coleman, A.E., J. Chromatogr. Sci., 11, 198, 1973.

36

00

wd

COaoow

T3

vO

O lO a

CO

CNl

p>

1—1oouo

TOeHoo

73

en

CM

eg

CN

inooO

enoo- 4-> r-H <U I E > -H O T3 00

CNII

en

CM

en

en

iT)

unoo

COo

CN

•H

CO I—I O -P T3 ^ <U -H I S 3

>• -H r-^ O T3 i^-i

00

-JC3^ COm

in

00

00

Csl

00

00u<o

in

COo

CNl

(Uco I u

r-H 'H >. rH

XI -H

4-) CO

OJ r-H S >. ^ XI - >^ P

CO

C OJ I <U S > X: -H O 0,-0

in

COo

CN

00

00

CMu<o

in

COo

CM

OJao 1 u

1—1 -H >.^

XS -H

4-> CO

(U i-H E >.

r-i x:

>, 4-» r^ C (U 1 0) S > x: -H O a-o

in

CM

(7^

COOO

00

C3^

1—1 CM

in

CM

csl o

OJu<o

in

CO

(Uao 1 u

r-l -H >M-(

x: -H

+J CO

QJ r-t s >. ^ x:

1-H >» -p

1—i

a OJ 1 (U E > j3 -h O CUT3

38
O

00

CTi :s

#s 1 >. CJ

•l-» o

•H •-3

> w

•iH d -

+J o tn U •H <r

1—

4J hj

dJ !-l C_) W

:s dj o

1—1

4_) (U I—

CI w

>. o x:

s: cii a,

j-> <u 00 u B C TO •H r—

O

?^ r-H -H CO o •H E 1 o O -H w l-H ^ W U5

dJ

u

r o

1

CO 1 00 W •H W

u

1

-CO

1 .. J

•HW

O

u

to 00

<

+J o o

T3

•H 0) a' c3 •H X!

7—1 <U > -H O T3

>. o cu

^J o < •iH •-<N H

> W3 1 zn

•H a u 4-1 o o - u •H O

(U 4-> i-H 1—

:t3 >—1 >—

OJ S-l 1 (>J w to u

OiQ Dh

:s <U C/1 o w ••

1—

w -

4-> <D ^ . *^ C W ON

r—•H nj i >^ o x: pm X! a o-c/2

4-> <u 00 u - E C (0 o

•H rH lO

?=r*; rH -H in o •H E 1 o O -H CJ

l-H XI W Q

on

I o

.(/I .o

I

n

I—I CN

>> lO

x: I

(u cn E

r-l O

>^ 4-i C

OJ ^

x: tc a,--H•H &« s O -H

r-4 W

I o

00 I

I

o

o

o

00

[fl

00 >

o

x:

0) -T-l E a

r-J r-l T3 +-!

I ; o 00 I oo W -H X

u W — CJ

I L

x:p

OJE

I—Ia

dJ x:O

CM

OO

I oI u —

1

r-l — cn —-e-

' 1 c

1 1

oo

I o

•H 'CO

ol-H r-~ CJ

CI

1—

>. • • XI w

4-> <u

<u w

E ns I—

XI

>. Oh d

0) M

XI tfl arH

•H

s-s E

uO •--I oo w

CJo

I •H

• cn —i-eI

oo

•CJ

o

o

LO

'J'o

(U

elo

u

1 -H

r—1 r—

>>>H

X! W

4-> OJ r-l S >>

rH XI

». >. P

00 d 0)

1 OJ E

> X3 -r-l o OiTD

o

o

in

*o

0)a

o

1 u

r-H -H

>,r-l X) -H P tA

QJ l-H E >.

r-l XI

>» P

r^ d <u

1 <u E > X3 -H O Ph'O

oo

CJ

I o

'cn- •CJ

o

o

LiO

no

(LI d

o

1 u

r-H -H >,rH

x: -r-l 4J W

<U l-H E >%

T-( XJ

l-H >. -p

r-H d 0)

1 0) E

> XI -H o OWTD

39
CN <t

00

1—1

00 LOo w l-H pam r^ C^

j-> I—1 w 1—1 ao

C_) v^ <N

I—1 w r—(

T3

I—1 O LO CM

C!O

>. CM

<L) «u -^j- ro S <r

Csl

CO CM^l-H

CM cx: uO

CI

<u>

r—I O

CO

-po

0-1 oXsoeH

•H OJ cr CO •H x:

hJ CM

OJu<o

LOCOo

CNl

X3

OJ (U B C

I—I o

>.

u

Cl -H

OJ r-i Si -H

00

CM

CM

CMCO

CM

LO

CO

ro

CO

lo

CM

CO

00

CM

00

00o

0)o<O

LO

COo

CM

01dou

•H

I—I i—t >% -H ^ W

4-1 (U r-i E >. ^ Cl CM >, (U CM fl X! 1 OJ a, > XI -H o OiT)

lO

I—I

CMo

OO

CM

lOo

CO

00o

CMo

CM

00u<o

LO

COo

CvJ

<uaou

•H

i—t I—1

>>-H

XI C/3 4-> V 1—1 s >.

-H

C

LO >. <U CM C JH 1 0) Cli > XI -H O Ph-O

00

C3^

CO

l-H CM

CM

COo

C3^ CO

LO

00

\0

00o<1-oH o

inCOo

CM

O

LO

COo

CM

>> siu

<ue

•HTD

rH (U >. C c o

T-H (U

u

VO Si -H 1 Cl,rH > •iH -r-l o T3 W

X3

+Je d H 00

I—I

(U >. Cl a o

CO 0)u

r^ x: '--I >• 'H -H O "O w

40
!-i (0

r-H O

•H LO S csi •H CM W 1 w eu

<u --I C/3

J-> >. o jid » j_i .. OJ W

S ojw

S-2 TO O j3 in &

cuu

o

d

s^

4-» CO

P o

;5 s

T3

•H D

CTi TO •H x:

l-J P-i

r o

CJ. M'

>.

4-1 •H /-N M +J o

O W o

U O CO m ^w/ 1—1

COo

d

si

O

I

r o

CO I U (73

O

O

lO

O

X

00

c

X!

Oh

X) W

<U r—

S >^

r-l C

CnJ >, CU <Ni c x: > Xi -H O OiTJ

c

(U X!

in

I O

I •H

I

r o CO I W -H u —cn- L

o

o

o

o

o

o

0)

cio

u

1 -H

I—1 r—

>.-H

X3 W

4-» (U ,-( s >.

i-H fl in >^ <U (N d xj

1 0) ft > XJ -P O ftT3

CI

OJft

CO

CO

r 1 o CO I CO W -H w

u —en —

I I

o

I -coo

o

o

o

m

o

X!

+-) (Ue

•H

I-H 0) >> c! d O

--H (D U

vO X! 'H

I ftrH > -H 'H O TJ W

w

0)M <r

.—

TO in >>X3 1 c ft W OJ CO

x: U

ft TO 1—

Csl

?r*: •H m in e 1 • •H w

in W w

I o

I

00

LOo

X

00

x:

4-> OJ s

E 3

•H 00

Id

rH 0) d o

CO QJ U

r-~ XI -H

I ftrH > -H -H O X3 W

41
4-1 cMco <f U v£) r-~ W

T)

1—

vo o m 00 c

>.

(U « c^ u <r CO s I—

CO

CO 0^

oo

CM o1-H

vD 1—

CO c>

r—

o

CO

•H

i-1 TO

i-Ho

CJOXBHoH 0)

cri TO •H x:

CMu<o

uO

CMO

CM

>. <u Si c

•P o

OJ o S -H

-—1 rH

>. -H

Oh

W o

S-l r—

& >%

LO X3 o O 4-1 I—

a (U 1 m s > >.-H o O 73 o

CO

00

CM

in

ON

CO

CMoO

CO

oo

COin

CO

00oo^-^

s:

CJ

a*

in

eg

I—I u

>>

a

a, o o u

!-l •^^ OiT—

O -H U W o O 1—

>i

CM "^-^ X! I -H 4-1 > S-l dJ O -U S O

CO00

CM

in

oooo1—1 CO

oo

00

in

CO

00

CO

CM

Si

cu

in

<MO

eg I rH 0) >1 d

CL,O o u

S-l -H

D4.-I O -H

S-i

w o O 3 I-H

.-I ^ >, CM LH x; I -H 4-1 > i-i 0) O -u E

in

00o

in

1—

CO

00

CO

ooo

04

OJD

r-1 (U >, a

Q,

O

C (J

S-l -H P-rH O -H

S-l

W o

in 3 T—

1—t rH >.

c^ vi x: 1 •H 4-1 > S-l 0) O Hi E

42
w

OJo

0)u

o

S-l 00

><

+J o

•H 0)

fO f^ w

I o <r W -H og III O 'W C_) C_)

I

ro

4-) o H /—

o

CO 4-1 LO o CO u u 1—

w ^—

•H>

>> 0) X! C

4-) O

0) u

S -H

T—1 1—

>>-H

Oi w O

S-i i-H a< >. LD J3 O O +J

r—

a <u

1 n: S > >.-H o U T3

:3 I-H I-H o 1+^ <f

<N

>.CL, acn

o

^a W

o 0) u w

o CO d -C

1—1 ft m

H !-i

!-l n3

4-1 1—

•H &« s O •H m w

I o

CO I U Ol.

I L.

ro

.CJ CJ

o

o

O

i-H (U >> CI Ph O

O U

i-l 'H

Onr-t O -rH

i-l w

o

CN d rH O rH >,

CM ^ 43

1 •H 4-) > S-l 0) O +J S

o

oI—

CM

>> 1 Qh Q

o en

s-l • ft w »- o OJ uO

s-l w ^

o TO CM

=! J2 1—1 i-H ft 1 4-1 W

H s-l Pm

S-l TO

4-1 r—

».

p-l 1—1 &^ s 1 o •H til in w oo

o

o

o

X

I rH 0) >. a

ft o

o u

s-l -H ft rH O -H

5h W

O O d r-H

r-H r-l >.

C^^ I4H JS

I -H +J > !h OJ O 4-) S

fto

!hftO

!-l O

d

4-» o

m

e

d

00

r-l (U >> cl ft o

o u

Sh -H

ft rH O -H

!h W

O

IT) d rH

1—

rH >.

CM 14H XI

1 •H 4-> e > S-l 0) d

o ^ S 00

43
OO c

4-> wCOu o w

r—I o in c

OS

CO c>

T—( o

•H

S-(

r—I o

OhOX

TOsHUo• -( <u

•H x:

CMmo

in

CM

(N

CsJ 00

CsJ

OO

CN

00

COcn

CO

00

CM

CM

0)u

CLi

CMo

CM 1 t—1 o

r-H >,

u

>. c •H Oh OJ 1—1 o s: •r-t U Cu w

LO CUr-( r—<

CM o >^ >^

Csl c x: x: 1 TO 4J 4-1 > >. OJ 0) o U S s

0^

00O

00

00oo

00

OJu<

CLi

\0

ON

00

COoo

00uo

r-i Xi

CvJ o

CM o

LOo

TO OJ O d

LO

d o

r~- TO

u

CM >. •H 1 u 1—1 > -H H O 'O w oo

COwXo

44
s~s

W -

in o

CN --^

rH 1 M - >.x

<U rH XJ

W +J >. +J o C 0) 2; 0) s ••

-fl i-<

w

ft >> OJ ft w

5^O t\3 IT) !-i J2

<N Oi ft Oc

CO>^u

uuW 4-J O C/3 O U

•H OJ S W H XI

1-J Cli

O ^ o r O

CO . I m -H O'—w-o vO

CO 1 x; l^; X, •H ro III u — CO CJ —-C_)

L ' 1 ooo . u CO > 3 o

<: 1—

. ,-1 X

+J o

;s s: 00

<u

C!O 1 i-H U ^ >>-H

>. CI n^

Oh 0) -H O J3 W

Vj &<

m Ph.—1 nH

CM

O >. >,

CN

G J3 X! 1 to +J +J > >, (U (U O use oooo

CM

COoX

03 0) O c

in

d o

r- (0u

(N >. •H 1 u r—

> •H •H O T3 W

cu

c:ou

•H OJ i—l d

•H CO W O

r—

X

>>

u

x; CO

4-1

u

0)E o 1 J-1 1—

tu • • d 0) <r

CO c

i-i CO o X o

XI o •H

!-i rH 4J

CO •H CO U w S-i

CO CO u u — I •H I oI •H

•CJ

Or CO

•H

K

•CO—u I c oI corn

CO u oo

CO

OJ

fl

COoXy>

COUICO •P

OJs oX

CO3o o o o o o

vC

O I-H CNl oo i-i CO <U ^ P.

•H 1—

w o X ft

0) o Q u

45
cri

00

4-) c

«3

4-) UlCo

T3o in c

(N c

a;>

(—1o

C/3OoX

to o

oc

ocoO

CJ

O

COo

<NO

in

00

ino

inCOo

CM

"O I—

•H (U •H 3 W W

cr (15

X

•w jn OJ 1^ a^ Q

COXQ

46
(Uoz

u

J-l u

en

•H /^> O CO u u

<

4-» O

c (U

OJ a

-C . c^ 03 Dh i^ S-i <u O

1—1 Q ^

>. >^ S^ xl 1—

1

TO

^-) o o

OJ Cu E o o

u J-» I—

1

(U • . c (D <XJ in

(0 C c

S-l o to •s o u X o

XI •H o •H ^ 1—

t

1—

J-> m •H •H TO CJ W w !-l

en X

o

I -o0-)

I

CO Xc_).

I o

I •H

• en

I o

en

I

on XC_3 X

X

• w CQ

O TO O !-i --• O X X3 O S-i i—i TO oa u

CJ X

CQ

O O

o o

o o

CM \0

o

o<!

T3 1—

1

•H (U •H 3 w W

cr TO X

•H XI OJ hJ cu Q

0)do

u

•H

1—

1

•H

CO

1

* ^ (D u a

CD. 0) TO

, p, O

F—

1

^ XI

>. u

JS Oi TO +J o U

<v u e o

1—1 4J r-H QJ >> d x; <JJ LD

TO 4J c

Vj 0) TO »- O o X o

Xi a o •iH V^ TO 1—1 4J

TO >. •H TO U U W U

X

-enCO X

1 o Z <N CN 1 fO

III X X -H X CJ CJ —-a —en —'CJ o fO 1 CO X -H X CJ —cni—CJ o OJ

1 o c o T—

TO oo 00 1 oo X S-l X X -H X o O

CJ CJ —en —

u

I—

I

XI

1 1 m U

• 1-1 u TO

II

CJ

1 00 TO X f—

U

CJ PQ i)

J h*w e

o o

o o

o o

On OsJ

•H

CQX

o

47
Adsorbents for Gas-Solid Chromatography

The following table lists the more common adsorbents used in gas-solid

chromatography, along with relevant information on separation and technique [1-3]. They are used chiefly for the analysis of gaseous mixtures. The

maximum temperatures listed represent the point of severe resolution loss. The

materials are chemically stable to much higher temperatures. The 60-100 mesh

sizes are most useful for chromatographic applications. All of these materials

must be activated before being used, and the degree of activation will influence

the retention behavior. Due to surface adsorption of solutes, some

experimentation with temperature may be necessary to prevent tailing or to avoid

statistical correlation (or a propagating error) among replicate analyses 1^2.

REFERENCES ;

[1 ] Jeffery, P.G., Kipping, P. J., Gas Analysis by Gas Chromatography , Pergamon

Press, Oxford, 1972.

[2] Cowper, C.J., DeRose, A. J., The Analysis of Gases by Chromatography , Pergamon Press, Oxford, 1983.

[3] Breck, D.W., Zeolite Molecular Sieves , John Wiley and Sons, New York, 1973-

[4] Bruno, T.J., J. Res. Nat. Bur. Stds. (U.S.), 90(2), 1127, 1985.

48
Packing

Name

Maximum

Temperature

°C Separation Effected Notes

silica

gel

300 H2, Air, CO, Ci to C4 normal

hydrocarbons, alkenes and

alkynes

used often as a second column (with

a molecular sieve); very hydrophilic; requires activation; can be un- predictable; largely replaced by

porous polymers.

porous

silica

300 Same as silica gel higher surface area than silica gel;

often used with a humidified carrier

gas; can be coated with a conven- tional liquid; Spherosil and Porasil

are examples.

alumina 300 light hydrocarbons at ambient temperature (Ci to C5)

H2 and light hydrocarbons at

subambient temperature

often useful with controlled waterpreadsorption after activation; can be coated with a conventional liquid

phase.

activated

carbon

300 H2, CO, CO 2, Ci to C3

alkanes, alkenes and

alkynes

requires oxygen-free carrier gas;

largely replaced by porous polymers.

graphite 300 light hydrocarbons, H2S,

SO2, CH3SH, sour gas

often modified with small quantities

(1.5-555) of conventional liquid

phases; requires oxygen-free carrier.

carbon

molecular

sieve

300 H2 (O2, N2 co-elute), CO,

CH^, H2O, CO2, Ci to C3

alkanes, alkenes, alkynes

high affinity for hydrocarbons; re- quires oxygen-free carrier.

molecular

sieve, 5A

225 air and light gas analysis;

H2, O2, N2, (CH^, CO, NO,

SFg co-elute)

synthetic calcium alumino-silicate

(zeolite) having an effective pore

diameter of 5A; CO2 is adsorbed

strongly; 5A usually gives the best

results of all synthetic zeolites;

should be activated before use, and

used above critical adsorption temperature; 21.6% (wt/wt) water capacity.

49
Packing

Name

Maximum

Temperature

°C Separation Effected Notes

molecular

sieve, 1 3X

200 same as 5A, but with C^ to

C^ alkanes, alkenes, and

alkynes being separated as well

sodium alumino-silicate (zeolite),

having a larger pore size than 5A,

thus producing lower retention times

and less resolution; 28.655 (wt/wt)

water capacity.

molecular

sieve, 3A

200 light permanent gases potassium alumino-silicate (zeolite);

20? (wt/wt) water capacity, smaller

pore size than 5A, thus different

retention characteristics.

molecular

sieve, 4A

200 light permanent gases sodium alumino-silicate (zeolite);

22/5 (wt/wt) water capacity; retention characteristics differ from

5A due to smaller pore size.

50
Porous Polymer Phases

Porous polymer phases, first reported by Mollis [1 ], are of great value

for a wide variety of separations. They are usually white in color, but may

darken during use at higher temperatures. This darkening does not effect

their performance. High temperature conditioning is required to drive off

solvent and residual monomer. The polymers may either swell or shrink with

heating; thus flow rate changes must be anticipated. The retention indices

(c) reported here are from the work of Dave [2]:

Index Test Probe

w Benzene

X t-butanol

Y 2-butanone

Z acetonitrile

The physical property data were taken from the work of Poole and Schuette [3]^

References:

[1] Mollis, O.L., Anal. Chem., 38, 309, 1966.

[2] Dave, S., J. Chromatogr. Sci., 7, 389, 1969.

[3] Poole, C.F., Schuette, S.A., Contemporary Practice of Chromatography ,

Elsevier, Amsterdam, 1984.

51
Packing

Name

Maximum

Temperature

°C

Material

Type

Free Fall

Density

Surface

Area

Pore

Diameter

Av. ,\jm

Chromosorb

101

275 styrenedivinylbenzene

copolymer

0.30 <50 0.3-0.4

Chromosorb

102

250 styrenedivinylbenzene

copolymer

0.29 300-500 0.0085

Chromosorb

103

275 polystyrene

,

cross-linked

0.32 15-25 0.3-0.4

Chromosorb

104

250 acrylonitrile

divinylbenzene

copolymer

0.32 100-200 0.06-0.08

Chromosorb

105

250 acrylic ester

(polyaromatic)

0.34 600-700 0.04-0.06

52
Packing Retention Indices Separation effected

Name W X Y Z

Notes

Chromosorb 745 565 645 580 free fatty acids,

101 glycols, alcohols

alkanes, esters,

aldehydes , ketones

,

ethers

hydrophobic, condition

at 250°C; not recom- mended for amines or anilines , lower

retention times than

obtained with

Chromosorb 102

Chromosorb

102

650 525 570 460 subambient temperature:

H2, O2, N2, Ar, NO, CO;

Ambient temperature:

H2, (Air + Ar + NO + CO), CH4, CO2, H2O,

N2O, CgHg; Above

ambient temperature:

C1-C4 hydrocarbons,

H2S, COS, SO2 , esters,

ethers, alcohols,

ketones, aldehydes,

glycols

may entrain some species; hydrophobic;

condition at 225°C; not

recommended for amines

or nitriles; little

tailing of water or oxygenated hydrocarbons

Chromosorb 720 575 640 565 ammonia, light amines,

103 light amides, alcohols,

aldehydes, hydrazines

hydrophobic; high

affinity for basic

species; not recom- mended for acidic

species, glycols,

nitriles, nitro

alkanes

Chromosorb

104

845 735 860 885 sulfur gases, ammonia, hydrophobic; condition

nitrogen oxides, at 225°C; not recom- nitriles, nitroalkanes

,

mended for glycols and

xylenols, water in amines; moderately

benzene polar

Chromosorb

105

635 545 580 480 permanent and light

hydrocarbon gases;

aqueous solutions of

light organics such

as formalin

hydrophobic; less

polar than Chromosorb

104; condition at

225°C; not recommended

for acidic species,

glycols, amines and

amides

53
Packing

Name

Maximum

Temperature

Material

Type

Free Fall

Density

Surface

Area

Pore

Diameter

Av . ,\^m

Chromosorb

106

250 polystyrene

,

cross-linked

0.28 700-800 0.05

Chromosorb

107

250 acrylic ester,

cross-linked

0.30 400-500 0.8

Chromosorb

108

250 acrylic ester,

cross-linked

0.30 100-200 0.25

Porapak-Q 250 ethylvinylbenzene-divinyl

benzene copolymer

0.35 500-700 0.0075

Porapak-P 250 styrene-divinyl 0.28

benzene copolymer

100-200

Porapak-N 200 vinylpyrolidone 0.39 225-350

Porapak-R 250 vinylpyrolidone 0.33 300-450 0.0076

54
Packing Retention Indices Separation effected

Name W X Y Z

Notes

Chromosorb 605 505 540 405 fatty acids from fatty

106 alcohols, up to C5;

benzene from nonpolar

organic compounds

hydrophobic, not recom- mended for glycols and

amines

Chromosorb 660 620 650 550 aqueous solutions of

107 formaldehyde; alkynes

from alkanes

hydrophobic; moderately

polar; not recommended

for glycols and amines

Chromosorb 710 645 675 605 polar materials such

108 as water, alcohols,

aldehydes, glycols

hydrophobic; condition

at 250°C

Porapak-Q 630 538 580 450 similar to Chromosorb

102

similar to Chromosorb

102; condition at 250°C

Porapak-P 765 560 650 590 similar to Porapak-Q hydrophobic; low

polarity; larger pore

size than Porapak-Q,

thus lower retention

times are observed;

not recommended for

amines or anilines;

condition at 250°C

Porapak-N 735 605 705 595 similar to Chromosorb

105; high water

retention; CO2 , NH3,

H2O, C2H2 , from

light hydrocarbons

condition at 175°; not

recommended for

glycols, amines, or acidic species

Porapak-R 645 545 580 455 ethers, esters, H2O

from chlorine gases

(HCl, CI2) nitriles

and nitroalkanes

moderately polar;

condition at 250°C; not

recommended for glycols

and amines

55
Packing

Name

Maximum

Temperature

°C

Material

Type

Free Fall

Density

g/cm^

Surface

Area

m^/g

Pore

Diameter

Av. ,[Jm

Porapak-S 250 vinyl pyridine 0.35 300-450 0.0076

Porapak-T 200 ethylene glycol- 0.44 250-300 0.009

dime tha cry late

Porapak-QS 250 ethylvinylbenzene-divinylbenzene copolymer

Porapak-PS 250 styrene-divinylbenzene copolymer

Tenax 375 p-2,6 diphenyl- 0.37 18.6

phenylene oxide

polymer

56
Packing Retention Indices Separation effected

Name W X Y Z

Notes

Porapak-S 645 550 575 465 normal and branched

alcohols, aldehydes,

ketones, halocarbons

high polarity; not

recommended for acidic

species and amines,

condition at 250°C

Porapak-T 675 700 635 water in formalin

(and other aqueous

organic mixtures),

retention characteristics similar

to Chromosorb 107

condition at 180°C;

highest polarity of

Porapak series; not

recommended for glycols

and amines

Porapak-QS 625 525 565 445 similar to Porapak-Q silanized Porapak-Q,

reduces tailing of

high polarity

compounds; condition

at 250°C

Porapak-PS similar to Porapak-P silanized Porapak-P,

condition at 250°C

Tenax similar to Porapak-Q highest thermal

stability of all

porous polymers

57
Cryogens for Subambient Temperature Gas Chromatography

The following table lists properties of common cryogenic fluids used to

produce subambient temperatures for gas chromatographic columns [1-4], These

properties are of value in designing low temperature chromatographic

experiments efficiently and safely. Due to the potential dangers in handling

extremely low temperatures and high pressures, appropriate precautions must be

observed

.

REFERENCES :

[1 ] Zabv^takis, M. G., Safety with Cryogenic Fluids , Plenum Press, New York,

1967.

[2] Cook, G. A., ed . , Argon, Helium and the Rare Gases , John Wiley & Sons

(Interscience ) New York, 1961.

[3] Brettell, T. A., Grob, R. L. , Am. Laboratory, 17 (10), 19, 1985.

[4] Cowpe'", C. J., DeRose, A. J., The Analysis of Gases by Chromatography , Perganon Press Oxford, 1983.
Liquid/Gas

expansion

ratio o

r-4

.—1 o o

CJ^ COso

iQ-i

in CO CO

CO

Critical

Temperature °C CY-l CMCO1

co' TCM1 1

C3>

CM1

Heat

Capacity,

Cv

J/kg.K 638.06

(15.6°C)

1686.99

(15.6°C) CTn

LTi

CO. <o cn . ^ LTi cn VCO '^ ^. 00 ^

cn CM

t^cn^ . ^ LPl cn -^

Heat

Capacity,

Cp

J/kg-K

CO o

cn LTi oo ^

2205.39

(15.6°C) v£5 ^-^ CO. LPi ^ ^

00. cn ^

<\J CM . cn ^

CM

cn ^-- •^.

CM CM

CM --^ in

in >>l

JJ

O

•rH »—

(0

X o to CO • •H CO > a,

CO o ^ o

^' CM -

CM^ CM

vo. CM CM ^

CM

CM CM ^:g- t^ LPi vo

CJN ^ CM

Thermal Conductivity

w/m-K ^ O

T— o o o

CD

=r

CM ° 'S

1—

CY-I ^^

LPl CM ^• CM

---

00 ^ ^^^. ^^

Vapor

Pressure (MPa) CM

O

I^- o in CM * * * * *

Boiling

Point,

°C

CO1 1

CY^ CO1

LO CO1 5LPl1

CM

CO\o

CM1 c

cubO CD o e

>. cO o Carbon

Dioxide CO2

"0C

CO x: ^ P X

CD 5: c

faO >. CM X c

bO i, < c

bOL CM

-P 2 2 s

•H^ X X

S-, 3

rH

M -p

CO > > ^ ^ ^ CD

i-H rH Cl. B > >

-P 4^ c C 4-> CD c

S- t. •H

CD d) £1 Ci cx

CO IP ,— T 1

4-> CO LP LP

rH

cd

.. •H

CO .p

-p •H

•rH i^ e .• •rH c i- rH • bn Q.

>, iU >,D

-P •H

X CO •H a:

r—

CO

•rH -rH JD

COa

f; •H

CO

D

ClH *

59
Some Useful Fluids for

Supercritical Fluid Chromatography

The following table lists some useful carrier fluids for supercritical

fluid chromatography, along with relevant critical properties [1]. These

fluids have either been used or proposed for use in supercritical fluid

chromatography or supercritical extraction.

Fluid Tc(°C) Pc (g/mL) Pc (MPa)

Carbon Dioxide 31 .3 0.460 7.4

Ammonia 132.3 0.235 11.3

Nitrous Oxide 36.5 0.450 7.2

Sulfur Dioxide 157.5 0.520 7.9

Water 374.4 0.40 23.0

Methanol 240.5 0.272 8.0

Isopropanol 235.3 0.273 4.8

n-?entane 196.6 0.232 3.4

n-Hexane 23*^.2 0.234 3.0

D i chl or of luorom ethane 178.5 0.522 5.2

Trichlorofluoromethane 196.6 0.554 4.2

Chlorotr if luorom ethane 28.8 0.578 4.0

dichlorotetrafluoroethane 146.1 0.582 3.6

dichlorodifluoromethane 111.7 0.558 4.0

Benzene 288.9 0.304 4.9

Xenon 16.6 1.155 5.9

Toluene 320.8 0.29 4.2

[1 ] Bruno, T.J., Proc. 2nd Symp. Energy Engineering Sciences, 81, 1984,

60
II. Tables for Liquid

Chromatography

61

Solvents for Liquid Chromatography

The following table provides the important physical properties for the

selection of solvent systems for high performance liquid chromatography (HPLC)

[1-5]. These properties are required for proper detector selection, and the

prediction of expected column pressure gradients. The values of dielectric

constant aid in estimating the relative solubilities of solutes and other

solvents.

REFERENCES ;

[1] Willard, H.H., Merritt, L.L., Dean, J. A., Settle, F.A., Instrumental

Methods of Analysis , 6^'^ ed., Wadsworth Publishing Co., Belmont, 1981.

[2] Snyder, L.R., Kirkland, J. J., Introduction to Modern Liquid

Chromatography , 2'^'^ ed., John Wiley and Sons (Interscience) , New York,

1979.

[3] Dreisbach, R.R., Physical Properties of Chemical Compounds , Number 22 of

the Advances in Chemistry Series, American Chemical Society, Washington

D.C., 1959.

[4] Krstulovic, A.M., Brown, P.R., Reverse Phase High Performance Liquid

Chromatography , John VJiley and Sons (Interscience), New York, 1982.

[5] Weast R.C., Handbook of Chemistry and Physics , es'"*^ ed., CRC Press, Boca

Raton, 1983.

63
Viscos ity uv Refractive Boiling Dielectric

Solvent mN'sec /m^ Cutoff Index Point Constant

(20° C) nm 20 °C °C (20°C)

acetic acid 1 .31 ^ 15) 1.372 117.9 6.2

acetone 0.30^ 25) 330 1.359 56.3 20.7 ^^')

acetonitrile 0.34^ 25) 190 1.344 81.6 37.5

benzene 0.65 278 1.501 80.1 2.284

1 -butanol 2.95 215 1.399 117.7 17.8

2-butanol 4.21 260 1.397 99.6 15.8 (^=)

n-butyl acetate 0.73 254 1.394 126.1

butyl chloride 0.47^ :0 220 1 .402 78.4

carbon tetrachloride 0.97 263 1.460 76.8 2.238

chlorobenzene 0.80 287 1.525 131 .7 2.708

chloroform 0.58 245 1.446 61 .2 4.806

cyclohexane 0.98 200 1.426 80.7 2.023

cyclopentane 0.44 200 1.406 49.3 1.965

o-di chlorobenzene 1.32^ 25) 295 1 .551 180.5 9.93 ^^^^ n,n-dimethylacetamide 2.14 268 1.438 166.1 37.8

dimethylformamide 0.92 268 1.430 153.0 36.7

dimethyl sulfoxide 2.20 286 1.478 189.0 4.7

dioxane 1.44^ 15) 215 1.422 101 .3 2.209 ^^'^ 2-ethoxyethanol 2.05 210 1.408 135.6

ethyl acetate 0.46 256 1.372 77.1 6.02 ^2=)

ethyl ether 0.24 218 1.352 34.6 4.335

glyme (ethylene glycol 0.46^ 25) 220 1.380 93.0

dimethyl ether) i heptane 0.42 200 1.388 98.4 1 .92

hexadecane 3.34 200 1 1 .434 287.0

hexane 0.31 200 1.375 68.7 1 .890

isobutyl alcohol 4.70^ 15) 220 1.396 107.7 15.8 (^')

methanol 0.55 205 1 .328 64.7 32.63 ^^=)

2-methoxyethanol 1 .72 210 1 1 .402 124.6 16.9

2-methoxyethyl acetate 254 1.402 144.5

64
Viscosity uv 1 Refractive Boiling Dielectric

Solvent mN«sec/m^ Cutoff Index Point Constant

(20°C) nm 20 °C °C (20°C)

methylene chloride 0.45^^') 233 1 .424 39.8 9.08

methyl ethyl ketone 0.42(^') 329 1.379 79.6 18.5

methyl isocimyl ketone 330 1 .406 -144.0

methyl isobutyl ketone 0.54(25) 334 1 1.396 1 16.5

N-methyl-2- pyrrol i done 1.67('') 285 1 1.488 202.0 32.0 nonane 0.72 200 1 1.405 150.8 1.972

pentane 0.24 200 1.357 36.1 1.84

petroleum ether 0.30 226 1 30-60

6-phenethyl amine 285 1 1.529(25) 197-198

1 -propanol 2.26 210 1 1.386 97.2 20.1 (^0

2-propanol 2.86(»^) 205 1 1.377 82.3 18.3 ^'')

propylene carbonate 1.419 240.0

pyridine 0.95 330 1.510 115.3 12.3 ^"^

tetrachloroethylene 0.93(10 295 1.506 121 .2

tetrahydrof uran 0.55 212 1 1.407 66.0 7.6

tetramethyl urea 265 1.449(20 175.2 23.0

toluene 0.59 284 1 1.497 110.6 2.379 (")

trichloroethylene 0.57 273 1.477 87.2 3.4 (is)

1 ,2,2-trichloro-1 ,2,2-

trif luoroethane 0.71 231 1.356(") 47.6

2,2, 4-trimethylpentane 0.50 215 1.391 99.2

water 1.00 <190 1 1.333 100.0 80.0

o- xylene 0.81 288 1.505 144.4 2.568

p-xylene 290 1 .5004 138.5 2.270

65
Modes of Liquid Chromatography

The following flow chart provides a rough guide among the various liquid

chromatographic techniques, based on sample properties [1].

MW < 2000

Low

polarity Reverse phase,

Aqueous mobile phase

Nonionic

Medium high

polarity

Liquid, solid, or bonded phase

MW > 2000

Acidic

Anion exchange/ion pair

Ionic

Basic Sample

Cation exchange/ion pair

Water soluble Steric exclusion,

Aqueous mobile phase

Water insoluble

Steric exclusion.

Nonaqueous mobile phase

[1 ] Courtesy of Millipore Corporation, Waters Chromatography Division,

66
Reverse Phase Materials and Solvents

The following chart provides a rough guide to basic solvent systems for

bonded reverse phase packings [1]. These packings are the most widely used in

high performance liquid chromatography.

Sample Column packing Mobile phase

Low/moderate polarity

(soluble in aliphatic

hydrocarbons)

Moderate polarity

(soluble in methyl ethyl

ketone)

High polarity

(soluble in lower alcohols)

Bonded C- 18

Bonded C-8

Bonded C-2

Methanol/water

Acetonitrile/water

1 ,4-Dioxane/water

[1 ] Reprinted with permission from: Willard, H.H., Merritt, L.L., Dean,

J. A., Settle, F.A., Instrumental Methods of Analysis , 6^^ ed., Wadsworth

Publishing Co., Belmont, 1981.

67
HPLC Column Packings

The following table provides a summary of the general characteristics of

the more popular stationary phases used in modern high performance liquid

chromatography [I-3]. The most commonly used phases are the bonded reverse

phase materials, in which separation control is a function of the mobile

(liquid) phase. The selection of a particular phase and solvent system is an

empirical procedure involving survey analyses. The references provided below

will assist the reader in this procedure.

REFERENCES

[1 ] Snyder, L.R., Kirkland, J. J., Introduction to Modern Liquid

Chromatography , 2^^^ ed., John Wiley and Sons, New York, 1979.

[2] Poole, C.F., Schuette, S.A., Contemporary Practice of Chromatography , Elsevier, Amsterdam, 1984.

[3] Krstulovic, A.M., Brown, P.R., Reverse-Phase High Performance Liquid

Chromatography, John Wiley and Sons ( Interscience) , New York, 1982.

68
•o -o c CO

CO CO •• •H rH 3 £1 to C^H -H L TD CX o O i. •H JD c -p H O • a o c

X3 .—1 -a ci_, CO

O E •H S O -P i—i • c H C E D CO Cm -.H CO o CO CO -0 c o TD .O

•-

C <i-i

O X3 o •iH o >> .p • X3 t. o •iH -p o i^ -a pp -p >. CO -P

COC

D CO E Jj CO -P CO

C •H x: 3 CO

CD -HC CO ---1 CO o bO ^ > > cx 3

x: CO •t-t •i-H -P 3 E H -H to rH E

Q. COO "O x: 5- .—1 O CO E a -p -p i- CD x: -H -p cx o c O -H bO •H

X o CO +j o p cx cx i, o CO CO o t, cx

r-l

C -P CO o o CO CO

O ^ c 4-J •^ r-l C p> CO H-l tn CO to 4J1 •-

CO £> t- 3 -rH

O t- o i- CO CO E CO c O CO -rH ^•^ cO c M -p o • o E rH o g Cn CO -P CO x: to x: 3 o >. x: CO CO S- .o

iH Q-i i. c o -P t^HC x: -p CO o x:

C -H . J-> i. -rH bO O o CO •rH •rH •H o O CO I>-

CO CO -O •-

C CO •l-l o 3 CO .- o 3 -H f—1 E CO o r—1 CO CO 4J o -.H 3 CO 1—1

•iH c E o -a

f-l

O

C Q. x: !L CO CO Jj •o c CO 4-> •- GO o o cx c

,—t Q.

O 3 O

O s_ Cn CO .- o 3 CD rH

O CO Cl c o -p L. -.H f-t t- -H c £1 O c CO c

ex

O "O S^

O J- c 3 i- cpi CO jJ •H •H CD 3 •P

O C\J < C bO jj CO •H f—1 CO CD " .—1

x: I—i CO •H

CO jj o -p •o

O L. -p -H p> o O -P c a x: CO i. CO c r—1 o O cx CO c CO 00 X S 3 c jJ) iD CO 3 3 o o to E cx o CO CO r-^ . to •^ 1—1 TO o i- t^ >> a x: o 1 O 3 I>- S CO O -p to CO ^ CO cx -P •H C CO pi

CO

—1 CX

C 3 c x: •H x: x: •p

N CD TD

O .-HO o o o bO o t. -p

H •rH .-H i. -O

C

-P >» Q-i JU .,-1 .—1 o >5 •H 4-> •H CO o i- CO •H CD O CO 4J O CO J-> c -P x: CO x: rH 3 CO x: -a 2 3 .^ jJ Q. c i^ -rH •H t- 3 o cx cx c rH bO C\J > C O L •i-H > x: -o cx CO E •iH >, -H C

>> -M

O -M o ^_^ -p i- • •H bO >> CO •H o x: •H c

.—1 -P -rH "O CO 4J CD to -p 3 x: >> L, rH to rH O 4J> -O o ^ o o o o r-H M 3 -o • -P

CO tU CO

L CO J2I •rH -H x: -Q cx §3 jJ

CO Cw CO

O

C 3 D ,-1 O cx TD s ^ M -p t^ E CD Jj J •H 4_) CO o c o o o •H .,H .—1 CD CO H •M x: CO O Cu to 35 CO p-H D -P CO -p 00 CO 00 CD O CO X 3 cx 13 O X E -Q

CO

t^ 1 CO T3 T3 o TD

CD > C C c x: -o T3 -o a o O o cx c c c c L

•iH •M •H o o o o

-U 4-> -P rH iD JH X3 X2 •• CO -a CX cx CO TD

J- o SL e i. CO i- CO i. CO t- CO CO

CO s: o o ^ CO CO to CO CO CD CO CD •O CD a CO CO o -H x: -H x: p-H x: ^ X c x: a a c o cx o cx o cx o cx o cx

00 <£. < tx a. &, Cu CQ 1 c

rHO -H

CO t, CD c --ox: o ex i-H >i O

—1 Z5 CM CM >. x:

4J

O 1 1 DC 2 X o o c O t- 1 1 2 o o 2 <o O c o 1 1 1 1 -O -X2 D CO O L

Cx. -P 1 CO o c o o o1 o1 •H O 1 •H

00 1 GO

D

m 1 -H 1 c cx C\J o o oo o o o o o >. o CM 1 1 1 1 1 CQ h- iH M •H t^ H M •H H

c/0 <c OO o OO OO 00 GO

^^ CO ^ rH

en CO

C T3 -a -H •a o o

CO cx

O

L •H S_ c t. .—1

J- sz >^ • M 3 e 3 O -H •O -P X3 O •a .p

Cu

H ^ CX 3 cx

C E C -H

C -H

C -H 00

•rH V_^ r—1 O CD o c o -a o c Q

00 < CQ CQ CQ CQ o

69
.. x: 3

<D jj jJ

O

CO o to -! x:

CO i. X3 sz 4-> x: o CL x: CO !*-, •-4 a. .. bO

CO

L s x: CO -!-> O —1

O CO

1- 3 a Cn bO CO •- 'r-i x: 3 •r^ C »

<D

O

C nH CO 3 • i. cx CtH o > o •.H CO O CO •-^ .-4 CO C CO -i*: L CO -a s S •' o 4-> i- to O CD o o CO CO e O C x:

JD .^ (0 Ct^ x: CO J-) CO

C

—1 E -o cx

O D. cx zs CO

CO 4-1 4J)

C • r-{ CD a >. O -^ to CO E >> >, c:x c a •' CO —1 E D t. 3 4J> O CO CO CO CO JJ O O o • -4 tH « CO a 4J 4-) C CO •O -H c > o x: CO c CO C c =i c c O -4

CO CO > a c O CO rH - cr CO

O E 4J c j-i ,-1 1 o X2 x: > --H CO "O CO •r-^ E O o o o -rH D. .—1

CO > 1 c to

.,-H o > • CO -l-> s. o > O CO

C o x: 1—1

4-> c >> t. to 00 CO

—1 C 3 O •-H 4-> >5

03 cu -^ ^ S- x: s: •a o c 4J>O t- CO

O x: •r-i > CO J-) f- s c to X3 to

•rH 4J CO i. cx o CO x: c t- c -o

.—1 c CO i,

a CO -i->

C -tJ CO to o £-

C

D, c o r—1

CO c c s: •^ CO ti-i r-H a. 4J to

a CO •'-1 o ti-H CO CO Q. 3 x: o o 4-> <c x: 4J D. O E x: 4^ D. CO ^ c

jJ to >, -t-> OO 3 CO

O

TD i- 4J

C o to CO -o j^ Ci-l • - -o 15 .-4

CC CO

C

C o > >, i.

C CO

O CO cr 4.5

m

O Cl CO -^ i- o - o c C CO c

.,-1 CD <L 1—1

4J 3 C 00 > .-H -r-l CO CO

O -^ • CO -U CO •rH a CO Q 4J to E c •-1 cn x: 4J> D <i-, CO r—1 C .^ o j_ to -i-> o C CO 4-> 4J> jj CD .-H C ti-H 1—1 O o O -iJ 'f-i CO c o C- o C O CD •rH >> CO i_ • —1 c a i- en 4J O o z CO CO x: TD x: O CO ll-H (0 c to >> to CO -4 Cw 4J 4J

i-H 3 4-:i C_ i:^-! cw x: CO >^ CO i- C^H

C

-^

C >> .—1 4^ 4-3 .-H 4J 4J

O t. CO 1—1

1—1 E 4J r-l 3 r-H CO bO

L c • CO •'-1 CO t.

.-H e 3 Jj (0 CO 3 O t. ^ CO iC -a ^ C ,-H >> c_ CO S- C^H CO s CO O CtH O CO to CO •^ Q-, JJ 3 Jj 3 rH 3 ^ i- Q. I. <Ui c -o cx bO to E <i-. O O CO C O CO o o o o 4J 3 o x: s- x: •M —4 O J =s bO H -JDS J cx c OO CO X2 o to OO O Cl 00 TD

CO CO bO

J- t. CO c bO bO

to CO c C > > x: x: to CO c Q. o x: x: o :_ i_ t. X o o

•iH

O

XX

-(-> <D •• » CO

CO -a •O

a -H e c L O CO CO CO o c c

CU S O CO T3 CO E > •r^ o o

Q. c sz c x: t- 4-> .-4 •rH 0) O Q. o cx O t, CO c c

CO CQ CQ 2 O cC cC o >,

r—1 c -^

L

CO CD

O

m

O to E c O Xi X < C 3 C\J o ex 1 i- O L "-1 •-V •M D C CO O C C^ P o o p. e -H 4J O X o :- o c r—1 1 c ^ E o c o ^ t. —1 >, o to E D >^ -O CO x: Cw 3 CO 2

Cl,

p >, x: o x: o o 00O' 1 » >1 tH

CO .—I CO CO CO •O CD .-H 1 c a O o o •-H CO O •-H r4 o >> 1 1 1 i- 3 1 S- J- CO E- rH •M i-H CO CO -^ cO CO 00 OO OO > 3 00 > >

CDbO bO bO

0) c c c

CO <D .—1 to ca CO CO O- >. x: x: x:

x: >^ c o o o

aH CO

C

X

C

X

C

X

(^3 s: x:

O

OO

O ^ Cl. 1—1 h-1

HH

70
III. Tables for Ultraviolet

Spectrophotometry

71

Solvents for Ultraviolet Spectrophotometry

The following table lists some useful solvents for ultraviolet

spectrophotometry, along with their wavelength cutoffs and dielectric

constants [1-4].

REFERENCES :

[1 ] Willard, H.H., Merritt. L.L., Dean, J. A., Settle, F.A., Instrumental

Methods of Analysis , 6

'^ ed., Wadsworth Publishing Co., Belmont, 1981.

[2] Weast, R.C., ed.. Handbook of Chemistry and Physics , 63'"'^ ed., CRC Press,

Boca Raton, 1 983.

[3] Dreisbach, R.R., Physical Properties of Chemical Compounds , Advances in

Chemistry Series, No. 15, American Chemical Society, Washington, D.C.,

1955.

[4] Dreisbach, R.R., Physical Properties of Chemical Compounds , Advances in

Chemistry Series, No. 22, American Chemical Society, Washington, D.C.,

1959.

Solvent

Wavelength

Cutoff

nm

Dielectric

Constant

(20°C)

acetic acid 260 6.15

acetone 330 20.7 (25°C)

acetonitrile 190

benzene 280 2. 284

2-butanol 260 15.8 (25°C)

n-butyl acetate 25M

carbon disulfide 380 2.641

carbon tetrachloride 265 2.238

1 -chlorobutane 220 7.39 (25°C)

chloroform '' 245 4.806

cyclohexane 210 2.023

1 ,2-dichloroethane 226 10.19 (25°C)

1 - stabilized with ethanol to avoid phosgene formation

73
Wavelength Dielectric

Cutoff Consi:ant

Solvent nm (20 'O

1 , 2-dimethoxyethane zno

N, N-dimethylacetamide 268 59 (83°C)

N, N-dimethylf ormamide 270

dimethyl sulfoxide 265

1

, 4-dioxane 215 2.209 (25°C)

diethyl ether 218 4.335

ethanol 210 24.30 (25°C)

2-ethoxyethanol 210

ethyl acetate 255 6.02 (25°C)

ethylene chloride 228

glycerol 207 42.5 (25°C)

n-hexadecane 200 2.06 (25°C)

n-hexane 210 1.890

methanol 210 32.63 (25°C)

2-met ho xy ethanol 210

methyl cyclohexane 210 2.02 (25°C)

methyl ethyl ketone 330 18.5

methyl isobutyl ketone 335

2-methyl-l -propanol 230 1 n- met hylpyrroli done 285

pentane 210 1.844

pentyl acetate 212

1 -propanol 210 20.1 (25°C)

2-propanol 210 18.3 (25°C)

pyridine 330 12.3 (25°C)

74
Solvent

Wavelength

Cutoff

nm

Dielectric

Constant

(20°C)

tetrachloroethylene 2 290

tetrahydrofuran 220

toluene 286 2.379 (25°C)

1 , 1 ,2-trichloro1 ,2,2-trifluoroethane 231

2,2, 4-trimethylpentane 215 1.936 (25°C)

o-xylene 290 2.568

p-xylene 290 2.270

m-xylene 290 2.37M

water 78.54 (25°C)

2 - Stabilized with thymol (isopropyl meta-cresol)

75
Transmittance - Absorbance Conversion

The following is a conversion table for absorbance and transmittance.

Included for each pair is the percent error propagated into a measured

concentration (using the Beer-Lambert Law), assuming an uncertainty in

transmittance of ± 0.005 [1]. The value of transmittance which will give the

lowest percent error in concentration is O.368. Where possible, analyses

should be designed for the low error area.

REFERENCE:

[1 ] Kennedy, J. H. , Analytical Chemistry Principles , Harcourt, Brace and

Jovanovich, San Diego, 1984.

Transmittance Absorbance Percent Error

0.990 0.004 50.227

0.980 0.009 25.242

0.970 0.013 16.915

0.960 0.018 12.752

0.950 0.022 10.256

0.940 0.027 8.592

0.930 0.032 7.405

0.920 0.036 6.515

0.910 0.041 5.823

0.900 0.046 5.270

0.890 0.051 4.818

0.880 0.056 4.442

0.870 0.060 4.125

0.860 0.065 3.853

0.850 0.071 3.618

0.840 0.076 3.412

0.830 0.081 3.231

76
Transmittance Absorbance Percent Error

0.820 0.086 3.071

0.810 0.091 2.928

0.800 0.097 2.799

0.790 0.102 2.684

0.780 0.108 2.579

0.770 0.113 2.483

0.760 0.1 19 2.396

0.750 0.125 2.316

0.740 0.131 2.243

0.730 0.137 2.175

0.720 0.143 2.1 13

0.710 0.149 2.055

0.700 0.155 2.002

0.690 0.161 1.952

0.680 0.167 1.906

0.670 0.174 1.863

0.660 0.180 1.822

0.650 0.187 1.785

0.640 0.194 1.750

0.630 0.201 1.717

0.620 0.208 1.686

0.610 0.215 1.657

0.600 0.222 1.631

0.590 0.229 1.605

0.580 0.237 1.582

0.570 0.244 1.560

0.560 0.252 1.539

0.550 0.260 1 .520

0.540 0.268 1.502

0.530 0.276 1.485

0.520 0.284 1.470

0.510 0.292 1.455

0.500 0.301 1.442

0.490 0.310 1.430

77
Transmittance Absorbance Percent Error

0.480 0.319 1.419

0.470 0.328 1.408

0.460 0.337 1.399

0.450 0.347 1.391

0.440 0.356 1.383

0.430 0.366 1.377

0.420 0.377 1.372

0.410 0.387 1 1.367

0.400 0.398 1.364

0.390 0.409 1.361

0.380 0.420 1.359

0.370 0.432 1.358

0.360 0.444 1.359

0.350 0.456 1.360

0.340 0.468 1.362

0.330 0.481 1.366

0.320 0.495 1.371

0.310 0.509 1.376

0.300 0.523 1.384

0.290 0.538 1.392

0.280 0.553 1 .402

0.270 0.569 1.414

0.260 0.585 1.427

0.250 0.602 1.442

0.240 0.620 1.459

0.230 0.638 1.478

0.220 0.657 1.500

0.210 0.678 1.525

0.200 0.699 1.553

0.190 0.721 1.584

0.180 0.745 1.619

0.170 0.769 1.659

0.160 0.796 1.704

0.150 0.824 1.756

78
Transmittance Absorbance Percent Error

O.UO 0.854 1.816

0.130 0.886 1.884

0.120 0.921 1.964

0.110 0.958 2.058

0.100 1.000 2.170

0.090 1.046 2. 306

0.080 1.097 2.473

0.070 1.155 2.685

0.060 1.222 2.961

0.050 1.301 3.336

0.040 1.398 3.881

0.030 1.523 4.751

0.020 1.699 6.387

0.010 2.000 10.852

79
Correlation Table for Ultraviolet Active Functionalities

Chromophore System ^Max ^Max

Ether -0- 185 1000

Thioether -s- 194 4600

Amine -NH2- 195 2800

Thiol -SH 195 1400

Disulfide -s-s- 194 5500

Bromide -Br 208 300

Iodide -I 260 400

Nitrile -C=N 150

Acetylide -c=c- 175-180 6000

Sulfone -SO2- 180

Oxime -NOH 190 5000

Azido >C=N- 190 5000

Ethylene -c=c- 190 8000

Ketone >C=0 195 1000

Thioketone >C=S 205 strong

Esters -COOR 205 50

Aldehyde -CHO 210 strong

Carboxyl -COOH 200-210 50-70

Amax ^Max Amax ^Max

215 1600

255 400

270-285 18-30

280-300 1 1-1

Reprinted (with modifications) with permission from: Willard, H.H., Merritt, L.L.,

Dean, J. A., Settle, F.A., Instrumental Methods of Analysis , 6^^^ ed., Wadsworth

Publishing Co. , Belmont, 1981.

80
Chromophore System Amax ^Max '^Max ^Max ^Ma) ^Max

Sulfoxide

Nitro

Nitrite

Azo

Nitroso

Nitrate

COs

00n

<v

n33

'-) C

oo

>S>0 210 1500

-N02 210 strong

-ONO 220-230 1000-2000 300-4000

-N=N- 285-400 3-25

-N=0 302 100

-ONO2 270 12

(shoulder )

-(C=C)2- 210-230 21 ,000

(acyclic)

-(0=03- 260 35,000

-(C=C)i|- 300 52,000

-(C=C)5- 330 118,000

-(C=C)2- 230-260 3000-8000

(alicyclic) c=c-c=c 219 6500

C=C-C=N 220 23,000

c=c-c=o 210-250 10,000-20, 000

C=C-N02 229 9500

10

300-350 weak

Benzene 184 46,700 202 6900 255 170

Diphenyl 246 20,000

Naphthalene 220 112,000 275 5600 312 175

Anthracene 252 199,000 375 7900

Pyridine 174 80,000 195 6000 251 1700

81
Quinoline 227 37,000 270 3600 314 2750

Isoquinoline 218 80,000 266 4000 317 3500

Note: $ denotes a phenyl group.

82


IV. Tables for Infrared

Spectrophotometry

85

Infrared Optics Materials

The following table lists the more common materials used for optical

components (windows, prisms, etc.) in the infrared region of the

electromagnetic spectrum. The properties listed are needed to choose the

materials with optimal transmission characteristics [1,2]. The thermal

properties are useful when designing experiments for operation at elevated

temperatures [3,5]. This listing is far from being exhaustive, but these are

the most popular materials used in instrumentation laboratories.

REFERENCES:

[1 ] Gordon, A. J., The Chemist's Companion , John Wiley and Sons, New York,

1972.

[2] Willard, H. H. , Merritt, L. L. , Dean, J. A., Settle, F. A., Instrumental

Methods of Analysis 6th ed., Van Nostrand, New York, 1985.

[3] Touloukien, Y. S., Powell, R. W., Ho, C. Y., Klemens, P. G.,

Thermophysical Properties of Matter: Thermal Conductivity of

Nonmetallic Solids Vol. 2, IF - Plenum Data Corp., New York, 1970.

[4] Touloukien, Y. S., Kirby, R. K. Taylor, R. E. , Lee, T. , Thermophysical

Properties of matter: Thermal Expansion of Nonmetallic Solids, Vol. 13 , IF - Plenum Data Corp. New York, 1977.

[5] Weast, R.C., ed. Handbook of Chemistry and Physics , 63rd. ed .

, CRC Press,

Boca Raton, 1

87
. x: o o

.—1 >> o CO :H -.-1 bO

03 o -u> J^ CO CO CO COC i. —1 L - r—1 3 :_ 03 03 -1 o

s_ o CO cj> -P t.

O .—1 C XI

C XI c ^

Q-i

C crs CO J-J Cw >H •t-H •rH •fH -U O 2 CO E x: -P E x: -P 03

C

m .- •.H x: .—1 Q. 03 jj x: "^.t^-a-P

O E S_ J-> -o jj x: t, 3 •M bO XI -^

x

D jJ CQ Ci-1 :- 3 -H j_ 3 -' O -P CJ

n

C -P .-1 -U CO 1 .—i o ^ O ^ D CO

CDO 03

O Oi 03L

O CO G. '+H CO Cl-H CO S_ ^ -O bO jj E 3 CO i. O 3 E o » a - O O C C •-H o E 3 c Cm 03 a —1 c > -o -< c > Ci_i CO CT3 -^ o s o to CO jj O -iJ XI - CO O 3 -^ O 3 -^ x: C O X3 3 03 •r-t C ^ C O !3r bO -P O CT bO P> -H i, — o

t.

O CO JJ 3 o o -o K) -rH

O -H bO -^O --1 3 2 jP 3

J-^ o 3 > CUH Jj -M -nH rH J_ CO ^ i. CO C^-, ^ cr

CD CO

D .-H .—1 fci2 ,—1 p P> c 4-> -PC bO - i_

O X3 CT CO o o CO Q-,OO i. -MO i, -M CO

—1 X -P S- S Oi 05 3 CO CO 3 O i- CO 2 O C CO 2 O C CO o x: o CO C^-i

^-^ ^-N ^—^ ^-^ ,-—s

^_^ ^_^ ^ ^ ^-x ,—^ ^—,^—. ^—, ,—

X ^ isi ii: i=i i^: iii :^ i^ ii^ isi i^ •:^ ^ >^ o o o o o o o o o tn o O O O o o o o o o o o O CM IXi O O O c ^ LO ^r Ln ^D J3- tn ^X5 cn CO OO ;=r LTi LPi rH O -U ^^-^ ^-^ ^_^ >-_^ ^_-^ • V ^ v._^ V ^ >. -- ^_^ ^.^ s • ^^

03 .^ -c E m . CD CO v£5 CO a> vT) vD o cn ^r C3> ^D ^ ^ o

J- c J

O ^ CJ^ CM CXJ ^ LO CM OO CM o cy>

—

m i>-

CD CO \ i- :=r CO o =r CO on C-- .—O - - CM ^ ^o

x: D.J CD . . • . E- X O Q. o o o o o o o ^ o o o o o o w

-'-~v ^-^ ^.^^ ^,_^ ^, ^ ,—V ^-v .-^ >, ^•^ ^ i^ ^ ii^ isi isi i^ i-^ ^~. JJCXJ ,~v ,^^ .-^ ^-- Li^ Oi OO O LTi CM CM CM bi; ^^ --^

•.H o isi iii ii:: ^^ . . • • • • • [>- ixi i^: > m o o in ^ CM CT^ m rg CO OO cn OO C7> CM

1—1 .^ >< c— o o c- o c— v£> ^ C-- CD IT, ^ CM

O

O

03 jJ

—'

cv c^ .=r CM

m on CM c>n cnmm ^T --' OO ^ e o i=d ^_^ ^^ N^^ V_^ N ^ S ^ ^^^ V ^ v^ y,.^ s ^ ^^ ^.^ V • ^ D • o

CD "O s ,— ,

in o tr~- o C3>

O LO o c:!> ^ ^ o ^

x: c \ ^n \D CO

O CX3 OO ^ ^ o o> t— c— . ^ ^ H O s . . • • . o • • o t>- v£) ^a- LPi ^3- ^3- o o o ^— o> ^3-

,,^-s. E

;l

CD eg >

-> Jj

JJ 03 CM oo o a LO \r\ o CM ^=T

03

X . . . . ^ T

t

CM CM

T Ci-i "Oc

CE 1—1

S- >— o

0) 1 LPi o 'S\ yO

X3 E CM o m CO o e o ^ ^r ^r CM t

D 1 1 1 1 T c - O o o O <—

CD

O o o o 1 CD M o o o o o > C •• - •> - I>-

03 03 o o in o vD 5 L ^T ^:t eg rg ^

x:JJ E

bO 3- ^jD LO LO C t

CM cn OO o^ - 1 1 rg 1 1 ,—1 CD LTi li^ 1 o IXi CD tiO CM CM ;=r Lf> ,

> C • • • ^ • 03 03 O O o o o

:3 S- E

r^

D

nja rH CD o E T3 •H E -M 1—1

CO -o i_ -rH r-l i, -a 3 -M

N

L :^ 5- o CO --H i- JO

—1 S- •^ i_ Cl, CD -H O 03 03 E cn > O bO > E CG O O 03 1 JJ -a ^. S j^ O i^ ,-H 1—1 =£ ^ O bO ,-H 3 O

to o jr o a- -^ x: •M i. <£ 03

—1 S CO o Q- X) CO o CO x: O Ci-i
COo

Shock

sensitive,

should

be

handled

with

care

Useful

for

C-Br

stretching

frequencies

Useful

for

C-Br

stretching

frequencies

Highly

toxic,

handle

with

care;

4255

TlBr,

5855

Til

a

4J>

•iH COo

-oE

3

3

O

CO >

Thermal

Expansion

AL/L

percent

iC •iC ^

CD O CD

CD CD CD ^ in ^

o-i ,- CO en kO CTy CM ^ ^

O CD CD

0.526

(400K)

1.063

(500K)

1

.645

(600K)

0.464

(373K)

1.026

(473K)

0.086

(400K)

0.175

(500K)

0.272

(600K)

0.033

(400K)

0.066

(500K)

0.102

(600K)

Thermal

Conductivity

W/m-K(X102)

11.7

(284K)

10.9

(305K)

10.5

(370K)

i^ i^ i^

•=r in in

CJ^ t- c~- \D en^^

CM en en ^ O v£> CM o tC7> CO t1.15

(277.

7K)

1.05

(296.

OK)

9.50

(360.

7K)

Refractive

Index

at

2ym)

en

CM

^3-

CM o inen

Wave

number

range,

cm"'' o

CO

1 o

o

o

o

o!>• CM

1 O

O

o

o

CM

1 o

o

o

o

CO

CM

1 o

o

o

o

CM

O

in

in

1 o

o

o

o

o

OO

1 o

o

o

o

CM

en

kO

1 o

o

o

o

in

Wavelength

range,

ym in

I

CMO

en

1 o

in

1

inen

1 in COT

inT

ino

CM

I o

CMO

t-H CO

•rH %~ 4J

CO

barium

fluoride

BaFp

cesium

bromide CsBr cesium iodide Csl

thaliura bromide thalium iodide

Tl

Br-Tll

(KRS-5) zinc

selenide ZnSe

germanium Ge

c

o

o

—1 -.H r-l 00

rH

CO

89
CO<u -po

not

useful

for

many

organic

compounds

Thermal

Expansion percent

0.075

(400K)

0.148

(500K)

0.225

(600K)

Thermal

Conductivity

W/m-K(X102)

CM '^ CM

. bti • on c^ CM o CM on

CM m ::^ ^ on CM

LTl ^ aCM CM ^

Refractive

Index

at

2ym)

1.76 ^

^

Wave

number

range,

cm~^

50,000-1538

625-33 en

CM

1

LTl

Wavelength

range,

ym

0.20-6.5

16-300

Ln

CM

.=r

1 '

CM

i-H OS

(D

4-5 OS

aluminum

oxide

(Sapphire)

AUO3

CDc

f—l

sz

4-J CDQ

cn.

mica

90
WAVELENGTH-WAVENUMBER CONVERSION TABLE

Wavenuraber (cm-M

1 2 3 4 5 6 7 8 9

2.0 5000 4975 4950 4926 4902 4878 4854 4831 4808 4785

2.1 4762 4739 4717 4695 4673 4651 4630 4608 4587 4566

2.2 4545 4525 4505 4484 4464 4444 4425 4405 4386 4367

2.3 4348 4329 4310 4292 4274 4255 4237 4219 4202 4184

2.H 4167 4149 4232 4115 4098 4082 4065 4049 4032 4016

2.5 4000 3984 3968 4953 3937 3922 3006 3891 3875 3861

2.6 3846 3831 3817 3802 3788 3774 3759 3745 3731 3717

2.7 3704 3690 3676 3663 3650 3636 3623 3510 3597 3584

2.8 3571 3559 3546 3534 3521 3509 3497 3484 3472 3460

2.9 3448 3436 3425 3413 3401 3390 3378 3367 3356 3344

3.0 3333 3322 3311 3300 3289 3279 3268 3257 3247 3236

3.1 3226 3215 3205 3195 3185 3175 3165 3155 3145 3135

3.2 3125 3115 3106 3096 3086 3077 3067 3058 3049 3040

3.3 3030 3021 3012 3003 2994 2985 2976 2967 2959 2950

3.4 2941 2933 2924 2915 2907 2899 2890 2882 2874 2865

3.5 2857 2849 2841 2833 2825 2817 2809 2801 2793 2786

3.6 2778 2770 2762 2755 2747 2740 2732 2725 2717 2710

3.7 2703 2695 2688 2681 2674 2667 2660 2653 2646 2539

3.8 2632 2625 2618 2611 2604 2597 2591 2584 2577 2571

3.9 2654 2558 2551 2545 2538 2532 2525 2519 2513 2505

4.0 2500 2494 2488 2481 2475 2469 2463 2457 2451 2445

4.1 2439 2433 2427 2421 2415 2410 2404 2398 2387 2387

4.2 2381 2375 2370 2364 2358 2353 2347 2342 2336 2331

4.3 2326 2320 2315 2309 2304 2299 2294 2288 2283 2278

4.4 2273 2268 2262 2257 2252 2247 2242 2237 2232 2227

4.5 2222 2217 2212 2208 2203 2198 2193 2188 2183 2179

4.6 2174 2169 2165 2160 2155 2151 2146 2141 2137 2132

4.7 2128 2123 2119 2114 2110 2105 2101 2096 2092 2088

4.8 2083 2079 2075 2070 2066 2062 2058 2053 2049 2045

4.9 2041 2037 2033 2028 2024 2020 2016 2012 2008 2004

5.0 2000 1996 1992 1988 1984 1980 1976 1972 1959 1965

5.1 1961 1957 1953 1949 1946 1942 1938 1934 1931 1927

5.2 1923 1919 1916 1912 1908 1905 1901 1898 1894 1890

5.3 1887 1883 1880 1876 1873 1869 1866 1862 1859 1855

5.4 1852 1848 1845 1842 1838 1835 1832 1828 1825 1821

5.5 1818 1815 1812 1808 1805 1802 1799 1795 1792 1788

5.6 1786 1783 1779 1776 1773 1770 1767 1764 1751 1757

5.7 1754 1751 1748 1745 1742 1739 1736 1733 1730 1727

5.8 1724 1721 1718 1715 1712 1709 1706 1704 1701 1598

5.9 1695 1692 1689 1686 1684 1681 1678 1675 1672 1559

6.0 1667 1664 1661 1568 1656 1653 1650 1647 1645 1642

6.1 1639 1637 1634 1631 1629 1626 1623 1621 1518 1616

6.2 1613 1610 1608 1605 1603 1500 1597 1595 1592 1590

6.3 1587 1585 1582 1580 1577 1575 1572 1570 1557 1565

91
WAVELENGTH-WAVENUMBER CONVERSION TABLE

Wavenumber ( cm" ^

)

6.4 1563 1560 1558 1555 1553 1550 1548 1546 1543 1541

6.5 1538 1536 1534 1531 1529 1527 1524 1522 1520 1517

6.6 1515 1513 1511 1508 1506 1504 1502 1499 1497 1495

6.7 1493 1490 1488 1486 1484 1481 1479 1477 1475 1473

6.8 1471 1468 1466 1464 1462 1460 1458 1456 1453 1451

6.9 1449 1447 1445 1443 1441 1439 1437 1435 1433 1431

7.0 1429 1427 1425 1422 1420 1418 1416 1414 1412 1410

7.1 1408 1406 1404 1403 1401 1399 1397 1395 1393 1391

7.2 1389 1387 1385 1383 1381 1379 1377 1376 1374 1372

7.3 1370 1368 1366 1364 1362 1361 1359 1357 1355 1353

7.4 1351 1350 1348 1346 1344 1342 1340 1339 1337 1335

7.5 1333 1332 1330 1328 1326 1325 1323 1321 1319 1318

7.6 1316 1314 1312 1311 1309 1307 1305 1304 1302 1300

7.7 1299 1297 1295 1294 1292 1290 1289 1287 1285 1284

7.8 1282 1280 1279 1277 1276 1274 1272 1271 1269 1267

7.9 1266 1264 1263 1261 1259 1258 1256 1255 1253 1252

§ 8.0 1250 1248 1247 1245 1244 1242 1241 1239 1238 1236 ^ 8.1 1235 1233 1232 1230 1229 1227 1225 1224 1222 1221

5 8.2 1220 1218 1217 1215 1214 1212 121 1 1209 1208 1206 ^ 8.3 1205 1203 1202 1200 1199 1198 1196 1195 1193 1192 ^ 8.4 1190 1189 1188 1186 1185 1183 1182 1181 1179 1178

^ 8.5 1176 1175 1174 1172 1171 1170 1168 1167 1166 1164 ^ 8.6 1163 1161 1160 1159 1157 1156 1155 1153 1152 1151

8.7 1149 1148 1147 1145 1144 1143 1142 1140 1139 1138

8.8 1136 1135 1134 1133 1131 1130 1129 1127 1126 1125

8.9 1124 1122 1121 1120 1119 1117 1116 1115 1114 1112

9.0 1111 1110 1109 1107 1106 1105 1104 1103 1101 1100

9.1 1099 1098 1096 1095 1094 1093 1092 1091 1089 1088

9.2 1087 1086 1085 1083 1082 1081 1080 1079 1078 1076

9.3 1075 1074 1073 1072 1071 1070 1068 1067 1066 1065

9.4 1064 1063 1062 1060 1059 1058 1057 1056 1055 1054

9.5 1053 1052 1050 1049 1048 1047 1046 1045 1044 1043

9.6 1042 1041 1040 1038 1037 1036 1035 1034 1033 1032

9.7 1031 1030 1029 1028 1027 1026 1025 1024 1022 1021

9.8 1020 1019 1018 1017 1016 1015 1014 1013 1012 1011

9.9 1010 1009 1008 1007 1006 1005 1004 1003 1002 1001

10.0 1000 999 998 997 996 995 994 993 992 991

10.1 990 989 988 987 986 985 984 983 982 081

10.2 980 979 978 978 977 976 975 974 973 972

10.3 971 970 969 968 967 966 965 964 963 962

10.4 962 961 960 959 958 957 956 955 954 953

10.5 952 951 951 950 949 948 947 946 945 944

10.6 943 943 942 041 940 939 938 937 936 935

92
WAVELENGTH-WAVENUMBER CQIJVERSION TABLE

Wavenumber (cm-M

1 2 3 4 5 6 7 8 9

10.7 935 934 933 932 931 930 929 929 928 927

10.8 926 925 924 923 923 922 921 920 919 918

10.9 917 917 916 915 914 913 912 912 911 910

11.0 909 908 907 907 906 905 904 903 903 902

11.1 901 900 899 898 898 897 896 895 894 894

11.2 893 892 891 890 890 889 888 887 887 886

11.3 885 884 883 883 882 881 880 880 879 878

11. n 877 876 876 875 874 873 873 872 871 870

11.5 870 869 868 867 867 866 865 864 864 863

11.6 862 861 861 860 859 858 858 857 856 855

11.7 855 854 853 853 852 851 850 850 849 848

11.8 8M7 847 846 845 845 844 843 842 842 841

11.9 840 840 839 838 838 837 836 835 835 834

12.0 833 833 832 831 831 830 829 829 828 827

12.1 826 826 825 824 824 823 822 822 821 820

12.2 820 819 818 818 817 816 816 815 814 814

12.3 813 812 812 811 810 810 809 808 808 807

^2.i^ 806 806 805 805 804 803 803 802 801 801

12.5 800 799 799 798 797 797 796 796 795 794

12.6 794 793 792 792 791 791 790 789 789 788

12.7 787 787 786 786 785 784 784 783 782 782

12.8 781 781 780 779 779 778 778 777 776 776

12.9 775 775 774 773 773 772 772 771 770 770

13.0 769 769 768 767 767 766 766 765 765 764

13.1 763 763 762 762 761 760 760 759 759 758

13.2 758 757 756 756 755 755 754 754 753 752

13.3 752 751 751 750 750 749 749 748 747 747

^3.^ 746 746 745 745 744 743 743 742 742 741

13.5 741 740 740 739 739 738 737 737 736 736

13.6 735 735 734 734 733 733 732 732 731 730

13.7 730 729 729 728 728 727 727 726 726 725

13.8 725 724 724 723 723 722 722 721 720 720

13.9 719 719 718 718 717 717 716 716 715 715

U.O 714 714 713 713 712 712 711 711 710 710

U.I 709 709 708 708 707 707 706 706 705 705

1M.2 704 704 703 703 702 702 702 701 701 700

14.3 699 699 698 698 697 697 696 696 695 695

U.i4 694 694 693 693 693 692 692 691 691 690

U.5 690 689 689 688 688 687 687 686 686 685

U.6 685 684 684 684 683 683 682 682 681 681

U.7 680 680 679 679 678 678 678 677 677 676

U.8 676 675 675 674 674 673 673 672 672 672

U.9 671 671 670 670 669 669 668 668 668 667

93
Useful Solvents for Infrared

Spectrophotometry

The following tables provide the infrared absorption spectra of several

useful solvents. The spectra were measured using a double beam spectrophotometer using a neat sample against an air reference. The physical properties

listed are those needed most often in designing spectrophotometric

experiments [l-^]. The refractive indices are values measured with the

sodium-D line. The Chemical Abstract Service registry numbers are alos

provided for each solvent.

REFERENCES ;

[1 ] Hawley, G.G. ed., The Condensed Chemical Dictionary , Van Nostrand

Reinhold Co., New York, 1971.

[2] Weast, R.C., ed., Handbook of Chemistry and Physics , 52"^ ed.. The

Chemical Rubber Co., Cleveland, 1971.

[3] Dreisbach, R.R., Physical Properties of Chemical Compounds, Advances in

Chemistry Series , Number 22, American Chemical Society, Washington, D.C.,

1959.

[4] Jamieson, D.T., Irving, J.B., Tudhope, J.S., Liquid Thermal Conductivity

- a data survey to 1973 , Her Majesty's Stationary Office, Edinburgh,

1975.

94
cn o

a>co

*>

0)o

4J

«• £i

t- ca

<1> »

J-> o

CO iH 3 i-l CO c

«H

C

CO

a> 1—i

sz

X5 Jj 3 1-1 iH ? o

CO o • •. X

4-) o c JJ

<u> >. • M I-l L. o

CO iH

-.H CO

k

x:C

iH • k o <u E a rH a XJ a

>. CO M g o & CO =r

iH I-l 4-1 X ^ O

4Jc

•oo

CO

4Jo

CO

0) •o

••-t c

CO>»o

x:

4JB o ^"N o o ^ o o • C\J o B

%-• C\J \S CO o on CX) 0) o O C\J t~- CM 1 f-i C-- o ^ LO v£> LTi 4J • v£> ^ CO t— O &. ITi • c>o t^ ,

1 0) iT ,

• • • in a 1 CO ,

o O h- o

t. Ou >>

CO P o

1-1 iH>

CO

X >. -H

>. l-> 4J £ •o •rH C) Ou 4-> 4J c > 3 c c •^ CO a T-l 1-t h c o o 0} o a a >

iH o

CJ t£ u) 4-5 iH iH c c O <4-l CO iH «-i CO -.H Fi

4-> iH t. o t. iH •tH «-l CD CI) co

Q) o d) D. x: <x E X) t. CO 4-> o J ' rrr-'T- —T

—,.j ^-

r" -.. p- 1 « j _ ' • 1 . —1 1

1 . ,1 —\—

J- t—i

—r— —\—==F^

—i—

—i

1 J 1 , " 1 , --— 1 , I.,.: 1 = —r— —1—

—t-v ." —r— 1 '

...I .. =b=

2-

-/"t

— « —\— —1—

P—

=^ .. y. CN 1 -—h—

—J

—f- 11'' —

—h-^ —t—- —1

' '1 = _ 1 ^ :

1~^ ! 1 1 " ;i, '

-+- . 1 1

'—1 ' i:" —1

; .1

9l '1,' ,: 1 ;—ffl

[:' 'I',.'

,': ,

'1 o

1=^

—1

- —t— ! .'{/

'!•;

',:'! 1,; ' ! U

k-t-H

'.\:::r

fitrrrr

yl;;—1

:—1_-

—-PP^^[^h^

fed

;::;[ , 1 'j :

';;: ,;i; i.''V;" U^r^''L--^^ ' ' 1 ,

fiC p_

_ . \\ , . . |, , . 1 i» ^ , >4_ ., ,. . . w- —I.. - — K^ 1

"777 &. ' 1 -r— ^ ', —>- 1 j——I ;,.—1——.,, 7 t—

'^^ r-Jri

—^

\—r^ ..If.... 1 .. -f - '

'I""' W— •' U-^ ' 1 , .,..:1.

—

—1

\— , 1,

—

—1

==|f -^ r-l— b^

=^#i^ -

'-^' ! , 1 -^ : .h.'i =t=^

\- }: 1 7^ r-Ji \==i=\

." ^-: U —rj—:

hrt— , ,' o 4—j 1 1" 1—j

P "\—

, 1 . ...... O, —4r- ^ L Yr-—h— —4-

1—4-

—1 1 —

H

-~—1

-rh-i < 1 1 !: . .1 :. -^m:

—-H

—1 : 1,

I-.. 1 . 4—i- —t— —1

:—

r

' 1 1 : 1 1

=1=

...

—1

1 —\—, 1 . . , • 1 —1

—1 f - —1 1 —M 1 —

-4-

=f=

-^-4— —1

. n—1

—r— J ; cj —1

—'~i—r

= _=4=1 —1—

9. = -^

r4=

—f- . ^ Li ' 1, ——t—

—1

.. )F—

J

—1

1 [ —1

1 r—

f 1 —

—

—I

^ i 1 , ....I ' —i

1 1 . ..!:' —1

:= -4^

—\—1 =4= —1

i~~ -r*-j 1 —1

' H 1 • 1 J 4 ! —-j

—

—1

. 1 . ' r ' ..,:i j 1 —1

"•4—-

—1

,.|.... 1 . —1

-_H 1 ——{—.. V—-—1 1 ——1—

U 1 -Sr- 1 1 —'—i

•—1

iT' \ 1 -J

— 1 1 I ' 1

ssz> §1O A OS

95
XOC

<DNC

QJ CO

•a c c -r-l CO C

1-t

O

iH

i-H <D 1 X> n rH CO 3

to X33

1—

4J

I-H o

en

(0

O JJ

1—

tn >,

*-. • » CorH

4-5 €)

(D to (fl -r-l > g O r-l

•k •^ «> JJ o E > c t- i. <y 2 n <u Cfl O T3 W

<u > o «H •r< o 4-5 I-H o «-l o O o u

;. tH z 2 n o 3 I-H B iH tn o o 3 x: •rH cc »H J= o •o <

4->

u

(i •o •> c E a) t. o (D 2 O E d) £> c <

£-

L £ i. 0) s:

CO iH 4-5

m •rH Z2

Q-. 0) o L zc

•»

C 4-5

k o • » CO o a CO a; X w

I—

1—

a CD s: o •> o •rH x: cc Q. o x: i. t. o I-H fH o o CD i—i Cli C X o I-H 4-5 o 2 o o -H £ CO >. o z +J CO oo

C\J

O s ooin

CNJ o (J

""^ oO o • o

(0 C\J o fc o

D_ s^^ .:T ^ o S '— IS CNJ ro o ^^ cv

CD o rO .=r 1 -tH o o CJN ,

crs r\j ^ fv-1 4-> o 4

o o r- J3- CO •3-

t. LPi • o LH co ,

<M 1 (D • o • . O. LH CO d f o o CM t^ O

t- a.

iH >.

ns 4J 4-> o •rH c

1-1 > CO

en

X >, rH 4-5 >. CD 4-5 4-5 cn x: 0) o •rH O c

Ou 4J 4->

b c > 3 o C c •rH CO a o

•.H »H CD t. c o o m a) W o o a Q. >

•rH o o •rH

M

M D. 4-5 rH f-H 4J c c O H-. CO o

iH -#-1 t- CO •rH E CD

4-> !—

o LO t. <-i 1—

•.-( o. Cw CD (1) CD V)

(U o 5

<D D. x: rH <; E X5 t. n 4-5 •o CJ

96
mmoOoeo

CQ

0)Ocm

s>

•fc 60 <u e c fi t.

t-t o o

•a 4-) 4h c ^-^ o o i. • 0) £>

•r-l o 0] fH

•a c X £ •^ E

<DO o o O

bO 4->

U

O > >, £>

t, >.

m §

-rH •a iH rH t. §) 5 E 4.}

<n f-H o •o <-i <D >, £ o c >.

4-> eH iH CO c o ^ • •» CO OJ 2: (0 (1) x:

<u f-H c c 4-> 3 £)

rt iH 0) 0}E " P 0) c

?3 E rH 0) •k CO i2 i3 0) tH r-i 3 c o «M rH » CO a co O

CO

mc

x:

4.> >, c o CD rH • • £) g

Q) • «h •—

t- o

4-> 4-)

B CO E

CO c D. o O

C.

a o i.

0) > t. J3

•o iH in •o •rH o o >. s- 2: <n ooo

in

CM oo o

.=r

4->

in:• ^^

CO o \ E o

a. CJ o \ o s •> CM :s o n o ".-^ CM CJ

0) o <X3 in ,—

— 1 .-1 o LO O o t— ^£> in

4J o • O o CO CJN cr. CO

£. CO 0^

O vD COO on 1 <U • .a- • • • • • in

O. CO ^— o «— CO o :3- f- o

t. a.

iH >.

(0 4J 4J o •rH c

.H > CO n X >. •rH 4-> >. 0) 4-> 4J (D £ (a •a •.H O C

a. 4J 4-5

h c > 3 o c c •.H CO T3 o

•^ t-4

m t.C o o m o bO o o a o. > o o •rH (c bO Q, 4J •^ iH 4J c c o «-. CO O

•.-• 1-1 t. CO •^ E 0) 4J .-H O L o t. rH

iH iH O. •i-. <u 0) QJ co

(U s 5

<u en. x: •rH <« E t. to 4J TD o

2- =b'' ,1.' Tn-tr—

1.14-—'- ^-t --- ^ . .]: : I: -+n^N

C«_ -

2--

»--

"1 

** ' 1 . —-r : 11 —i

, i —;— e> —tr— 1 ' r 1 =t=

=^

"I

a

—-1— 

K-

: I . 1

i;

J : h

(—

_1LI

""<•-=

-4-0

...,|..C> . r1 • 1 —1

-+- —1

^^

—t—

,.,.1 .

=4=

;-f:' :-44_

.-l-d ' i::

:l li—

i'.J

c4=

—TV

<?:

CD.I9-

::ii

sfc

fl-- ' ==^

'..i .. ^

.. 1 ': pi— —\— 1 —1— 

—J

—rr—

—1

—1—

_ 1.. 1 -—1—

-ii-i:

—he1—

—

-p—1

,, .|...

—fH —i—

—4— , 1

'. ;;;

H-i ' 1' -—^—

——t—

....... H—

\~^

,: 1 ,,:

-+- ... ,.... ' , 1 1 r

tH m'1 ——1

M Zo

cti. Mr

T—1

H—

—f^ —:|

_:=:~T" ' 1 :'. : I .. —1

—1

:• i: ....... . —1

9.

t»»_

,:L.

'|...-).-J

....... 1!

h-t—

L_« :!:

['. i ," 1 — !-;: ; e

^— 

—fk-th """1

r ; — Q

.. . f> ; ..1 ,

-^ 1

... ..

;:.,!..,:; ;, 1 :,' ' 1 '

--

—h-*- : 1,,.,

9-

9.

—

—

1

I r- t |— -1 m

—1

...... .,

y^n^

—

-fu_HJ 1 —t.

—

r

1=^^^—

—^^

=1= —1—

ri1 ^ M=1=

=4= '—t—

,1' ^—1—

1 —1—

"—p-—

—

: ..

1, , —-H 1 1 . 1\ 1 1 1 1 —

. ':!.:.: ; ^ —1

-+-1

=:= 1 r

—

—(

4—t— 1

—f^

—r—1 —1

—J

—1—

—\^

—1—

1 -4— h- 1— .

,—1—^— « — —1-- 1—_:_-

r:::J- -J-- —:—1

— 1 1 1 —!

—\—

1 ' 1 ' "1

SZszUi> O2S

97
0}

0)

4-5 o

<M O

0) T33ncomo

0}

0)

f-i

s.

0)ao

nton

>.

x:

a.

t-

«> • m. •rH n t. <— CO 1—

V o 4-i C c

jn

m

O •rH 8 3 5 0)

(—1

C 4-5

O

03 •>H 0) c

13 CO c (D t. iH rH d-, J2 O 1—1 <u 3 o

i-H i-H 03 4J ^ o 4J >.^ 3 03 H

rH Fl o O >> rH rH

03 -H 1—1

X

4-5 o

jJ s §^

4->

C •H •rH >,

QJ 1—

03 r-l >

1—

03O ^ O •> Q. -rH 03 03 X J=

i~ 03

?a

O ^^ • » s: ^^^

1—1 4-3 4-5 o OJ iH c a X3 <u T3 m C3 >. C £- iH 03 £ 0) <U CO Q.

JJ QJ r-H <»-*v CO C Q-H O E

S- 0) LH ti

0)

N >» D. •o C t- a o 03 03 c o

X. J2 > CO C\J

Co

COo o o o

'- vr>

in

u CNJ /—

o

^-^ o LH .^

CM o

CO LH \ o

D. CM in

O

S. v_^ <M CM

%.• >^^

O

CO CM 1 3- m o ,_ in ^ CM v^ 3- 1

o ^ CM ^ 1 • • • • in o »— t— CM c— UC

01

X t», 4.J 03 4J 03

<D

a •rH c

4-> 4J § c > n c C rH CO o

•rH rH 03 t- O o 03 CI) bO o

a. Q. 03 > rH

t. T-^a ;, bo 00 D. 4-5 rH 4-! c c O 4-1 O

rH rH e CO rH 0)

4.) f-H o i. o 1—1 f-< rH Q. 4-. 03 03 CO

0)

O CO 03 D. .rH <

fc: £3 > t- 03 o O

98
n

0)o oo

•a

tHoo

(0

i. U0)CoO

n

S-

<v 0) £ i-i

4-> Xi

<u 3

r-H » O

05 03 • «

i-l

C o o •^ -rH x: X o " o o 05 J-> H M

CO •^ >> o .H c <u tH Jj E n

0) o L.

r-l

B 4J i3 X 3 o 0) rH c o (0 • * n 0)

<u rH

.» c J3

4J (U CO c r^ g

<u c £ > o CO

f-1 £> I-l o <i-l o

(7) •> 1 •^ E c c k fe oc

0)

i-H Q-i o o O .«. c

D. t- £- •H o o o c l-t 4-> ;. o sz CO CO 2 o 5 o

0)csoho

0)ex

0)c

l-> o

(.o

x:o

CO Jj

0)

4-> o

in

CO

CO Cl ooCO ooo

CO

m

<uo.o

COon

>»

x:

a. oOmCOI o o

CO

CO c—

CO o o ^

inCO

CX3 on

CO -- o

4-> co

o.

bOc

4-> coa

bOco

Xi

0)

0)

o.o

a.

f-i >

CObO >

•H o o3

•ocoo

4->H

H

O <« CO

CO •H

B

t- o t-

<i-. QJ 0)

Q) Q. x:

Sn 4-S

COc

CO

03coo

I.

4-> o

0)

I-H CD

inI en

COI in

CO<

99
o

3:: ooh

r-i o

s:jj •« ^ t- 3 •^

•> CO &. •0

0) 0) c

x:

N • » •«-( jj •^ C

<u r-

0)

•. jJ c

CO ns

m n3 1—

4J E tCO t. 0) x: 1—

>, Cm

r-l Jj

1—

r—

<D >—

nJ § c

0}

C CO tc r-t <» »-i 3 tn X

4J

0) » £ Jj z i-H £3

Q.

>1 •^ 3 •^ jJ iH c

r-i

C

0) ^ to

CQ iJ > 1-1 CO CD JC c c • i- tH 03 ^ B Q. 0 x: c c t- 4-5 a; 0 03 0) (D > c 4J E

1—1 03 0)

r-i rH • » Z.

n 0) J=! ^—N C c 03 e r—

?3

QJm c a .c S j:: g a c*

1-1

C j-> 03 -^

QJ -H t-

—

a. £1 e

CNJ

Cl-H 4J t nJ LO \ B

o. CM \

2:

— CM 3 (M

03

a >_• >*_•

m 0) ro CM •a- 1 ••-1 in ^ CM in 'sO vD vT)

4-> • r\j 00 ^ 00 »— VD

t. en • =r a- «

CO 1 «) vD ,

• • • • C~- cx 1 J— t

3- vX)

i. a.

rH >.

nj jj 4-3 iH c

•-1 > m

CO

X >, •^ 4J >> (1) jj JJ CO £ <D •0 •^ c

CL +J jj

b c > 3 C c -^ 03 •a

f-i 1-1 CO t. c

CO 01 bO D. D. CD > a

(30 bO D. 4J i-( 1—4J

CC Q-i 03

^-i iH t. OS •^ e CD

4-) 1—

t. t. t—

r—

•^ D. 4-1 <U (U CD CO

(H

m 0)

a x: --I < E i2 > t. CO jj •0

9_-

OS* o I o Az><

100
CM Xo

(1> cXO

iHO

<D d) 4J c

OJ Q) t N

<y c C •o <u iH oE

X3o

Q) t. iH • *k •a

i3 <y >. D i-i £

iH £1 CO o 03 ^-^ X n

O. • •k ns o.

4J iH •> c ^ o (U <u o c > • •k m 0)

n nH a> x:

0) o c » 4->

4-> 03 0)

u £ o N •.H a 2 C C CO CO o <u c

£> £1 c CO i. iH X

<0 QJ Q) o C 0) x: o o o

t. Jj c « •o 0) CO o

>, o i. c £ (0 1—

fe

•. o >. n Jj £

rH iH Nw^ 4J o o 0) a s: o E o •.H CO c o X X o 1-1 o o 2 rt 4-> s:

n

0)

1-1

0)o

Ou

COo

T-l0]>.

JS o

^—

in y~^ CO

C\J ^-^ CJ >—

s C3 ^"^

•=r ist: CO \ • a. C\J E

2: ^-' CM CM 1 w ^— en CM ^— VD cr> CO CO DD

t— ,— CM t- CM CM 1 • .3- t^ .— • • • • • 4

CO «— CM r—

>.

jj 4->

1-1 c > CO

X >. •.H 4-> (D Jj *J 03 •0 •rH C

4-> j-> fe

C > D c c •^ CO •0

•r-l fH tn tC

CD a> bO

a D. 0) > T-i t. •<-{ i- bO M a 4-> -H 1-1 4J c C Q-i CO

•<H •rH (. CO •^ E <D

J-> 1—t- t. r-H iH »H Q. ft-l <U 0) 0) CO

0)

B

ffl <v D. £ •»-( < E > i- m Jj •0 i —i

m1—1

'—'—

f—

—11

^1 1 -+- —1

—1—1 l-c

\-

—r-^ =i=—1

r-C

.. .. c>

—i—

^~

—

__i

I 1 , 1 ' '—r~"

... ,.

—

r—

H' ^-i H

"^ 1 1' 1 —r— 1 '—-1—- —f-

—

-4—

.. ...... —i -—

^

....v..|

yr P-I—:. .^..

-trr~ '—-*-! K—

—-j

. - —'-~c- —j

P-

—1

^^^:=

—^ 1 1 ' ' ':i =T=i CD. ; 1 —^

-^—

^" 1 . i , , |,,.

—. »< "I

—

i— H- h— ; ...• ! —y . —Kf

9J =4= —\—-+-i

T'OI

—1—

-4- 1 1

\— ^ - —1

—

\— -—r-o f— >-q , CN 1

t-::

.,! '1

'I. .11 1 ^—h—-r 4- —

h- ]

...... .....

!? 1 —1 1

-I- _J 1 \ '"?'*—1

— r"" ' \ ' 1 :^v+—

-^——

1

—' 1 ^ H P_ 1 'I,.' ; 'j1 \ —t—

—

...!^-^

—

r ^ , " 1:. , , .,..:n \~7r . .;. •' "" —1—MH[•-'—...... -]—: .}::: ::::!::J 2 t^ 1, :— 

A~=^1 1 ~ —'— i ' \—

0- ^^^ ' 1—^

^ r-

—ii r •—\=^ '. 1 1 —rr-? 1 1 ; j i —p—H i

[j \ \ —''

—

—'—' ' '1 ' ! J ' 1 i m ^" 1 .. —r!5—;—

—I——J—

L'i .| i L. 1 '„ . ;

1—^ 1 —\—, 1—(N

—;—1—1—1

—

r 1 -f-T 1— 1 —-1—r-l 1—

i ' , 1 —"^—

i i ' .1,1, :,; 1

P-

—1—0

M—

1 : ~—1—i

« 1 ' ; '; -—1

'—r""***"!

—

: 1

^ —f~r "'^1 j—:

1 ' ! : 1 1 . \ !— 0( —~^fr=^—

'A '^^\

—\— i ^_ ^ ': 1 : _4; 1 . ..J

-r—r——!—'—

J

—^— '—

—; >— ~r

—1 '

1' " 1 ' 1 ' L J. ..,.,., ....

P. C_

^11

—^—^- j , 1——rr- , 1 ' ' 1 '—1

^—^

-^ 4—

-:..l r-^

—

—-^-j—1—'

N

H

— , { !' I -T-i h-T— ! 1—;

^ 1 1 "l^^ ,|.-j l^.j..- mm^ ' 1 : H^ 1 —— 1 1 > L——[—1—

m p= 1—^

-— i , L_|

u

HIs3ZUi> 8^O w

otozuj><

101
o

00

CMon Xo

T3

1-1Xo

Cm

I—

00

>5

x:E L

0) • u c

CO ^ 3

en c

-H

cu 4-5 iHz: n 3 (U 1—

+i

O CO

CO

4-5 • «

4-> c c 0)

0) o. >

i-H >» o l-l n iH

•a o CO iH (U 4J t. o

t. • flk o. (U

CO J3

1—1 •p-l 3 JJ

%-i 03

t. 3

0) X3 o 3 E CO O O s:

a.

O

Q oo n CM in

0) o >.^ 1 •M o O OO

jj LTi o ^

vr>

:. • 0^ o 1 (H CO CO C-- Cl ^ ^— ^— o o

t. a.

1—1 COo

tH

tn >.

>» 4.} sz T-» a. 4-> 4-> > c c CO o

1^o fe

a D. o

bO tc iH c c <i-4 1-1 iH 1-1

4-> i-l o

rH iH 0) C/1 QJ O u. < E £J CO o

102
Xo

CM oo

OJ Xo

CO Xoooc

caXo

ftQI

T3 o §

--1 o 3

t. 4->

O

4J >> ^ v m iH 4-> •o ? §, •o , t-lX c •^ 0) ^^^ o sz

>H £ i3 E •r-l 4-> L, a •o

(U ...

O o.

r-H (U CO CD J3 i-H £> o c c 3 n CO o CD .H CO rH I-l O c • » >, >>

CO

g c •> x: s:

(0 o t. 4J 4-> 0] • M iH 1-1 t-H 0) 4-> «-i Jj CO •wt >1 p c CO •o X o <u • > ^ c 1 o z > CO CO •^ .=T 1-1

<-t 4^ JC » T3 o c c Q) ,—

CO CD ••H

O « > c •>

fe

1-1 T3 CO t. o o c t. 1-1 I-l CO CO 0} £ X o iH +J o

o. c; c O iH

•^ o 4J •o

>, c -.H -w

1-1 CO 4-5 c

Q) bO CO c c

4-> L. •^ .H

(0 o tx> ^ >. iH

;. c 03 £ sz

0) 4J •^ 4-> J-> T3 CO O O o >. x: •.H iH

— S E i3oo

in

4J

OoO

T3 •o "—

oo

CM

O

CO

OO o

0- CJ CM

O s N-^ N.^ CM ^

CO o v_^ 1 0) o m , v£) ,

•H on in C\J ITi en cr. Jj o • o CM m o 1 c. o ^

o =T O CM r<\ 0) V— o • m • CM a r— ^~- o ^— ^— CM ^_ o

i. Cu

fH

CO JJ O C ft CO m X >> j-> >. cu j-> CO £ CD •o •rH c

CL 4J 4->

h c > o c c •^ CO o

•rH •^ CO o o CO CD fe o

o. D. cu > 1-1 c •r-l o StiO CO a J-> iH 4J c c o <iH o

•^ iH £- CO tH

4-> iH

O t.O r-l

H •^ o. Cm CO

0) s 5

CD

a iH «* E $- CO T3 o

103
aoomj:o

0)

03O

s:

J-3

i. • • r^

s. CO •^

(d

C

•H > c

CO —1 <P

<-\ o o n c

x: jj >> CO o -^ jd :. o s OJ rH -H o --1 m rH -r-l o ^ X ^ • o >—

t. OJ Jj

0) 1—c

jj J3 >5 o

ctl CTJ r—

-H 3 p C 03 CB L

f^ ^ t. o

tw (U CO

<u o n

1—

• o CO £1 CO E 3 1—

C

r-( H-t • M •rH o o ^^ ^

en >1 cCO • • ^

T3

jj o c c S t- CT3 (D a; > •o Q. C

r—

c o • O 03 CTv -H '—

CO Jj hi M o cfl <i ^

4-3 r—

Cfl Q.

.—1 £ CNJ iZ

O o jJ * C o

CL 0) CM •H ^

OS s:

o.

(0c

bO

d)C

i.o

4-S (0 s.

OJ

4-> o CO

1-1 Q) Jj

(U .-1 o >.

CC £

4J

•> t-0) •a

sz r-4

4-> o

CO o o

tH •H

+J Jj o o

CO CO oo o

CM '•"•• o ~^ Oo

•3- ^^

COO o u

Cl, CM CM o o S >.-^ ^^ in vO

CO o CJ CM 1 CD c— on en >_^ C3D •H LH v-D cr\ CM o c~

4-3 • O

O c- o CM 1 t. c^ O m cr> O ,— CO f- • • • sQ. 1 t^ o ^

o MD y^ O

t. a.

r-HCO *J o C

rH CO

(0

X >. 4J >> 4J CO £: T3 rH c

CU 4-3 4-3

h

C > o c c 1-^ CO o H •rH CO t. o o CO 00 o

Q. o. > -H

t. •rH o ;. U) 60 Q. 4J -rH 4-3 c c O <i-l O

-H •rH t. CO •rH

4.3 1—

O ;. o t-t rH •rH Q. Q-. CO O cfl Q. rH < s JD > t. <n •o o

104
0]

a>o mXo

CVJ omXo

a>c

OSX

0) XIc

03

<1) MP

;.aoo

Qu

0)co

+i c

<u o o • •» •^

03 (V 4J

.H 03 « J3 03 CO CO bO rH p c o g •»H x: ca o fH T3 o Q-> C

r-l CO

rt ••> L. c c Q) o

•^ jJ iH • m *J ^-s. <u 3 CO E M i-H o.

£>

C CO o. 3 i-( s:

iH c o o •r-i o 03 M in

S2 >> • > 3 £> «> 4-> .—

t- c O o ..H

(1> 03 .-1 CO > C X

f-H ••-t o c o 4-> •^

03 «

03 >» 03 ^

t.

M

O

Q) <u c

.H JC 4J CO o 4-> CO t- a. 03 L. 03

03 r-i c T3 •o o o C O J-> 2 CO B —

c

COX

x:o O ^^ o o o CM in /-^ o *.-• CVJ o ^T o •^ Ui ^-N o o • o

CO CM CM b: o

a. N.^ ^^ ^v

O o :s: 3E CM

m o VO t~- ^^ 1 CM CM CO m t>- •a- o •3" CM ^ CTi «^ o in o t~- CM c^ in CM CT> 1 in • O cn v£) «— CX3 o

cr. CO • • • • • •—

VXD

O »-

O ^ ^

>.

4-> 4J

iH c > to

X s*. 1-t 4-> Jj 4J 03 T3 T-4 o c

Jj 4-»

b c > 3 o c c •^ CO T3 o

•rH •^ 03 s- c o o 03 bO o o a ex 0) > ^

t. 1-1 o t- U3 bO D, ^ ^ l-l 4-> c c <:3 <«H CO o

•^ 1-1 L. CO 1-1

B

4-> iH

O t- C3 S. iH

t-{ 1-1

a <M C/3 Q) o CO a £ 1-4 < E £) > t. 03 4J T3 O

105
o

aso

CMon ooc

(dcuo

{>o.o

0} o

•^

OJ 4-> rH CO £1 r-i • CO CO CO c J=

r-l

g c O CO tH

j:: r-l o <i-l T3 o C

rH • « CO

OJ CO

r-l c

•> T-t o

t. o •^

<B 4J

+J T3 CO m C (U • 1 eO M ^-^ c B c ff) •.-1 Q,

•.-(

C O, o >»

<D J3 XJO

^^ t. o

J3 CO o .=r 3 o T^

r-l o X - o t. o t01 o 4-> iH

>. CO .. £: >.

4J rH c c >> (D -H ^ § CO Q)

.-1 s L

O o (U c

en > T3 CO

to

O t. ^

t, £ 0)

(1) rH

r-\ £ aO

O 4-> c JJ

Ou (U CO o

s:oo

D.O

t,D.1O

0)

enoc

X3

COo

>>

Oc

COD.O

t,O.I CM

CO CU

CDoO

CM^»O

CM

Oo

0} CM

O

<u o •=r v£> cn

—

1 •H o o .3- in M3 on

43 o ^ o c- CX) CO vo

t. M3 • o cn t~- • 1 <D CX3 CM • • • CO c— a 1 CO o ^— o «

<J3 o

t. Ou

l-l(d 4-> o C

1-t CO m X >> 4J

>, o jj cn

rt OJ T3 t-i c

a, 4J +s

h c > o c C iH CO o

•r-l •H en s. o o tn 9^ bO o

a. Q. <D > t-t t. •H o t. bO bO o. 4J -H 4J c C O <i-l o

iH •H t. CO •H CD

4-> iH o £- o rH iH •H o. <i-. CD CU CO

<D o 50) <X •H < e jQ i. CO o o

106
CM Oo

on Xoco

>>

&.

<u s:

4-> 0) 13 M a> CO > O

r-H •>-> •r^ O tn JJ • £ o o ^-^ o i-i o s o g- t. o.

r-l

m Q.

OJ <u c

V.—' o •> .- o

;. 0) ^N CM

cu r-t JJ jj n c «

nj 03 t, ? p o •^ g ;> rt c rt <u

•r-l rH Q. c

«-l •<-t <U O

r-( >. «^ CD X3 .-) O 3 ^ o

4J c

cd

O •^ t,

03 s: CM

rH

.• .- » o

4-)m t. -U c i-H •r^ —

<1) •rH (0 > o c

rH c o o >, •r^ •r^ 05 § n

?3 £ rH

r-l •a e x: o c rH c

a. cd rH tH

0)coc

CO Jj3

i3I C\Jo

4J

x:

x:

4J

(U o

in

CM o o • '-^

CTJ o o t= o

QUO •3- \ o Z CM v_x s O

0} o >-^ CM

m

0) o o C3> in in N.-^* 1 •^ =T o CM CT» in VO m u • VO t^ CM •3- in CT>

(. vO • O cn CX5 r— • 1 <u CO a\ • • • • CO CX3 a 1 c- o ^— o o »— t— ou

Cu

r-l >>

n) 4J 4-> o •rH c

•^ > CO tn X >» •rH j-> >. (O 4J 4J (0 £: <1> •o •rH O c

Ou P -p

h c > 3 o c c •rH CO T3 o

f-» •rH CO c C o O (0 o bO o o a a 4) >

•rHO o tH

00 to O. 4-> •rH r-\ i> c c O <i-. CO o

•^ f-t t, CO •rH s <u *i iH O i. O t. i-H rH •rH O. ^ a) (U CO

<o 2 5(U o. x: •rH < s t. CO -p T3 o

107
o

en Xo

C\J XomXo

0)c

cd uooIc

I.

(1) o,o

Ouo

CO

Ou

Q) .H C JD o CO

4->

€

0) c o CO

(0 1-4

<•-•

b

1—1 .. o L

s: CU o 4J o CO

i-H 3

0) »—<. 0) i-t s

f-^ J3 a.

£> 3 o. 3 1-1 rH O o O CO o m a-

»m •» 43 " (. c CO •^

<u c CO > o

iH J3 c o c H-l CO COo (U k o oc

1-1

n CO o >. t. Q. x:

1-1 c o o o c jj 2 CO ^—

0)c

CO

4-> oo o o

CX3 t— 0^ vO I

v£>

CVJ o

in

CO a.z

CVJ oo

CJo

.=r

Ooo

CM

CMO oo

CM

CO

CT^

C7\I in1 ^ o »- o ^ ^ uc

CO

X >>. 4J

0) 4-> CO <D T3 •^ c

Jj 4->

h c > o c c 1-1 CO o

•^ •^ CO

u o o CO OJ tc o

o. Q. a> > •^

L. •.-1 o (. bO CO Q. Jj fH 4-> c c o 4-4 o

•^ •^ t. CO »H 0} u iH o :- o rH

1-1 i-t o. •tH QJ V)

OJ 2

CO CU D, iH < £ > t. CO •o o

108
3S

i.O

T3

tn o o

I-) coc

4J

0}3

(0

05 3 5

0) O"

O 4J t-t o o rH 2 >.

0) l-{

f-4 4-> J3 §, rH

l-> •r^ o

05 r-( 3 05 iH JD m s • •> £- o C (1) o O C

•^ 1-1 * 4J E

05 (0 3 t- • O (TJ iH a o

05 <B •<->

-.-» £- 3 > O. 2

>» U

•^

05OO

05

t-(>

05 T3

(U

C

tH ca M

t. 05

0) <B a o o m

OU ^

rH c

n] o o

»H •a

05 c

>. <D JS O.

a.

0)

&.

0)Q.O

I.

«' f*->["

— i'"t"" ]!• 1 1'" :j^r^' 1 1" h—- 1 ^-T—

—h—

—rr-1

H

[... 1,... —^

—t— . 1 —J

r—

_ ==^

-L... ... i —;...J.::. ;. .:. 1—~~—1— .. r ; —t—

—4— ' 1 i ' 1 ! 1 ^3 —r'

=^^^

2,

'. 1'

L- i

[—rj-

—' ' ' '— 1

La -L—;;-J—i—1

-^—

r 'r- 1 1—j—1—'

,. , .y...^ --f-r-

.i;:.J

pim.;

|t-43y

1' 1

r-|: -p'T- i —\—-4—

—I 1 1 -f1

\—\—

-H i -^

-_l .—

—^

m: :

h4-

-;t:::- —^—, —'—\—1—1 -—^c

-i

—I—1__

—r^1

J...I... t^c-^' , " , , \ —J

— 1 i _4_

-i, 1 i' 1 '

'' [—

-—-f,—-—

—

: i \

....!.... j' '•' 1"

—f— 1 —j_

^—

I~

:-..i : ,i , _1_ _^4 ,—, [ _-L

'j—

T ! ' ' j ' ^ —i-

— ,.-.-j,— .1

—y-

— f— 1 1 . 1 ..

—

r»— - —I 1 1 ,.. .

>• __ --!

—

—, —1|

—1

, ^^ 1 1 J :.;i , f

.. ,- , ' 1 —H 1 ' .;: 1 _ H

HI =f= , U— ' ; I —1

1 '^ \ :..,. .. .-.1.:

M i

9-

t=i 1=

tToa

—pj

:—

—U--0—i

; e

.. . ^

,, 11

.. ,|.,, ... .

:' 1 i —I h—

-H ' |-

r—]—' ' , . 1.

:=^

rjr-:.... ; I' f—1

1

:=: =iii:^

1. 1- .1

1" ' : ; '1 ' ' . 1 1

9-

—\~° F1 1 UU==

U—i 1

1 1

ri

-—U

^S1 . i : 1—i

; i j 1 ' 1 1 1 1 -—-\ • =4==^

t-r—1 . 1 ^

i-

—1

H . - ^ ,- ^^ 1 1 , T—

—^- . 1 ' —^—' —p

4.-...L ' —J ': ' 1 7:4^ i 1

9. • 1- 1 N=4=H .1 , 1 1

\==]

—\ ' H

—^—1

-1 ,1 H—1 . m ' : f^—1—1—:—1

,. 1 i —1

_

—

1 —i

1 ' , ' — . 1

—'—1—

J

—. , h— ^ r—

I.. —i ' ' i H—1 —1 '———j——

—-- ! —n 1 >4 r 1 T ..:.,.. 1 . ; !,;..[ I , .

Ou, OS

25

109
03

0)O

CM Xu

CO

CM X

CJ

CM X

CJ

J oo

>.

s:

COo

f03

0)

0)o.o

au

COo

03>>

s:

•o -^ c X

CO <U o > 4-> su --i dj 03 >.

4->

O rH

CO3 Q. ^ X •^ C 0) JC

•.-1 ^-'

(U .^ ^^

iH 03 ^

iJ .H c 3 J3 CI) i-t CO o O E t. • 03 s 0) ^^>. CO o. E • « .-1 Q.

j-> <;-. CXD O. C . ^ • m. r— O > 03 <— o i-l 4-> C\J o C o

03 03 4J

m > t.

k o

CJ

CO

r-i 03 > O L. c

a.

O ^ ^

t-t CO >> c (U

r-l

r3. c o

03

4-5 CO

t,

(U T3O

t,O

03Os

03

4-> c

CO

1-1 Oo

CX4 X

EOo o

Ln o o o o CM o \

CM o N.^ CM <JN o 1 CTt o

CX3 CO

CTi1 -3- OO cr> • • o '- o ,- X >.

(D *^ a I-l

J-> 4-> c > c

f-l c •^ CO o o CI) bO Q. Q. >

1-1 <y

ttf bO 4J •rH c C O <i-. -^ •^ CO iH

J-> i-i c. o

I-l •^ <i-i 0) CO

0) S

Q. <

Is t. 03 o

jj

.1-4— t.

—1 —;—1= t=±x^ ^-T—

W

e^^^=^=^

r ! '

1

'—1—'

yZ^... ....I

I' i —i

^—i— 4 ——(N

t;::!

«.

H 1-^ 1

!— =F5

77~-

Q

^i^ ' :' .1 :: 1

^-^-1

1 \ -T -^ r2- -^-

;:::r ::

p ^

'1 1 ' i ' ::n:1 1 1' -

»-

-:-4- - —1

—t—

-1-~1 i -f-

' ' ' ! ' 1 ' 1

••• \ —1

i_ ,. i 1 -r—

—h—t—1—

—+—

—

H 1 M-— 1-—

—-j—

—l—

—ir"*" 1 —r

—T'"

,-= ;

-—1 11 —1 — V- ^^—t

-1 ^ —'

^-'—\

I.J ... ..._j —1

\—1

9:

-^

—u:- j OS " ' (C 1 I'd ' 1 ,. 1 =r 1 \ 1^

*k _|—"—r~"

—^—:::_L 4.. _;_...

T

r

—T.

—

r-3t^ ' i

., ;

:• 1 ,, ' v - - 1. 1 h ' i 1

^_pi .,.,1 ! —\—

=^=F=

J\— if 1 ^

<t>-

—rr— ^^S' i—'

W— i —h^

-. i--\ . - -+-TT^=1—1 . 1 . T-r-*=::= , I ; z ] :_J

—\——p— —|-—1 —^- '1 1 1' 1 , . 1 !

'J- !

f—

:i:' —J

—

U -+-

—i , '1

!;; , 1 ' —1

t=i= j

,— 1—1——^— 1 i '',

<?-

1-

—.

[—1 !

....1. . P1

\—1

,.-. t,.:i

r-^-l1

-f-r

^Q

J i—CH . 1". ~r= 1 ,. i' =4=

J -H K-^^ ' .—^-^ . m=|—1

i 1 ' ! -^

-y-

', . ^3SLi 1- 1 1 i,^ '. 1" i . *

,..,.... ^

Lf- 1 1 i

,1 ^ —. 1' ' 1 1 i^

'.•t'---l 1 • '

.... j . p...

.. ...... ' 1 -n

rH - —1 ;r : ,

\—

'^ i.-.T

a

—

V

—t—

"'-f-i —1

r-c 1 \1

—4—4

—t—11 u_

n : ^— . .:; ,. 1 .. 1 r-l-

_J

--):

It—1 1—t

1. : 1 «I

-4 ^ 1 —t—

-H—. ). i ^^

—1 1

{—[

—

—]

—1

-^.^i.' ' : ..-4— JJJM _ ;-^^ 1 ' - —1

—1 —t—^ i M e«>1 . I 5I r c•

sz3z> OSO ujAz><

110
no oco

En

0)ao

Cuo

CO

CO nH c O 0) .- o • £ rH ^•> •r-l y-^\ o i3 4-> 4-> S o OJ c a. a fH g 0) t- o.

CO E o o

nj t, tn o » r-l o X3 o

<u (»-• a. nj C\J c

0) >> t- X) t. N iH c •rH c

0) ^ o m CO X3 •^ c c £ t~- o •rH c C\J •r-l •^ • «k • 4J CD

t, r— CO

O

0) 0) .-) c

r-l 4-> t, CO CO £) m •r-t s: I. D 3 nJ c cu

i-H •r-l ^-^ O C c o n •r-l 1-4 C

J->

••. OT

O

j-> .-1 4J •r-l c c X5 •r^ 4-» •rH

<i>

D e CO ^ > r-l •r^ Q) CO

.-1

O rH to o 03 c Q) OJ C c •r-l x: fH O jj o •r-l >.

•^

A to £1 £:

4->

n

O

M

m t. 1—1

O 3 s (U o. •rH O o s: X X c jj 0) o ^ < 0) —

4-> 4J c

CO .c

0)

r-t>.c

cuo.

0)c

cuc

cu J3iH

>>

sz

J-> cuso ooI oo Oo

in

CO a.

onoo ooO

CM

O

OoO

Cvl

.=r

.=r • \ E O \

c\j :sCO

vo c^n CO T-

'- o ^ ooin

CM

m

CO

CT> CO

C~- I on CO • o CM r- co

t)0 c

cus coaco X

CU CD -a b .S

CO

CO

CD

>>

4-> >

CO

StiO

•rH

O oDCoo

s-o

o.5

4->

CO Cm

CD ^ CO

•-• E O t.

CD CD Q. £: m -P

•pc

CO P

(Ocoo

4JO

CU

CD CO

•rH <<

•o o

111
co

-p

X3

CO O

S-, CDs3C>c

£->!

-P

>!o

CL, s

J- +Jo

<uo.

CO

0) -pco

CTj

CO

0)a

CDo

4-)

•o

<uc

bO

•rH

CTj

CTj CO

CObOC

•i-i o

CO

CDL

CD £3EC

CD>

CO

CD

CObOC

iH3Oo

Cm

CD

(T

ji"-^ ir\ ^

e . 3- =ro O ,— LH

4-) x:

CO bO

cr, •rH 0) (U c 3 ^o

?3 jr r—1 H 3O E 0) nH 1—1

fH o

tL, s

po •r- ^r cj^ CO iX) (X) c» CO LTi ^ (\i o o>

LO >— <—OO C3^ VD 1 00 I CT^ I I O T- 1 C\J I 1

t- o

C\J Om

(M

C\J

>-

O

O vX) ^ O -^r >- ^ ,-

LTi :3- CO

O

OO C7^ CO 00 vT) I I ^ CM I I 1

112
113
114
Infrared Absorptions of Major Chemical Families

The following tables provide expected IR absorptions of the major

chemical families [1-13].

Abbreviations:

s Strong

m Med i um w Weak

vs Very strong

vw Very weak

sym Symmetrical

asym Asymmetrical

REFERENCES ;

[1 ] Nakanishi, K., Solomon, P.H., Infrared Absorption Spectroscopy , Holden-Day, Inc., San Francisco, 1977.

[2] Conley, R.T., Infrared Spectroscopy , 2nd edition, Allyn and Bacon,

Boston, 1972.

[3] Silverstein, R.M., Bassler, G.C., Morrill, T.C., Spectrometric

Identification of Organic Compounds , John Wiley and Sons, New York, 1981.

[4] Williams, D.H., Fleming, I., Spectroscopic Methods in Organic Chemistry , McGraw-Hill, London, 1973.

[5] Kucsman, A., Ruff, F. , Kapovits, I., Tet .

, 22, 1575 (1966).

[6] Kucsman, A., Ruff, F. , Kapovits, I., Acta, Chim. Acad. Sci. Hung., 40, 75

(1964).

[7] Kucsman, A., Ruff, F. , Kapovits, I., Acta. Chim. Acad. Sci. Hung., 54,

153 (1967).

[8] Shah, J., Can. J. Chem., 53, 2381 (1975).

[9] Tsujihara, K., Furukawa, N. , Oae , S., Bull. Chem. Soc . Japan, 43, 2153

(1970).

[10] Lambert, J.B., Shuzvell, H.F., Verbit, L. , Cooks, R.G., Stout, G.H.,

Organic Structural Analysis , MacMillam Pub. Co., New York, 1976.

[11] Fuson, N., Josien, M.L., Shelton, E.M., J. Am. Chem. Soc, 76, 2526,

1954.

[12] Meyers, C.Y., Eighth Annual Report on Research, 1963, Sponsored by the

Petroleum Research Fund, American Chemical Society, Washington, D.C.,

1964.

[13] Meyers, C.Y., Estratto dalla Gazzetta Chimica Italiana, 93, 1206, 1963.

115
CO o -— c3 1 o e

Q.

O

OOco

:_

COoo

t. o

>,

3:

r—1

CO

a

O CJ . c Cl-H -H '-^

(D LO

O -U CD iD 5 j_) CO —1 O1 O o J- CO -H c a > O -^

CQ

sz ,_, o 3 rH

-U -— CO

CD o . i. O Ci_ .rH '-- jJ O O -1^ CO OO O D 1 4J CO >—1 O1 O O ^ CO o c en > o CM v^

•. .—1

y ^ *'—V^"^ CO

CO CO bO .—1 o

^—V ^-^

——

C •• CO •H

CO CO LTN

O •H r—1 O S- - L

-~^ -~^ ^ C\i bO 1 -H -l-> 3 CO O O ^ !>- bO X i- .. 3 CD ^ D- <- CO O -!-> t—1 g o O C ^ m 1 1 3 CM CD 1 S CM r—1 (0 ^— <

^—V c O >! i. CT^ ^ '-^11" ID '-- on E 0"l CO O 1 •• rH

a CO o o ^^C 3 X >. --^

C E O --- CO c \. v£> CO bO CO ^-' O CO f^ 15 ro w E ;=r m C •• O —

X ^ CJN c o

12 \ *—

r— -H '—^ bO Lf^ 1 1 •>

O " CD •H -H 3 ^ fcD c ^ E ^ e 4J i- -( • "r; --- .. O C H T

r—1 ^-^ 1

\ ^ ^ bO

OO '-- 1 ^-^ .. n -H JJ 1 >, CO C -H CO >!-' O o E ^ CO ^ CO o x: o --H O 'H •H JD CO o ; o >^ E -H o •H LTl -u t^ >^ >- ^ CO H 03 E

LO CO >>

O

O 3 o-i

m --- i^ c<^ •- -~-

O -H o o ^ CO CO CO i. 4-) — E <- -P HO - rH 3 ^ JJ X31 « rH O r-l CO 1- CD

CO c —' -H LO 3O 1 1 C\J CM CM o o jJ O X5 1 CM C 1 rH PO CY-lX X X E CO 3 t. CT^ D jj roj-> X CO O X X O CJ CJ) OO o O-l O C X o o x: ^

cri o o /^ /^ ^ o ^ -o jJ ^ -o HOC /\ J^ ^-

^-v ^-^ ^-s ,--, CO 1 CO CO CO CO E

V_^ N_^ c x: o o o o o CO JJ vO f- CM ^ ^ o

C5> CO C7^ OO rH CO

O

CM CM C\J CM 1 1 1 1 ^-^CO CD r—

CO CT)

OO

O

O 3 O CO x: O CO ro vD > •H

O o O CXD C3^ OO -^ rH J_ -!->

-!-> '^ CV^ CM C\J CM

O

O

O

Q) s C7^ >, c a.

i. \ .. CO

O -H

D

-IJ C/5 ,—V .. ^^ .. cu CO

CO

— E '-- E '-

>> E >^ E 1 c en C -H 1 O CO >> CO >>

^3- CO CO CO CO ^-^ •H CO -H

i_ o o CO -— --^ v^ ^'

CMO 1 1 CM CM o on mx X O X X o o

c^ o o ^ ^ o

C^O X1 o

Same

as

ring

st

frequen

ro Xoc / rH CO ^^—

-'

X . / \ CO i-H C\J CM m 1 \ ^ D + X CE c \ CD e c O X r^ -^ / C i~ CM —

CJ cr \

CM / o

CD t.O

XC

Xm 1 \s. ^ ^ o cc ^o^ C

l-l OJ x;o o

4-> >v o x: x:

r—1 • rH bO o o

•rH .-H •H c •H E o CO CO rH

CO - >,

L s_

O

[x. CO o

Q) to

a:

4-> CO

•H

H

•H

>>o

X3

116
o3CCO I o e

COcDo

D-EOOco

X3

JtOoooX

4-> • O (U . C rH J= -p X) o c

CO bO CO jJ CD CD C TD CD CO -P •rH C t, J3 O ^ CD -P m 2

C-H

roc

too

dep 1

>C=C< s

may

be

^^

Q) .^—

TD

C c c ro o

CD .—1 y-N ^-^ -rH 1 CO '-^ ^ bO 'bO "hO E P v_^ CO X tM ,-v ^—

in c '-- c ^ CO E 1 1 o E E t- .rH CO -H CO -rH O £_ 1 O 1 — —

VO J5i --' ^ --' ^ CX5

O 1

II 4J LPl O^ 1 o in o o o 1 Q-H O D CJ^ <- LPl O <o o o> o O CD /\ O CT^ CT> r- t. CJ^ L CO e =r -O

'-' 1 ( ^- ^-^ ' ^-' ' ^-^ CXD v_x

•—V ,^-^ '-- c D ^-. E bO E O C CD --^ C ^-^ •r^ CD C LTi -H ir\ JJ

X3 tfl >-

L ^r-s [>- CO ^'-^ .—

rH =r

O E CM E E 3 X D. -- CO ^..x -- S- ^w^ — 1 1 1 CO vO 1 o LTl LO 1 CJ> c O -H o LTl Ci-H ,— ,— 1

II -rH C\J o .:3- CM CD ^ =r o —

^ CO X— cn -a T— »—

/\ ^^ 1 ^^ ( 1

'e 's 'e "9 3 o v—-• N»^ >—

N ' V

' x: o o LTl o o O

X o o o X

CM OO ^ OO 1 -p en o O O O E o

CLJ) CD

m CO cn cn •-' CY1 1

II t- CD 1 1 1 1 o 1 1 O -P > C\J o o O CO o 1 /\ CO o OO m cn C7^ C7^ C7> JD o o o O CM o

CO cv^ (V^ cn CY~| ) cn E E 'e 3 E S V ^ >_• Nw-* N*.-' "_-.' N—

x: o O C3D CM CO CO LO ^^

V o o ^ .=r in VO ^ VO s O -P VD ^ v£5 vo <o VO ^ >

II CD «

1 1

^

t

1^ v_-^ U L 1 1 1 1 1 1 1 o

/\ -P o f- C30 CM c» OO in t^

CO 1^ ^ LTi VO t^ Lf> f- MD

vO vr> MD VO vO vr> ^ »— ^ ^ '" " 1

^~^^^^~^^^~

OJN

m J- r-H CO C\] ce X X CC X X X ec CC CC

CC -H

X

VV

vV

v

t. 3 o o CJ o CJI o

CD e c II II II II II II c s- C\J X o o o o CJ

CD

O

X o - /\ - /\ -- /\ CM -•• /^ (N -^ /\

N

O fc^ co CC

CC

X ce

X CC CC CC CC cr CC o o

CD ^-~^ TD CD P> 1—

CD 4J 1 ^—

CO 1 >> 4_> CD 3 •H

CO hO •rHC 3 c -P +J c D Jj -^ jJ CD •rH CO

•-< •"-J CO > M T3 J-> £1

<^-,

C X3 v_- JJ 1 •-f CO 3

CD

O o 3 CO CO 1—

n CO

r-H -rH o CO "O Xi 1 c >, 3 CO -a

>.

O rH 1 O CD 3 CO CO

C CO S- CD f—

--

O c C -P CO •T~i S- •iH •rH 4-) -P

•r-H >> o O 3 •f-{ o 4J > t- CD 3 E CO o c E -P a -P P -P

CO CD <

Cx.

C • • ^—v /—

/r^V •'-^ CD •• ^-v CO £) o -a

J^ --^ •iH >._• N_^

i—i 1—

—

< --•

117
in

<i-f C\J o c m 1

CTi c o c o •^ CO o M x: t- 0) •^ c -U x: >,

-u -t r-l o 4-> o m Q-, 3 fH c

bO 0) -tJ f) CD 3 r—1 V CO CD D • •^^ o o s CO cr-- C II o rH Q> 1 o c o i- OJ i- E

cj> n3 /\ CO S- t^ o

CO CJ 1 •^ 1 CO 1 1 u '—> 3 CO CD x: a 4-> CD i. o x: CO •rH CO Ci-, jj jj • JJ to

•rH Q-. CO CO CD

C

j- 3 o •a JD 1-V o

jj c 3 O C3 •^

CO o x: o CO c II J-> • cu o n •fH CJ a. >> V 1—1

jj 1—(/\ !.. o o D. Jj >i c o c

IID t- c ^ o 0)m d) o O ^ 0) 1—1

•nH x: X)

D

/\

O CO o <c 4J> 4-> CD cr

>> bO O x: c c j-> •rH d) •r^ i- 3 2

cr bO

COC

i. •^

C-H CO CO

CO CO ^

CJ> s_ SII o CJ o c

/\ •rH -o

to

•o c c C CO f-i r—1 ^

X3 la o 1 o X ti-i t- 1 o •^

11 -p o O 3 <X5 ^ O O^ —' 1 V

^ >-- bO O IT. C

LTl CM -H 00 vO bO 1 1 bO O f- CO CC C7^ 3

CO ^ -^

C

•i-i co

CO X3C3O

C.Eo

(^co

X3

i.

COoo

s^ T3

>> o ,—V c

a; c

J2l CO 1—1 X Q. o C

11 •rH o N ^

CO 3 o o o o 0^ f- O o o o o CO

C\J t— oo

CO

i_s3C>

CO

X o 1 -u O

II in

/\ CO 3>oo Oomc>-)

CT. o

COo V o

c:) +j

11 c.:> L. /V -U E >>

^—^ r—I O -P ^-- O C -P vD^ 3 rH 1 CT X3 O 3

-- iO

v£5 tn TD o o o <o 1—1

(J^ ir\ J^

r— ^ CO 1 1 '-< o O i. o ^ CO o <o >

CM T— o

CO

\/

.—1 CO o

CO

—1

II t. 3 o E 1 C S- o o 11 O b-,

•a

4J> COhO3

•--^ >> C

.—1 o

•rH o E

CD • . U. -—

oo

II o

CD3 o E •--1 3 r—1 O o

>. • • o

C\J Xo

II oo

I—I

-I

CO r—I c o

s_ >.o

4J

O

X

X

W

118
L

X hO

<D o c

s: s 1 s: o •H o o o 4-J •o

-p tn <;-l -p c o t, o o 0) o

S- rt t. zs XJ

jj c -U -p CD •a n m m J- c

OT x: 01 i. 0)

X •^ jjX CD bo 1 2 x: o o o Jx: c 1 o m L

III rt 01 •.-1 o T3) C) CD x: S- s: i- >> 1 Q. -tJ o 5 n x:

a

<D3C

-I

-Pcoo

CO DCOsoOco

£1

s-oo

S- •o

>> X

•ac X CD I .o o n o 0) v_^ CM c o OJ o ,

T

4-3 ^ 1 S- 1 o CD o ir- > o on o

I^ r—

—

CO o 0) CO o 0) (0 o CD --^ CM c --^ CM C --' CM C O CM o O CM o O CM o t— 1

-p , T -p ,— %— 4-> vX) 1 t- VD 1 L ^ 1 i- 1 O cu 1 O a> 1 o CD o c- > O l>- > o t~- > o on o o on o o CO O

t>- T- ^-^ t— ^ ^--- t>- ^ —

CO

S-<D X3EDC

CD>

(0

x:a

X P I CD

(_)L

III -P O CO 1 OO

CM -^ 1 t. O CO OO CO ooCM •^

CO ex 1 i- O 03 ^ x: CO CO

x: 1 o

c; -p

III CD C3 t- 1 jJ

CO oo

CM1 O 3>OCT^ CMI O

<o

CMCM

O '-- o <u CM rH - £3 O D O O

CM -O

CM -^

O (i> CM rH - £1 O DO

CM TD

CM -^

i-H 03

03 <-^

(D S C L

CD

O

a ci-.

CM1c

CM Xco X1 o

III o1

-D

CD

4-5 03bO3Coo1co

CO c

CDc

CD

4-> I CLJ

III OI XI o

III1 o

III oI

CMcc1 CJ)

III o1 o

III oI

03 CO C o C

•H CD •r-i s 4^ t-\ s

t. 03 03 i- CD bO c CD 4J 3 r-i 4-5 1 •1—) S 1 c C L c o O <D o c o +J c

119
oc 1

(fl oo • c o o ;- o (\J •^H 03

•.H J-> sz Jj c 03 o

03 0) E c <p O c

•pH 3 t. t.

m

n -U 03 0)

0) e (D 4J ^ o iD 4-> o o a; 03 2

j^

CO C/0 Q.

03 c c

CD 03 • o 3 i2 1 4J 3 0) s 3 O c o JJ ^ o .^

CO 4J o -U

t. o CO

.—1 CD lO £1

r-l > ^o

D

•a: o >— CO

•oc

4-)coo

CO •cc3o

Q.sooco

03oo

{. •o

>> c O 03 C ^

<D

a

iD 1 Ci-i X o 1 1 O 4Jo

COs

CO CO CO CO o o Ln o o o

on a^ on LO a^ t

c— <o f— f- ^ CO o o o o o oo

t— ,c— ,

,

oo

c~- D- c— <x> C-- CO

CO E E CO CO E o in o LO O LO

VT) o c

o ^

^o

C^ 1 CO) CO1 CO1 o LO Ln CTi LO o

CX) 3- CO Cvj v^ oo

t— t- ex: OO CO r^

V o

II

CO oo

inI oo<^ oo oo

in ooITi oo co oo oo oo oo oo oo oo

szo V *J o

li £- o 4-5 /\ CO oooenI oo o o o o o o o o o

on o-^, r^ o o o o o o o o o o o o o o o m m on o o o o o o

CJJ CiCO aco

Q.EOa

03EO

t. 1

CO i3

CO -o OC JJ O 3

•o3

>-> CO I 3 . .

CO .- ^

on

Jj 1 CO on

jd . 3 o CM

CO rH Jj ^_

i. 3 H 4-> ••

on

120
<u3C

r-< -Pcoo

•oc3O

Q.eooco

£i

t.

COooR c

•O fO c ^

(U D.

£1 I X o I I o -uo s3

0)>

CO

V o

II CD O iCO I O o cu

II

L

/\ en

r—

Cfl CO -H

t. 3e c ^

CD o oo

CO o in

in CO o

CO

O

CO ooo COI oo

\r\ 3O

I—

QJ X3 o O O O o o O O o

u^ LO in LO in o O o o o o O o o o vT) ^X) UD vO ^o o o o o o o o o o o o o o o o

CY^ on oo r<-| on o o o o o o o o o o

-U 1 1 1 -l-> •.H CO .=r LPi LTN CO 4J

JD •. •t « JD CO 3 en cn ^ 3 X3

CO . . . CO 3

CO -a CM CM CM CO TD CO -o >, i. 0) •^ ^ •. 4J CD CO CD 1—

4-> 4-> ,

,,

c jJ

X 4J

•.-( CD 3 cu 3 CD 3 E E- -(-> • . • • • • CU 4-) X -P

CO /^^ ^—

^-—

tu ^-^ •i-i ^f-^ •r-t ^^ '—

121
CO o

co

Q.E

O

C

G

bO>>X

o

c

03bO

£- O

COG

-Po

See

Organic

Halogen

Compounds.

a-unsaturation

decrease

>C-0

stretch

by

30

cm"'.

Liquid

spectra

of

alcohols

show

a

broad

out-ofplane

bending

band

(769-

650,

s).

D

C

G

J=> X

1 O

1

1420-I300(s)

~l420(m)

and

-1330(m)

(coupling

of

0-H

inplane

bending

and

C-H

wagging)

~l420(m)

and

-1330(m)

(coupling

of

0-H

inplane

bending

and

C-H

wagging)

only

one

band

(1

420-

1330

cm"'),

position

depending

on

the

degree

of

hydrogen

bonding)

x:G

p

G

j-> CO o

1 CLJ /\

1195-1060(s)

(three

bands)

1055-1040(s)

(sometimes

obscured)

1 BE1 1 B 00G G G

ITi LPi V- ^ T T 7

s:u

G

-P

CO X

1 o

3650-3584

(s,sharp)-for

very

dilute

solutions

or

vapor

phase

spectra.

3550-3200

(s,broad)-for

less

dilute

solutions

where

intermolecular

hydrogen

bonding

is

likely

to

occur.

Intramolecular

hydrogen

bonding

is

responsible

for

a

broad,

shallow

peak

in

the

range

of

3100-3050

cm"'.

iH 03

oi —

fe i

G O

(N X "

CC 1 cc O C5 O

1 R-C-X

X=halogen XX00 X

CM X N OJ 1 m X001X CC K CC

1 CC CC CC cc

>.

rH

•i-l E

03

CO .—

oi p

G

G

<

COG

o

•iH

.—1 03 x:

rH>.G

<

Alcohols

(i):

Primary

(ii):

Secondary

(iii):

Tertiary

122
aC

r-t cooc3O

D.eoocwXoc

CO O

CO

CU -POS C

CD

CD -P 1 5 CO CD

4-) i. •a

'-^ a> -rH •—{ E ^ ^ CO fao ^-N •—

c E o cp -a CD -^ —

x: CM o c x: TD o o t>- C CO P c LO

4-> CM CO (D oCD 1 c x: Cm £1 CM

tn o o o ? ^^

JJ - CO -!->

X o

CO ^ 0) CD E S- L

CD 1 c o E -P 1 O CO CO o --' CO O E 1 = o

-282 form C-H

1- —1

CD -O > >> o x:

O

O

CM CO so

CO

j- X3 3 C

X3

H

O

CO •H

B CO r-\ bO D £ o o C C o ex E •H

0) -p 1 -o > CD . N ^-^ ^-^ ^-^ ^^ CO CO c

CO S- CO CO CO CO CO -H t. o • IS +J ^-^ ^-^ — ^_^ ^^ JJ XD ^.

CO o LO o o LTi bO

C E ,

CJ> c» ^o ^ C -H

C !U

/-—

o ^- \o M3 VO VO -"H o CO

II ,— ^ J- o bD Cm

—

o 1 1 V 1 1 4-> O o /N o un O o o 5 i- -H ^

CM o O CO t^

O

a o cI~- ^- t- vO ^D rH D >^ c ^

'— "" >" '" ^ --^ -o x: 1

X,1 o —o c X 1 X

M CO i-t 1 o 1 hO

CO 1—1

>.

M O:O II o —o X o

tn

D a:: ^ >> 1 o 1 1 H

(D E 1 rH t. o 1 CJ o —^o CO C t. cj=o CO CO II o 1 1 XH

CD

O 1 II II o II o —o o X II

O Cr. in a: cc ^ o 1 1 X ^ •o o •o ! TD

-.H ^3 1 4-> 4J J-> •> 4-> 1 o

CO CO 1 CO :>- CO o -o •-{ s- x: rH ^. ^ - t. +J >> CO

CO 3 ex >l CCL 3 x: x:

>, CD Jjl -rH iUa 4J « 4-> ^ 1 .—1 •a CO 1—1 < CO a CO 1 -o s

•M >, OO CO • • CO CO CQ

H E j:: • • ^ c •• c CO • • CO CD • •

<-

—V

•H 3 '-^ 3 • • *^-^ tu -o ^—

•H •r-t > ^-^ •H

.-H iH •iH •f-< •rH > > < '

^^ ^-' " — ^-^

123
•oc

C

O

(J

CO o

c

Z5oc

e

oo

c

(DbO

>>X

o

c

tobO o

CO

CDO2

See

Organic

Nitrogen

Compounds

x:o

CD

i4-> CO o

1 o

1300-1050(s)(one

or

two

bands)

1300-1050(s)(one

or

two

bands)

1300-1175(s)

950-910(s)

x:o

j-> CO o

II o

/\

~l820(s)(asym)

~1760(m/s)(sym)

1795-1775(s)(asym)

1735-1715(m/s((sym)

Ring

strain

raises

band

to

higher

frequencies

(up

to

1850

and

1790

cm"

^).

Conjugation

does

not

reduce

the

frequency

considerably

,-H CO

03 —

i. D

CD E C ^

CD O

N CM O O

cc cr CM CNj O O O O 1 1

1 1 O O O : O

O O 1 1 O Q O 0=C0=0 1 1 _0 S- 5^/ \^ -'-'"-II < /\

cc a: ^-^ o (\^^y)

r—

e

03

Amides

Anhydrides

(i):

Saturated acyclic

(ii):

Conjugated

acylic

(iii):

Cyclic

124
Ccoo

•acO

Q.Sooc

0)bOXoc

bO

£- O ^ o 1 c ^ -IJ •iH 0) ti-H O +J >,

bO CO

O -U c CO CO

n

O CP CU 3 X3 CD

s. o >) S- o 3 CO >> O 3 O -l-> -o CO CO o

>> -a

C CO ^ . CD

C • x: d) CD -^ ^ c S_ CD -

CO t- 3 >,'< CD

O 3 1 cu t—1

CT

OO 1 bO

C CT E

-U CO bO CD 11

C E o ^ <D

O o C C L O CD O 1—1 i_ s

-P c c o

Cn /\ 3

CT LTi CD CD CD ^X) x: x: i- ^

CO X1

uent hef0-20

H-i X2 ^ JJ C^H >— e JJ 4-> ,— 1 4-3 1 4-> •-^ ,—s - 3 .-. - 3 '-- o m CO E O CD E O CD c \ \. v_. v_, c — --- C

0) ^ E O ^"^ CO o ^^ to X2 o o

VX) T3 rH CO CO CX CO CO CX 1 in in

CM 1 O 1 1 O 1 o1 1 / CJ^ o j3 o

C3^

x: CO

m CO o v,_^ s.»^ »....• -tj o o o

CD o o o

<L LTi •-^ . V in '-- in '—

j-> CM CQ CO OM T3 CM XD n 1 — -—

1 CO 1 CO o O o o o o o

^^

X o in o O tO SL- ^ 1 on in m m i3 CV~) X3 1 o PO en ro on cr-) s 1 o

CO

c_ x: •^ ^^ ^—

N

(U o s E E

X3 4-> ^ ^ v-^ CO v_^ CO E (D o O CD '-^ O CD '-^ D j_ ,

(X> E 4-> CX) E 4J

C 4-> OJ CM -r-l CD CM -.-H CD

CO ^ 4-)

M T- 4J rH > 1 o o 1 CD JD 1 CD X3

03 o o CM o in E 3 in E 3 3 1 CM =r =T ^ O O ^ o o o on ,— ,— on CO -O on CO -o

/\ 1 i

x:o y^^ ^'^ ^^-N

-i-> CO CO to

0)

v

y

N

X >—

i- o o ^ o 4-) cx) **—N, ,

o CO

CO ^ CQ I^ c- VO ^

V_^

T t

T

o 1 o 1 1 1

11 o VD o o o o >X) t^ PO CM o

/\ t- 1 l>- tr- c~-

ee cc 1 1 ^ ^o o-"^ -o

f—1

cti

O ^ 1 1 f—\ CO r—1 X X >, L D X ,—1 c E X K o X >, X CD c i- o O 1 1 O ^ 1 o :^ o 1 1 o=o 0_ ^ i-H 0_ ^ --I o tL, o1 O CJ>1 o 1 1 0 ^-tJ 1 1

to

11 cc cc < cc en ce cc ^ tT o ^ .^

i- -D CD -.H t- -o o

CD CD E -U CD

L -O -r^ o e -p O CO E 4J CD CD 4J

•r^

O CO

C E •-H CO E 4J CO >> .-H C I- O O o i. •-( CO E ^ >> O 3 E S. 3 o S- o

•iH

X CO E 4J CO .. jj, 3 L e o -o CO • • --- CO 4-> CO

cfl X3 -M • • CO ^~N •rH CO '-^ 1 CO

fc< t- o ^^^ r-i -.H > CQ CO tCO CO iH •rH •i-H •r-l "CO o ^^ ' --'S3--'

125
c

•r-l coo

CO •aco

a.sooc

bO

>>Xoc

tobO

J- O

COC2

See

Organic

Nitrogen

Compounds , s >^ = -^ x:

fco >5 CO 1 CO o C CO CO O \ 4-> M ^^ E

t- » '-

— --' ^

^^ bO (0 CO o J-J --- C --^ —' CTN CO CO -H O O '-^ C3^ •— x: ^ ^ -c 0^ X O -i^ OO CX) C 1 1 m CO 1 1 o o

r\j o o £5 in

— ^ t- LTi ^T O i J2l CT^ CX3 m

x:o

j->

SL.

CO o1 o 1Oo• 1 >> o

CO o ^ . o

4J

i- o

II ^ s

CO >=

--- CO o

LTi '--

ir\ CO T o o o 5 'i^

rH CO

CO

—1

t. 3£ C LO O fci 1o11 cc ot

III O1 CC

CC a:

\/o

/\

— rv CC cc 1—1 E

CO

Carboxylic

acids

(cont.)

(v):

salt CO -p

COc

CO o

CO TJ

•rHXo

c.

126
o

s:oo o

x:oo

CO o m ^-v ^-v o CO o1 T o o ^ o 1 v^ ,

o o T—

•a

CDDC

•r-t Co o

CD O1 O

CO •ac3O

o,Eooc

CDbOXoc

cfl bO O o

CO o

.'-^ c

CO o m en

v£> CD ^

4->

T CO 1 j-> o CD ,— O

C\J CCJ

CO CO - o o /—

un LO

CO C\J

O v.^ <

1 o 1 1 CO o o ,

o o

T— CV-| C\J o

LTi

C\J oo o

on o

CO o ^

Ln CO

C\J > ,

^~y 1 o o ,

o CM m T— T (

CO

su

CD X3EC

(D>

x:o

CD

CO O

II o C CD S o CO o

•.H CO JJ CD o D L CO

J-> c;

•rH c o

JJ •-H 4-> CO Xi C D.

J<-^ 3 CO

D ^-^ ^^

m CO

—

CO CO v—^ C ^-^ v^-^ LTi c •nH >, in LH

(Y^

O ,

,

C—

M CO c ^- I~-

T

O JJ CD ,

,

1 M 1—

3 1 1 o n3 3 CT o O

LO x: CO (D oo CO

l>- 1 CD J- c— t^

»—

a i- Cl-l »—

CO inI o

en

inT

O t. oI O : 1 :0

CO

II

cd

•rH CO e t.

to CD

li, -p

CO

CjJ

•o o

CD rH

J-:' -U

CO CO

Sh x: 3 a

4J •rH CO iH

CO CO

>, ^

1—

CO r-J

II ceo

CC 1 o •^ 1 X o

II II o

CC /^1CO

t,D

4-3 CO CO

CD CO JJ c

CO 3 B 1 o

t- CQ CD O •V J-)

Cl-H S

>, ^

CMCCoI o = I tco

:0

OvJ KO

II a:

rH CJ

>, 1 ^ o

CO O:

II 1 :0

ce a:

>. ^

ce

CD

COoNC

CD X3

TD

127
•ao3C

•iHCoO 1 o

0) o1 o

CO ocDO

D,sooc

CDXoc

bO o oo

CM o O

on o0^

COO

4JO

inoToo

on

05ao3o

LPi o1 oom

o,o

J-5 o

inoToom

CO

<D £1e3C>

03 o

a;

CO o

ii o

/\

CO o oT

in co

•H

4-> mN

rH (M rH ce O o co 1 ^—^ ,-—

r

•)—

—(-> -^-^ CO CO o 1 • CO

N • V -' 4-> • N • LO O c:) • LO on LH o II X on

c~- VO 3 / i>- T T a o1 o T

r-H CO 03 .—

i. 3

<D e

0) o

LTi X

^£5 O1 o1 o = 1 :0

>. CC ^ o

03 o

11 1 CC o1

:0

:0

CC

CCo1 O : I _o1 (J) : 1 or;

>^

M S- CC 03 o1

II o1 =o CC

CC coo .—

>,

— >.

(—

c

-H CO (U

id t- x:

OS CD

a

tx. -U

CO /-

—

u (1-1 o

4-51s

bO

CO

CO

CDO

4JI CQ

CD

4-5

CT3

M

O

>. tsl S- C

03 CU i3

128
a

<DC

•H

4-5 CO

CJ

COcDO

cxEooc

CDhOXoc

CObO o

CO

CD •po2 l660-l6lO(m)(>C=CC) ~1000(m),909(m)

(>C=C-H)

(wagging).

See

Organic

Nitrogen

Compounds.

See

Organic

Nitrogen

Compounds. o

II o

II CJ

/\

CO o

LTi1 1 so

CO

CD

>C-0-C<

stretch

symmetrical

very

hard

to

trace

1075-1020(s) 1075-1020(s) 3C

<D>

CO 3:

>C-0-C<

stretch

asymmetrical

1150-1085(3)

branching

off

on

the

carbons

adjacent

to

oxygen

creates

splitting

1275-1200(3)

(high

due

to

resonance)

1225-1200(s)

(high

due

to

resonance)

CO CO CO CO o in on LH

>JD CM UD cv-i >- ^ o o T T T T o in oo Lo

C7^ CTn C7^ LH

T- r- C,

O

rH CO

CO

M

CD

O

rH

rH

M rH

N CO >,

M >>M

CE II ^ >>C >> \ Ot rH t, -H t. O Ce CO CO > CO 1 - II II II II CC CC CC CC CC CC

CM O

II o1 cc o

II o

II1 cc

N " CC ^

cc 1 CE O C5 O 1 O

II o

II o

>>

rH•HE

CO

Ethers a)

aliphatic

b)

aryl

alkyl

c)

vinyl CO

(D •o

•HEM

CO

CD 4J

COC

CO>ioo

CO (H

CO .H

CO -p

<D

CO

(DC

CD -P

(D

129
V)c ^ o CO -^-~ rd • •n^ CD ^ CD ^^v -P CO 1 3 3 3 s: cd R —1 o (D O >> o O jj t. t,

w o en CD

O lO CD

CD -=r i- c CM > . -U oo t. 4-) •r^ 1 ,-—. O ) o CO o CO - 2 C ^_^ •rH 1 CD CO o O s C cu i: ^^ 'r-i ^ .c o O rH o ^ JJ o o

+J (-1. /\ 1 03 Jj -u o

J^ id id

C CD o

0) CO a; o <v t- t. CJ^ > CO CO hO -U 4-J C\J o CO o O CO CO 1 •o cu C\l .—1 o o •^ S- 1 CT3 O X o

II rH o o ZC II 1 -- o o ,

1 o o en ^ m a ~

£5 /\ /\ ^-^

CDC

•rH Coo

CO -acO

D,SOOc

CDbO oc

CIS tiO o

CO

iL. CD i3ec

0)>

CO

x:o

CD -P

CO Vo

II o

/\ oo y-^ VO B t

^—

1 o o ^

in MD ^ »— t

i o o o o O -rH O -H

-"—V in 4-> LPi 4J s ^ CO <- CO - S - S o o o O O

-^

OL tn VD vo CO MD CO

x:o

CD -p

CO o

CO

CO oI o

CM

i>-

coc

CO

SL. -P 1 I CO CO

CO CO o in LT^ C7^ [>- ^ vi) 'jD M3

in o LTi >x> <^ V£) VO VO VD

O tL, 1 O : CC

rH

r-HCO

II

cc

O: o

II <M o

CC 1—1

CM 1 >> N C) ::<: 1 1 I—1 o . o CO II

II II CJ o (N /\ /\ CC —

CM

CC1 <-\

c:i >, 1 rH ,-\ L C ) >, ^ >> to

II J^ >> ^ 11 c:) rH i. M OJ 1 CO CO CO CC o 11 II II ••

11 CM ^ CM ^ o CC CC CC CC

/s o -o

•rH CD

-(-> -p

CO CO >, x: s- iH CO Q. 3

r-\ CD •rH jJi id C r-t, CO

CO

O CO CO u. JJ ,—

^ CO ; 1 -a o

4-> - CD CD

to QQ. 4_J 1 4J

CO « CO 'O CO c " i- ~ J- rH 3 -a S3 D >- 3 >, 1 CD 1 4J - -p rH i- oa 4_) ca CO CO. CO >> cO " CO - CO " CO t. •rH S J. 3

CO TD

130
<DC

C

oo

C

o

eoo

c

bO>>X

o

c

CObO O

CDs3

C

>

o

CD

t,

4-> CO V

o

II o

o

4-> CD

CO o

II o

rvn J3- LPi VD M

M n3

nj 1—

1

i- 3 O

CD S II c ^ /-<-^

CD O /^

O faj f

I O:

1 O :

1

•n —

1

c 1 CTl H

XJ o

a: o

o o

1 tC\l -o 1 cti o

O o

L o

X3 en

:2 4-> o CO .—

1

1— ^--^ en f; x: a- CO o

Cl-H

tfl 1—

1

s o

o c

s:w

nJ f; O o

i- tn Xi Ct-i

•> eg E M CC

^-^ o 1 o c c:> —o

CX) 1 • in •X. • T— o o X.

1 Jj 11 1 o o o ^ 1 VD D ^

T— TD cc

T3

J-

^—s ^—

s

^ N ^—

s

Cl) • ^ CO CO CO CO Xi O '-- —" —y —y — fci •H O

o o LH \r\ 4J -rH LTi CO ^r ,

d 03 4-> CX) I>- I^- t>- 1 x: CO "" '— "" ' •r-l o

CO O -D •o •a CTl CO (0 o

x: V c

C- L C- i- jj .—

.

y~^ ^^ y—^ CO

Q) CO CO CO CO XI X3 xs Xi Xi t. ^^ — —

—y s e e S m o o o o

bO o CM CO CvJ 3 s s fc: fcd k

^- t>- MD f- +J

1 1 1 1 T T T

^ '—

CCcj=0

CM XO

1 CJ) :

1 CC =o

4JC

oo

^^^ o

>, •rH 1—

1

CO rH

l-l C) s c >>

CO o O

Uu Jj

--^^

i>i; faO

COc

O CO o

4-> Sh J->

+-) ^ 1 ^

1 to 1 S w QQ

131
S= CO o o

0) .H c^

J-> c o 03 c

2: bO n) • J. bO CO O o o

t. c

(D -1-)

D

CD •rH o

00 2 D.

CDC

•f-i

•4-> co

CJ)

CO •ocO

Q.eo

(j>c

bO oc

03bO

S_ O o

0)L

CO OI O

CO

03

<Va.o5

j-3

CO

03

CDa.o3

CO

03

<DCXO3

CO CO ^ jx: 03 OS

CD 0) Q. Q. o o 3 3

4-5 -l->

CO CO CO ^ js: ^

OS 03 OS 0) <D ex D. en. o o o 3 3 3

4J 4J jJ

CO CO CO CO CO CO CO CO o O O o o o o o

LTi LTi LO in LTl ITi LTi LO O O O o o O O O I oo

on ooon 1 ooon I I o o o oon en oom

CDO

on 1 ooon

CO

CD X3S3C

CD>

03

x:o

CD

CO oo

CO CO o o ^"^ ^~v CM ^ CO CO U3 LTi

>.-• '^—.^

T t in o 1 1 CO MD o o VO vO in t>- <— .— <0 LO

s:o

CD

CO o

II o

/\ c

bO ^—

LTlO Jj in t- CD I^ -n .—1 1 X33

LPl 1 O

CX3 s o

f— •k '— c

0) ^_^

to

JJ x: -p in • V ,^-v ,'—

,-

—V^^ CD 3 c y—

^•—V ,

CO CO

m CO CO ^ (D CO CO t—

^^.-^ >. -- ^. ^ —V • n ^ CO •^w--' v_^

T LO o o o O 3 1 CD o o 1 on tr- ^g- C\J LPi O id i. <D a^ •in t- I>- co t^- t- •a o a. C— f— r*

T T T T Y

^"^

YJ tM Oj 03 —I L 3

CD S C L

(DO

1—1

CO

•rH S S 03

03 jJ

U. o

03 _J

C >—-o co

•rH / X i- 03 ^-^ ^r on C\J ^^ cn .3- on ~ >1 S I '^ , a. 3

\, ^ /

II II II II II 11 II II 1 O o^ s O

^—' X

X

XXXXXX "

Ci) 1 x: 1 x: x: 3

T3 1 4-> t. 4-) 1 J-3

C

£- 3 J- -o

4-5 3 o -U o 3 o C bO

03 4-> 4J 03 4J jJ J-> 03 >,

S- 03 CO 03

X 3 CO 1 rH c 1 CO 1 rH O

CO jJ c 3 >5 3 a c s >5

a) 03 3 c .'^ c 3 C c CO 1 1 1 - o o • • •» •> o x: o <o >- ca • • •o XJ II ^-^ -o bD -o X3 4-) 4J .. ^-^ CD L o 'j-\ >, ^—

t. o ^-^ y-^ ,—^ ^^ ^ JJ m /^ •r-i -p X > -p 03 o

Oi -M 03 J2i o 'f-i 03 o -

•rH

m o •rH 03

O -iJ _J ^^ —' ^^-^

132
a>3

C

•iH c

oo

CO TDC

3

O

cxE

oo

c

bOX

o

c

CObO

S- o

CO 4Jo2

See

Organic

Nitrogen

Compounds.

See

Organic

Nitrogen

Compounds.

See

Organic

Nitrogen

Compounds.

See

Organic

Nitrogen

Compounds.

See

Organic

Nitrogen

Compounds.

o

0)

CO o

1 o

o

0)

4-3 CO

\/o

II o

/\

x:o

o

11 o

rH CO

03 i-H S- 3

CD S

c t.

CD O o

2

1

C\) o

2

1

o

II 2

1 OJ 2 Cd

1

.—

E

03

CO

CDc

E

0) 4J2

CO

CD -U

03 2

CO o

c

3

O

Q,E

OO

O

S4-> •H2

CO

CDc

•f-l E

rt

COo

•rH 2

CO n)C3

O

CXE

O

o

o

COo

-p•H2

133
oo

zsc

•rH coo

CO ac

=!O

D.soocXoc

CO o

COCO

4-5 o2 1 o1 o1 - £ 1 o e 4J> O CD O -P

LTi CO OO1

•acX1 o1 O7 o

CD

CO o

II o

/\

'^ CO CO CO CO O O O O O LH 1 <— OO CO LO o CO i^ [^- ^- o T T T V 1 O O LTi LO O O C\J O O CO 1 CO CO OO t--

2_LPi -P ro CD

t^- ^ ^ X3 1 3

LTi

O ^ -o o

CD

t, -P

CO1 o1 oc c

•rH

CO CO ^ CO o

CM to --- on o i: 1 S- o o -Q o o o

f>o CO 1 OO CO cr: o

(DiJ-) CO o1 o 3 3 > ^^ > '^ 1 o > o > O OJ ^ C\J --^ 1 OO o OO o O 1 O 1 o 1 o o o o O CT^ ^ 0^ ^ 1 OO ( OO (

CO o

cvT

CO CO o o o —O "" ^ 1 O ^ ^ 1 CO CO o ^ ^ 1 LPl O 1 CO I>-

r—1 CO

CO i—1 ^ i C i-

(DO

>, rH rH

O rH .^

N :^ >> >> -rH >,

O

C: rH t,O JJO -rH 1 CO CO CO CO CO -i-> O II II II iH II CO 1 (NJ fsl N Q, (M E o oc cc a: -^ cc o 1 ^ . rH - i. - - - CO - CO a: CE cc en ^^ cc ^ TO1 o1 o —o 1 o

C\J 1 M O >, rH 1 ^ >> O :^0 '-I t. : CO CO

II 11 cc ^ -

>>s

CO

Peroxides

(i):

aliphatic

(ii):

aromatic

(iii):

acyl,

aliphatic

(iv):

acyl,

aromatic CO •o

•rH o

CO>1Xo

(D

CI.

•> CO O rH rH

•rH -O >, >, O -* J^ i,

CO S- rH CO >1 -O CO X >, ox: .. ^ ^ C ^ .rH CD CO .rH -rH a. ^^ -^

134
CD3C

•i-i 4-3 coo

CO ac3O

CXEooc

CDbO

>^Xoc

CObO O

CO

CDO2 .

See

Organic

Phosphorus

Compounds.

See

Organic

Phosphorus

Compounds.

See

Organic

Phosphorus

Compounds.

See

Organic

Phosphorus

Compounds.

See

Organic

Phosphorus

Compounds.

See

Organic

Phosphorus

Compounds.

ac

CD

Di:1 o1

broad)

(inplane)

-650(m)(out-ofp1

ane)

x:o

<D

C- 4J

CO1 o1

~36lO(m,

sharp)

(in

CHCI3

or

CCli4

solution)

~3100(m,

broad)

(in

neat

samples)

x:o

-p

CD

4-> CO o1 E

en

CMT

iH CO

CO

—1

i- 3E C sCD O O [^

>!

CO 1 II

11 CU

CY-l

II

a.

:i CU

a:

X

II

Oh

CC

X

11

Cu

CC

CM

II Cu1 CC

>>

r-l

•i-i CO rH

CD x:CU

CO

CD

CO x;CX

CO

x:Cu

CO

CD

4-> COc

CO

x:

CO

CD T3

•rHX

CDC

•H

x:CX

CO

x:

CO

CD JJ

COC

x;CX

CO

£1CU

CO •0

•r-H

CO

CO3

x:CX

CO JC

CU

CO

CD

J-i CO x:CX

CO x;CX

>, Cu

135
o

0)c

•-(coo«

•oco

D.eooc

0)hO

>>Xcc

bO o

on en o en cn en en -c tn c •o c T!^ 7^ ^ o 3 c c C c 3 O 3 ^ 3 3 ^, 3

c:^

O o O

Q Ci.

O

C^ a. c c •", c Ci. O B c £= £= C s o oo oo b oo

CJ oo c c o i- i- t. J_^ 0) o 3 3 3 3 tc b

•rH ^ c^ Cu- 5,-, c 4-. ^H ^H ,—i ,—.

r-J ,—1

C-H o: •rH 3 3 3 3 c 3

CD 00 OO CO CO CO

"-^ 00

-PO o o O

O

O o o 2 'r-\ • ^ ..-* •^ •^ •l-f ^ C c c c c c c

CO CO CO CO CO CO CO M to tiO bC bO bO bO

i- t. I. !L s_ t- t. o o o C o O o

<D a; o (D (D o; o

0) GJ <D CD CD 0) 0) w 00 OO OO 00 00 00 ^o

Jj y—

^—V

0) CO CO

i- v-^- >.»-.' Jj o o en o o

\0

\y ,

^— o ( 1

II o^

x:a^ • s ,-

—

en CO ^ N_^ x«_-^ jj uo LO m 1^- o

II

T 1 o

/N

r—1 nj CO >—i o

t. 3 J^

(D e li^^^ ,<'^N C L ^ f T

0)

O

O Cx. O^ o c

cn

c; en •o GO cn en >> o .w CD (D a) r—1

en i 1 c en c J-) en r-J TD o

rH CD C^J ,zr

C 3 CD CO CO o >, —I rH E C ». • O O J-> C c c C !- X

nj o :, ^—

O Q. COO o O o c o 1 JLj c •rH £ C^ C-H Ctj Cu^ Cw —i

c^ • ,-H ^ S ^—V

-H

O ^H .—1 1—1 I—1 ^ SI

—< 3 CO iD —1 o 3 3 3 3 3 O 3

cy CO CO CO CO CO CO CO

136
CO •oc3

O

Q,EO

o

c

bOO

t.

4->

c

CObO

S- O

CO

4-> o2

Lowering

of

N-H

stretch

occurs

in

solid

samples

due

to

hydrogen

bonding;

hi^er

values

arise

in

dilute

samples.

Lowering

of

N-H

stretch

occurs

in

solid

samples

due

to

hydrogen

bonding;

higher

values

arise

in

dilute

samples.

CO

x:4JO

>C=0

(I650)(s,

solid

state)

(I690)(s,

solution)

>C=0

(1700-I670)(s,

solution)

(1680-I630)(s,

solid state)

band

due

to

interaction

of

N-H

(bend)

and

(C-N)

(stretch)

(~1250)(m,

broad)

>C=0

(1680-I630)(s);

higher

values

are

obtained

with

electron

attracting

groups

attached

to

the

nitrogen

X

1 2

3520(m)(stretch) 3400(m)(stretch)

1655-I620(m)(bend)

860-666(m,

broad)

(wagging)

3500-3400(w)

(stretch)

1570-1515(w)

(bend)

860-666(m,

broad)

(wagging)

3500(w)(stretch) 3400(w)(stretch)

l650-1580(m)

(scissoring)

909-666(m)

(wagging)

2

1 O

1

1

400

(s)

(stretch)

I400(s)(stretch) l400(s)(stretch)

1250-1020(m)

(for

nonconjugated

amines

)

1342-1266(3)

(for

aromatic

amines)

iH CO

CO 1—

1

J_ 3

E

C i-O

CM cc N x X cc <" 2 2 2 CC

1 1 1 O C) O XJ o —

o

1 1 1 cc cc cc

CM X2

1 CC

E

CO

Amides

Primary

Secondary Tertiary

Amines

Primary

137
T3

<U3

C

-pC

O

o

CO a

cO

Q.EO

CJ> c

CD

faO O

tohO O

CO

CDO2

1 EO

CO

t.CD SZ-Po

CO

CDEC

(D>

CO x:2

3350-3310(w)

(stretch)

1515(vw)

(scissoring)

909-666(m)

(wagging)

CO

(0

CDD.

CO E til E E

o o in ^3- O O CO >- o CO CM CD LTi ITi CM CM -H '— '—

1 1 i- 1 1 O O CD O O CO O LH o 00 -^ vo in m CM r- ^

2

1 O

1250-1020(m)

(for

nonconjugated

amines)

13^2-1266(s)

(for

aromatic

amines

)

1250-1020(m)

(for

nonconj

ugated

amines

)

1342-1266(s)

(for

aromatic

amines

)

rH CO

CO .—1 S- 3

CD E C iCD O

CM CM CC cc X 1 '^ 2 Z CC

1 1 CC DC

1Xmtc + 2

DC

>>

r-H

•rHE

CO

Amines

(continued) Secondary Tertiary

Amine

salts

Primary

138
COo

o

T3

0)C

c

oo

COco

CiE

O

CJ)c

CDbOO

i_

4->

c

cdbO

s- O

CO

4-) o

CO

(D £1S

C

CD>

CO

I

CO ^

tfl 0) ,_^ ^^

D. ^^ ^_^

CO B ChH E CO

-—»—

C) ^—

-—

o o o o

o u^ CO ^£3 LO c^ (M CD /—> LO CM

C\J

1

C\J

1 3

1 CM

1 o o 0) o O O

o o Cfi o CM O

o t^ ^^ o >-D t^ m CM C\J .— CM

O o

0^ '-- oo

LT, 5 t— O O LH

in VD ^ t^

T T T

1 3: o o

o

1 =O o1 o

^^o

c

o

Jj '-^

•« •* 1- o ^—

CO CO dJ c CO — — > o ^_^ o o o £> IPI o o —

'

caD ^ ^-^ o •^ ^^ ^ ^^

CM -D CM a s ,— a

1 CO 1 CO ^^ 1 c O O C^ o o o 0) O i. Cvj L ,

in X3 ^ J3 CO £) VD LO —

•

PO CvJ t— >—

I o

O tj

X

CM X

2

CvJ

>,E

CO

CO TD

CO C

CO -^

-pc

c O

—I o

CO -ac

o

o

00

X 1 n:: X

+ 2 + 2

on ^

cc CC>.

i. >, CO

i- C

cO L

-H (D

4-> jJ

i- CO

CD D H C?

o

o

o

1 d:CJ

1

CO

o

o

o

I o1

on

+ +

x;o

o

o

1 X

o

.

1 X

CO o

•.H ^-N o CO

CO ^

a. o ,-H c CO tH v_^ E

<

139
oo3ccoo

CO oc3o

CIeooc

a>bOo

4-> c

CObO

i- O

x:o

4-3 CO O1 2

/\

CO o

CNJ To

CO O 2 2

x:o x: ^ o

S_ CD

-!-> t. CO 4-> CO

CO ^

CO CO

CO CO O LO ^ C7^ ^ <\J

CvJ ^ X1 2

'co "e" O CTN ^ O O t~- '-- ro ^ CO 1 1 --- O O CJ^

C\J on o ^ m c\j T— 1 2

11 21

forbidden

in

IR

but

allowed

in

Raman

spectrum

(1576)(w);

peak

is

lowered

down

to

1429

cm~*

in

unsymmetrical

pelectron

donating

substituted azobenzenes

r—1 CO

CO --H i. 3

CD E C ^O +X2 21 / ^ 2 C11 CO 2 1-

V ^

cc t2

11 21

r—1

•He

CO

IJL, E3

•.-1 Co c E O E -H <

CO

CD

ISl

CO ac3O

a.EOoo

tsl

CO -oC3O

X E o o

lAO
(P

c;

m :3 jj •a C CD

<D i- S a)

<D

a sz

tH

D 4-> CD O

Ci-l CD ao O

ra >

Q) •iH S >^

4-> 4-5 III 4-> o 05 C ) .-1 2: bO CO c

<D CD c o C £1 CD •H O jJ 4-> 4-> £- d o.

4->

O •.^ SO -P o

CD CO 1—{ 1 x: X5

CD

a -P CB o

C\l ^-~ CM S

III I 2I O ^-' CO

cv

C\J

bO bO c C

•rH •-H 1 c^ 1CD

C_

X

a > o

•H CD •i-l CD

CO S- Cm

L

CD o X3 ^-^ i3

11 s II fi o CD CJ CD /\ s /\ S o o o o

t— c^ t

r

0>n o o ,

1>- f- c—

CO

CD TD

•iH C

Cti >loo

CO

CD

CD OO

CDDC

•1-1 4-> Coo

CO •oc3oeooc

CDbOO

4-5

•i-l o

•iH c

CObO

f- O S

COo

X3

CO 5 o O o LTi o CV-i (\J OO O

c^

CM ^

(M T—

x:o

4-) 0)

CO OOO

CMI o^3-

a s o e •a

CD -p

OS 505

O 4->

O ^ OJ C\J CM x: CM o) bp

CM ex CM 1 —I I O rH O

vT) o) ^r

CM ^-- CM

CM CM e 3 O -o

4J •iH 01 -P 00 x: CM 0! CM Ci CM S 1 •rH 1 r-\ t- 05 0)

.:3-

N ^ C^ '^-^ CM CM

iH 05

Oi iH L 3

!= 2;

C t- III lu 1 1 X 2 2

III 1 2 +

CE

K

:0 o

II o

II 2I

CJI

CO

II o

II 2I

>>

CO T3O CO ChE ^ O -H O S- O -P C —1

OS

C

O

COc CO N 0

05 •rH

CO

CO CO r-{ -rH

4-5a s- 03 •rH P> C C -1

03 03

C

>> >.

CO -H

CO CO ^-^

CO 4Jm

CO c

03

.-H >,

•rH i- -P •rH

*t-i x: c 4J

CO CO ca

141
•o

<D3C

•i-i jJCoo

COc3o

exsooc

0)bOo

s-c

CObO o 1

0) +jo2

•ocon

iHnDO

•a

,-.

O >H CM

II , o ,—

II X .* 1 ^—

y~^ ^— x: x: o o a 4-5 J-> <D (D o

-p J- S- CO JJ J-> r—(

CO CO

D

V ' v^-y' e O o D LTi o o ,

o

OJ C\J

CD

.—1 D.

•f-i 4J -O

rH

C

D

O E J=i 11

r-\

m

Cfl r-H I t. 3 O 2:

CD E II II C L o o

CD

O II II

a ci- o o

-A . -/^ .

cc cc cE ce c

>, rH

r—1 e 1 •r-i CD ""* B c c

CO CD CD

Dl. J-) 4-> CD CD i^ i^

CO

CD x:o o O 4J I <D 2 E

/\ E

>,

COo

-p o ty I E S E

/\ >>

CO

CO I oO fc,

CO

CD

O >

<D CD E I 3 o

4->

4-> CO CO

CO bO O 3 CO I •'H Eo o

Ci_i

C ti-i O o1 CO

to

M o c C —I

<D3 V

cr o

CD II t- a < <i-i ^

Q.3O

J_bO ii

CD o O E C

CO •>-i o ^ bO

bO

C

C -rH o

•O CD CD ii. (D JD i3

bOC

CO CO <4-( o

COo

xs c o CO o

a. 1 1 o O O O LO

II i^- o ^ X o <o t— t— 1 ,^ r- ,- ^ 2

bOc

•iHbO

bO

CO3

rH CO

r-i E E CO

CO jJ> U. O

CO J o O

CO C7^

LTi <\J ^

^-N , ^^ 1 o ^ o f. (M CO CM CO VO CO oo (0

C\J oI 2 _ 1 cc

COc

•r-l E

CO

4-)

142
CD3

C

C

O

cl;

CO •oc

3o

soo

c

<X) bOO

Sc

bO

1- o

CO

CD -PO2

CO -oc

3o

e

o

o

o

c^

o

(P 00

CO

CD o

S E O

>. >, jj ---

CO CO CD TD

CO CO S-, C

v-' --^ 4-> CD

CO JD

CO CO

LTi LTi CO CO CO CM v_- s_. o CM mo <— »— en a^ II OO v£3 O O O O 1 1

II ^ri o 1 o m 2 ^D CY-) 2 t~- vO

1 <- ^ /\ CO tr-

-N=0

stretch

1680-I650(vs)(trans)

1625-I6l0(vs)(cis)

>N-0

stretch

850-750(vs)

>N-0 (

symmetric)

>N-0

(asymmetric)

2

1

>H CO

CO <H

s- 2 CD S

c t.

CD O

a t,

CM O

2

1 O

DC

2

III O

1

o

II 2

1 O

cc

>>e

CO

CO

CD

4-5 CO

t. -P

•rH 2

Nitriles

(cyanocompounds)

CO +j

•H

!L -PH

2

143
CD3

C

4-> coo

COcO

D.E

O

CJC

CDbOO

S4->

c

CObO

t. O

CO

CD

4-i O2

CO

i_

CD x:

4Jo

eo

) •oc

CD JDO

2

CLJ

>N-0

stretch

(1520-1500)(s)(vapor)

(1500-I480)(s)(neat)

N-N(1150-925)(m)

>N-0

(stretch)

^^ CO CO '^ i. O > CO Q) -H ^^ v^ 3 4J> O O O CO

c\j .=r rH x: en m (X ^ T— 4J ^

1 1 CO rH O '^ CO o> in X3 on (>n j_ c ^ ^ O CO

CO x:

-N=0 (

stretch)

,^ .^ X3 4J

CO CO ^^ '-^ CO > > CO CO CO ^^ v^ ^- v_, CO CD O O CO O O -H

^3- c\j o ^r '^ o

Lpi on Ln on 4J c

,— -—-,— ^^-^ COCD

1 E 1 ^ 1 E 1 '^ E a

in >5 o E CO >> vo E o cr ^C0<7^>> J3-cnLn>>t-<D vocoonco LPicflmcocOS2

1 O

870

(difficult

to

assign)

General Formula

r—

ovj :^ >> O i-H L 2 CO CO

1 II II CC CC cc

o

II 2

1 2

/\ — (N CC cc

1—

E

CO

Nitrocom- pounds

Aliphatic

Aromatic

Nitrosamines

144
•o

Q>3C

•rH C -- OO I

CO oco

o.Eooc

<DbOOc

bO O ^ 1 y'-^

y—

3 O O Q) !-> CXD OO 1 r-i -1 tr- CO O -O -P 1 ) m CO CO in o O 4-> J- CO X3 C7^ C\J 3 f- O

b ^ h

4^

C !L CO --^ •-' . Cw Ci-i cu, -H D O .. O 1—1 M rH

CD c O

C

C CM 3 3 3

CD 0) •rH ..OO t- CO 00 00

-U 1 L bD 4J

C --H -rH

O CO

C CO t, -p -P - o . o . o • 2 O CO •^ CD 3 .— 3 --v •rH CO •rH CO •rH CO o CO L • S_ ^ 4-> in ^ O c -cj c -o c -a

CM -O iU CD 4-> -rH .rr •-H t-- CO

C COC CO c C CO N 4_) CO -P t— -P C-- bO 3 hO 3 bO 3 a 3 cy -^ O Q. CO 1 CO 1 t. O L O J- o C O S- s. CO X3 LTi £> O O c:x o cx O Q.

CO Q. CD S^C 3 LTi 3 ^ s E E E -o e CO O CO t- CO CO CD O CD O CD O o o C -H x: .^ 1 v_^ 1 ~-^ 0) o O O CD O ^ O CO -c? O -P £3 cQ 00 00 CO 1 1 -1 o CD LPi rH t. C c^n

CO CO ^ '-- o ^

CO (U -P ^ » « ^ c i, x: - o o --^ CO CD O O

CO cv^

m

O -H > 4J

O

L ^-^ -

CV-i Ci.

O CD LPi CD •—s ,^^ O 1 '- ^ t, tsz x: CO CO CY-) Ci_, CO '-~> -P

-p

O -— ^-^ - O --^

O COO o

N=0

stret

1585-1539 phatic)

151

1-U95

matic)

N-H

(3075

C-H

(out-

(920-720) (2000-165

C=C

ring

(1600,157 o

•fH i- o -^ 1 d) 2 Ss

>,

CO ^

^^o

-rH t. JJ o <1> 1 s 2 S

>.

CO

CO ^ 21 O ^

en r-H CO / CE CM

n3 r-H / V 1 X

i- 3 /rt^ 2 2 2

CD E o 11 CM III C !- II < { ) 2: "^v O o

<D

O 2 \v

J/

-/ \

CC CC

00 CO

O Cl, 1 v-^/ 1 CC 1 CC

CO -o CO 1 >, 1 c CD 1 1 c

1—1 O 3 C •rH CO CO

•iH CO

O •^ .-H COC CO >, E O Q. a ^ d) O (D O CO

CO i. E •rH Q-,

C c^-, -a

O CD t, J^ O L rH -r^ rH •r-l •rH 4J

•^

O >, 3 E 3 E x: CO 2 a. OO 00 H

145
CO ac3O

cxsoo3

Q-i 1—

3

00C

CObO

S- o

COc

CDssoo

Only

popular

frequency

around

that

region;

lowering

of

50-150

cm"'

due

to

hydrogen-bonding. 1 eo

CO

CD x:o §

\/1 OO1 001 3oo

LTi

C\J1 oo

C\J X1 001 5O

<o1 oo1 001 cc

CO ooT

LO <oo

II o c

•rH

CO

CD JDE32 1

II 00

CO oo

CO

CO

LTl

CJ^1 I>- CO

CT>

CO o1 o

CO0^

CD>

CO o

.H

J,

O -JJ

II CD

cy^ e

/N e

>, OO

CO in

CO1 oo

C\J

CO

LTl ro1 o o

•r-i J- -P

O CD

II

B

00 S

CO <

CO o

OOOO1 in

^3-

CO CO O O o m CM o 1 1 O ITi CO C7^

C\J

O

iH CO

CO 1—

t, 3

CD e c tCD O

cc1 001 001 X1 001 cc

cNj O

II 00

CM o

q::

fslcc1 001 cc

cc1

II 00

C\J en

cc11 2

II 00

CM

cc1 2

II 00

CM

cc

CCCM O

001 If00

CM

CC

>>

.-H • -—

CO

CO

CD

rH3

CO

•rH Q

COc

CO -p

Q.

COo

CO

CD jj

CO

Ci-i r-l 3

00

CO

CD a

•f-t <^

r—

3

OO

CO

CDcB

•iH ^H

•nH

Ct-( rH3

00

>.o

CO1

1—

>1

rH

CO1 2

•H

r-H co

Q-. rH3

CO1 2

•rH •rH •rH

146
CO pcEEOo

Solid

phase

spectra

lower

wave

numbers

by

10-20

cm"^

Electron

donating

groups

on

the

aryl

group

cause

higher

frequency

absorption.

Hydrogen

bonding

reduces

the

frequency

absorption

slightly.

Hydrated

sulfonic

acids

show

broad

bands

1230-1150

cm~^

(Continued)

cm~^ )

CO

-po

CO CO o tfV-1 c\J CO en m ^^ 1 1 ^ O O LPi a^ O vO en en CM en en en O O r- CM X X 1 1

Compounds

Numbers (

in 1

II 00

rganic

Sulfur Wave

>S=0

(Symmetric)

CO

LTi To

CO T

C3^

CO o

CM1 o

to o

inT

CO

LPi

LTl o. too

CO To

CM o

>S=0

(Asymmetric)

co

LTi

CV-) OO1 O

t>- en

CO

LTl

CV-I en

,_1 CMen

to oo, 1 o

LTl ro

CO

CMonTo

inOO

CO

LTl

COO

CO o

COOO1 o

rH CO

to rH L 3E c uo

CM X

CM O

001 o1CM O

001 CC

en1CM O

001 CC

X

OO O

001 cc 1 OO O

001 cc

,—1 o

CM O

001

r-i E

to

CO -aE

COo

C<-H rH3

00

CO p

toco

Cl-H .H3

OO

COco

Cm

rH3

00

Sulfonic

acids

(anhydrous)

COo

too

•-{ C CO O -P

Cm i-H rH to 3 CO 00

CO

.-H -a

>, •M C L o o

Cm rH

r-l £1 3 O

00

147
T3

<X> 3C

•.-I 4-> coo

CO oc3oaEOo3

Cw

I—

3

COc

CObO O

CO pic

CDEEoo

Hydrogen

bonding

reduces

the

frequency

absorption

slightly;

electronegative

substituents

increase

the

>S-K)

frequency

The

(+)mesomeric

effect

of

sulfur

is

larger

than

its

(-)

Inductive

effect

COc

CO P>cx

COo

s_

CO

CO

CD x:

4-) o

CO o

c^oTooof

00

CO o

CMO1 O

LO

CM

OO

II o

-C=N

(2175-2l40)(s);

higher

values

for

aryl

thiocyanates

-C-

(I690)(s)

(S-alkyl

Q

thioester)

(1710)(s)

(S-aryl Soo

LH

CM1 Oo

CMX1 OO1 1

II 00

>s=o

(Symmetric)

>S=0

(Asymmetric)

.-1 CO

CO iH

t- 3E C !Uo O IJ-i ?

00

CM

CC

X

eg1 o —^oo 1 2

III CJ)1 001 CC

CMCC

001 o —^o 1 cc

X

001 cc

X

OO1 <

--I

•rH E

CO

CO •o

•rH Xo

Q-H iH3

00

Thiocarbonyls

(not

trimerized

into

cyclic

sulfides)

CO p>

COc

CO>,oo

r-{ x:

CO

i4-> CO

I-H o

•rH x:

CO rH

•2

x:

COoc

x:cx .2

x:

E- 1A8
a -p S o tfl o ^ S m t. -a o v^ -rH c C\l O *<-! CO CO

CO

C X3 1 vo o o

on o >, r- 1 v-' xn CO

x: 1 o o +j 1 CD

•r--\ i- 00 43

/\

m

CO 4-> o CD 1

t—1 1 £) o 3

o>

O o -a o .'-^ o •rH ^-v y~^ o C/J CO CO ^

1 ^^ v_^ 1 o (Y-) o o 1 LPi CM t

•rH

O

O »— w «

^—

I /

CMCOo

CO oco

D.eoocoo

00

CObO O

5:: -O 1 C O CD /\ X3

bO bO faO C C c

iH rH •rH ^ ^ ^ o o o o o o

£- i^L

fciO bO c c H •rH ^ JiC o o o o

S- iCO CO CO CO CO o o o O O

>X) >^ VD VO MD

CM CM CM CM C\J

CO

t-

<DSC

CD> V o

00 CD I i^ O -P o O ^—^ ^—. o oC3^

O CO CO cr> CT\ 1 CO1 O LH 1 1 O o ^ LO o o

C3> CM CO t- C3^ CJv CO CO 1 1 CO CO 1 00 o

OO oOO oCO o

C7> CO oC3> CO o

CT^ OO

szo X -p 1 CD

•rH t. 00 4J o o o ^^ LO

,_ CO ,— 1 in

CM1 o en O

OO ,VO ,

CvJ CO

CM ) CvJ

,—1 CO CO i-H S- 3 >> cv^ CM

(D e tn nc

X

C i- •rH ,H r-t CD O 00 CO OO O tj X I C^

an

•rH COPO

CE cc cr: cE ^ iH >. iH >i ^

>. CO ^ l-l

.-H (0

O tH CO

•rH Q)

C CO •rH id c o •rH tn CO CO s Q H

Ix^

M

a:o^^—^ l-^ r-\ 00 OO ^ -x

cc cc

rH>^ ^

1—1

CO >>

CO

X

t- o

•p ^

CD r-^ H <

00I o1 •H

00

a:: o

COX

a:

tn

CO 1 CO o t. o s

CD r-{ CD •rH CD •rH CO

C. •rHC r-\ 6 rH i.

CO CO CO

O -rHO -P

X •rH

X >. s^ >> CD o -o O O .P O -P

CO o 00 1 CO

>-, CD X C O CO

•O •H >» CO

149
0} T3C

3

O

CI. EO

o

CO3

o

x:a

COo

x:

c

CObO

J- O

CO

4-) o2

>P=0

stretch

can

shift

up

to

65

cm"

due

to

change

in

solvent

.

-OH

stretch

>p-o-c<

stretch

'—- r—

1

^ >! >. ;- .^ 03

0) '-^

--^ CO

CO LO ^^ t— o CO

LA 1 o o

^ en

1 C7^

^-~- 1—

1

r-H >>

:^ 03

r-{ ^—

-

03 '--

-~^ CO

CO m

O CO

LTi I O O -- m 1 CJ>

'—^ r-H

i-l >^ >. s.

.ii: 03 .H ^-'

OJ '-^ •-' CO

CO in -^ c— o oo m 1 o o ^ in

1 C7^

>P-H stretch 'e 'e 'S. o o m

CO — x: on c^ CO CM CM ---

^ 'e o o

CO CO

CM CM

CM CM

1 1 O O

m ro

CM CM

O

CM

CM

1 O

in

CM

o O 4J

II o

' CO

1300-1100(s)

(doublet

)

1285-1260(s)

(doublet

)

1315-1290(s)

(doublet

)

CO o

CO

1 c

CM

CM

CO (0 O LTi in <T> »- o

1 1 LO, LO CO ^

CO o

en

CM

1 in

CM

1—1 03

03 >—

1

^ i

c ^

O

O

a,

11 o

o

1 a.^—

o

CM tr

a;

C- —

o

1 X

o

cT ^O

1

1—

1

E

o;

Phosphates

a)

alkyl

b)

aryl

CO

J-> 03c

x:D.

COO

x:

Phosphine oxides

a)

alkyl

b)

aryl

CO Jj

03co

§.

COo

x:

150
0)c

4-) c

oo

CO a

cO

o.Boo

to3

o

COo

C

CObO o

CO

4-> o2

x:o

4-3 o tCO

2700-2200(3, broad)(assoc.

)

x: o o

1 4-> o <u

1 c

CL, 4J

/^ CO

x:o X 4^

1 0) a, t- /\ 4-> CO

x:o O 4J

11 0)

/^ 4J. CO

CO>oC30 T

o

CM

CO o

o

CMT

LO

C\J

1310-1200(s)

(single

band)

r-H (13 CO .-H i. 3

0) E

C t0) O O Cx.

X

o

o

II

a- cc

cc

CC

CC

o, —

o

CM O

CC

CM

CC

o. —

O

1 o

1 a. —

o

CM

o::

>> —

1

•rH s

CO

CO3

S.O

x: CO

CO •'H o o

x: to

CO3

O CO x: Qj D. -a

CO -rH o s

SZ CO

1COo en x: o

ex 4-> O CO

s- x:

>-> ex

Cu

151
COc3O

Q.EOOc

(DbOO

-—I

CO Xc

CObO

J- O

x:o O

-IJ CD ,

J_ <—

4-> 1 CO O 1

CNJ o

II • y

—

E • o

>i E

CO >>

+j CO CO

en v_y V_'

s- o o

-p

O CO

CO CM

O

rv-)

TT

X

O

O

(J)1 cn o• y—V E • ^^

x:o

>, E

CO 5^

g

^~. -i-j CO CO >i ^ ^—^ — CO '-^ 1 i. o o CO • E jj O CO --- s o COCM

CM

O 1 1 C7^ CO

CO

X o o 1 o

S- o Ln

O LTi CNJ CD /^ on CM ^ kO

£1

r—

T

CO 1 EDC>

cfl IS

x:o

4-J o O 0)

0) ,— CO c

i_ o o ^ o o o 4J t

O r- ^ C7^ o

CO 1 o

in 1 i- 1 O CD CM1 CM1 X CM o ^ > f- o 1 t

ro LPi

O ^£) o o T CO ^ ^- vX> in

/^

i-H CC r-^ S,

CO .-1 t, o CQ 1—1 L aE II 11 II 11 C J- <D O X X X X O tL,

CO CO >> CP <u CO r—1

•a

a CD CO

l-i •r-l ••-I

a cu E e S- •iH •a

CT3 o o s •rH

[x. 3 •-t o •a

.—1 x: t. o

tL, o CQ (—1

152


V. Tables for Nuclear Magnetic

Resonance Spectroscopy

155

Tables for Nuclear Magnetic Resonance Spectroscopy

The following tables provide valuable information on NMR spectroscopy. These

tables are by no means meant to cover the whole field of nuclear magnetic

resonance but should be more than adequate for the routine determination of

organic compound identity or structure [1,8].

REFERENCES :

[1] Silverstein, R.M., Bassler, G.C., Morrill, T.C., Spectrometric

Identification of Organic Chemistry , 4th edition, John Wiley, New York,

1981 .

[2] Williams, D.H., Fleming, I., Spectroscopy Methods in Organic Chemistry , 3rd edition, McGraw-Hill, London, 1980.

[3] Lambert, J.B., Shurvell, H.F., Verbit, L. , Cooks, R.G., Stout, G.H.,

Organic Structural Analysis , MacMillan Pub. Co., New York, 1975.

[M] Abraham, R.J., Loftus, P., Proton and Carbon-1 3 NMR Spectroscopy , Heyden,

London, 1980.

[5] Bruno, T.J., Tables for Instrumental Methods of Chemical Analysis , Center

for Chemical Engineering, Chemical Engineering Science Division, Boulder,

1985.

[6] Jackman, L.M., Sternell, S., Applications of NMR Spectroscopy in Organic

Chemistry , 2nd edition, Pergamon Press, New York, 1969.

[7] Varian Associates, High Resolution NMR Spectra Catalogue , Vol. 1, 1962;

Vol. 2, 1963.

[8] Bovey, F.A., NMR Spectrometry , Academic Press, New York, 1969.

[9] Tsujihara, R., Furukawa, N. , Oae , S., Bull, of Chem. Soc . Japan, 43,

2153, 1970.

157
Magnetic Properties of Some Nuclei [1,2]

Element Isotope Abundance

(?)

Spin Number

(magnetic

moment)

Resonance Frequency

at 4.2276 Wb/m^

(Hz)

Hydrogen ^H

^H

^H

99.984

0.016

<10"'

1/2

1

1 /2

180.0

27.6

192.0

19.34

Boron log 18.83

81 .17

3 3/2

57.75

Carbon

i^C

98.9

1 .1 1/2 45.3

Nitrogen

15^

99.64

0.36

1 1/2

13.0

18.24

Oxygen 16Q

^'0

99.76

0.04 5/2 24.40

Fluorine 19p 100 1/2 169.34

Silicon 2«Si

^^Si

^°Si

92.28

4.70

3.02

1/2 35.76

Phosphorus 31p 100 1 /2 72.87

Sulfur 95.06

0.74

4.2

3/2 13.81

Chlorine ^=C1

^'Cl

75.4

24.6

3/2

3/2

17.64

14.68

Bromine ^^Br

8lBr

50.57

49.43

3/2

3/2

45.1

48.6

Iodine 1271 100 5/2 36.0

REFERENCES :

[1.] Silverstein, R.M., Bassler, G.C., Morrill, T.C., Spectrometric

Identification of Organic Compounds , 4th edition John Wiley, New York,

1981 .

[1 . ] Streitwiesser , A, Heathcock, C.H., Introduction to Organic Chemistry , MacMillan, New York, 1985.

158
> I I 1 1 1 I I ^ I 5 8 IllB^ld 5 i i

E

Q.

sz

4-i

•oc

0)

159
Proton NMR Absorptions of Major Chemical Families

The following tables give the region of the expected nuclear magnetic

resonance absorbtions of major chemical families. These absorptions are

reported in the dimensionless units of parts per million (ppra) versus the

standard compound tetramethylsllane (TMS):

CH3

CH 3""S i""CH 3

CH3

The use of this unit of measure makes the chemical shifts independent of the

applied magnetic field strength or the radio frequency. For most proton NMR

spectra, the protons in TMS are more shielded than almost all other protons.

The chemical shift in this dimensionless unit system is then defined by:

^ ^ ^^f ^ X 10^ (V -1)

where Vg and v^ are the absorption frequencies of the sample proton and the

reference (TMS) protons (twelve, magnetically equivalent), respectively. In

these tables, the proton(s) in question are indicated by underscore. For more

detail concerning these conventions, the reader is refered to the general

references listed in the introduction of the tables for NMR.

160
Hydrocarbons

Family 6 of protons underlined

Alkanes CH3-R -0.8 ppm

-CH^-R -1 . 1 ppm

-CH-R -1 . 4 ppm

(cyclopropane -0.2 ppm)

Alkenes CH3 CH3-C

>C= C< -1.6 ppm >C=C< -1.0 ppm

-CH2 -CH2-C

>C= C< -2.1 ppm >C=C< -1 .4 ppm

-CH -CH-C

>C= C< -2.5 ppm >C=C< -1 .8 ppm

>C=C< M 4.2-6.2 ppm

Alkynes CH 3""C— 1.^ - -1.7 ppm CH3-C-C=C- -1.2 ppm

-CH^-C=C- -2.2 ppm -CH^-C-C=C- -1.5 ppm

-CH-C=C- -2.7 ppm -CH-C-C=C- -1.8 ppm

R-C=C-H -2.4 ppm

Aromatics G

PRange: 8.5 -6.9 ppm

G=Elect ron withdrawing G=Electron donating

(e.g. , -C-, -NO2, -C=N) (g., -NH2, -OH, -OR, -R)

o-p-closer to 7.3 Ppm

(more upfield)

o,p-c loser to 8.5 ppm

(more downf ield)

161
Organic Oxygen Compounds

6 of protons underlined

Alcohols

CH3-OH 3.2 ppm RCH^-OH 3.4 ppm R^CH-OH 3.6 ppm

i I I CH3-C-OH 1.2 ppm RCH,-C-OH 1.5 ppm R2CH-C-OH 1.8 ppm

R-Q-H (1-5 - depending on concentration)

Aldehydes

CH3-C-H 2.2 ppm RCH,-C-H 2.^ ppm R2CH-C-H 2.5 ppm GOII II ~ II

I I CH3-C-C-H 1.1 ppm RCH2-C-C-H 1.6 ppm

I II I II

Amides

See Organic Nitrogen Compounds

Anhydrides ~CH3-C-O- 1.8 ppm RCH,-C-0- 2.1 ppm R2CH-C-O- 2.3 Ppm

II00II ~ II

1 I I CH3-C-C-O- 1.2 ppm RCH2-C-C-O- 1.8 ppm R2CH-C-C-O- 2.0 ppm

I II I II ~l II

/C. /C,

C yc 1 i c CH^ \ CH-^ \

CH2 / CH^. /°

3.0 ppm 7.1 ppm ^C

1

162
Organic Oxygen Compounds (cont.)

6 of protons underlined

Carboxylic acids

CH3-C-OH 2.1 ppm RCH,-C-OH 2.3 ppm

""11

II

R2CH-C-OH 2.5 ppm

~ll

CH3-C-C-OH 1.1 ppm RCH2-C-C-OH 1.6 ppm

"~l II ~"l II

R-C-O-H 11-12 ppm

II ~

R2CH-C-OH 2.0 ppm

Cyclic Ethers

2.5 ppm [^^^0

1 . 6 ppm ^^ -^ 1 . 6 ppm

\q^ 3.6 ppm

2.7 ppm

i1.7 ppm

/ \ 3.6 ppm

V,

1 . 9 ppm

\ y 3.8 ppm

1 .7 ppm

3.8 ppm\ y M.7 ppm

6.3 ppm

7.4 ppm

1 . 9 ppm

4.5 ppm

/ h.2 ppm

Epoxides

See Cyclic Ethers

163
Organic Oxygen Compounds (cont.)

5 of protons underlined

Esters

CH3-C-OR

R = alkyl

R = aryl

1 . 9 ppm

2.0 ppm

RCHj-C-OR

2.1 ppm

2.2 ppm

R2CH-C-OR

2.3 ppm

2.4 ppm

CH3-C-C-OR 1.1 ppm RCH2-C-C-OR 1.7 ppm R2CH-C-C-OR 1 .9 ppm

CH3-O-C-R 3.6 ppm RCH2-0-C-R 4.1 ppm ~~

II ~"

II

R2CH-O-C-R 4.8 ppm

CH3-C-0-C-R 1.3 ppm RCH2-C-O-C-R 1.6 ppm R2CH-C-0-C-R 1.8 ppm

Cyclic 1.5 ppm

2.1 ppm 4.4 ppm 1.6 ppm// \ 4.1 ppm

2.3 PpmX ^0 2.3 ppm

Ethers

CH3-O-R

R = alkyl

R = aryl

3.2 ppm

3. 9 ppm

RCH2-O-R

3.4 ppm

4.1 ppm

R2CH-O-R

3.6 ppm

4.5 ppm

CH3-C-O-R RCH2-C-O-R R2CH-C-O-R

R = alkyl

R = aryl

1 . 2 ppm

1 . 3 ppm

1 . 5 ppm

1 . 6 ppm

1 . 8 ppm

2.0 ppm

164
Organic Oxygen Compounds (cont.)

6 of protons underlined

Isocyanates

See Nitrogen Compounds

Ketones

CH3-C- RCH^-C- R2CH-CR = alkyl 1.9 ppm 2.1 ppm

R = aryl 2.4 ppm 2.7 ppm

2.3 ppm

3.4 ppm

CH3-C-C- RCH,-C-C- R2CH-C-CI II I II "ill

R = alkyl 1.1 ppm 1.6 ppm 2.0 ppm

R = aryl 1.2 ppm 1.6 ppm 1.9 ppm

a - hydrogens 2.0-2.3 Ppm (n>2)

3.0 ppm (n=2)

1.7 ppm (n=1

)

hydrogens 1.9-1.5 ppm

Lactones

See Esters, cyclic

Nitrocompounds

See Organic Nitrogen Compounds

Phenols

Ar-O-H 9-10 ppm Ar = aryl

165
Amides

Organic Nitrogen Compounds

6 of proton(s) Primary Secondary Tertiary

(underlined) R-C(=0)NH2 6,ppm R-C( = 0)NHRi 6,pprr R-C(=0)NR,R2 6,ppm

(i) N-substitution

-C-N-H 5-12 5-12 — w>

) a) alpha

-C-N-CH3 -2.9 -2.9

h

-C-N-CHg- -3.4 -3.4

1)

-C-N-CH- -3.8 -3.8

i

b) beta

-C-N-C-CH3 -1 .1 -1 .1 ~1 .1

I '

-C-N-C-CH^- -1 .5 -1.5 -1.5

)

-C-N-C-£H- -1.9 -1.9 -1.9

6

(ii) C-substitution

a) alpha

CHj-C- -1.9 -2.0 -2.1

"'CH2"'C~ -2.1 -2.1 -2.1

6

-CH-C- -2.2 -2.2 -2.2

""II

166
Amides (cont.

6 of proton(s)

(underlined)

Primary

R-C(=0)NH, 6,ppm

Secondary

R-C( = 0)NHRi 6,ppn'

Tertiary

R-C(=0)NR,R, 6 ppm

b)beta •

CHj-C-C6

-1 .1 -1.1 -1.1

-CH,-C-C1

-1.5 -1.5 -1.5

1 -CH-C-CD

-1.8 -1.8 -1.8

Amines

5 of proton(s) Primary Secondary Tertiary

(underlined) R-NH2 6, ppm RN-HR 6, ppm RRRN 6, ppm

(i) alpha protons

>N-CH5 -2.5 2.3-3.0 -2.2

>N-CH^- -2.7 2.6-3.4 -2.4

>N-CH< -3.1 2.9-3.6 -2.8

(ii) beta protons

>N-C-CH, -1.1

1 >N-C-CHy1

-1.4

1 >N-C-CH< -1.7

Cyanocompounds (Nitriles)

:

(i) Alpha hydrogens 6, ppm (ii ) Beta hydrogens 6, ppm

CH,-C=N -2.1 CHj-C-C=N -1 .2

-CH,-C=N

1 -2.5

1 -CH,-C-C=N

1 -1.6

1 -CH-C=N -2.9

1

1 CH- C-C=N -2.0

167
Imides

i) Alpha hydrogens 6, ppm (ii ) Beta hydrog ens 5, ppm

CH,-C-N-CH

-2.0 CH3-C-C-N-CH-1.2

-CH^-C-N-CH

-2,1 -CH.-C-C-N-CI 1 OHO

1

-1.3

-CH-C-N-CH

-2.2

1 -CH-C-C-N-C1

1 OHO

-1 .4

Isocyanates:

(i ) Alpha hydrogens 6, ppm

CH^-N=C=0 -3.0

-CH,-N=C=0 -3.3

-CH-N=C=0 -3.5

Isocyanides ( Isonitriles) ;

( i ) Alpha hydrogens 6, ppm

-2.9

-3.3

CH3-N=C;

-CH^-N=C;

-CH- N=C: -4.9

Isonitriles: (See Isocyanides)

Isoniocyanates 6, ppm

CH3-N=C=S -3.4

-CH,-N=C=S -3.7

-CH -N=C=S -4.0

Nitriles 6, ppm

-CH2-0-N=0 -4.

Nitrocompounds 6, ppm

CH3-NO2 - 4.1

CH,-C-N0.

-CH^-NO 2 - 4.2

'CH2 ~C-N0 2 - 2.1

-CH-NO2 - 4.4

-CH-C-NO, - 2.5

168
Family

Organic Sulfur Compounds

6 of proton(s) underlined

Disulfides CH3-S-S-R ~2.H ppm

-CH2-S-S-R -2.7 ppm

-CH-S-S-R -3.0 ppm

CH3-C-S-S-R ~1 .2 ppm

-CH,-C-S-S-R -1 .6 ppm

-CH-C-S-S-R -2,0 ppm

Isothiocyanates CH^-N=C=S

-CH,-N=C=S

-2.4 ppm

-2.7 ppm

-CH-N=C=S -3.0 ppm

Mercaptans

(Thiols)

CH3-S-H -2.1 ppm

-CHg-S-H -2.6 ppm

-CH-S-H -3.1 ppm

CH3-C-S-H -1 .3 ppm

-CH,-C-S-H -1 .6 ppm

-CH-C-S-H -1 .7 ppm

Sulfates (CH3-0)2S(=0)2 -3.4 ppm

Sulfides CH3-S-R -2.1 ppm

-CH2-S-R -2.6 ppm

-CH-S-R -3.1 ppm

CH3-C-S-R -1 .2 ppm

-CH,-C-S-R -1 .6 ppm

-CH-C-S-H -1 .9 ppm

169
Family

Organic Sulfur Compounds (cont)

5 of proton(s) underlined

Sulf ilimines CH^-S=N-R2

R»

-2.5 ppm

Sulfonamides CH3-SO2NH2 -3.0 ppm

Sulfonates CH3-SO2-OR -3.0 ppm

Sulfones CH5-SO2-R2 -2.6 ppm

Sulfonic acids CH5-SO3H -3.0 ppm

Sulfoxides CH5-S(=0)R

-CH7-S(=0)R

-2.5 ppm

-3.1 ppm

Thiocyanates CH^-S-C^N

-CH^-S-C=N

-CH-S-C^N

-2.7 ppm

-3.0 ppm

-3.3 ppm

Thiols See Mercaptans

170
SOME USEFUL ^H COUPLING CONSTANTS (IN H^)

1 ) Freely Rotating Chains 2) Alcohols with No-Exchange

as in DMSO

H

I 5 >C—OH

.)-

1 ° - triplet)

2° = doublet) broad

3° = singlet)

Then add TFA, all = sharp single

~0

3) Alkenes

1 H** ^H

I .-.. I C C

// W

C C

>c^c = c^

•H

I .c<

k) Alkynes

. -2

6) Aromatic

1-2

>C —C=C- ^

5) Aldehydes

2- 3 H-* te-H

I / ^ C

' W // w

c, /

Adapted from the work of Professor C.F. Hammer, Georgetown University,

Washington D.C.

171
Solvent Positions of Residual (Impurity) Protons

in Incompletelv Deuterated Solvents

Solvent Formula Group 5 (ppm)

d.-acetic acid CD, COD Methyl (CD 3-) 2.05

dg-acetone

dj-acetonitrile

dg-benzene

d^-chlorof orm

di 2-cyclohexane

d^-dichloroethane

d^-dimethylformamide (DMF)

(CD,),C=0

CD3CN

CsDe

CDCl.

CeDi

CD2CICD2CI

(CD3),NC-D

II

Hydroxyl (-0D)

Methyl (CD 3-)

Methyl (CD 3-)

Methine (CD-)

Methine (CD-)

Methylene (CDj-)

Methylene (CDj-)

Methyl (CD3-)

Methyl (CD3-)

Formyl (D-C-)

10-12^

2.05

1 .95-2.05

7.2-7.3

7.25

1.M0

3.69

2.75

2.95

8.05

dg-dimethylsulfoxide (DMSO)

dg-dioxane

dj g-hexamethylphosphor amide

d^-methanol

d2~methylene

chloride

dj-nitromethane

(003)280 Methyl (CD 3-) 2.5

Absorbed water 3-41

^0

\ /

[(CD3)2N]3 P=0

Methylene

Methyl (CD 3-)

3.55

2.60

CD30D Methyl (CD 3-) 3.35

Hydroxyl (-0D) 3-6^

CD2C12 Methylene (CDj-) 5.35

CD3N02 Methyl (CH3) 4.33

172
Solvent Positions of Residual (Impurity) Protons

in Incompletely Common Deuterated Solvents (cont.)

Solvent Formula Group 6 (ppm)

dg-pyridine

d g-tetrahydrof uran

dg-toluene

-N, o

CeDsCDs

dj-trifluoro- CF3COOD

acetic acid

d2-water D2O

C-2 Methine 8.70

C-3 Methine 7.20

C-4 Methine 7.58

a-Methylene 3.60

B-Methylene 0.75

Methyl (CD3-) 2.3

Methine (CD- ) 7.2

Hydroxyl (-0D) 10-12^

Hydroxyl (-0D) 3.5-6-A 1

^ Exact value depends on the solute nature and concentration.

173
^^C Chemical Shifts of Useful NMR Solvents

Solvent Formula Chemical Shift (ppm)

acetone-dg

acetonitrile-dj

benzene-dg

carbon disulfide

carbon tetrachloride

chloroform-dj

cyclohexane-di2

dichloromethane-dj

dimethylformanide-d.

(CD,)2C=0

CD3C=N

CeDe

CS,

CCl^

CDC13

CeDiz

CD2CI:

(CD 3),,NCD

29.2 (CD3) 204.1 (>C=0)

1.3 (CD3) 117.7 (C=N)

128.4

192.3

96.0

76.9

27.5

53.6

I 31 (CD3) 36 (CD3) 162.4 (DC=0)

dimethylsulfoxide-dg (003)2 s=o 39.6

dioxane-dg "C> 67.4

methanol-d^, CD3OD 49.3

nitromethane-dj CD 3 -NO 2 57.3

pyridine-dg 9 124.0

1 ,1 ,2,2-tetrachloro- CDCI2-CDCI2 75.5

ethane-d2

r—\^ tetrahydrof uran-dg

O'

25.8 (

trichlorofluoromethane CFCI3 117.6

Water (heavy) D2O -

136.0 150.0

174


VI. Tables for Mass

Spectrometry

177

Natural Abundance of Important

Isotopes

The following table lists the atomic masses and relative percent

concentrations of naturally occurring isotopes of importance in mass

spectroscopy [1-3].

REFERENCES :

[1 ] Rose, M.E., Johnstone, R.A.W., Mass Spectrometry for Chemists and

Biochemists , Cambridge University Press, Cambridge, 1982.

[2] Weast, R.C., ed.. Handbook of Chemistry and Physics, 63rd Ed. , The

Chemical Rubber Co., Boca Raton, 1984.

[3] McLafferty, F.W., Interpretation of Mass Spectra , University Science

Books, Mill Valley, 1980.

179
^_^ ^ ,_^ >—

,_^ in ix^ cn CM =r C7^

C\J ^ .=r CM -=r o ^

t^ ^ O CM

•« CV~I <o C^ ^T

^~^ CNJ ^- CO

m v£) CD C3^ o> [— v£) ,

O C^ • VO o> C7^ c CJ^ <7^ CT^ • rt • CM ^ O TD C- — OO ro CO c ^ on s^^ V ^ D - ,.' •^ v_^ X3 CO 1—i

tCO oCD o

J- o m

+J ^ m

m CD c .-^

CD ^^ C^ O /-—V

OJ ^ N y—

N • •—

i- in ,— ^=r ^3" oq; ,

o • • Q. o CXD '- o

CJ> o

•. o •> •> •» .:q- •h 1—1

,— LPl T— ^ v£)

D •* on on ,

t^ xr E o c^ m o C3> rt T— o o o • t~- 1 1 ^r o o o CO

CM

CTN

CO o ,—

m in CM

m • ^

T t

cn

03 (\J

N ^ N_^ ^^^ t-t s_^ E CO

^-^

X

CD o 2: ffl CN CO

m OJ r-, ^ ^ m ^-^

(D

O Q. ^—V

,-—V

,'^ ,—

,—V o ^-v ^-^ ^-N ^-~. o CM o O LTl /^ o 4J -—

CO C7^ ^ CO • cn o o c^ • • • • o CM o LTi LTl • ,

m <^ CT^ CXD o^ a^ o O o C7^ C— o M

c^

»" <J^ C7^ CTn "— ^ ^ ^

LTl ^ jj CT^ *< * •« ^ ^ cn » t- LO •k ^ c ^3- O C~- ,— o CTN vO ,— CO m .a- CO ^ o> O o a> -3" ^ l>- O CO CO o ^ cn <M o CY-1 ^r co c— m CM VO ,

C^

S- tX3 ,

o o o> CJ> <7^ c- t— CTN c^ • o t- O o o o> o> • cr^ a^ • . <o

ex o • • • • • !>- • • =r CO CM E o o CM -=r in OD CM o r— cn >- ,—

•^ • t— T— r— ^— T—

— cn 0-)

—-^—' -

T

•v„^ ^—^ ^—^-^ v*^ x^ V—

o —

iH 1—1

t. 1—1

t. CQ o 2 o li, CO cu CO o CQ r- o :i: o CSI J- ID 01 CO CM m (T) CM s "* '^ ^ '^ ^ ^ CM m m cn t^ "

<4-< o m

0)

=ifc Q,o cn ^ I>- t- CO v^ CO ^- o ^ I^ cn

r-i JJ , , , CM

COO

4J CO O -rH ECOD c c Q) iL 0)

-!-> Q> 0)

C c O c (D

C hO c bO c •M o i: i- •iH

C Q)

CD

O

C o o <D I- o ex

D su •M c E S- o Xi J_ bO o •r-4 CO Cm o E M

(U TD t. C- Jj >,

D .-< o r—1

r—1 O •o

iH >> o CO 1-1

X r—1

•r-l x: 3 x: i. o W a: m o 2 o tL. CO D_ CO o CQ 1—1

180
Rules for Determination of Molecular Formula

The following rules are used in the mass spectroscopic determination of

the molecular formula of an organic compound [1 ]. These rules should be

applied to the molecular ion peak and its isotopic cluster. The molecular

ion, in turn, should be the highest mass in the spectrum, must be an

odd-electron ion and must be capable of yielding all other important ions of

the spectrum via a logical neutral species loss. The elements that are

assumed to (possibly) exist are carbon, hydrogen, nitrogen, the halogens,

sulfur and/ or oxygen. The molecular formula that can be derived is not the

only possible one and consequently help from nuclear magnetic resonance

spectrometry and infrared spectrophotometric data is necessary for the final

determination.

Rule 1 : An odd molecular ion value suggests the presence of an odd number of

nitrogens. An even molecular ion is due to the presence of zero or

an even number of nitrogens. Thus, m/e = 141 suggests 1, 3. 5, 7,

etc., nitrogen atoms while m/e = 142 suggests 0, 2, 4, 6, etc.,

nitrogen atoms.

Rule 2 : The maximum number of carbons can be calculated from the formula

Relative Intensity of M + 1 100

Relative Intensity of M 1.1

where M + 1 is the peak next to that of the molecular ion (M"^). This

rule gives the maximum number of carbons, but not necessarily the

right number. Thus, if for example the relative intensities of M"^

181
and M + 1 are 100? and 9% respectively, then the maximum number of

carbons is

9 100

X 100 1.1

There is a possibility for seven, six, etc., carbons but not for

nine or more.

Rule 3 • The maximum numbers of sulfurs can be calculated from the formula

Relative Intensity of M + 2 100

Relative Intensity of M"^ ^ 4.4

where M + 2 is the peak next to that of the molecular ion M"^.

Rule 4 ; The number of chlorines and/or bromines can be derived from the table

showing the relative ratio of the isotope cluster of the molecular

ion.

Rule 5 : The difference should be only oxygen and hydrogen. These rules

assume absence of phosphorus silicon or any other elements.

REFERENCE ;

[1] McLafferty, F.W., Interpretation of Mass Spectra , University Science

Books, Mill Valley, 1980.

182
Chlorine - Bromine Combination Isotope

Intensities

Due to the distinctive mass spectral patterns caused by the presence of

chlorine and bromine in a molecule, interpretation can be much easier if the

results of the relative isotope concentrations are known. The following table

provides peak intensities (relative to the P"^ at an intensity normalized to

100 percent) for various combinations of chlorine and bromine molecules,

assuming the absence of all other elements except carbon and hydrogen [1-3].

The mass abundance calculations were based upon the atomic mass data of Weast

[4].

REFERENCES ;

[1 ] McLafferty, F.W., Interpretation of Mass Spectra , University Science

Books, Mill Valley, 1980.

[2] Silverstein, R.H., G.C. Bassler and T.C. Morrill, Spectrometric

Identification of Organic Compounds , John Wiley and Sons, New York, 1981

[3] Williams, D.H. and I. Fleming, Spectroscopic Methods in Organic

Chemistry , McGraw-Hill, London, 1973-

[4] Weast, R.C., ed ., Handbook of Chemistry and Physics. 63rd. Ed. , The

Chemical Rubber Company, Boca Raton, 1984.

183
Relative Intensities of Isotope Peaks for Combinations of

Bromine and Chlorine (P"^ = 1005^)

Bro Bri Br2 Br3 Bri4

P + 2 98.0 196.0 294.0 390.8

Clo P + 4 P + 6 P + 8

96.1 288.2

94.1

574.7

375.3

92.0

P + 2 32.5 130.6 228.0 326.1 424.6

P + 4 31.9 159.0 383.1 704.2

Cli P + 6 P + 8

P + 10

31.2 187.4

30.7

564.1

214.8

30.3

P + 2 65.0 163.0 261 .1 359.3 456.3

P + 4 10.6 74.4 234.2 490.2 840.3

CI, P + 6 10.4 83.3 312.8 791.6

P + 8 10.2 91.7 397.5

P + 10 9.8 99.2

P + 12 10.1

P + 2 97.5 195.3 294.0 393.3

P + 4 31 .7 127.0 99.7 609.8

P + 6 3.4 34.4 159.4 473.8

C13 P + 8

P + 10

P + 12

P + 14

3.3 37.1

3.2

193.9

39.6

3.0

P + 2 130.0 228.3 326.6 4.2

P + 4 63.3 190.9 414.9 735.3

P + 6 13.7 75.8 263.1 670.0

C14 P + 8 1.2 14.4 88.8 347.1

P + 10 1.1 15.4 102.2

P + 12 1.3 16.2

P + 14 0.7

184
Relative Intensities of Isotope Peaks for Combinations of

Bromine and Chlorine (P"*" = 100^)

Bro Bri Br2 Br3 Br4

P + 2 162.6 260.7 358.9

P + 4 105.7 265.3 520.8

P + 6 34.3 137.9 397.9

Cl^ P + 8 5.5 39.3 174.5

P + 10 0.3 5.8 44.3

P + 12 0.3 5.7

P + 14 0.5

P + 2 195.3

P + 4 158.6

Cl6 P + 6 P + 8

P + 10

P + 12

68.8

16.6

2.1

0.1

P + 2 227.8

P + 4 222.1

P + 6 120.3

CI7 P + 8

P + 10

P + 12

P + 14

39.0

7.5

0.8

0.05

185
Common Fragmentation Patterns of Families

of Organic Compounds

The following table provides a guide to the identification and

interpretation of commonly observed mass spectral fragmentation patterns for

common organic functional groups [1-4]. It is of course highly desirable to

augment mass spectroscopic data with as much other structural information as

is possible. Especially useful in this regard will be the confirmatory

information of infrared and ultraviolet spectrophotometry and nuclear magnetic

resonance spectrometry.

REFERENCES

[1 ] Pasto, D.J. and C.R. Johnson, Organic Structure Determination . Prentice-Hall, 1969.

[2] McLafferty, F.W., Interpretation of Mass Spectra , University Science

Books, 1980.

[3] Rose, M.E. and R.A.W. Johnstone, Mass Spectrometry for Chemical and

Biochemists , Cambridge University Press, 1982.

[4] Silverstein, R.M., G.C. Bassler and T.C. Morrill, Spectrometric

Identification of Organic Compounds, John Wiley and Sons, 1981.

186
iH 1c Cm

g

CO tlH

O >> CO •'HQ

C

O X2 rH 4-5 £- Cm

•H

L ,-{ CD CD <4-l

O

bO CO CO CO £1 bO

r-l CO o + u •H --'CO CO

C

t. o ^ o O > C o >. O rH ^ a: ti-. CD CT^ C CO CX CM O CD o

•H

•H 4-5

4-5

L • (D •- t. "^H- CO X5 rH CO C

x: ^ O

X d:: <D II

L

O >. e '^ o

J-) E E o:0

CO ^ X

CO « CD O CO •rH S- Cm •H O CO 4J

CO •o r< i. (LJ .^^ -^ 4J CO • Cm

J CO ^ c C O ^ CE CO E CO (D C CO O 4J

03D (0 ^-' cv^ CD x: XD c •« s: c

Q)

O x: II CX jJ> CX 4J •H

Cu JO t. 11 CO rH CO c CO 1 CO S

ctS 0) 3 CD ^ 8 -rH •H x; C-H hO

O E O CD \ . 1 ^ > o N > CO

•iH CO Cm \ E CO S (0 o 5 X ^ JJ-> •o O E rH Jj) 4JI o C Cm

CO

C rH x: -p o bO £3. c rH o o c

•rH

O rH JJ JJ (0 X^ c -a CD •H f^

L

L JD

O -rH CO

O

O bO CD E • •^ CO CO

X q; >, 3 ^ O L c x: CD x: rH C-O

4-> o O ^ (0 rH 4^

O

O bO o •o 3 tJ rH o 1 >> CO CD CO CO L CO C c c E <

(0 o >, rH CD D. V-- 4-> 4J CO CO CO

LC 1 tn £1 CO ex o CO 4J t. £h O O CO

Cfl o» 3 4-) CO

C CO c • X3 ^—V

Cm •H rH

j:: >>

O -!->C CD - CO 4-5

N 4-5 o Di: rH (D C CD L bO'-^ C CD c Cm X r-t •H -H 1 rH C CD C O O CO -H tn • O o CO CO Q ••• o CO CO C -H C|_i L CD to ^ CO ^—V •

II JO

CO 3 4-3 -H S a -a sz >-> CM 4-5 CO (N Q.

O

4-5 •. CO rH E O + >5 >>

O jj S-,

X

C 4J

X

C E CC o 3 3 O L X x: x: ^ <x CJ> •H C o O 4J

0) 1 E S- Ci.:o CD <M CD o bO o s CJ) • 1 -rH CX O O -a O Cm CO Cu E SL. bO c CO .- N •M rH Cm •H CO CO Cm

rt ^ o o .. CO cd XJ CO CO CO 4-5 bO 4^ o x: •«

S- .H £)

N

C CO rH >> CO

J c H x:

C •H 4J '-

Dl, (0

L

X -rH rH

O 11 x: o o o c 4-5 CO c CO 4-> CO ^ Cm o x: CD -r* rH S bO 3 !U 3 4^ Cm c; c Cw O CD x: o o a jj O 4J SL •H O (D o O OO rH O CJ \ rH CO .- .- t. ^ CO CO CO S s s O ^ O O rH E cO E '-^ '-- T3 ,

CM 3 CO s (D -H rH CO O + CD >, C 4J bO O bO T3 cin -o CO -a (m s_ o w) x: Cm bO iM «M C C O CO >> O C o C O CO CO O CO S O O CD CO > x: CO C ^ CO III > CO > o E ^

CO QJ CO -rH CO x: CO

p CO CO -C3 CO CO 5b

L

0) 73 CO

O CO S. o CO 4J

O CD £ CO

C CO CO CO CO rH rH o t^ x: o (\j O -M X rH CO O r-\ CO O O tCJ CO rH X O Cm + rH IS --- O bO <-i O t. r-i rH Cm t.

CO rH

CD

O

rH x:

.Q

O <M

CO o O CO

4-i rH CO O CO CO O ^ CD CO

(TS 4J rH o c

(U CD >. :-{ •H

ex.a cs] c >. c jji (D >> ^ o O -D 4-5 rH M c •H CO

CO -H

L. .- o C

O CO CO O Cm c

tH C\J 4-5 CX •H 3 bO C CO <M O °» c >, >> >, CO •H

CD o 4-5 4-5 4J

C rH

M o SL. •H •H • M €c ° O r- 4-5 CO CO CO 4J s CO c C c c •H O O L CD •H x: s- -H o .- 4J 4J 4-> 4J rH Cm o c C C L LOO on •H H •H >, ^ x: x: rH o

CO t- 3 5 3 4J 4J

CD

O o O

O CO CO 1 Cm S <M rH rH rH S- t. t= o o o

•rH ^

>> CO x: o -'-^ rH CO CD C o >, CO •H CO rH a CO -r-l c o CO c s rH O >, CO CO •r-i -H

CD CO x: x: c x: tn r-i

C Cm

t, j-> o CD CO o CQ <c o o -a ^ -^ rH o rH r-i rH '-~ y.—>S -'—V

•-^ o < < < < CO X3 o < ^

187
1—1 • •.H CO c

JJ CD

O o c c 4J X3 s_

... 3

Nl o 03 s o o CO c C O S- c o CD x: o (—H ^ •rH bO X3 o (t <i-i r-H 03 E O O CO g 03 0) CO r—1

S. 4J £ <u CX

cfl

O 4J 03 x: i. o c

x: =5 03 bO 4^

O t

•rH -rH tn r—i

CK^ 1 4J E

j^ <D Q-HC .—1 O •o >> Cl-, s: 03 cC 03 x: •^ o 4J • •rH 4J O ^ E

0) 4-> Cl-H 03 CO E ;- 03

O

O

0-

O j:: o 03 CO 4-3

L -H

Cu o x:

C Ci-, Q. OJ 03 r-H o o 0) 4J x: o c^^ •a t. o

•r-{ CO C>-l o -is: «

C7^ OJ •rH

C >>

4-5 CO 03

O bO 03 .—1 LO

J E CO •o •rH

O

m CO

O c 4^1 03 03

O 03 03 o

•M

m CO —1 4J II S X) E ^-~. c

SL- e c CO >> 03 (U, Ci_ i. U) 2 —1

CD •M

O t.

O

O C|-i

O

C • - *-

O

4^ (D -1 s_

C ^^

O Cf_ .H

V ^-^

X CO

O x: • N 03 •rH :. 4-5 E S_ 2 + CM -^ c

CC 4-S (i-l

x ..

O 03 CQ 03 > >i o X o

i- 4-1 CM ^'-^ x: x: •rH 4J> 4J CM

O II 2 + t~- X2

m

O

O o -H

C

O 4-5 4-1 03 •rH

X r-^ CM c

x: Jj o o x: 03 r-H CM Jj)

O 11 03 o •a Cl-H X X3 Cw 4-3 o O ^ •rH CJ 03 ^ CU, O ^ CD O --- i- O 4J r4 05 X3 e CM O • -

CT3 i. 03 bO •o •rH C-i o bOX OS

CO 3 cfl CO vX) o CO c k c Q. cn

O t.

C o CO x:

-i-> CT CD CO

m CO •H •rH en 03 •rH CO Cl c CD .—1 o O >i .—1 o CO a O r-i Q) O 1—1

i. x: -1 t- -rH CO

a CO CO r-H o r-i CCS e CO O 4J L E ">. 03 O —1

oo

bO jj. (D • #• •" 03 • •nH E JD • -^ r-H •rH •- 4J

cfl

C i. ,-—V

•-^ o ^ O ^—V

CO

r

N cc >> II

m 03

t. CD 03 b-, r-H ^ :_ 1—1

4-5 .- CM .•^ Cl, B X o en c v_^ c 03 ^—- X 4->

C c c

fcO to x_^ -^ c ^ o o (Ni +2 • C bO "V, •H o c 03 C o x:) t- •H ^ X x: 03 E E -I o i. CD O LTi -Q a^ t. fM 4-3 03 +2 1 E 3 > 03 4-3 E i-i bO CM c^ L t- 03 ^

OS

X 03 4-5 03 e o 03 o 4J a II o o bO " 03 O 4J o Q-i ,-H O-H <t-i O Ci-l Ci-i c C X r—1

•H

C o O cfi O o O O bO O II 0) o O CO 4J

x: 03 x: e c s:-

O 03 E

CO CO CO S CO 4J CO bO o II CM I. o o! c E bO

CO .—!

CO CO E CO CO 03L

X 03

X 4-5 •rH

O 03

O .-H o O 03 o o o i- 4J o o 2 E C sr-H 03 f—i rH bO ^ 4J 1—1

Cw CO s. cc X3 OJ 03 Ci-i

CD

O

CO •rH 03 bO r—1

<D c Ct-i &^O

L C^ o •iH

O >> o --t •r-i o &-( •r-{ o c 4-5 4-> c CO o x: ^ C •.H CO m o CO a

CC o •rH •r-l D. o ... c

0) ^ x: £-

L cn r-H CO CO 03 Cu 4-5 

' 03

i- -.H J-5 4-5 jO c O c OJ 5 bO O O j_ >> >, •rH .r—1 o r—1 c 03 03 o 4J 4-> c E 4J

)—1 3 CO •.H :_ :- o • -4 •H •H 03 03 o CD x: >, 03 03 CO CO E

t- CD CO o 4J x: SZ i- c c o O

03 r-< 03 c •—( o o r-H •rH s_

i-H

O I-H (D (fl CO i- s_ x: 4-5 4^ JOJ 4-> 03

D E t. s_ c .- .. 4-> c c 03 03 O V o X2 CD >. 40 >> 4J o •rH H 4^ x: S- 0) Ci-, CD 4J 4J CO 4-5 CO O CX O

rH

O !- -o •a

CM

D •rH

D c &'c §,

•rH Cw

O CQ c ^ CO 1—1 CO

—1

03 4-) r-H S CD >, 03 c o c o x: •H o •r4 03 >1 O V 4-) 3 4J x: t. x: •o 4-3 c •r-f O Jj 4J CO 4-5 O rH

03 I-H CO Nl .—1 C Q.

C D. t- i. o e >1 •rH CO CO o o c • ^ •rH O •^ O -c r-H r-H C c CD CO >> 4-> 4J "& 'rH x: M x: o O c 3 V 4-3 i- 5 O 3 O 4J 4-5 0- >1 4-3 •rH X3 C c CD O CO O CO -H ccJ 03 1 03 03 o C E

03 tt^ •r-( ^ > .—1 -' T—1 -^ x: x: ^ p= t- x: 03 •rH ro

COCD CO CO a CO

•r~i

aa CO >. r-i --I •rH o 1—1

03 s- t- •.H TD

•M s: o O E •rH CO E Z5 rH o •o CO CO

(T3 .-1 r—1

x: t- o c

t. >1 C^-i o 13 •<H

a

•rH c

•rH ^ ^-N ^-~, ^-v ^-v r-H E E

<c 03 X3

D < eC =c
CD

CO LH

O

C CO ^D

4J> bO

O o 4J Cm

C CO II

Cfl -rH J-5 CO c

4J

L

O •H r4 jii: .*. (D •« CD CO \ ^^ CO J3 hO CD ^ c ^ a> E 1 Cd c x: i4-H (D X ex GO

03 CO -rH -P (D tiO o 4-> 1 C3>

•rH -a

L

O 1 bD CO c > C --CD L •-' C >, ^ •H -^ O CD '-^ M •a ^ X3

X3 c e -u >, t--

L CO II ^^

m CD 3 -P x: ^ 4J TD s ^ a: CD CO -.H -H 1 CO ex . cC x; x: c .-H -H <0 C|_, J.J \ ^^ X

0)

O J-) 0) rH o bO 3 E C -^^ a. jD >> >. (*-( ^^ c 4J

II 4J> ^ Q. S_ •H CO CO 4- . •H 4-> -M I>- o CO O CD CO "O X t. 4J CO <\J

•r-i

X t~- t, > —- O -1 1 4-3 CO E

4J

O CU t- -P

N .—1 o CjO CO x:i CO 3 II CO CC W v_^ CO ^ CO Zi :^ -r-i •rH CO II CO a: •- 00 .- CO CO ,-H J- d-^ > ,- x: o ^ c 1 ^^ i-H v^ O CO CD CT> --^ DC -4 CC 1 a >, E

+J CD \ C

O ,0 CO

X ex.

O

C .-H S - O o x: 1 bO -0

CO

OO '-- -rH II CJ> o 4-3 1 --'

CL c U -.H jj -a 4-> ^ 1 N 4J CO

cfl jJ •- CO CD 3 OJ

J 5 r-H CO s- ^^

x: to ^^ 4-3 4->

X LO i- CO C3^ t- 4J ^ o E 4-> CO 3 .rH o ^ o 3 00 CO r- CM e C -i^ P 4J -.- x: CT x: cjN X •* O CO -4 CO II CO -0 4J 5 2:

CO "^H S CD 4-> X3 o C •- (N 4-3 CD ex CO 3 VD CD L CO x: ^ C .- hO £1 CO \ O \ Cm CO 4- • 00 • CD C C - 3 II S E ^~^

>" ^- e •r4 CO M CO rH CO CO X

a

bO cfl SC 1 >, 4-> TD ^^ 1" .zr -H

CO x: t, "H o -^ \ CO "-• CO 4- .

II CO "O UD E L O CO J, C iH E O C X —1 ^ cfl tL. CD O CO . ^ CO •-H !/) x: tM II C

CD 1- o E e 4-> CO Cm go ^^^ 4J iH Ln c a .n4 Cm 3 CO o X 3 ^ Cm o •iH >> 4-5 >i O J-. ex -M 1—1 —

CX5 CO \ .—1 e CO 4-5 to i-H 4-> ^ 4-> 00 4_> E 3 s S- E --H C O CO •- CO ^0 . ^ CO o !i-i CD O CO O CD 4J S Cm MD Cm .-V t, -H -t-. cO 4J1 00 Cm o o Cn j^ .M .M a ex c o 4- C

Cm CO

O 4J CO CD S3 CO CO

II in ,-H CO

m

CO CO CD -^ CO CO

X •HEX CO

N

COJ ex CO <D CO CO CO " E >^ CO

C o o x: CO o x: CO t. Cm \ •H S^

i-H S 4J CD ex 4J X3 ex

M E rH -^ CO Cfl ^ p-H X3 1 JO tC- !L CO x:

-M

4J "§)

C CO •H ^ E x: bo

CT3 E ^ c L Cfl 4-3 -M

IXC CO

•r4 ex 3 -a

X) c C CO <*-! O x: -H >, >. ex

1—1 4-3 CO 4-) CO 1 •M CO •H c jj> bO CO £1 CO tcfl "& c3 c ^^^ C S- rH3 (D •rH M 4-J >> 4-> O CO (fl c 4-3 c CO

CD c s_ •- ,-t •M •H Cm

C

r-H (D 4-3 CO CO ^^ O 4J CO "O 3 c >> 5 4-J S c .r-( rH Jj C

•H

CO .—1

4J rH C CO

M Cfl x:

•H

i. ti-HL

H i- t- 4J S- CD CO x: .ii: -rH T3 x: ob

x: c x:

4-3 CO r-H -4 4-3 4-> cfl 4J

CO >> CO •H bO Cfl x: CO

0- 5 X CO L. x: --' ^ +jU

CO

m c CO o CO i- a

>> X2 •M •H

1—1 O i^ ^ .H TD CO x: E

r-( •H CO CO >! •1-4 CO 4J Cfl E 4J CJ CD X Cm ,-H 0 C

nJ CO

O

C CO <-i •M t S t. CD X3 T3 3 c Cm -H Cm O -O L L —1 CO f-H x: nH

t, >. CO CO •t-4 x: 3 4J 3

=i: x: '— CO

Q a. 00 V-- 00

189
o

JJ -o i-H •k ^^ -M

CO

C r—

>> ,-^ .—1 CO CO N Cm X bO o • »

CO

D c o o -^ CO >> ^-v

O ^ - cr c > o X .M

CO cr X3 <i-l

C !<-( CO ^ CO CO >, GO 4-:> o CO o o o 0) E i. 4-> 1 CO

CIL - c Cw •M '^ li rH .-

gO t. E

U-, Ct-. -^ s O 4-J CO o "r s^ >>

O - o O E CO Cw CO CO CO X Cm X L + bO o CO E O o \ CO O ^ Cm CO O CO jJ CO o t. '-I ---E X O Cm O CO •a

CO CO CO CO CO CO o crx

m .M

J t,

w III CO CO CO o c Cm -O a> Cm -H

X 11

O 4J o ^ s o ^ <U CO • M c C\J o (0 O S D Cm

CO o CO o E c a CO --- ^-' bO o 4-> CD 1 (D C •rH Jj c 11 CO • CO /^ X3 •M -—

a. cc x: •r-i

a o CO "O CO CO

O CO > --^

C 4J CO

-p v^ o x: ^-^ c O i_ CO CO CO (l:) o C-H c jj> o Ci-, c o \ —! 11 C caD XI -^

•^~^ o « r—1 - Cu^ X2 E X

O rH CM 3

4-> •- ^ cn CO o 11 faO . j_>

O j-i o bO CO ZT

m CO ce r~\ 4J >> o CO /\ II CO ^r

•l-( CO o CO c L. o o X 1 ^ ^ CO > X

S- CO 1 CO '-1 cx r—

x: o o O •—1 r—

4-) CO

O II <D E O o CO II -p N O >! X rH \ 1 -P Q. C .^-v zs i- Cm X CO c 4-> >> XI E :—{ ^^ o Q) III £! cr CM o x: o dJ -r-i Q) X o \ m x: jj fcO X jj ^ C X O 4-> CO Cm CO E

t. -P o c o -o o CO a. 4J> -rH

O CO r—'. CO + !_ c x: O bO O —1 E > X o -o

x: o E -o CO \ -p JJ CO ro c^ TD

a CO DX c o J-> C|-H >1 c oo • > o rH 4J CO t—\ O CO O M x: »> CO CO CO CO 11 c X rH C O CO o • *^ rH c ^—

jJ •iH 4J .M

O CO rH rH -—

CO CO'

w CO CO d:: CO Cw > -p .—

CO CO E i—\ CO CO -p 3 CO J- -p o o CO X2 o \ CO '-- 4J i^ •- CO X c cr CO t_ 1 X :^ X o Ego 4P O bO 4J> •M Cm O

<D 0) E CO JO>

u o CO CO o tN]

O •'X CO Cm

CC 4-> o •— E 1 + CO cr c C CO <M C O CO •M

fcO CD CD

L CO cc

a o O

O -I ^ CO cvn t. CO c LPi CO \ SZ —

,—1 Ct-i X2 XD -M O- ^ L •M CO

—

l- E -P >i Q-( Cl-H

O o CO --^ C3^ C! CO :- • o

tL. 4->

O o cc .> o CO CO "CM o II ex t. 4J

X II jJ O i. -'—

CO a.

O

X i- t. c 4J c CO -P CO c cr: CO 4-) Cm CO --H O -O bO CO 4-> o Cn O CO •M o =: o D o -- c 1 \ >5 -rH Cm E O \ s ^ ^ ^ C CO 1 1 1—

Jj cc CO Ct: E 4J CO 4J E E CO CO CO E c CJ o rH 1 CO LO i- c bO O CD Z5 J CO + »• Jj bO o + Q. ^ ^-• Cm 4P CO C C Cm . O a cT O bO II CO CO CO :3 o O CO Cm bO CO CO O CO S S- x: o S- X3 > 11 O II o Cm O C i. ,—'. •—{ Q. jj ^ CM D CO :. -^ CO ^ CO c o i- •rH CO O

CO o X -p CO

M bO CO CO

X -o 4-> CO E CO -rH CO ^ m. ^-^ o >, o CO 1 r-l X 1 -V, CO O O >) •M O X

X) E CC CO -p x: o OO a: E CM -H Q. s:

X ^ ^ CO rH 4J

i-ioX

t. oo

S)'^ ^ X bO

to c

4-> -M a. 3 -a X c c >> >, o o J^ >, 4J >, D. M

CO 4J

•M

•M

CO ^ CO •M

I- c CO c CO SCO c C J-

.—1 4^ 4J o D c -p C 4J O O •M c •M c M M Cm

r—^ ^ o O CO 3 3 S

rather

we

O1—

C- X

-P

CO

•MX

:_ X

4J

CO

O 4J

<-i CO X X c

4-> CO CO X C 4J

CO >. c

iH CO ^ •rH » CO 4-> CO e CO cr; co a. ,-i CO t. o i. C CO O I fc, 1 •J-> CJ

CO 1 to a: =o X

-p o

4->

Merc (thi

190
E 1 OL

Cm

... S ^"^ 1 C •- O

CO

O

O -- x:

CD CD

C o •rH i- + . CO 3 CO

CO ^ 4-) <M CO * X

>, CO

O <-i CM

O CO CO £> o II •rH D o CO

CO

C 4-5

O CO CE -O

CD .- Cm o c CO cc •rH L '-v O \. X3 0) CO I-H O X

a+ s S- t- o o o 4J

O

ra 2 CO s 4-> <M ^ £- 11 CO 4J> O Cm c I-H rH m CD O CO CO Cm •rH E I-H CO 3 & X

>) o CO —1 ^ O CO 3 CO (X iJ .^ s: -o L 3 cr

•-1 o tn c CO ex

O ^ cr o /—

—\ o s: 1 ••-> •rH

I-H CO o •H /.

—v\

-P +J V-' cc !<-l

Cl-, 2

Q. 3 4J

•rH Cm

O

eg CO -^

4J> CO CO+ '/^N\ ( ) >

•1-1 w CO

CD

CO o E O 2 CO e E vVs^/ J X. bO .c i_ CO ^ o V 1 L >> ,-1 o k

4-> CO Cm E L

VCD M ^ s: Cm Q. CO O CO t^

+J 1—1 CO

O iH 4J

O Cm c CVN

O CO 4-5 » • ' CO <£> nH CO

O .

03 •rH

O ^—s

CO .* ;q- CO ^ ^^

£-O CD a:: CO ,—V o 4^O CO I-H

X +

(0 CD 4-) 1 O + II

C rH CO CO

O cn

x: D. cu +2 r-t o sz

O 00 + 1 o CO X3 II 2 O 3 •" I-H Cm 1

tJ ...

—

.. '—' +J c -^ a- CO

O II o^ ,X\ II CO E -o ... ^T*^ ^^

m 3 N 1—1 O t- CO c CO CO ^

-p

L X3

X X2 o^ J=l Cm iH 3 CO

X c CO o •-{ S o 3 O a O O

w * <uE (i ^

CO CO

CO II CO CiE

i-\X

-H v_^ tn

*5:^

^s>^^

bO

a ,

o ,-H

O •~

O o •- CO CO

ffl CO 5 ^ Q. •\ rH

C • ^-v

O CU. ,— ^ S- E CO CO o o I-H X [i. >. CO II 4-5 CO -o 2 1. 3 O II II CO -r-l C jj C £1 C '-^ 4-5 CO • c e CO •M CO 3 •H

""^

^-v o ^ -^ S O O C o C— "^ \ X E C CO e • .is: ^ .- D. CO 4-5 '- E E +0' S O hO CO CO O CO E o ^ in o •H CX ^ C 2 O Cm •M CO L Cm 4-5 4J X o CO CO C Q. OI-4J O O 4J CO O CO CO 10 ,— t— S_ II '-< o CO a I-H O js: :- N <^ L i- CO E •M CO -i^ ^ ^^ + 1 CO CO c CO X 4J -U CO o c E CO CO CO

CO C_) •rH -r-i o s, o •M

O fv^ s: s cx i. £1 £) ^ C C .—1 CO -rH CO iH D. cx a> c

•rH TDc

4-i CO a ^-^ ^ 4-) O 2 CO ^ X o

CO

m £1

CD

X

Q. •o C_) ^ ^_^ 4^

CO

C 4-> 2 O O o ^ M rH

4-> -H

in CO

£- t- tM 5

CO •a 4J o .H •iH >. o 3 c t. >5 >> O X5 o > 4^ 4^

CD 4-i iH > L •M •rH iH O •rH CO CO O -IJ o i- t- CO c c S CO 4-5 O £1

>1 •rH

O 4-5 4-5 i-H <<-, C C c o o +:> E •M •H ^ •rH C O

•H

f-\ CO

O CO -a

I-H ^ ^ C CO S- £1 •M •H 3 O G. CO CO x: x:

CO ac3O

o. CO

r-H >, E S CO CO O CO o

•i-H o •H S rH 4J c X

CO rH •rH o o o

fa-, 4-> •H

is

,-t

4-5

•rH

Cm3

Cm

rH3 2 2 2 cyo CO

191

VII. Tables for

Qualitative Analysis

193

Organic Group Qualitative Tests

The following flow charts and notes provide a step by step process for

the identification of functional groups which may be present in an unknown

sample [1-7]. These are meant to augment and confirm information obtainable

using instrumental methods pf analysis. It will usually be necessary to use

gas or liquid chromatography before these "wet" chemical tests in order to

determine the number of components present in a given sample. Since many of

these tests require the use of dangerous compounds, the strictest rules of

laboratory safety must be observed at all times. The use of a fume hood is

required.

Note: ppt = precipitate

cone = concentrated

dil = dilute

REFERENCES:

[1 ] Paste, D.J., Johnson, C.R., Laboratory Text for Organic Chemistry , Prentice Hall, Englewood Cliffs, 1979.

[2] Sarlo, E. , Svoronos, P.D.N. , Experiments for Organic Chemistry , Burgess

Publishing, Minneapolis, 1983.

[3] Roberts, R.M., Gilbert, J.C., Rodewald, L.B., Wingrove, A.S., An

Introduction to Modern Experimental Organic Chemistry , Holt, Rinehart,

and Winston, New York, 1969.

[4] Hopkins and Williams Research Laboratory, Organic Reagents for Organic

Analysis , Chemical Publishing Co., Brooklyn, 1946.

[5] Hodgman, CD., Weast, R.C., Selby, S.M., Tables for Identification of

Organic Compounds , Chemical Rubber Publishing Co., Cleveland, 1950.

[6] Kam.Ti , 0., Qualitative Organic Analysis , John Wiley and Sons, Inc., New

York, 1932.

195
[7] Vogel, A. I., A Textbook of Practical Organic Chemistry , Longmans, Green,

and Co., London, 1951.

196
Protocol For Chemical Tests

Ceric ammonium nitrate : To 1-2 ml 5% eerie ammonium nitrate add 10 drops of

the compound to be tested. A change to an orange/red color is indicative of

an alcohol (detection limit 100 mg - compounds tested Ci-C-iq)-

Dichromate test ; Add ten drops of the alcohol to be tested to a mixture of

1 ml ^% Na2Cr20y and 5 drops cone. H2SO14. A blue-green solution is positive

test for a 1 ° or 2° alcohol. 3° alcohols do not react and, therefore, the

solution stays orange. (Detection limit 20 yg - compounds tested C-i-Cg).

2,4-Dinitrophenylhydrazine test (2,4-DNP) : Add 10 drops of the compound to be

tested to 1 ml of the 2,4-DNP reagent. A yellow to orange-red ppt is

considered a positive test. The 2,4-DNP reagent can be prepared by dissolving

1 g 2,4-dinitrophenylhydrazine in 5 ml cone. H2SO11 and then mixing it with

8 ml of water and 20 ml 95X ethanol. The solution should be filtered before

reacting it with the unknown compound. (Detection limit 20 pg - compounds

tested C-i-Cg) .

Ferric chloride test : Add 10 drops of 3% aqueous FeCl^ solution to 1 ml of a

5% aqueous (ethanol) solution of the compound in question. Phenols give red,

blue, purple or green colorations. The same test can be done by using

chloroform as a solvent (detection limit 50 yg).

Hinsberg test : To 0.5 ml of the amine (0.5 g, if solid) in a test tube add

1 g of p-toluenesulfonyl chloride and 8 ml ^0% NaOH. Stopper the tube and

shake for 3~5 minutes. Remove the stopper and warm the tube with shaking in a

197
hot water bath (70°C) for about one minute. No reaction is indicative of a 3°

amine, which is usually soluble upon acidification (pH = 2--4) with 1 0X HCl.

If a precipitate is present in the alkaline solution, dilute with 5-8 ml H2O

and shake. If the precipitate does not dissolve the original amine is,

probably, a 2° one. If the solution is clear acidify (pH = M) with 10? HCl.

The formation of a precipitate is an indication of a 1 ° amine. (Detection

limit 100 mg - compounds tested C-j-C-ig.)

Iodoform test : The reagent calls for the mixture of 10 g I2 and 20 g KI in

100 ml water. The reagent is then added dropwise to a mixture of 10 drops of

the compound in question in 2 ml of water (or dioxane, to facilitate the

solubility) and 1 ml 10? aqueous NaOH solution until a persistent brown color

remains (even when heating in a hot water bath at 60°C.) A yellow precipitate

is indicative of iodoform (CHIo) formation and is characteristic of a methyl

ketone, acetaldehyde or an alcohol of the general formula CH^CHOH (R = alkyl,

R hydrogen). Aldols (R-C-CH2-CH-R' ) also give a positive iodoform test by a

II IOH

retro aldol condensation first yielding R-C-CHo + R'-C-H (detection limit

II II

1 00 mg).

Lucas test : The reagent is made by dissolving 16 g anhydrous ZnCl2 in 10 ml

cone. HCl with cooling to avoid HCl loss. Add 10-15 drops of the alcohol to

2 ml of the reagent. 3° alcohols form an emulsion (the alkyl halide) almost

immediately, 2° alcohols form it after 2-5 minutes while 1 ° alcohols react

after a very long time.

Sodium fusion test : 10 mg of the compound to be analyzed are mixed with a

fresh piece of sodium metal of the size of a small pea in a 4-inch test tube.

198
The test tube is warmed gently until melting of the sodium metal and

decomposition (indicated by charring) of the compound occurs. When it appears

that all the volatile material has been decomposed, the test tube is strongly

heated until the residue becomes red. After 3 minutes of constant heating,

the mixture is left to cool ^to room temperature, then a few drops of methanol

are added. If no smoke appears, an excess of sodium metal was not present and

incomplete conversion of the elements (N, S, halogens] to their anions (CN~,

S~^ , halides) is very likely. Addition of another tiny piece of sodium metal

and repetition of the heating process is necessary. If smoke appears then the

test tube is plunged in a small beaker containing 10-15 ml distilled water and

covered with a watch glass or a wire gauze. The test tube might shatter and,

therefore, having the small beaker inside a larger one is recommended. The

contents of the test tube together with the broken glass are ground in a

mortar using a pestle, then transferred in the small beaker and heated for a

few minutes. The solution is then filtered and the solution divided into two

larger parts and one 1 -ml part.

Detection of nitrogen ; To one of the larger parts add 0.5 ml of 6M NaOH

(pH adjusted to 13), five drops of saturated Fe(NHi|)2(S04)2 and five drops 307°

KF solution. The mixture is boiled for 30 seconds and immediately acidified

with 6M H2SO21 with stirring until the colloidal iron hydroxides are dissolved.

The formation of a blue color is indicative of the presence of nitrogen,

presence.

Detection of sulfur : To the 1-ml part add 10 drops of 5M acetic acid and

2-3 drops of 5% lead acetate solution. A black precipitate is indicative of

sulfur presence.

199
Detection of halogens : To the other larger part add ]0% H2S0i| until the

solution is acidic. Boil off the solution to 1/3 its volume to secure

evaporation of H2S and HCN gases. Formation of a precipitate upon addition of

10% AgNO^ solution is indicative of the presence of a halogen - white for a

chloride (which is soluble in 6M NHijOH), pale yellow for a bromide (which is

only slightly soluble in 6M NHi(OH) and canary yellow for iodide (which is

insoluble in 6M NH4OH). Should the color of the precipitate be difficult to

provide satisfactory identification of the halogen, proceed as follows: the

working solution which has been acidified with ]0% H2SO14 and boiled down is

treated with 4-5 drops 0.1 N KMnOij solution, with enough oxalic acid added to

discharge the color of excess permanganate and 0.5 ml carbon disulfide. The

presence of a color in the carbon disulfide layer indicates the presence of

bromine or iodine - purple if iodine is present, red-brown if bromine is

present, colorless if chlorine is present. Should the compound to be tested

carry both bromine and iodine the identification will be difficult (red-brown

to purple carbon disulfide layer). Addition of a few drops of allyl alcohol

decolorizes bromine but does not decolorize iodine.

Tollen's test : The reagent is actually made by mixing two solutions (A and B)

.

Solution A is a 10^ aqueous AgNO^ solution and Solution B is a 10^ aqueous

NaOH solution. When the test is required, one ml of solution A and one ml of

solution B are mixed, and the silver oxide thus formed is dissolved by

dropwise addition of 10^ aqueous NHijOH. To the clear solution, 10 drops of

the compound to be tested are added. A silver mirror is indicative of the

presence of an aldehyde. The reagent mixture (A + B) is to be prepared

immediately prior to use, otherwise explosive silver fulminate might be formed.

200
The silver mirror is usually deposited on the walls of the test tube

immediately or after a short warming period in a hot water bath. It is to be

disposed of immediately with water and/or dil. HNO^. (Detection limit 50 mg -

compounds tested C-1-C5.)

201
mc o

(D ,—1

X5

hO 03 o O C 4-> C Ci-i '-^

.-f CO

O

•.H ^

CO

O co c s: 4J rH x: rH

CD

O e +-) bO -P

bO *s 4^ -* ^ jJ * i. COO

O ^ c 3 COC 3 Q.

S- <D Ci-i a.

O CO

J-> ^ CO

D CO Cw s: •M 1—1 c o 4-> CO c D S_ c t- <4-l •iH m a. x: b£l Q. •r-{ JC o -i-> CO !i-i Jj c o —

CO c

CO

J-Q.

Cl-H

CO

CO D

•r-i Xo

COC

CO CO Jj c Oc

CO

CO TD '-^

•'H t- CO

r-H Q.

C CO

CO if o bo -a

CO

O -H 3 D =!

C0_g

CO

O 3 O i;-* O Cm

i. .-H x: o D CO

CO CO CO E CO

(Doc

COao

CO

B ^

CO CO CO 3

U-i

O ^ x: 3 CO

CO ^~-

CO ao

2: co

Cm Cm O .-I

CO o

COC

Q.

O

•M

!LO

•M

x: CO

-1-5 CO -M

x:

CO J^ oc3o

Q.EOoc3cc

^cc

CO3

CmoO

CO co

•.H 4J

-u

O c CD

CO

CO ^—V

00 CO

J_ •M

C3.

H-l

CmOo

x:

CmO » C

s_ CO CD •a

CO bO

CO

p. CO

M i_ Ck

r-H CO CO 1—1 a

CJ- o CO

V

M o o x: o C

.—1 •M •M CO o

GO CO 1—i

l—{ 1—1

.—1 o c x: CO CO >. CO S2 x: c CO

fcO -* r-H o 3 -* o >, ,—f ^ Cm O

.—1 ^ >! >> r-H x:

CO :—{

O S- 3 CO CO

X CO CO CO CO

—

—

c

bOO

I. -PC CO o 1o

CO

Jj Cm Cm c •> 1—1 O

CO CO CO 3

CO o •a CO 3 o C c O o

L.

M 3 3 p. x: c

C. E O

O ^—

N

CO

CO O. C. CO ^^ CO c cr ^

•^

O o .—1 CO J- bO ^ CO O o •M Q, O O o t. o

S- c s_ c Jj • M

O

-P

M 4-> CO •rH e CO

•I-* cr •M >>

C CO rH

2: CO c c ^—

c CO

X33

I—I o

COc

x:o

on X CO 2 ac e 3 O O

Q. ^ E C rH O • M i-H O E O

CO E i.

CO -P o M c c ^ p c o CO m 4J 3

*t -p c bO

C\J X3 > JD x: o o CO CO on

,— c •M

^_^ • M 3 X bO o

rH CO

C CVI iH •r-( 3 c P

CO o

•-H <

o " s

CO CO o

t-a. CO

CO o

a. c3

CO o

on 3 Q. X E s 2 P>• M oo C 1—1 o O rH c

'-^

I-H x: CO CO p >1 c E • M ->• o rH

•rHm 3 • M E »• Jr CO :^ CO 4-> o •rH o c

x: r^ •^

—

o E —

CO

202
h c

CO rH

(n CD 0) jC

r-l

m .—1

£) Jj) 3 (U 03 o m S- C 4-> C Cm

*» G.

O s: 03

O -> •rH hO ->• c a« JJ •r-l ^ CD

0)

mO s j-> bO

fciO c c 4-> in 03 ^—^ o Zj CO c 3 a c

s~ bO <i-( ex CD

O o -!-> o D CO Cm x: H •iH rH J_ o CD 4-3 4-> c 03 0) SL. J- CD Q-i O

x: x: bO D. CD •M CD o j-> CO Cm CO c o acO

o.soococc

COCD

4-> co

•H

CO3

<<-. E3

•rH o

CO

4-> c

CD

CO

CD

CDc

CO CD

CD CO "O (D

CO COc

Q- -> CO "O CO 03 .—I . . CD -rH 0) 4_) >> cti

S- CO a c CO

CD CD

O fciO -o

CO

O •rH

i-H S ^ go 3

00

X c ex c

•rH

O

O CT)

O 5

(i_,CM<i-l OQ-H 0<mCm

r-HMi-H t^MX: OrH 3 3 3 CD 3 CO 3

CO CO CO S CO ^^ CO

C

C -P

CD CD CO

CO bO

CX 03 x:O 4J M QJ CO x: 3

jj) Cm

CQ bO S C 3 - O •rH H S -O O 03 O ^ ^CO

CO Cm CD C -rH CD .J-) bO c O (D 03 rH T3 •rH 03 -rH >

CO

CD CO CO 3o -^

x: 00

CO ^- Cmo

CO

CD CD TD O

—I

C

CD (D 03 CO TD "D X! (D •M •rH s^

03 <-! f-H x; n3 03 x: x: co

>, I—I rH Cm ^ >, >, ^ M O L 3

03 03 ro CO

0)oc

CD

CO

CDao

CO rH

033 2 O

X: Cm

COO o

CM X

•o•o

03

CDhO

03a.Xc

CO

•ao>o

a: o \ CM mn: 1 o \ s r-t bO O < c

03 •a x;

CO

a 4-5 CO 03 -a a •M

•<H 1—1 ^ ^x:

iH >,

>. ^

i- iH

03 03 c

>. o

-l-> •M

•r-i 4-J CO O 03

•rH

L

x> 4-) 4J

T~1 03 •rH 4J r-H e c

Ci 03 o

D, -> x: s^ 03

03 •rH

O •-\ > C >. ^

S- o O 4J

03 CO CO x: .—I O 03 4J co • •^ •rH S- 4J3

CX rH

03 o

CX CO

CO oo 3 o s s 4J bO

•o •rH <

r-i CO > C

r-i x: •M

D

O 4-> •rH > •rH bO M 3 C ^ 03

•rH x:

rH -^ rH O o X) rH X XI >,

x: 3 O o XI 03

l-H CO bO < •C3

•rH

«« iH

t- 03 4J CQ -> x:

Q, bO

CX < 1—1

>>

•. -^

i-H rH

(l:i 03 bO < 1 o o CO bO

4J Cm iH ^—.

03

C ^ •• r-H 03 OO CX

CO CO CO 3

CO o -a CO 3 <Vh CO a c c O o 3

t. •M 3 3 •• x:

O

CX e O

O .—^ CO 'i-i 03 CX CX CO s o > C E E c •> o o <—{ CO t. bO -^ CO o o •M CO ^ CX O o o t- o

tC s^ c 4^ •M ^

4J •M 4J 03 •M E CX

•rH e •M >,

C 03 CO s 03 c O C

203
4Jc ^^

s. o CO 3 m Q) Cm q; CD bO

rH j- rH

n CO

13 Q. rt Q.

CO c 4J ^ o

•rH ^ -^

O5 c (p 4-) •rH 4P

Q) bO o E

bO

O c -P -U

•rH r-l 3 m c X

t- fD Cl-H Q. 0) CD -P x: D CO C

•rH i- o C t. 0) iU t- CD o x: bO Q. CD O J-) CO C o 

CO

cxeoococc

4-3 CO

(D

J-> Co

•rHCO CmSD

rH

T3O

CO

CO3O

CD D.

C

CD

CO

CDQ.3

C/1

CDOC

CO

CD CO a CD

•rH S_

,-H Q.

CO

CO 'O

CD -rH •a X M O

Cm <m

r—I I—I 3 3

CO CO

COc

CO n3

CD

CO x:

COc CO CD CD bO -O O

CDOc

CD

CO

CD

J-Cio

CO

-P >i CO ex c

CO

O 3 O c^H o

i. rH i:

CD 3 CO S CO ---

CO o e o

CO CO '—- 'rM C 2 c O 3 O

Cm

O Cm Cm

r-l X:

O rH 3 CO 3

CO ^^ CO

•M

X

rH

O

•rH CO X3 2 3

rH

C

O -rH CO

O

CO

C

C

CO bD Q) O tn rH Q.

CO X

CO - - -M

CO CO rH

O CO •M TD TD x: rH -M -M

CO

Q>O ~ c

CO

CO

a

ex

CO cO ^ CO '^

x: x: c 00

:-\ 03 >> rH rH C^^ O Cm ^ >, >, ^ x: o

rH

O S_ 3 CO

CO CO CO CO -—'

bO

COa

CO3o

•M>

D.

CO

.Q3o

COc

"^ 0

CO • i—i c

rH Cm

CO

C

JJ

•M CO

4-> jP

•M

•0

•0 CO

CO

4JQ,

CXo

CO ->•

Cm

C\J CO r-^ •0 c ^ 3 •rH X

J-> • CX •rH • c B a rH rH

•a •rH 1 CO •0 CO 1 C/)

t. x:

-p

rH

rH

CO

CO

4-> Q) D. ^ c

D.

<M

rH

C 3

CO

(0

CO "O

•M o X

4-> -M

O

CX ->• c^H Ct^

en. rH rH 3 3

CO CO

W0

•M

CO

r-i •Q3 M

rH ->

C

CO <MrH3

CO

CO

4-i c

Ci CO Ci 4-5 Q,

.^ ^ CO

CO t.

•—1 X3 s C3

•P

J

X3 Ex: >>

CO JD

•rH s S

CD c x: •M 4->

4-> CO 1 to

4-> Cm •—t ,r^ ^-^ c •» ^ •• r-\ CO 00 ^

CO CO CO 3 bO

CO X} 0 CO 3 Cm Cm CO a c c CX

i. •M 3 3 *. x: £)

CX e

^-~- CO CO

CO CX CX CO ^^ 3 c e e c bO • •—< CO CO • M

bO -> CO

G •M CO ^ CX >

i. o

!_C iC 4-)

M ^ i4-> • M jj fO •M s CX CX

•M e •M >.

C CO CO 2: CO c c ~~^

204
c3oaBOoc3oc

::£ C

:=>

mco

•iH CO3S3

•iH oO

CO

4-5 c

CO

<uQ.

COc

(UbOO

rH

Oi JCO3

COcO

4-> c

0)CO

CD

£-Q.3

CO

a:oct3 3O »

CO

CO •oc3o

D.eoo

CD x:

4-> o 3

CO3O

•i-t >

0)

CD

CD bO O CO

(0 D.

CO T3

CO --I ^ O O (TJ C

<D

O

D.

Mo

x>

t.

CO

4-> c c bO O

CD CO -^

CO Q. 4J> O o L •a D. C CO

->• o

CO

O CO c CD -.H CD CO x: bO 4-> O

1—1

CD Cm

CO CO

O

ac "^ c

•iH (V >^o|

Jj o •rH X

1—1

CO •M 2: X33 . 1—1

i-i

O •rH CO o

.p

D.

D.

CO

CD 0) bO •n CO C >.

CO -> jc c

£- o O a -p c ,, o 4J en

•i-H CO

M

Jj o 3 4->

I-H Ci. o CO c > r-H o £ ->• o •r-1 4J c 4-> •rH '~>

C\J CO 3 C o x: E o o a. i. CO -rH rH t. -P o Ci-. O 3 c C .-H .-< O o o o O CO c •rH o o

•iH CO

4-> 3 o

•*!-(-> •rH O <-\ > >>Xo

C\J •O o L o CO o o

CO Ci-l . o c c r-l O

bO CO

t. c

hO CO 1 x: bo o C 3 CO rH O L

•O c o + 4-

CO co

f-f rH o o

x: x; o o o o

r—1

-H

CO CO o o

CM (V^

4-3 c C O

bO -H

CO CO .P

Q.

O

t.Q. 4-5 CO c C O CO

S_ •rH bO -* Cm x: O 4-> S- 4J Cl-H •rH CO O

205
CO

Q,EOOCOCc

:=>

CO +JCo

•rH CODD

r-l O

CO

4-3c

(DCO

0)

!_cx

COc

CDbOO

r-JCC x:

j_o3

Ci-i

i3

r—I o

COc

00

4-3 0)

C

C

M o

CO c jjO

SL. -a Q. C CO o

CO o CO C '-I 0) CO -C

tiO jJ O (U r—I

0) <<-i

cfl CO

O

+J c C CD O

<D bo -^

CO CO 4J 0)0,0

S_ CD Q. 4_) CO

CO

(1) -.-I -f-i fco 5t-, x: O 4-> L CD

4-> (D t>-i •^ CO O

CO

CO •oc

=3ooo

i.<D x:4Jo c CD

CD bO

hO CO O D.

J- CD

j-> r—1

CO •M ^ X! —

c

rH 5 o O > c C

CO CD

L.Ci

CD

CD

CD o CO 4J bO •M ^^^ c CT5 +-> CD Q. o

CO (D CD a CO L :- Q. •r-i x:

CO

b

40 x:

4-5

Ci-. <D r—1

CD Cm 3 CO o

o.

en.

CDbCC

CT5 Ooc

CO aco

o.soo

0) x:4Jo

CDbO

COQ.

4.^ D. CO CX DO

CD -rM w >

0)a.

(00} co

.—I o

CO o

<D

i.

CO oc3o

CX

(D

O

bO ->

O c

(D x;o

4-3 CO

<D O

\.

C\J i. CD c .—s o 0) rH bO

4J (T1 D a

r-l o CO

CO 3O o •^-i CD >

S. CD •\ L

Q) Ci bOC (D (0 CD ^ CO o ^—

o

1-1

(0

tsl o

1-H oo

(D -oOc

CO DC3O

Q.EOo

s_(D X

4-3 O

4-)CO

(D Xo

c\ X

4J3

CO

4-3 c

CO

t.CD

4J> CO

CD

CO

to J_-

CD <D c .c

CO 4-3 ^ CD

CO

S- > >>

CO (0

CD CQ C '-^

CD .C 4J

•rH 4-3 to TD -rH 3 4J o

CO >.

X) '—

rH ^ CD O CO CL 'H (U CO O 4J QCO --' ^ C CD C O > O -rH -rH O 4-3 4-> CO -rH - E CO

CO t.

O

-rH Q.

C <^C

rH

O cO

rH4^

->• CO rHo

r-H o

CD

CO3OX

CO

CO CO

4-> c c en. >> >. CX

:^ .is: .-H i-H .is: CO cfi o

to - r-H i-H CO CO .O C C -rH •• E J^

.is: i. CO rH

to 4J 4-3

toC <-

i-Hto oXoo

to o

>, •«- s:

<u •o

CO

CDco

4-3

jx:

4- c 1 o

'•-^ 1 rH

4-3 > o 4J C •T-^ L CO

CO 4-3 -o

C 3 CO >5

CNJ

C 4J

X bO

tc

I-HoE^ ' >

<1> itn (

CM X

^^J - CO

CO c c •" >,

CO js:

r-i r-1 a c CO n •rH rH

CO o toc C • ^^

"-)

B ^ c Jr-\ o

to o 4-) co

•rH

4-3 O

CO<0 »

CD c

S-. to J^

4J I-H CO CO

CO

sz

4-3

XoCO

(0 rHO

t- •o

>»

x;

CO •o

•o

>,

x;c

CO oN

>,

r-l o

rH .C co m

t.

0)

050)

CO

<Dc

>>

bO X+Xo

CM X

CO COC c iH

>1 E

:^ SI-H CO 4-)

+-> D.

CX

iH

x:a

4-3 CXCX

•rH5

c^ o

bC oc

CO x:

COc

t.a) X3 c

rH o

<t: r^ 1 4-3 CO O

rH to • r-t ;- a ^

4-3

O:. CXOc

•o to

to toc C rH

>i E

I-H CO 4-3

0}

<DC

(D

-I

4-> c

CX o

CX -> o

206
Inorganic Group Qualitative Tests

The following tables list some simple chemical tests which will indicate

the presence or absence of a given inorganic cation or anion [1]. For most of

these tests, the anion or cation must be present at a relatively high

concentration (approximate lower bound is 0.05 percent). It may therefore be

necessary to concentrate more dilute samples before successful results can be

obtained. These tests should be used in conjunction with other methods such

as the chromatographic methods or spectrometry and spectrophotometry. Since

many of these tests require the use of dangerous compounds, the strictest

rules of laboratory safety must be observed at all times. The use of fume

hood is required.

REFERENCES ;

[1 ] Barber, H.H., Taylor, T.I., Semimicro Qualitative Analysis . Harper

Brothers, New York, 1953.

207
00

00oM

•a;

CL3

00

EOOw

ErJ<Mo

CXoo

Effervescence

with

all

acids,

giving

CO2

which

renders

limewater

cloudy

Acidified

solutions

liberate

I2

from

KI

(brown)

Acidified

solutions

decolorize

KMn04

solution

Cu

or

Pb

salt

solution

gives

black

precipitate

i-iC

S^bO

CO

•HbO

•aH s

CO CO Cm

sClH 4J

Cc

4-:

r-^c

cc p

cc

ct cc

j-c

x:a

give a

yellow

precipitate

2.

HjS

gives a

dirty

yellow

deposit

ofS

J- o

00

a:•o

CD

4-> CO

4-i c

CDOCoo

Effervescence ,

liberating

CO2

(odorless )

Liberate

NO2

(brown)

Liberate

SO2

(pungent )

00

4^

CO

JD

•HJ o

CD

Dirty

yellow

precipitate,

soluble

in

hot

water

White

precipitate,

darkens

upon

heating

(slow) CO White,

soluble

in

HNO3

or

NH^OH c3

-0

CC o

CO c

•H

r-i jO3

•-\ ^

CO :r: - Q)

Q) 43

4J 3

•H rH ^ -H

3: -o

If

pure,

no

precipitate • c

•M

rH SI, X33

rH rH

CO X.

M - 4J m

+J 3 X

•H rH <M x; -H

IS -a :i:

rH

rHX

CM1 m

CL.-'

CO

CD 4J

J2l

CO 1 rg 2

en

4-> •H

4J

•H2

OJ1 m

00

CO 4J

rH

Cm

,-{ 3

00

CM1

CO a

•MCm

rH3

00 1

cc

CO 4^

CO

CQ

eg1 f

t,

CO

4-3 COEk

208
o

0)3c

4-> Coo

COH

CO

CdHo

(D CO 1 rH x: £> x: tsl •-{ 4-3 C

•n^ 4-) •rH •C fij •iH •rH « •f-i £- SZ C 4J X 3

•iH 3 o 4J 03 •M

C CM > rH •rH 5 •rH c c sx CD o 5 tM •rl CQ >. 4-> o O 4J - ^ CM 00 iH rtl 4-> 4J •H a 03 t, t H C 4-> o 4J 03 01 " S: rH s: CQ 00 O •r^ 03 O 4-:> -o O 5 X3 4J CO CM M ^-x D. 4J C -H X3 2 1 3 03 t OO

E- •.H r-\ •rH CX >,X 1 rH S- c o m O £) CX CO -H rH o 4-3 J- ^^

J

m CD 3 C •rH

O

O Cm rH CO c x:

OC < 03 ^ t- .-H O o !L. e o iD 3 00 -H bO

1—

nH tiO cu

O •-< CX 4-) i- 3 > o N

C

O

w c CO 4-3

L rH CX E •-I

C

X i- 05

u •iH CO 3 CXC 03 3 O

O 4J

O 4J t, Ou CO >> 3 a rH •M CO 5 •rH C CO 03 O 03 + 4-> O

CO 0) i.

O o OC

C 4J 4J 4-> 03 ^-^

r -o c r^ CO 4J)

N + ^ O CO •rH •rH >1 •rH rH CM 3 o •H Cm • rH + J- rH E CX L CX Cti O t^ 4-> C 4-3 iH •rH J- x: ho X s i- CM .rH 'rH CO C rH 00

0) CD 03

O o o S S 2 >-i OS CX rH

O > O S O CJ

jJ .—1 J- •rH

C CJ i^

Ct, «w CDX o s • . 03 S- Cm

L . . D:: 05 o :s < :^ ^ CM cn a M CX CO t- CM

J- o •. c »• CO o o TD CM w (D ^ TD i- X 4-5 05 3

CO iH

C

jJ CQ

03 o L 03 X3 U S- -

0) 4J CO 4J bO 3 4J S4-> C t. 3 03 •* Xi C CQ

(t

X

O 4J INC

X

t- o c -^ o o Cm

O

4-3

C CD •rH c:i.

O •H '-- o C c O > +J -H 4-> J- O >

<D

O

M 03O + -rH E t- OSO rH

O o l-l

O S) rH

O bO

O c <^-l > t- X3 3 <M > o l-H CD a Q, O -H Cn o to I-H o

>,

C rH

•rH

C j_> .- en . >> m , o C •M x: X o

H) o s rH O rH •rH 4J •rH j-x

4J 2 .O

X 3 rH

X

m 3 S,^ 3 O bO rH CO 2 c O o I-H J- < o •r-{ 2 —1 •rH C O X CO - c

bO I-H rH •rH CO 2 o s: -r-l o < CO 4J CO r-{ X - rH - S- 3 O c

••-* •M X) 3 rH 3

>> jO

O

O r-i

O Xi rH

+J 4J 3 rH " 3 03 rH 3 O

S- •H rH rH

O -O J^ rH rH CO

*r-) .C

O 2 r-^

O

C

Q S CO >H

X CC 03 >H CO •rH c d

•rH •H

C

•rH 4J

i-H 03

CD I-H 4-3 x> XD r-i J_ •t-\ CM D 3 £1 O CX

-H i-H I-H 3 •rH O o o rH rH o

03 CO CO o o

CO c

•r4 •S

<M

CO

X- O - o - O 4-3 <^ m 4J m 4J 3 X 4-3 4J

4J>

X •H 4JX •rH rH IM •rH •rH •M CNt £1 •rH N X; -rH O C x:

x: o 3: SZO 13 -O

X 3: 3 3 X 3 X

Cvl 1 OJ 1

CM1 CD OJ

m 1 J- CM

X o J o 1 J- 1 •rH o CL. J- o 1 Ci. 00 eg o S- CJ co 00 CO CQ

to CO

CD CO 4J CO 4J CO a 4J 05 05

•r-l 03 4-> -C 4-3 J- -a

S_ o 01 CX 05 03 ;-{ O •rH I-H CO <M 4J e D r-H 01 o r-f L o

r-H •rH

X x: 3 05 tU OO o a. cr H a: 1

209
CD3Ccoo

00

E-COO

h-1 2<

^^ .C c 1 L x: TD

C

i- 4J CO CD 3 c c -0 c rH C - 3

rH -p 3 r-^

C i. 3

CO •H sz -Q X3 t.

CM 3 bO 4J

CC 3 .C v^ •Q o t—1 C 3 CO -P + ^—

N c CM •rH rH •rH CM C J- CO M CM t r-H CO 4-) CO .. J- CM H o - 1—1 t CO CO CO ^ 00 00 N CN t- -P CP 4P ^ CM 00 2 M t 00 + 00 + X 1—1 i-H CO CiH 3 CO X CM H o o c:x CD I-H rH rH x: X t

J- J- ^-^ ^^ i. 3 t- CO -o

J o + O + 4J 4->

X -P bO CO x: < 00 c oo CO CM CM 3 CO > CX - 4P jp 2 M N i_ O CM J_ rH CO 000 •a •H -o CO J- CO •H O X -M X O a. 3 cn c 00^- bO cx t. 3 CO M -p -u> 4_) H r-H + X t. ^ bO •r-\ <X1 -P

a. + CO CO + CO > x: X2 CM bO

C CO -a tp CO c T3 '-- 00 3 i. s ^ J- C CO " -H "O -rH 3 [JH ^ 3 to

CM

O CM i. cx <a .—1 rH •H JP TD s bO e TD

O 1^ -—i O CM OS CO 00

X J- > CLJ -rH rH CO -H JP 0 c c L e C .—1 o C M CO JP CM (M 4P •rH 000 •H -a •H CD t- 3 2 O O s o o 00 -o X 00 hO IJH X3 00 x: =£ l—^ < t. 3 CX cp, ^ Cvj T- C\J m ^ cm' ^ <AJ ^ CM

J- J- o •> - c

oo o o i- CO CO

CN a; CO 0 x: CM X

CO

jj> CM CO 1—1

bO CM •rH 3

rH

X

a i. i.

C .-H x:

CD JJ rH -p - H 00 JP -p

4-J c o ^ C 1—1 > CO •i-i CO CD X -P X - JP 3

:_ o c o CtH JP -^ •rH Jj C CU CD C CO c ca

a c O > bO o > J- O M c O rH S- i. e o O D o •Q S- ;- c c^^ > CX Ch > •a •H bO CO o M CD ^-^ M rJ ^ -O 3 o

CD jJ >,

CO i-H

C JJ 4_> .-. en rH .,-1 Cx. CD -rH H J-X

rHO r-H

X fn X3 CD CO 2 C o 3 J- fH 2 ,-1 D, - c

bO

O " X: -rH < CO S_ O2 » - X X 4J o x:

x:

X -H

ellowis olublensolubl 3 2 3 >H CO -H

--1 - o

CO oa 1 CM 1 1 m 1 .—1 X I-H

m

O 1

CM CJ> 2

CO

M CO

CO CO •a CO JP

•.H 4-) (0 jp

t- T3 CO S- CD O •H JP :_

r-H -a ^ jp

x: x: ^

c_) h- cl c_ 2

210
CO

E-COw

E-W

CD CD JJ J-3 CO CO CD 43 4-5 JJ

X •^ -r-l CO o en. D. 4-J

J- •r-l -rH .rH

C

^-^ X.

OO D, [SI

CM s CD -^ + S- t. O t,

CM x: Q. Q. CD

O

bO 4-3 J-. X •f-\ <D C Q. 3

"-' 3 bO CD C_) C CD 1—1

COcCO S- 4J CO C bO —1 CD

X CD o 1 x: 4J>

IX. ^ ) >> 3 CO => L 1 CD 1 S

CJ cfl cc o O bO J- 00 w J. 1 O .-) s:

CD -P

•.-1 x:

O 1 CO CO N l-H CM e

b^; i:.^

X •< ^ CM (>~) ^3-

,_^

CO3O

CD

4-J bO CO CD X 4J> 43 H CO 4J

•H •t Q. 4-) CO bO o •rH tH 4-> < CM X O D. -rH (D -H CX CD

•^

L

O -H 4-J JO Jj CX CD O CO a. O X t, CD 4-> 1 ^—V

x: o C Q. t. -H 1 + J- 3 CX CX

^—

bO

C

X

O 3 —1

1—i < "H 2 £-030 CJ \ ,/ JD ,-H O CD X CD C M ,H Soc: M -H - iH CX

CD DO JO

O >>

-P > D CD >. ^ D J .-1 i-H t- 4-J 1 O M 1—1 O £>

•.-1 CO CO 3 1 bO JM o C i-H -H O

J- •^

O i3

O -H a, 1 >. CO t. 1 X 1 JD

CD

O 1 <N CO

CM

M CO CM CD -P ^ ^ 2 X

-P •rH CO x: • • . . 4-i s r- CM oo .=r

•iHD.

•l-i O

CD

S-CX

s_

l-H CD 4-5 CO a cti 4-> 43 D 3 •rH CO O CX 4-:> 4-5 43

t- -P ••H CO •'-1 CO o O O 43 CX 43

^-N x: •H •rH •rH N t, CX CJ CX + c CX -rH .rH JD •I-) O t. O

Cu 3 CX

CD rH ,-H CX CX

Q XS iH 43 < D 3 •rH ^ W iH >> o x: o J o

CO

CD -P•H

x:

13 1 rH 3 CO 1 rH 1 ,-H

J- 1 X3 O >> J- 1 S- 1 O 1 O 1 CO CO

CM I-H CM CM a:: i^ -x. tc

,— CM oo .=r 1e

t.

•rH >, CO

<4-H J- 43 C O CO O 43 O CO 9-

m+

•H .^

CD o

CO 3O

X CQ I-H

E-< 1 iH 43 3 c .M c S 3 C >> x: CO CO O 3 1 3

I-H JO 1 1 •. CQ CQ J- J- 1 X3 X5 O X

CO 11 S- o o J-

*k HH CMX

CO i^ •i^ 2 <

•« ,

CM CV-) r-\ CQ

p^ bO X

43 » CO 3 rH 43

CJ)11

X33

I-H CX

•H

•—s O o

.-H CO o ^—V

L

X CM ••

C CX + M

bO .X 43 43 X O CO i- 43 3 s.^ CO 43 O •H

>-\ rH •rH x:

•rH HH CQ CX 3 3 o hH 1 •H o 3 O >. Cm >-l O CO > O CC I-H t- CO ZD r-H a CO 43 O CO CO x: O CC >H O S 1 c CxJ o CO 1 s t- X bO X.

CO 1 rH

O 1 CO JL M C E X

CX i^: -H < 2 c , , , •rH -— CM on

CO

CN X

CO >, CO X3 oX

43

CO 43

C

•rH ,-

—

•rH CX CN •rH + O 3 IJH rH O X)

C- t- 3

CU hH

O I-H O

I-H jic:

C CO

H o N

I-H CC CO •k [d .-H C

CX CU CQ E O 3 3 Cu CO I-H o O I-H CO X3 L o Cm 43 1 o Co

•H 1 CO X O O

CX J- X

C3 2

CM OO 1s

t- .M >> CO Cm £- 43 C O CO O 4J O CO ^

211
oC

•H

4-> Coo

00H

00O

h-i <

E-

_JN + C M c

OO '^ — X 3 nH o o XI M pH 3 C O s I-H r-H tSl D s o -o < >H CQ C

^'-^ E-i o ;- TD CO

0) ^ OO -P CO 3c P '— CO r-H

•i-H y—

X

•rH JO -P 03 -P N CX K D. -rH CO c + •rH g £ J- o c O --^ -o 3 CO O o GO 1 3 C —

i- 3 >> 1 OS

C CX o ho 3: c 2 c 00 5 M C o c

00 o O CO >-i

O J- COO o t. t^ CX a: 4-> c ^ 2: CQ 'X. >5 00 2 OO 03 £1 s

CO < • • • . E-H ^ C\J (Y-l ^ •« CO

CO <^

•rH CQ

bO c X iH ^

:3 rH o1 X)3 1 ^-^ rH 3

^-^ fn

OO '^

M + CO +J o X) C CO x 00 O

v^ PC/0 4-3 <D 03 PJ 4-> -P >H bO 40 ^ -H x;

:3 s C •pH J- CO CO rH o CO CX g o t. •H s t, •rH g CX 03 o M O O --- S

E-^ -o

Cn 2 L 3 CO o < CX o Js: rH O >

CD 00 rH 03 •rH O t^ rH O C 3: >. CO ^

CO • • • CD ..— eg OO

iL. CXc

•H

CO

(N DH

•rH >>

x:i rH

CD XI

-p ,—

X 3

03

m rH 3

jJ + O CJ '-

•H CO CO 4^ U < C CO •M —

O o 3 4-3 CO 4-> O o 03 IM 4-> Sh I-H .—1 4J) ^ •M x:

a. 2 <-\ ••-f ^ CO CO —

M CX X O i. 00 >^ •rH S CX 03

t-( cc 0-^0 5: M <c -o

S^ 3 CO Q. CX O ^ D rH O > O OO rH 03 •H

t. t^ rH

O o ix; >, CQ ^ ^ (^J fvi 1S^

•rH >> CO tM i- 4J c o CO O 4-> O oJ E-i + X + o c

03 o t, 2

4-3 o C 03 4-> •rH L

^^

O 3 -a

m rH rH + rH O .O

O

N

XI

O 3 X t, 3 CX -o

v_^

M 73) 4-3 O s- c

HH CO iO 1 hH c 1 1 o

I-H r^ 1 rH CO

«> cj) 03 2 •> 03 '-- X c ^—. o c •o 2 o IX 3 1 o -o •H I-H O 1 ^ c .c v^ !U 2 03 4-3 XI O tL, 1 OO J- C >>

ClH •o Ui i>i Nl XI

•• cc . . . S- ,

c\j CV1 o«

r-^ <11

4-3 03

4-> iH X •rH CJ o CX

J- 03 •H 4-3 X 2 o 0! s 4-3 c t. •H

Cm ^—

X

•H CX CX

O

m •rH + x: o

s« •-\ CO

O CJ> XI •rH 1- c c s 3 C CX

rH

CO T. o c u

ZD CO i- bO

L >-t bO ) CX s: •s 1 S- 1 o C 1 bO -o c DC m 1 03 •H X O 1 CJ S- CJl J- XI

3:; hO eg

O o 1 ^-v D.

X

J >. JX 03

•X. ^ tc

N

L 2 S- 2 03 O

CLD 2 CQ >>

XI ^ CM CY^

4-> 03 4J

n

•rH HH

CX

O •rH 03 o 2 CO3

t.C

O 4-3 D- •rH C

•rH 034->

4-> r-t I-H •-\ 03 CX

I-H X> r-\ r^ M .-^ 3 O m rH bO 3

CX + O S- rH 3 rH CO CX XI o < 4-3 1 S-. •_• •• •H 1 c:3 CO x: 4-) 40 s 3 3 •H CO :3 O 1 x; 2 c 1 4J 3 4-3 HH •rH ro 03 1 s 4J O 4-3 1 N

rs 03

O •H J- -—

J rH (N CX o " < ,—.

•rH CU

O

hO -t X

O

X 2

(N --^ 2 S- 03 O

4J—

CX 2 CLJ

•rH x; . . . IS "" CM m 1SL

•rH >> CO <M t. 4J c O CO o 4J o 03 E-"

212
o

CDCcoo

CO00o

Cd o - c m

CD JN

O ^-^ CD O •H 2 S- w CD o rH a X •H + rH 1 o •H (0

Q) X3 1 o X >, fc Z5 J- O X3 c

v_^ .—1 r-H ^—

o •H o o 2 c .^ >>'n M CO X o 1 on rH + >>

t-1 1 r-f cH » c 2 -O Ci-i 3 s ^ -rH Cx. 3 o to o o O <MrH 00 CO o rH

cr CO :^ X3 i^ ^ cd 4-> CO M .—

^_^ pa • CM on

CO3 bO O c

•H> O

<u Q) rH S- Du

CM X3 o " CO £1

<. + D CO 1 •rH fH r-H 3 JJ> -rH a

2: 2 o rH CO -O CO CO v^^ CO "-H X3 JJ CO

o. c o 1 •H >, £) o J •rH X 1 D, rH o o W X -H ^ X X

iiC - c o o o CO

•s CJ ^ —1 J- •rH

L c 1—

o X t- 3 c O s 2 CO 2 cx CT 'l-i CQ • CQ . . c ,— OvJ Nl1 1 1 .—

> 3 ^—

N CD l-H rH

rH + rH .—1 o CO X5 O o £1 O C > CO CO 1 .* o 3 X CO 1 X N_^ r-i 4-) -H o o S O CD tn CO TD X CO M CO -P hO jJ

Q-i l-H

C

D 1 -H >l XD o •.-1 rH 1 D. r-l c H •rH X -H ^ •H X

CO

J - -a o o o CO o < ^ J- -H bO t. c CQ o c X t- 3 c O O (0 -H 2 Ci CT •rH CQ m CJ) H

CD CQ . . t- ,

CM

D.C

••-{ CM .s bOc

00 + •H 1 c\ c Nl S

^-^ s: l-H rH CO J N..^ n - -o 1 E D rH 43 -rH 1 2 1—

rH

O •H 4_)

X •a HH O X ^ CO O CO >. CO 5 -P c

X3w CD 1 •H >. 3 X3 00 - J-) 1 O, rH o -p

0)

w x:

D

X -H TD !L

X CO JJ 2 CO rH O O -H JD CO >,

CO < •H -H J- cx ^ s: -P o ^ -o X i- CO o o -p

-.H 2 c 2 cx t. -p en cx < H

iH S Du • • o ,

CM

L

Q- rH -p c o CO > •H 4- o 1 -p M ^-^ X c 1 -H N CD 2 CM cx

Ci + r-H 4-> CO

O -H 3 C £3 rH •H C IN m o O ISI 3 O x: -rH o u X

tn •s_^ rH

X 3 ^ cx CM

C

a o 1 X o cx o CO CD 1 rH a> c J- 2 -p X .Q CJ l-{ X M « 3 O 3 X 2 4J M CD rH -J- r-i 00 •H 4J -rH X O i. CM Cm x:

•rH -O 2 CO

O

X

O 3 ^

:s ^ CvJ 1E

t.

•rH >. CO

<4-l t, 4-> C O CO O 4J O CO H

rH

,—{ iD O 3 X r-H O

O

COC

4->

C 1 ,—

3 •H 1 CM l-H r^ + •M O CO X3 CM o JJ L — C •M O

•H x:N

s: 3 :^

Xi 1 1—

rH 1 TD E o JD J- eg C 4-i CO J 3 O O CO CO rH < ,—\ CM m 4-5 <M o O OX t^ -rH CO N CM O CX

CO •^ j-x

X

a c o X CM CD CO -P 2 C O S. t.

•^ •H •v-- -M

X cx o

t. x; 00 5 .— CM CO

co" CQ11

<-\ o c

•H

J rH X O 2 X rH

X3 Cm 3 O O -P r-H C

^—s 3 O 1 CM rH CO 1 o + •M c^ c i- T3I O

00 CM CO c 4J Ss, s

•H HOE x: CM CO cx :3 3 ;^ H M rH 1 c^ c H JD 1 -o

•rH 2 3 J- c 4J -a O rH O CO CO m cc O CM -Pi. o E- CO O CM N •H o 00 « o o CX 4-5

CN •v ^-v COm -M ^

^—,

J'

XX

O bO

J- -p

X CM CM CD •M

X •MgOO iL. i. 2 x:

IS

v_^

X

X cx CQ

>. T— CM on

JD

4-> CO

4-> c

•H •H a 3

•r^ rH o o O rH rH X Xn r-i L 3 0'--

Cu rH >i

C

^^^ +J

O 1 -H 3 CO 1 CO > ,^~N rH r- 4j

CMM

O 0- CX + •a CM (P 3 CO 4-5 L O O

J- CQ •Hc HOC x: CM 3 o 3 i^ —

S 1 r^ ,-i 1 -0

HH £) JC 4J> E

Cd 3 O CO cO CO < rH CM 4-> rH

CQ o O CM CM •M Cm

CO NO o cx

,—^ mm .M

C

•s j-x

X o X CM CM CD

4-> 2 O

O t. S- •M ^^ :c ":!: cxiD

x:

:3

,— CM

m 1e

t- • M >> CO <M L 4P C O CO O 4J O CO H

213
0)

73C

•rH

4-5 coo

CO

E-Ww2OoJHW

X ^—N C O + o CO ^ 2 X CO 2 CO x:

v>^ bO 4-5

J- ^

PC s m 3 ^ ra X

C

M 2 hC o •* 2 C •f-\ m O CO •rH 4^ s 2 E 3 s > L rH

•» < •.H CO

O

lie;

O 3 CO

w

•rH fH s

CO CO ^ rH M d-i

<£. ,_^ 3

<D + O

x: CO .H 11 2 rH S

•o 1=3 JJ M C

4J

Q CD

(0

O 4-5 4J CO CO

.-t •iH D. CO •H £- O <U

<u Pu

f-D.

>>

i-H

•r-( o

nJ

CD •—

t, +

-P •.^.^ cO o rH C s Cm

^•~^

M

O

M 00 CO

I-H CO r-\ > •a; rH a O 3 CL OUo ^oX c o 4J O c 4J CO •rH

•rH 3 4J 4-> ^-^ rH •rH 3

J- (N •rH D. rH o + o •rH O

Dl, bO

O CO DC s C N -^.^ •rH S- T-^ CO Q, O 2 M s J S n rH X

>i 1 M X3 4J 2

X3 1 CO 3 •rH ^ rH x: c

Q)

M 2 O 3 -rH 4^ O o CO 1 OS ^ < 1 4J X. 2 «• " •-\ •^ 2 O X3 Q, 4-J O 3

•rH <i-l •rH

N rH

O

O £1 CO

O

13 2 CO

L 0) D- O

V--

C

Q)

M CO > (D

t. D. Dh DO

t- a

214


Vlil. Miscellaneous Tables

217

Xo

Q-H 1o e

KOH

(solid)

NaOH

(solid) o

a. >C >

CDc >CDc

CD>c m2 >C

CDC >c

CM oO

a •o •o 0) X3

O

J- o

00

CO 2O

J- o

00

CO Ooo

00

CO

m ooCN 1

COO

CO 2

Family

i-H o

x:oo<

CO

0) -a

>>

sz

<u o< aT

•1-rs1Dg

C/aci

e:

J

CO

a;

•iH r—1

CO x:

r—>> < 1o

.—1

>> c X T O T

X3C S- C CO

CJ>

HJ

CO

ICO w c

bOOo

CO x:

4-3 bn •^ c 3

•.H 4J CO

c; -P

CO o

(D CO

S^ CD -u 4-5 S- '— 3 c 3 :2 o CD O y^^ m > .—1

>> cr

bO rH CO -p ^^ C O •«-H •fH CO -p L CO

JJ>

D

D CD ,—1

C) £i Q,

C

CO CO CO E -r-f CO o «« CD -H S

CL >,X CO c L -P CD C

r-{ 3 •rH r-H

O o

D. C-) a. S CY1 -P CO s E C 1—1

Ci o O JCD 1—1

ro o OO

•—{ crt C) ^^ <4_, r—1

CO

0) -tJ sz s (D >i O CO bO t. S -H. X QJ •rH o —1 C

DJ CQ

X U-.

JO

>HM

tii CO X5 o o CD Q-i ooac

CO

t- 4^

COO2C

CO > . , .,_ Q

LTi CJ^ •k »—

•. 4^ C CO O •^

•a E c CD o x: J o

•* o • •iH o C o CObO

oa

O

CD

C

CD r-t J_ O CO 4J

•.

C

CO <D c E

CO •iH e i- bC CD C CX • • o X

00

J

u

wo a 2 . (D M >. to CC J- •rH td 4^ 4-> tu CO •r-4 tJ •.-1 C

CC E :3

CD x: > o

[li o • •rH 3 c

CO ws bO c

i^ CD O 3

1—1 O

CO s o

•rH • M

4-> . o <

CO • S- o

cu .

Q-H <4-l O

CD J^ 3 oo (D £1 -a

4-) c X CO

CD > H

a:

•t • a^ • cc ^ 1—1• « as =3: (D I-

•« 4->

O

rH CO >H

0) 3

hO CD 3 O L CD > m 2

219
-pco

o

T33

C

nJbo

Sh O

s-o

m

4-5 c

0)bO <

hOC

•H

>>

Sh Q

C

O

e

E

O

o

CD>

CDc

o

o

o

o

o

1-o

o

ex

. .

• •

• •

COco o

£l —

1

i- 4-> 03 rti O E o o

i, £, -O cti

COc -o O (U i3 -P O 3

O -P L CO a CO X

- -a

CO CD C -P O CO

C. 3

n3 -P O cfl O CO

a, c ^^

X

COo

CD

CO

CD 1—

1

•rH 4J2

c

CDbOO

o

CO

s:

4-> bD H

C 5

•H

4-> CO O 4J

CO O

CD CO

iU CD 4J 4-) tn -^ 3 c > :2

O 0) O ^-^ m > rH >> CC hO M CO 4J --^ C o •H

•M CO •p t- CO 4J 3 3 CD rH CD X3 CX C

Cfl CO CO B -H

CO o •* CD •H S

ex >. X CO C t. •P CD C

•H 3 H rH O o

cx C) CX g m 4-> (TJ S g

C iH D. o O sCD -H CO o o o

rH Cfl CJ ^ Cw

iH CO CD •P SZ f= CD >> O CO bO L E rH X CD •H O •H C

w CQ X U. J O >-l w^ (fl XJ a •a CD Cm

220
Flammability Hazards of Common Liquids

The following table lists relevant data regarding the flammability of

common organic liquids [1,2].

REFERENCES;

[1 ] Turner, C. F. , McCreery, J. W., The Chemistry of Fire and Hazardous

Materials , Allyn and Bacon, Boston, 1981.

[2] E.I. du Pont de Nemours & Co., Inc., Data Safety Sheet, Wilmington,

Delaware, 1985.

AutoBoiling Flash ignition How to

Specific point point point extinguish

Solvent Formula gravity (°C) (°C) (°C) flames

acetaldehyde CH3CHO 0.8 21 -38 185 a.bsC

acetone (CH3)2C0 0.8 57 -18 538 a,b

acetonitrile CHjC^N 0.79 82 6 a,c,d

acetylacetone CH3COCH2COCH3 1 .0 139 41 — a,b,c

acrolein CH2=CHCH0 0.8 53 -26 277 a,b,c

acrylonitrile CH2=CH-CHC=N 0.81 77 481 a,c,d

allylamine CH2=CHCH2NH2 0.8 53 -29 374 a,b

amylmercaptan CH3(CH2)^SH 0.8 127 18 a,b

aniline CeH5NH2 1 .0 184 70 768 a,b,c

use masks

anisole CeH50CH3 1 .0 15^1 52 a,b,c

benzaldehyde CgHsCHO 1 .1 179 65 192 a,b,c

benzene CeHs 0.88 79 -11 563 a,b,c

bromine Br2 3.0 59 — CO2 (never

H2O)

butyl alcohol C^HgOH 0.8 117 29 366 a,b,c

a - alcohol foam, b - carbon dioxide,

c - dry chemical, d - water

221
Flammability Hazards of Common Liquids (cont.)

AutoBoiling Flash ignition How to

Specific point point point extinguish

Solvent Formula gravity (°C) (°C) (°C) flames

t-butylperacetate CH3C0(02)C(CH3)3 <27 b,c

t -butyl per ben zo- CsH5C0(02)C(CH3)3 >1 .0 112 88 8 a,b,c

ate

butyraldehyde CH3(CH2)2CH0 0.8 76 7 230 a,b,c

carbon disulfide CS2 1.3 47 -30 100 b,d, use masks

crotonaldehyde CH3CH=CHCH0 0.9 10^4 13 232 a,b,c

cumene hydro- 1 .0 153 175 a,b,c

peroxide

cyclohexanone 0° 0.9 156 143 420 a,b,c

diacetyl (CH3C0)2 1 .0 88 27 a,b,c

diethanolamine (H0CH2CH2)2NH 1 .1 269 152 662 b ,c

diethylene glycol CH3(CH20CH2)3CH3 0.9 189 83 a, halons

diethylether

diethylether (C2H5)20 0.7 34 -45 180 a,b,

halons

diethylketone (C2HJ2CO 0.8 101 13 452 a,b,c

dimethyl sulfate (CH3)2S0^ 1.3 188 83 188 a,b,c,d

dimethyl sulfide (CH3)2S 0.8 37 -18 206 b,c

1 ,4-dioxane < >

1 .0 101 2 180 a,b,c

ethanol C2H50H 0.8 78 13 423 a,b,c

ethylacetone CH3COCH2CH2CH3 0.8 102 7 504 a,b,c

(2-pentanone

)

ethylamine C2H3NH2 0.7 31 -18 384 a,b,c

a - alcohol foam, b - carbon dioxide,

c - dry chemical, d - water

222
Flammability Hazards of Common Liquids (cont.)

AutoBoiling Flash ignition How to

Specific point point point extinguis h

Solvent Formula gravity (°C) (°C) (°C) flames

ethylenediamine H2NCH2CH2NH2 0.9 117 34 385 a,b,c

ethyleneglycol HOCH2CH2OH 1 .1 198 1 1 1 413 a,b,c,d

formaldehyde HCHO 1 .0 99 88 427 a,b,G

furfural r>Ho 1 .2 162 60 316 a,b,c,d

furfuryl alcohol ^3^H20H 1 .1 171 75 491 a,b,c

gasoline C7H16 (isomers) <1 .0 38-218 -43 257 a,b,c

hexylamine C6H13NH2 0.8 132 29 a,b

isopropanol (CH3)2CH0H 0.8 82 12 399 b,c

isopropyl ether ((CH3)2CH)20 0.7 68 -28 443 a,b

kerosene CH^ series

mixture

<1 .0 149-316 38-71 229 a,b,c

methanol CH3OH 0.8 65 1 1 464 a,b

methylamine (aq) CH3NH2 0.7 31 -18 384 a,b,c

methylaniline CH3NHC6H5 0.8 151 49 533 a,b

methylethyl CHaCOCHjCHa 0.8 79 -6 516 a,b,c

ketone

methylethyl C.H3O2 63 a,b

ketone peroxide

naphtha (mixture) 0.8-0.9 149-216 38-46 277-496 a,b,c

paraldehyde

CH3

1 .0 124 36 238 a,b,c

a - alcohol foam, b - carbon dioxide,

c - dry chemical, d - water

223
Flammability Hazards of Common Liquids (cont.)

AutoBoiling Flash ignition How to

Specific point point point extinguish

Solvent Formula gravity (°C) (°C) (°C) flames

2-pentanone See Ethylacetone

3-pentene nitrile CH3CH=CHCH2C=N 0.83 U.5 40 b,c,d

peracetic acid CH3CCOOH 1 .2 105 40 a,b,c

petroleum ether <0.7 38-79 <0 288 a.b.c

propionaldehyde CH3CH2CHO 0.8 49 8 207 a,b, c

propylamine . CH3CH2CH2NH2 0.7 49 -37 318 a,b,c

propy].ene glycol CH3CHOHCH2OH 1 .0 188 99 421 a,b

sulfur chloride S,C1, 1 .7 138 118 234 b,c

sulfur yl chloride SOCI2 1 .7 69 — a,b,c

tetrahydrofuran C/ 0.9 60 -17 321 a,b,c

th i on yl chloride SOCI2 1 .6 79

toluene CSH5CH3 0.87 111 4 510 a,b,c

triethanolamine (H0CH2CH2)3N 1 .1 360 179 b,c,d

triethylamine (C2H5)3N 0.7 89 7 a,b,c

xylene (o-) CeHjCH3)2 0.88 144 32 463 a,b,c

xylene (m-) C.E.iCE,)^ 0.86 139 29 527 a,b,c

xylene (p-) CeH,(CH3)2 0.86 138 39 529 a,b,c

a - alcohol foam, b - carbon dioxide,

c - dry chemical, d - water

224
T3 CO <D >1

CO

O j_ o D c D o •• 1 o •a •K X3 CO CO CO X3 CO 1 >> bO CO - rH L o CO c CD o o E j- E U cu eo CO o CO 4->

CO •a o •H hO •H X CO -P

rH c o o O o X} CO CO •nHCO co E o o E L •r-\ L r—1

CO •rH •*

L .P 3 Q, ••-1 P> 3 •K o

4-5

X c ^ x: o -P ^ CO CO u CO o 4-> CO CO o cx

s- \ x; o •rH Q. •r~^ o E

<D c o x: s E o x: •H D. o CO •rH E CO B •rH s bO ^

<u -P - C " - - Ja; 4-> •rH -p 4-> •rH -P -P -p jj o c CO CO X CO CO CO CO o s bO •rH x: o l-H x: ,c E x: x: x: x: CO o

SC

CO o 3 •rH o O 4-> o a •-{ •• :. c jJ 1 o 1 1 1 1 1 1 CO bO c 1 CM 1 1 1 1 1 1 N •H •-H •3- CO CO O o o s: -P Du

•r^ 3

i-i <^H < O o

CO CJ> CO o

CO <D iT •^ D iH CO •P 1 vr> I 1 1 I o 1 o -U (0 c 1 CT^ 1 1 1 1 t^ 1 o L l-H r-t ,

J- CD U-,O

CO D- Cu

SI

O

CT3 X D.

bO

Oo

<i-i jJ c - O C •rH •P

m o o 1 o o 1 1 CO ^ C U3 cv^ o- 1 CO 1 1 CO 4-> •rH •rH m CM ,

CM

(D t. o O CM

•^

O pa CU jJ

J- s

•rH

O

Q. bO o O CD c - o CM

O 1 CM CT^ o o

S. S- •rH Jj cr, LPl ^ 1 C3^ KD

Oh os

4->

f—1

CD

C

•rH o

^D

a •o

O

y

—V

Cl-. •rH >>o O Cm J-> o

•HH o CM PO I>- 1 ^ t- ^- 1 CD O > CO • • 1 1 E 1—1

CO ^ ,— ,— CM CM ,_ ,—

O C\J CX t, -P

CO

CO 1 1

(y^

O CO

eg 4J CM i:

(0 >.

O o c-^ •M t. CM o ^—-

rH o CO ^-^ o cn cn ^ 4J fH O o rH cn CM o

CD CO

D CJ) J- .—1.—1 O

OO :—{ 1-H S- E cn ,—V < o M 2 2 u £) o L X (M =i: :3- ^ =r

4J

CO Xi

O o XM 2 X 2 CO .—1

t, o < g 2 ^

fciO c iH •H CO JJ •D s o CO •H P> -P o •rH o L £- CO •H

1—1

Jj) •rHOO

L J- 1—1

>>

X .—1

rH -P -P -p o <-l o o x: x: •H *f-\ CO

Cl-i COc

•rH O o o c c O

(D CO Q. CO E e E E E E -H

JC :3 3 3 3 3 3 x: H (D iH o c C C •H •H •H o ^ >, ^r-i •rH •rH •H c c C S-

•t-> (D 4J D, E E E o o O E ••H 3 3 3 s E D. c CO O •o 1—1

rH rH E E E

rH 2 CO CO CO CO CO CO CO CO

CX5

CTi CO

4-> COO

CDCoo

CO PQ

T3C

COC

CO CT^ rH , CO •H •V

SL, C- -P CO

CO 5 s CO iH

CO3 Q o

•o •« J- C • • CO o

CA) ISl •p W CO bO C) X C 2 •H M TD E

a:

C .H

td CO •H

[xj :3 CJ

cc S_ - •H p

Ijh Cm x: o CO

>, >> L -p

Jj

CO Cm

•H CO E CO

x: - o oc

x: IH H

CO . O

:3 o

-D oa

COc •• CO o >> £^ n t. 3

5-

O

CO E o L o O 2 L O o T.

>5 •a

CO x^ - iH t. • 4-) CO O a u, c O ^ • o

•H jj o Du E CO •a CO c c • 3

x: CO CO •H i. o O CO CO t-o c • >i O CMO -p H S- IH L CMO C\ x: 3 • -O X O X 3 o Em UJ

CO X3

O TD <M

225
m

>i Q)

L

O

L CD

C 3 1 o > CD

0) -o CO X3 CO CO CO CO 1 ^ Q-H CD CO CO •> bo a> ^ CO C ,Q

s- o "v—

0) o o S t- W (X -d

•V 1 H

CO E O

t.

O CO o CD o

rH

N •« CO c c •r-{ s: M •o o CO CO •o jj CO SL •rH

•r-{ hO J- •H •H

HH o

ra

L CD

X s L CO cC CO o g O N o c CD L

.—1 m •rH o -p -P

C • ex -H hO TD bO •<-i o CO H bO tsl X c i_ C rH C 4J CO E £- •H

td n3 CD

O

X

O o -P • O o \ x: JJ tn o su •rH c CD o c •rH c o CO -U 4-) S-i o rH c •H X O CD 5 CO «» CO Ci-l o £> o o

-H S CO COH o "

4J •K •• o •^ o •• •K -P t, tn tn •« •rH •4J Jj 'r-i J-> rH 4J -p 4-:> Jj CO •S, CD P CD CD -p c CO CO o CO O CO CO CO CO 3 bO P> CO 4-) p> CO

faO CD CD CO CD CO CD CD CD CD JD rH CO CD CO CO CD 1—(

x: £ i:; .C x: sz x: x: 3 s: 5 3 s: co

•-H

O 4J O

•HC 4J 1 1 1 1 1 1 1 VO 1 1 1 1 o M c; 1 1 1 1 1 1 1 vD 1 1 1 1 ^ •H -H ^=r CM o o

-P CU 3

<t: oo

x: -

CO JJ 1 1 1 1 1 1 1 ^ 1 1 1 1 1 cti c 1 1 1 1 1 1 1 ^ 1 1 1 I 1 rH -H

tL.

O

(Xo bO o C

•H 4J) LO 1 1 o o LO 1 Xi o en LO [>- XI -H C >- 1 1 en o v£> 1 3 t>- CO CY~1 o 3

•rH -rH cn LTi Ln I>- CO ^D <— cn >— CO O O ^— r

T T ^

m exo

bO o C " o 1 1 o o ,— o [>- CJ^ O-l o^ ,— o H 4J en 1 1 LPi c» C\J CD I^- C\J ^ 1^ LO o

JJ c vD CO (?u cn -a ,

fT ^ ^

r—1 -H

CD

O S (X o ~

•rH >5

O

d-i 4J o c^ OO LOl

•rH •rH

O [>- ^ ,

^ c» V£) 1 o CJ^

O LO t- C\J

O > (N • * • • • 1 • • • • • • CD (fl UD ^3- =T m ,

OO ,

r— -^ o ^CvJ

aL +J OO o CO • o

CO c? o

r—1 m in o ^£) D X3 CJO OO CO CD -a ^^ O ,

CO c<j •H bO 4- E 00 X3 X) CD CD o <-{ CM X O M J S ex

t. CTD 00 o X o o CO ;q- T

IX o o

•o

CD CD

CD 4-> tn

CD

a •H

-D •r-i t. •«

•f-i Cm o CO Cm i-H E rH E 3

>> >. 1—1>,

D Z3 •C 3 J- c C D c CO rH E s o L E •rH O o O CO o CO e 1-H 3 3 o o E CD 3 CO x; e B •rH e -P 3 rH •H H Q. s: 3 C H CD ex

<D •rH '7-{ t. •rH

C rH >, E o >, ex

H -H .c c CO s JJ 4-> -P -P CD t. J- TD rH s: E CO -o p> bO o

CO

C c c P. CO CD CO CO CO CD

O

H CO x: 2 CO CO CO £1 £> O o o O -H iH E ex

COco

.Q

tn

COooL

-a

>>

CO .c H L

CO

Oa o Cm CD

•rH -p s CO a CO

fl) c c

x: CO CO •H o CO CO o

>, o CMO 4J iH

t. C\JO C\ CD x;

•oXOX 3 o m X3 O TD CD Cm

226
CO

OJ >! c o O 3 •^ c -a o X3

<D <D X3 •s 1 X3 X3 CO CO X3 X3 *k bO o CO 1 CO L Q)

(D

O S S- Cd Cu

.cJj CO CO «> >, •o •H o o CO

1-

C 3 •M •H CD c •o CO c c E o -P CO CO CO

•.-1 " J.

O 4-> CO bO faO rH

CO CO -P 3 CO o S- t. t- Cm O E t. CO Cm -P CO 0) o o

iH to (D (D rH c ex Nl *s O. •-1 SI x; CO 3 CO o E •H .c jC CO X c •rH (D o CO 3 o •rH a -p pi CD W CO -o L » •rH O •H •rH •rH O \ x: •rH CD t. O *• L •• CO • X 5 3 CO c o X x: •rH CO rH o c o c CD o Cm O CD o D. CO CO x: o H o t. P> 4J t. CO

•-4 S CO •> o a. •H c •H 3 «• o O 3 ^

+J *k

O -P tn o CO -p CO -p -P c CO CO CO JU •H -p E CO CD S- o o bO o CO CD 4-> p> CO c CO 4-> •rH JJ CO x: •H S-. •H •M P> c C p> a

bO CD CO

O CO x: Q. i- o t- o CO o O

O CO

M x; E 3 o Cm Cm E 5 o O x: co

•rH

O

4->

O

•H •- C 4J o 1 I^- 1 C7^ C7^ 1 1 1 I CM bO c CV-1 1 t» 1 cr> O^ 1 1 1 1 <o

•H -.H CM C3> CTN ^ o o

4J CI- 3

<t;

CJ> -P o C

£: - CD CO -P fH 1 CM ) 1 1 1 1 1 1 1 CO c ^ 1 =r 1 1 1 1 1 1 1 1 1—1 -r-t s

tu

O CO CuO

bO o C -

•^^ 4J C!> JD ^r o o o o 1 CJ> CO I M C t^- 3 ,

CD o CD C3^ 1 t>-

X 1 •i-H -H C\J CO LO -a ^3- a CO cn OO o o

CQ CL.

y—^

O o

bO o C - ^ t^ ^JD CO ^ CX3 OD o t- ,— o •-1 -P •=r ^ D- vO CY-) c» C^ o o D^ •-^ -P C T CvJ ro cn OO CO cn CO LPl rH -.H CM

0) o CM S CL, o ^ ^

•rH >,

O

Cm jJ o CM C^ C^ t-

•M -rH

O OO I^

O 0"1 ,

<3^ C^ C7^ cn ,

1 O > C\J • • • • • • • • • 1 CD CO x^^ ,

^ CM CM CM ,

o o CM CvJ CX J. -P

COO CO

CO 2

CO

m cn <-\ in in O m (M m N o 3 J- 1—

OO r—

o o CO x; o O OO S D, O N CJ) 2 2 2 CO 2 2 f^ L a. Du ^ t»i t^i; 2 CO CO X O 2 2 CO b-, o

CD CD (D -P +J +J

•rH CD CO ^r-^ s: o CD 1- L CD CD CD CD s

J- •M •H

a

•rH P

CO P

•M

C

CD

». •H o «K <^-,

C c; e t- t- S_ (D

CO CO

M CO rH CD T3 •P P >. -P 3 3 x: 3 3 E jj E E >i •rH •H P> to

i- £- o i_ CO 3 CO 3 3 x:

n c CO

C

O

O CDO CO •H S- •rH •H

O

jC x: j-> x: 4-> CO o CO CO E E E E E Cm

O. Q.

C (i c CO rH CO CO 3 3 :rs 3 3 rH

Q) CO CO CD CO CD CO x: CO tO •H •M rH •rH •H 3 s o o C2. o D. -p o -p p D XJ a a -O CO

CO sz x: s: o O o O o o o o 2 o. a. ex Q. CL ex CO CO CO CO CO

CO

c;o

xi

s^. COooL

T)>.

CO x:

rH t- CO o a o Cm CD •M p E CO -n CO CD c c ^ CO CO •H O CO CO o

>.

O CO o -P .—

S- ouo c\ CD x: -U p:: O X 3 CJ

CO -QO -a CD Cm

227
n

0) >> s. -o O D -o •> c -o * o O CT3 m. bO o JZl S- CD *

CD

Om S t, W Dy~-^ c

<uNC c CD o X3

l-l CO CO O B <D

1—1 CO

O

Q. -H 3 X c T3

Cd CO

O \ sz L c o CX O N..^ ^ s

4J t. JJ

•rH J-> CO c CO J-3 bC CO x:

1—

i: 3 co

•^ CJ> +J o

•.H C JJ OJ o bO C en CM

1-1 .rH CM C\J O O

J-) a- D<

CJo

x:

CO 4-> t^- 1 CO c o 1 <-H •-< C\J u, o

CuO

fcO o c - •^ 4^ LTi r-—

r-l

C ^T ^T

•r-l •M ^ fv-i O o

CO D-O

bo o c - LO vC

•.-< jJ t

ty-) -p C .— .— O S a. o ^ •rH >1 O

ti-H J_)

O I>- 1 •rH -rH O O 1 CJ > CvJ • CO --- CM D. I. JJ CO O CO

CO r—

E

i-O

CO

CO oco

i-o

J=

r-' >,c

t-3 x: c^ o_

f—-" -H

Z5 ;_

C/} 4-)

COcO

£>L

COOOL

•o

>,

CD s:

r-H tto o a fj (i_

••-H iJ e CO t:: CO c c

Xl CO CO

—

o CO u: o

>> o CMC J-5 .-H t. o. o cv fl^ x: •o X CJ X 3 o

:0 -O

C

zzy
Hazardous Material Log Sheet

The many chemical hazards present in the analytical laboratory must be

subject to strict control. To assist in this vital function, a log sheet for

each hazardous compound is helpful. The following example, adapted from that

suggested by Pfaff [1], is currently used in the analytical laboratory of the

Thermophysics Division (774.03) of the National Bureau of Standards, Boulder

Laboratories.

[1] Pfaff, R.C., J. Chem. Educ, 62, A282, 1985.

Analytical Laboratory

Hazardous Materials Log Sheet

Name of Material:

Date of Receipt: Name of Receiver:

Quantity: Container Size:

Form of Shipment (i.e.. Federal Express, UPS, etc.):

Condition of Shipment or Sample:

Distribution of Material: Amount: Building:

Room Number: Name of Principal Investigator:

Date: Signature of Recipient:

Exact Storage Location:

Material Safety Data Sheet Available: Yes No

Approved Safety Plan Available: Yes No

Disposal: Amount: Date: Program:

Disposal Data:

Health and Safety Impact:

229
Unit Conversions

The international system of units is described in detail in NBS Special

Publication 330 [1 ] and lists of physical constants and conversions factors

are tabulated by Mechtly [2]. The American Society for Testing and Materials

(ASTM), American National Standards Institute (ANSI), and Institute of

Electrical and Electronics Engineers (IEEE) have published a joint standard

for metric practice [3]- The most recent guidelines for use of the metric

system are given in References 1, 2 and 3. Selected unit conversions are

given in the following tables.

References :

[1 ] The International System of Units, National Bureau of Standards (U.S.)

Special Publication SP-330 (Aug. 1977).

[2] Mechtly, E.A., The International System of Units, Physical Constants and

Conversion Factors, NASA Special Publication SP-7012, 1964.

[3] Standard for Metric Practice, ANSI/ASTM E-38O-76, IEEE Std. 268-1975 (Jul

1976).

230
Density

kg/m^ g/cm^ Amagat Ib/ft^

16.018 0.016018 178.216 1

1 0.001 11 .126 0.062^128

1,000 1 1 .1126 X 10'' 62.i]28

2,015.9 2.0159 2.2il28 X 10" 125.85

0.089881 8.9881 X 10"^ 1 5.61 11 X 10"'

Specific Volume

mVkg

(L/g) cm'/g ft Vlb

0.062428 62.428 1

1 1 ,000 16 018

0.001 1 0.016018

4.9605 X lO"'' 0.49605 7 9458 X 10"'

Pressure

Torr lbs/in,

MP a atm (mm Hg) bar (psi)

6.8948 X 10"' 0.068046 51 .715 6.8948 X 10"2 1

1 9.8692 7,500.6 10.0 145.04

0.101325 1 760.0 1.01325 14.696

1 .3332 X 10"* 1 .3158 X 10"' 1 1.332 X 10"' 0.019337

0.1 0.98692 750.06 1 14.504

231
Enthalpy , Heat of Vaporization , Heat of

Conversion, Specific Energies

kJ/kg

(J/g) cal/g Btu/lb

2.3244 0.55556 1

1 0.23901 0.43022

0.49605 0.11856 0.21341

4.1840 1 1.8

Specific Heat, Entropy

kJ/kg-K

(J/g-K) Btu/°R

4.184 1

1 0.23901

0.49605 0.1 1856

2.0755 0.49605

Thermal Conductivity

mW/cm-K J/s-cm-K cal/s-cm-K Btu/ft-hr-°R

17.296 0.017296 0.0041338 1

1 0.001 2.3901 X

10""* 0.057816

1 ,000 1 0.23901 57.816

4,184 4.184 1 241 .90

232
Viscosity

kg/m-s Centipoise Ib-s/ft^

(N-s/m^) (10"^g/cm-s) (slug/ft-s) Ib/ft-s

1.48816 1,488.16 0.31081 1

1 1 ,000 0.020885 0.67197

0.001 1 2.0885 X 10"^ 6.7197 X

10""*

47.881 4.7881 X 10"* 1 32.175

Velocity of Sound

m/s ft/s

0.3048

1

1

3.2808

Surface Tension

N/m dyne/cm Ibf/in.

175.13 175.13 X 10^ 1

1 1 ,000 5.7102 X 10"'

0.001 1 5.7102 X 10"'

Temperature

T(Rankine) = 1.8T(Kelvin)

T(Celsius) = T(Kelvin) - 273-15

T(Fahrenheit) = T(Rankine) - 459.67

T(Fahrenheit) = 1 . 8T(Celsius) + 32

233
NBS-114A (REV. 2-8C) U.S. DEPT. OF COMM. BIBLIOGRAPHIC DATA

SHEET (See instructions)

1. PUBLICATION OR

REPORT NO. NBS/TN-1096

2. Performing Organ. Report No, 3. Publ icatlon Date

April 1986

4. TITLE AND SUBTITLE

BASIC TABLES FOR CHEMICAL ANALYSIS

5. AUTHOR(S)

Thomas J. Bruno and Paris D. N. Svoronos

6. PERFORMING ORGANIZATION (If joint or other than NBS, see instructions)

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

7. Contract/Grant No.

8. Type of Report & Period Covered

9, SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State, ZIP)

Gas Research Institute

and

United States Department of EnergyOffice of Basic Energy Sciences

10. SUPPLEMENTARY NOTES

[]]J Document describes a computer program; SF-185, FlPS Software Sumimary, is attached.

11. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a si gnificant

bi bliography or literature survey, mention it here) Tables of important data for use in the analytical chemistry laboratory are provided. These tables contain information for use in gas chromatography,

liquid chromatography, infrared and ultraviolet spectrophotometry, mass spectrometry, and wet chemical techniques. Tables relating to safe practice

in the analytical laboratory are also included.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons)

chemical analysis; instrumental analysis.

13. AVAILABILITY

^Xl Unlimited

[^ For Official Distribution. Do Not Release to NTIS

^(X] Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402. Q^ Order From National Technical Information Service (NTIS), Springfield, VA. 22161

14. NO. OF

PRINTED PAGES

240

15. Price

USCOmm-DC 6043-P80

i-U.S. GOVERNMENT PRINTING OFFICE:1986- 671-586 / 45170
TM he National Bureau of Standards' was established by an act of Congress on March 3, 1901. The ^ Bureau's overall goal is to strengthen and advance the nation's science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research and provides: (1) a

basis for the nation's physical measurement system, (2) scientific and technological services for industry and

government, (3) a technical basis for equity in trade, and (4) technical services to promote public safety.

The Bureau's technical work is performed by the National Measurement Laboratory, the National

Engineering Laboratory, the Institute for Computer Sciences and Technology, and the Institute for Materials

Science and Engineering

.

The National Measurement Laboratory

Provides the national system of physical and chemical measurement;

coordinates the system with measurement systems of other nations and

furnishes essentiaJ services leading to accurate and uniform physical and

chemical measurement throughout the Nation's scientific community, in- dustry, and commerce; provides advisory and research services to other Government agencies; conducts physical and chemical research; develops,

produces, and distributes Standard Reference Materials; and provides

calibration services. The Laboratory consists of the following centers:

• Basic Standards^

• Radiation Research

• Chemical Physics

• Analytical Chemistry

The National Engineering Laboratory

Provides technology and technical services to the public and private sectors to address national needs and to solve national problems; conducts research in engineering and applied science in suppxjrt of these efforts; builds and maintains competence in the necessary disciplines required to carry out this research and technical service; develops engineering data and measurement

capabilities; provides engineering measurement traceability services; develops

test methods and proposes engineering standards and code changes; develops

and proposes new engineering practices; and develops and improves

mechanisms to transfer results of its research to the ultimate user. The

Laboratory consists of the following centers:

Applied Mathematics

Electronics and Electrical Engineering'^

Manufacturing Engineering

Building Technology

Fire Research

Chemical EngineeringTTie Institute for Computer Sciences and Technology

Conducts research and provides scientific and technical services to aid Federal agencies in the selection, acquisition, application, and use of computer technology to improve effectiveness and economy in Government

operations in accordance with Public Law 89-306 (40 U.S.C. 759), relevant Executive Orders, and other directives; carries out this mission by managing

the Federal Information Processing Standards Program, developing Federal ADP standards guidelines, and managing Federal participation in ADP

voluntary standardization activities; provides scientific and technological advisory services and assistance to Federal agencies; and provides the technical foundation for computer-related policies of the Federal Government. The Institute consists of the following centers:

Programming Science and

Technology

Computer Systems

Engineering

The Institute for Materials Science and Engineering

Conducts research and provides measurements, data, standards, reference

materials, quantitative understanding and other technical information fundamental to the processing, structure, properties and performance of materials; addresses the scientific basis for new advanced materials technologies; plans

research around cross-country scientific themes such as nondestructive

evaluation and phase diagram development; oversees Bureau-wide technical programs in nuclear reactor radiation research and nondestructive evaluation; and broadly disseminates generic technical information resulting from

its programs. The Institute consists of the following Divisions:

Inorganic Materials Fracture and Deformation

Polymers

Metallurgy Reactor Radiation

'Headquarters and Laboratories at Gaithersburg, MD, unless otherwise noted; mailing address

Gaiihersburg, MD 20899. "Some divisions within the center are located at Boulder, CO 80303. 'Located at Boulder, CO, with some elements at Gaithersburg, MD.
U.S. Department of Commerce

National Bureau of Standards

Gaithersburg, MD 20899

Official Business

Penalty for Private Use $300

POSTAGE AND FEES PAID US DEPARTMENT OF COMMERCE

COM-215

SPECIAL FOURTH-CLASS RATE BOOK