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422

Chapter

I I

nmo

(mfn)

Fig.

14.15.

Separation

enantiomeric compounds. Reprinted with the permission

ref.

[27].

(-)-Pseudoephedrine;

11,

(+)-ephedrine;

111,

(-)-ephedrine;

IV,

(+)-pseudoephedrine. Electrophero-

gram

which

shows

the separation

the enantiomers and diastereomers

ephedrine and pseu-

doephedrine. The separation was achieved with the

pm capillary and

p-CD-SBE(1V)

mM Tridphosphate buffer

(pH

2.5).

The

field strength

was

210

cm-* and sample concentra-

tions were

0.4

mM.

Note the

two

adjacent chiral centres and the baseline separation of all four

isomers.

(including waste water, smoke emissions, working atmospheres and biological

fluid monitoring). The ease of use and low running costs make CIA attractive for

the determination of ions in chemicaHpetroleum plants. Applications range from

deionized water to waste water

[30].

Figure

14.17

shows the analysis of waste

water from a polyethylene plant. The separation of organic acids

also an im-

portant application where CIA offers fast analysis with little risk of error from

interfering compounds. The determination

of surfactants and impurities in sur-

factants is still difficult by HPLC or IC. CIA has been shown to offer an excel-

lent solution to this problem

11.

Monitoring manufacturing processes, mainly by CIA is now well accepted in

the pulp and paper industry

[32]

and in the atuminium industry

[33].

Organic

acid impurities in the manufacture and processing of terephthalic acid are now

widely monitored by CIA. The analysis of agricultural fertilizers, especially the

analysis of nitrate and nitrite is being developed. This has revealed a further use

for

in forensic analysis. Both inorganic (nitrate and chlorate

[34])

and or-

ganic compounds

[35]

are present in explosive residues and can be detected fol-

lowing acts of terrorism. The forensic determination of drugs of abuse has also

been published

[36].

The determination of ions by CIA for environmental control is well estab-

lished

many areas. Samples range from tap water to surface water, rain, air

and waste water. Inorganic anions and cations and organic acids are readily

Capillary electrophoresis in the petroleum

industry

423

0.W

200

Retention time in minutes

Fig.

14.16.

The analysis of a pharmaceutical formulation by capillary ion analysis. Note the pres-

ence

sulphate

a contaminant, the presence

sulphate caused discrepancies in the mass-

balance calculations for this formulation.

I"'I"'l"'l"'l"'l"'1'

2.60

2.80

3.00

3.20

3.40

3.60

3.80

minutes

Fig.

14.17.

Capillary ion analysis

a water sample from a waste water treatment plant.. Analytical

conditions:

sodium chromate,

0.5

CIA-Pakm anion-BT. Hydrostatic injection for

Indirect

detection at

254

nm.

Peak

chloride; peak

sulfate; peak

nitrite; peak

nitrate;

peak

organic acid; peak

bicarbonate. Courtesy of Millipore.

References pp.

425426

424

Chapter

analysed. Organically bound metals require extensive sample preparation proto-

cols before final analysis by CIA. The results obtained by CIA in these applica-

tions are in good agreement with those obtained by other methods and CE is

faster and more flexible than IC and can frequently replace gradient IC.

14.4

CONCLUSION

The interest in CE and the rapid evolution and acceptance of the technique

suggests that the market for CE instrumentation will probably grow to the size of

the HPLC and GC markets. It is important to remember that CE should be con-

sidered as a complementary technique to HPLC, IC and GC and not as a rival.

The main advantages of CE include high resolution, speed of analysis and sensi-

tivity when expressed as minimum detectable mass. It can also be considered

be a user-friendly technique due to the absence of a packed column which is

of-

ten a source of problems in HPLC and IC. Another important aspect is that the

low sample volumes required means that CE can almost be considered as a non-

destructive method of analysis. The low consumption of solvents, buffers and

gases reduces the environmental burden .As in any new method, there have been

impressively rapid developments

instrumentation and applications.

The small diameter of the CE capillary can be considered a limitation of the

technique

that the sample size is very small. In terms of minimum detectable

concentration, HPLC has a lower limit of detection. A further limitation

the

inability of the capillary to accommodate widely different analyte ion concentra-

tions compared to

and HPLC. The linear range of the detector can be limited

to only three orders of magnitude but improvements in technology are taking

place. The low sample capacity of CE may be a disadvantage for those interested

in collecting the separated fractions even when using optimized devices such as

a membrane fraction collector

[37],

even so the size of the collected fractions

remains very small.

The electroosmotic flow can also be considered to be a limitation although the

main advantages of CE are due to the EOF. The EOF permits short migration

times, migration of non-ionic substances and the separation of both anionic and

cationic species simultaneously. It is difficult, however, to maintain a constant

EOF and therefore reproducible migration times. EOf fluctuations due to tem-

perature changes or to electrolyte exhaustion have been solved by the manufac-

turers but injected samples may modify the capillary wall and cause a change in

the EOF. Coating the capillaries, the addition of a zwitterion

cationic surfac-

tant,

purging the capillary between injections all help to stabilize the EOF. In

FZCE

MEKC, the most reliable method is to thoroughly rinse the capillary

with extensive base washes before use followed by frequent rinses between

Capillary electrophoresis in

the

petroleum industry

425

analyses. For compounds insoluble in water, CE is not always the best method to

use.

CE is a new technique; if it follows the same development and growth pattern

as GC and HPLC we can expect

see many improvements in the near future.

The 5th International Symposium on High Performance Capillary Electrophore-

sis (Orlando,

1993)

presented a good overview of the developments in

CE.

These

were concerned not only with those techniques covered here but also with many

others. It is now possible, for example, to reduce analysis time down to a few

seconds or too carry out hydrolysis or derivatization reactions in the capillary

prior to separation.

Instrument improvements will include the control of EOF using an external

radiofrequency field, sophisticated control of the applied voltage for better re-

producibility and improved

detection. Interesting hrther developments in-

clude the miniaturization of the CE system and its auxiliaries by etching onto a

silica chip. It may be possible in this way to reduce the overall size to that of an

electronic component and to be able to use it as an in-vivo sensor

[38].

14.5

REFERENCES

A. Lodge, B.A. Thesis

(1886).

Compton and

Brownlee, Biotechniques,

6 (1988) 432.

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Hjerten and

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K.D.

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56 (1984)

111.

A. Cohen and B.L. Karger,

Chromatogr.

397 (1987) 409.

B.B. Van Orman and

G.L.

McIntire, J. Microcolumn Separation,

6 (1989) 289.

S.F.Y. Li, Capillary Electrtophoresis,

Journal

of Chromatography Library, Vol.

52,

Elsevier,

Amsterdam

(1992).

P. Jandik and

Bonn, Capillary Electrophoresis of Small Molecules and Ions, VCH, New

York

(1993).

J. Vindegol and

Sandra, Introduction to Micellar Electrokinetic Chromatography, Huthig,

Heidelbert

(1992).

T. Tsuda,

Liquid Chromatogr.

12 (1989) 2501.

M. Merion, B. Bell-Alden, E. Grover,

Neue and

Peterson, poster presented at HPCE

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1).

K. Otsuka,

Terabe and

Ando,

Chromatogr.,

332 (1985) 219.

K. Otsuka,

Terabe and

Ando,

Chromatogr.,

396 (1987) 350.

Otsuka and

Terabe, J. Chromatogr.

???

(1989) 150.

Terabe,

Otsuka and T. Ando, Anal. Chem.,

61 (1989) 251.

Terabe, Y. Ishihaua,

Nishi, T. Fukuyana and

Otsuka,

Chromatogr.

545 (1991) 359.

Nishi, T. Fukuyana, M. Matsuo and

Terabe,

Microcolumn Separation

l(5)

(1989) 234.

426

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J.R. Mazzeo, J.A. Martineau and

I.S.

Krull,

Methods,

4(3) (1992) 1.

J. Liu,

Y.Z.

Hsieh,

Wiesler and M. Notovny, Anal. Chem.,

63 (1991) 408.

AS.

Cohen and

B.L.

Karger, J. Chromatogr.,

397 (1987) 409.

R.W. Wallinford and

A.G.

Ewing, Anal Chem.,

(1989) 229A.

R.W. Wallinford and

A.G.

Ewing, Anal Chem.,

60 (1988) 258.

P.K.

Dasgupta and

Bao, Anal. Chem.,

65 (1993) 1003.

R.D. Smith, J.H. Wahl, D.R. Goodlett and

S.A.

Hofstadler, Anal. Chem.,

65( 13)

(

1993) 574.

C.S. Weiss, J.S. Hazlett, M.H. Dam and M.H. Danzer, J. Chromatogr.,

608 (1 992) 325.

G. Bondoux,

Jandik and W.R. Jones, J. Chromatogr.,

602 (1992) 79.

Y.M.

Liu

and S.J. Sheu, J. Chromatogr.,

637 (1993) 219.

D.R. Salomon and J. Romano,

Chromatogr.,

602 (1992) 219.

S.C. Grocott,

L.P.

Jefferies,

Bowser, J. Camevale,

P.E.

Jackson and

B.F.

Kenny,

Chro-

matogr.,

602 (1992) 257.

Kishi, J. Nakamura,

Komo-oka and

Fukuda, 4th Int.

Symp.

on Analysis and Detec-

tion

Explosives, Jerusalem

(1992).

Kleibohmer, K. Camman, J. Robert and

Mussenbrock, J. Chromatogr.,

638 (1993) 349.

Tagliaro, C. Poiesi, R. Aiello,

Dorizzi,

Ghielmi and M. Marigo,

Chromatogr.,

638

(1993) 303.

Y.F.

Cheng,

Fuchs,

Andrews and W. Carson,

Chromatogr.,

608 (1992) 109.

427

Subject

Index

additives analysis by

HPLC,

366-368

amperometric and conductometric detectors

associated gas analysis by temperature pro-

associated

gas

higher boiling compounds,

16-21

two

detectors

series,

ASTM

for

CE, 419-420

gramming,

D1160,41

D2001, D2002, D2003, D2549

and

D3712,

371

D2892,41

D3710

for gasolines,

atomic emission detectors

(AED), 160-200

D86,41

applications of,

191-197

excitation sources for,

161-162

historical development of,

162-164

home-built,

164-1 84

linear dynamic range of,

177-1 80

microwave cavities,

164-168

microwave power supply for,

166

operating limits,

170-180

scavenger gas for,

176-177

schematic diagram of system,

165

selectivity of,

180-1 83

spectrometer for,

167-169

upper limit

detection,

174-1 76

backflushing

in gas analysis,

10, 13-16,

summation of backflushed compounds,

techniques,

244-245

baseline assignment in quantitation,

382

biomarkers in crude

oil,

137

249-250

calibration curves for quantitative analysis,

capillary electrophoresis

(CE), 401-426

392-393

capillary tubes for,

412-413

applications,

421-424

detection methods,

5-42

development

of,

401404

free zone

404-408

future prospects,

424-425

gel filled

411-412

injection methods,

414-415

power supplies,

techniques and apparatus,

404-421

temperature control,

413-414

capillary ion analysis

(CIA),

421-424

capillary isoelectric focussing,

412

carrier gases for high temperature

GC, 71-

coal and shale,

13 1

column switching

a sampling technique,

258-263

modes for multidimensional

GC, 235

techniques,

241-250

coupling a capillary pre-column to a capillary

column,

260-262

coupling a packed pre-column to a capillary

crude oil,

sulfur

compounds with an

SCD,

cutting techniques,

245-249

column,

262-263

224-227

data handling methods,

375-399

Deans

switching of multi-column systems,

deconvolution of partially resolved peaks,

detector linearity in quantitation,

380

detector signal processing,

380-384

dielectric constant detector for

HPLC, 360-

361

diesel fuel

hydrocarbon group analysis by

SFC, 336-

343

sulfur compounds with an

SCD, 221-224

253-255

3 82-3 84

428

Subject

Index

diode array detectors for HPLC, 354-355

electro-osmotic flow, 405-407

electrochemical detectors for HPLC, 355-356

electronic filtering of detector signals, 381

errors in quantitation

due to baseline assignment, 390

due to peak asymmetry, 386-387

due to peak overlap,

386

transmission of systematic errors, 387-389

from

noise, 385

errors in quantitative results, 384-390

FIA

analysis of gasoline (ASTM D 13 19,

IPl56), 370

gas analysis

detector response factors, 27-28

precision, 26-27

gas samples, air contamination, 25

gasoline

anti-knock additives in, 143

composition, trends in, 144-146

emissions from, I44

hydrocarbon group analysis by SFC, 330-

oxygenated compounds in, 143, 146-147

oxygenates with an atomic emission detec-

sulfur compounds with an SCD, 218-220

geochemistry, high temperature GC for study

334

tor.

197

of, 127

heterocyclic nitrogen and sulphur compounds

Hewlett Packard

AED

columns for, 186

computer controls for, 190

photodiode array spectrometer for, 189-

plasma cavity for,

187-1

sensitivity and selectivity, 190-191

fiPLC

analysis of petroleum mixtures, 347-374

apparatus for petroleum analysis, 348-361

columns, 351-353

evaporative light scattering detectors for,

by HPLC, 365-366

5921A, 184-191

190

9-3 60

FIDfor. 356

future trends, 372

history

application to petroleum analysis,

pumps, 348-350

sample injectors, 350-351

table

applications in petroleum analysis,

with mass spectrometry, 356-357

with

NMR

and

IR,

357-358

hydrocarbon gases

calibration mixtures for, 38-39

quantitative measurement, 25-28

rapid analysis, 21

sample handling, 37-38

hydrocarbon group analysis by

SFC,

328-329

hydrocarbon type analysis by HPLC, 368-

hydrodynamic chromatography (HDC), 95-96

HDC

block polymer analysis, 106-109

CO~U~~S

for, 103-104

detectors for, 102-103

effect of column coiling, 103-104, 117-

instrumentation for, 100-104

metal detergent sizing, 109-1

separation of polystyrene standards,

104-

tubular pinch in capillaries,

1-1 17

FIDC

in capillaries, 11

1-1

in microcapillaries, theory of, 96-99

HDC applications

in capillaries,

19-1 20

in microcapillaries, 104-1

in packed columns, 120-124

347-348

363-364

370

119

105

injector design, effect on quantitation, 378

integrator calibration, 390-393

integrators

accuracy and precision, 384-385

role of, 376-378

kerogen

and other macromolecules in crude oil,

pyrolysis-GC-MS

of,

129

kerosine and naphtha hydrocarbon group

128-130

analysis by

SFC,

334-336

Subject

Index

429

light scattering detector,

86-87

limitations of the detector signal in data han-

live column switching,

255-258

dling,

378-380

macromolecules, size by

HDC, 98-100

mass spectrometric detection for

CE, 420-421

metal porphyrins in crude oil with an AED,

methyl tert-butyl ether

(MTBE), 144

micellar electrokinetic chromatography

microwave cavities for atomic emission detec-

multi-column systems,

23 1-268

analysis time reduction,

232

extended column life,

233

for natural gas,

11-16, 19-22

improved detection limits,

233

increase in resolution,

232

instrumentation for,

250-258

strategies for application of,

263-266

multi-dimensional

GC,

definition

of,

233-234

197

(MEKC), 408-4

tors,

164-166

natural gas

analytical procedures for,

10-28

backflushing higher boiling components,

calorific values,

4, 5-7

compression factor,

dewpoint,

4, 8-10,

genera1 properties,

isothermal analysis,

10-1

relative density,

nitrated

PAHs

HPLC, 365

noble gases in natural gas with an AED,

197

12-13

0-FID

detector,

143, 147-152

applications other than gasoline analysis,

for

total oxygen determination,

154-155

quantitative analysis of oxygenated com-

response factors for various oxygenated

selectivity of,

155-156

optimisation of quantitative analysis,

395-397

0-FID

156-157

pounds,

152-155

compounds,

153

PCBs

HPLC, GPC

and

GC, 371

peak area measurement,

381-382

peak asymmetry ratio,

377

petroleum geochemistry,

130-13 1

using

GC, 133-135

using GC-isotope ratio

MS, 137

using

GC-MS, 135-137

using

and

TLC, 131-133

using

LC-MS, 137-138

using

SEC

and

SFC, 138

pneumatic switching

multi-column systems,

polyacrylamides by hydrodynamic chromatog-

polycyclic aromatic hydrocarbons by

HPLC,

252-253

raphy,

121

3 62-3 65

quantitation

by area normalisation,

391

by internal and external standards,

391-392

by peak heighupeak

area,

390-391

HPLC, 361-362

recycle Chromatography,

250

refinery gases,

28-38

adsorption columns for analysis of,

31-37

sulfur compounds with

SCD, 216-218

retention of material on columns, effect on

detectors for

HPLC, 358-359

quantitation,

379

selectivity tuning of serial coupled columns,

separation performance of columns (no. of

possible peaks),

serial coupled columns,

235-238

with

AED, 296-297

with

FTIR-MS, 298-299

with

MS, 294-296

withMS,300

signal smoothing algorithms,

38 1

signal to noise ratio in quantitation,

379-380

silica particles by hydrodynamic chromatogra-

simulated distillation

ASTM

Method

D2887,42

23 8-24 1

SFE-GC, 291-299

SFE-HPLC, 299-300

phy,

122

430

Subject

Index

hy SFC, 322-327

capillary columns for, 44

definition of, 4 1

for

coal liquids, 45

for

crude oils, 50-51

for

gasolines, 46-47

for used engine

oils,

51-52

lubricating oils and residues, 47-50

multi-element, 45

precision of

ASTM

D2887,42-44

process control, 51-52

SFC

for,

48-49

with an

AED,

191-197

stopped flow techniques, 250

sulfur chemiluminescence detector

(SCD),

applications, 216-227

chemiluminescence cell, 204

columns for, 2 14-2 15

flame source for, 204

flameless version, 2 12-2 14

principle of operation, 203-204

relative response factors, 208

schematic diagram

of,

205

sensitivity and selectivity, 209-212

sulfur-selective detectors for GC, summary of

supercritical fluid

definition of, 269

properties of, 269-270

supercritical fluid chromatography

(SFC),

applications, 322-343

column ovens, 309

detectors

for,

3 10-322

history of the technique, 305-306

instrumentation, 306-322

pumps for mobile phase, 307-309

sample introduction, 309-3 10

with supercritical fluid extraction, history

supercritical fluid extraction

(SFE)

advantages

of,

271-275

after derivatisation, 283

equipment

for,

275-280

201-229

currently available, 202-203

3 05-3 45

of,

270-27

of liquids, 281-283

off-line applications, 284-290

off-line, 283-284

on-line applications, 291-301

on-line with an analytical technique, 284

under dynamic conditions, 280-281

under static conditions, 280

tangenVperpendicu1ar peak splitting in inte-

two

detectors in series, 10, 16

type analysis of crude oil fractions, 13 1

gration, 390

Unresolved complex mixture

(UCM),

134

UV detectors for CE, 4 16.4

UV fluorescence detectors

for CE, 418-419

for HPLC, 355

UV/visible detectors for HPLC, 353-355

validation of quantitative analysis, 393-395

valve switching

multi-column systems, 25 1-

viscosity detector

for

wax analysis, 88

252

wax analysis, 55-93

waxes

by IP method 372185, 57

carbon number distribution, 75-78

detectors for, 64-65

general properties of, 55-57

high temperature columns for, 65-70

programmable temperature vaporizer

quantitative analysis, 70-75

sample introduction, 6M4

size exclusion Chromatography of, 81-89

Wobbe Index of natural

gas,

(PTV), 61-64

SFC Of, 78-81

Xanthane polysaccharides by hydrodynamic

chromatography, 121

Zinc dialkyl dithiophosphates by

HPLC,

371

431

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