1573_C07.

fm Page 301 Friday, November 14, 2003 5:12 PM

CHAPTER

Ultraviolet Spectrophotometry

CONTENTS
Solvents for Ultraviolet Spectrophotometry
Ultraviolet Spectra of Common Liquids
TransmittanceAbsorbance Conversion
Correlation Table of Ultraviolet Active Functionalities
Woodwards Rules for Bathochromic Shifts

Copyright 2003 CRC Press, LLC

1573_C07.fm Page 303 Friday, November 14, 2003 5:12 PM

SOLVENTS FOR ULTRAVIOLET SPECTROPHOTOMETRY

The following table lists some useful solvents for ultraviolet spectrophotometry, along with their
wavelength cutoffs and dielectric constants.16

REFERENCES
1. Willard, H.H., Merritt, L.L., Dean, J.A., and Settle, F.A., Instrumental Methods of Analysis, 7th ed.,
Van Nostrand, New York, 1988.
2. Strobel, H.A. and Heinemann, W.R., Chemical Instrumentation: A Systematic Approach, 3rd ed., John
Wiley & Sons, New York, 1989.
3. Dreisbach, R.R., Physical Properties of Chemical Compounds, Advances in Chemistry Series 15,
American Chemical Society, Washington, D.C., 1955.
4. Dreisbach, R.R., Physical Properties of Chemical Compounds, Advances in Chemistry Series 22,
American Chemical Society, Washington, D.C., 1959.
5. Sommer, L., Analytical Absorption Spectrophotometry in the Visible and Ultraviolet, Elsevier Science,
Amsterdam, 1989.
6. Krieger, P.A., High Purity Solvent Guide, Burdick and Jackson, McGaw Park, IL, 1984.

Copyright 2003 CRC Press, LLC

1573_C07.fm Page 304 Friday, November 14, 2003 5:12 PM

Solvents For Ultraviolet Spectrophotometry

Solvent
Acetic acid
Acetone
Acetonitrile
Benzene
sec-Butyl alcohol (2-butanol)
n-Butyl acetate
n-Butyl chloride
Carbon disulfide
Carbon tetrachloride
Chloroforma
Cyclohexane
1,2-Dichloroethane
1,2-Dimethoxyethane
N,N-Dimethylacetamide
N,N-Dimethylformamide
Dimethylsulfoxide
1,4-Dioxane
Diethyl ether
Ethanol
2-Ethoxyethanol
Ethyl acetate
Methyl ethyl ketone
Glycerol
n-Hexadecane
n-Hexane
Methanol
2-Methoxyethanol
Methyl cyclohexane
Methyl isobutyl ketone
2-Methyl-1-propanol
N-Methyl-2-pyrrolidone
Pentane
n-Pentyl acetate
n-Propyl alcohol
sec-Propyl alcohol
Pyridine
Tetrachloroethyleneb
Tetrahydrofuran
Toluene
1,1,2-Trichloro-1,2,2trifluoroethane
2,2,4-Trimethylpentane
o-Xylene
m-Xylene
p-Xylene
Water
a
b

Wavelength Cutoff, nm
260
330
190
280
260
254
220
380
265
245
210
226
240
268
270
265
215
218
210
210
225
330
207
200
210
210
210
210
335
230
285
210
212
210
210
330
290
220
286
231

6.15
20.7 (25C)
37.5
2.284
15.8 (25C)

215
290
290
290

1.936 (25C)
2.568
2.374
2.270
78.54 (25C)

Stabilized with ethanol to avoid phosgene formation.

Stabilized with thymol (isopropyl meta-cresol).

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Dielectric Constant (20C)

7.39 (25C)
2.641
2.238
4.806
2.023
10.19 (25C)
59 (83C)
36.7
4.7
2.209 (25C)
4.335
24.30 (25C)
6.02 (25C)
18.5
42.5 (25C)
2.06 (25C)
1.890
32.63 (25C)
16.9
2.02 (25C)

32.0
1.844
20.1 (25C)
18.3 (25C)
12.3 (25C)
7.6
2.379 (25C)

1573_C07.fm Page 305 Friday, November 14, 2003 5:12 PM

ULTRAVIOLET SPECTRA OF COMMON LIQUIDS

The following table presents, in tabular form, the ultraviolet spectra of some common solvents and
liquids used in chemical analysis. The data were obtained using a 1.00 cm path length cell, against
a water reference.1,2

REFERENCES
1. Krieger, P.A., High Purity Solvent Guide, Burdick and Jackson, McGaw Park, IL, 1984.
2. Sommer, L., Analytical Absorption Spectrophotometry in the Visible and Ultraviolet, Elsevier Science,
Amsterdam, 1989

Ultraviolet Spectra of Common Liquids

Acetone
Wavelength,
Maximum
nm
Absorbance
330
340
350
375
400

1.000
0.060
0.010
0.005
0.005

Acetonitrile
Wavelength,
Maximum
nm
Absorbance
190
200
225
250
350

1.000
0.050
0.010
0.005
0.005

2-Butanol
Wavelength,
Maximum
nm
Absorbance
260
275
300
350
400

1.000
0.300
0.010
0.005
0.005

n-Butyl Acetate
Wavelength,
Maximum
nm
Absorbance
254
275
300
350
400

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1.000
0.050
0.010
0.005
0.005

Benzene
Wavelength,
Maximum
nm
Absorbance
278
300
325
350
400

1.000
0.020
0.010
0.005
0.005

1-Butanol
Wavelength,
Maximum
nm
Absorbance
215
225
250
275
300

1.000
0.500
0.040
0.010
0.005

Carbon Tetrachloride
Wavelength,
Maximum
nm
Absorbance
263
275
300
350
400

1.000
0.100
0.005
0.005
0.005

Chlorobenzene
Wavelength,
Maximum
nm
Absorbance
287
300
325
350
400

1.000
0.050
0.040
0.020
0.005

1573_C07.fm Page 306 Friday, November 14, 2003 5:12 PM

Ultraviolet Spectra of Common Liquids (continued)

n-Butyl Chloride
Wavelength,
Maximum
nm
Absorbance
220
225
250
300
400

1.000
0.300
0.010
0.005
0.005

Cyclohexane
Wavelength,
Maximum
nm
Absorbance
200
225
250
300
400

1.000
0.170
0.020
0.005
0.005

Cyclopentane
Wavelength,
Maximum
nm
Absorbance
200
215
225
300
400

1.000
0.300
0.020
0.005
0.005

Decahydronaphthalene
Wavelength,
Maximum
nm
Absorbance
200
225
250
300
400

1.000
0.500
0.050
0.005
0.005

Dimethyl Formamide
Wavelength,
Maximum
nm
Absorbance
268
275
300
350
400

1.000
0.300
0.050
0.005
0.005

Dimethyl Sulfoxide
Wavelength,
Maximum
nm
Absorbance
268
275
300
350
400

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1.000
0.500
0.200
0.020
0.005

Chloroform
Wavelength,
Maximum
nm
Absorbance
245
250
275
300
400

1.000
0.300
0.005
0.005
0.005

o-Dichlorobenzene
Wavelength,
Maximum
nm
Absorbance
295
300
325
350
400

1.000
0.300
0.100
0.050
0.005

Diethyl Carbonate
Wavelength,
Maximum
nm
Absorbance
256
265
275
300
400

1.000
0.150
0.050
0.040
0.010

Dimethyl Acetamide
Wavelength,
Maximum
nm
Absorbance
268
275
300
350
400

1.000
0.300
0.080
0.005
0.005

2-Ethoxyethanol
Wavelength,
Maximum
nm
Absorbance
210
225
250
300
400

1.000
0.500
0.200
0.005
0.005

Ethyl Acetate
Wavelength,
Maximum
nm
Absorbance
256
275
300
325
350

1.000
0.050
0.030
0.005
0.005

1573_C07.fm Page 307 Friday, November 14, 2003 5:12 PM

Ultraviolet Spectra of Common Liquids (continued)

1,4-Dioxane
Wavelength,
Maximum
nm
Absorbance
215
250
300
350
400

1.000
0.300
0.020
0.005
0.005

Ethylene Dichloride
Wavelength,
Maximum
nm
Absorbance
228
240
250
300
400

1.000
0.300
0.100
0.005
0.005

Ethylene Glycol Dimethyl Ether

(Glyme)
Wavelength,
Maximum
nm
Absorbance
220
250
300
350
400

1.000
0.250
0.050
0.010
0.005

Heptane
Wavelength,
Maximum
nm
Absorbance
200
225
250
300
400

1.000
0.100
0.010
0.005
0.005

Methanol
Wavelength,
Maximum
nm
Absorbance
205
225
250
300
400

1.000
0.160
0.020
0.005
0.005

2-Methoxyethanol
Wavelength,
Maximum
nm
Absorbance
210
250
275
300
400

Copyright 2003 CRC Press, LLC

1.000
0.130
0.030
0.005
0.005

Diethyl Ether
Wavelength,
Maximum
nm
Absorbance
215
250
275
300
400

1.000
0.080
0.010
0.005
0.005

Hexadecane
Wavelength,
Maximum
nm
Absorbance
190
200
250
300
400

1.000
0.500
0.020
0.005
0.005

Hexane
Wavelength,
nm

Maximum
Absorbance

195
225
250
275
300

1.000
0.050
0.010
0.005
0.005

Isobutanol
Wavelength,
Maximum
nm
Absorbance
220
250
275
300
400

1.000
0.050
0.030
0.020
0.010

Methyl-t-Butyl Ether
Wavelength,
Maximum
nm
Absorbance
210
225
250
300
400

1.000
0.500
0.100
0.005
0.005

Methylene Chloride
Wavelength,
Maximum
nm
Absorbance
233
240
250
300
400

1.000
0.100
0.010
0.005
0.005

1573_C07.fm Page 308 Friday, November 14, 2003 5:12 PM

Ultraviolet Spectra of Common Liquids (continued)

2-Methoxyethyl Acetate
Wavelength,
Maximum
nm
Absorbance
254
275
300
350
400

1.000
0.150
0.050
0.005
0.005

Methyl Isoamyl Ketone

Wavelength,
Maximum
nm
Absorbance
330
340
350
375
400

1.000
0.100
0.050
0.010
0.005

Methyl Isobutyl Ketone

Wavelength,
Maximum
nm
Absorbance
334
340
350
375
400

1.000
0.500
0.250
0.050
0.005

Methyl n-Propyl Ketone

Wavelength,
Maximum
nm
Absorbance
331
340
350
375
400

1.000
0.150
0.020
0.005
0.005

1-Propanol
Wavelength,
Maximum
nm
Absorbance
210
225
250
300
400

1.000
0.500
0.050
0.005
0.005

2-Propanol
Wavelength,
Maximum
nm
Absorbance
205
225
250
300
400

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1.000
0.160
0.020
0.005
0.010

Methyl Ethyl Ketone

Wavelength,
Maximum
nm
Absorbance
329
340
350
375
400

1.000
0.100
0.020
0.010
0.005

n-Methylpyrrolidone
Wavelength,
Maximum
nm
Absorbance
285
300
325
350
400

1.000
0.500
0.100
0.030
0.010
Pentane

Wavelength,
nm

Maximum
Absorbance

190
200
250
300
400

1.000
0.600
0.010
0.005
0.005

-Phenethylamine
Wavelength,
Maximum
nm
Absorbance
285
300
325
350
400

1.000
0.300
0.100
0.050
0.005

Pyridine
Wavelength,
Maximum
nm
Absorbance
330
340
350
375
400

1.000
0.100
0.010
0.010
0.005

Tetrahydrofuran
Wavelength,
Maximum
nm
Absorbance
212
250
300
350
400

1.000
0.180
0.020
0.005
0.005

1573_C07.fm Page 309 Friday, November 14, 2003 5:12 PM

Ultraviolet Spectra of Common Liquids (continued)

Propylene Carbonate
Wavelength,
Maximum
nm
Absorbance
280
300
350
375
400

1.000
0.500
0.050
0.030
0.020

1,2,4-Trichlorobenzene
Wavelength,
Maximum
nm
Absorbance
308
310
350
375
400

1.000
0.500
0.050
0.010
0.005

Trichloroethylene
Wavelength,
Maximum
nm
Absorbance
273
300
325
350
400

1.000
0.100
0.080
0.060
0.060

1,1,2-Trichlorotrifluoroethane
Wavelength,
Maximum
nm
Absorbance
231
250
300
350
400

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1.000
0.050
0.005
0.005
0.005

Toluene
Wavelength,
nm

Maximum
Absorbance

284
300
325
350
400

1.000
0.120
0.020
0.050
0.005

2,2,4-Trimethylpentane
Wavelength,
Maximum
nm
Absorbance
215
225
250
300
400

1.000
0.100
0.020
0.005
0.005
Water

Wavelength,
nm

Maximum
Absorbance

190
200
250
300
400

0.010
0.010
0.005
0.005
0.005

o-Xylene
Wavelength,
Maximum
nm
Absorbance
288
300
325
350
400

1.000
0.200
0.050
0.010
0.005

1573_C07.fm Page 310 Friday, November 14, 2003 5:12 PM

TRANSMITTANCEABSORBANCE CONVERSION
The following is a conversion table for absorbance and transmittance, assuming no reflection.
Included for each pair is the percent error propagated into a measured concentration (using the
BeerLambert law), assuming an uncertainty in transmittance of +0.005.1 The value of transmittance
that will give the lowest percent error in concentration is 3.368. Where possible, analyses should
be designed for the low uncertainty area.

REFERENCES
1. Kennedy, J.H., Analytical Chemistry Principles, Harcourt, Brace and Jovanovich, San Diego, 1984.
TransmittanceAbsorbance Conversion
Transmittance

Absorbance

Percent
Uncertainty

0.980
0.970
0.960
0.950
0.940
0.930
0.920
0.910
0.900
0.890
0.880
0.870
0.860
0.850
0.840
0.830
0.820
0.810
0.800
0.790
0.780
0.770
0.760
0.750
0.740
0.730
0.720
0.710
0.700
0.690
0.680
0.670
0.660
0.650
0.640
0.630
0.620
0.610
0.600
0.590
0.580

0.009
0.013
0.018
0.022
0.027
0.032
0.036
0.041
0.046
0.051
0.056
0.060
0.065
0.071
0.076
0.081
0.086
0.091
0.097
0.102
0.108
0.113
0.119
0.125
0.131
0.137
0.143
0.149
0.155
0.161
0.167
0.174
0.180
0.187
0.194
0.201
0.208
0.215
0.222
0.229
0.237

25.242
16.915
12.752
10.256
8.592
7.405
6.515
5.823
5.270
4.818
4.442
4.125
3.853
3.618
3.412
3.231
3.071
2.928
2.799
2.684
2.579
2.483
2.386
2.316
2.243
2.175
2.113
2.055
2.002
1.952
1.906
1.863
1.822
1.785
1.750
1.717
1.686
1.657
1.631
1.605
1.582

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1573_C07.fm Page 311 Friday, November 14, 2003 5:12 PM

TransmittanceAbsorbance Conversion (continued)

Transmittance

Absorbance

Percent
Uncertainty

0.570
0.560
0.540
0.530
0.520
0.510
0.500
0.490
0.480
0.470
0.460
0.450
0.440
0.430
0.420
0.410
0.400
0.390
0.380
0.370
0.360
0.350
0.340
0.330
0.320
0.310
0.300
0.290
0.280
0.270
0.260
0.250
0.240
0.230
0.220
0.210
0.200
0.190
0.180
0.170
0.160
0.150
0.140
0.130
0.120
0.110
0.100
0.090
0.080
0.070
0.060
0.050
0.040
0.030
0.020
0.010

0.244
0.252
0.268
0.276
0.284
0.292
0.301
0.310
0.319
0.328
0.337
0.347
0.356
0.366
0.377
0.387
0.398
0.409
0.420
0.432
0.444
0.456
0.468
0.481
0.495
0.509
0.523
0.538
0.553
0.569
0.585
0.602
0.620
0.638
0.657
0.678
0.699
0.721
0.745
0.769
0.796
0.824
0.854
0.886
0.921
0.958
1.000
1.046
1.097
1.155
1.222
1.301
1.398
1.523
1.699
2.000

1.560
1.539
1.502
1.485
1.470
1.455
1.442
1.430
1.419
1.408
1.399
1.391
1.383
1.377
1.372
1.367
1.364
1.361
1.359
1.358
1.359
1.360
1.362
1.366
1.371
1.376
1.384
1.392
1.402
1.414
1.427
1.442
1.459
1.478
1.500
1.525
1.553
1.584
1.619
1.659
1.704
1.756
1.816
1.884
1.964
2.058
2.170
2.306
2.473
2.685
2.961
3.336
3.881
4.751
6.387
10.852

Copyright 2003 CRC Press, LLC

1573_C07.fm Page 312 Friday, November 14, 2003 5:12 PM

CORRELATION TABLE FOR ULTRAVIOLET ACTIVE FUNCTIONALITIES

The following table presents a correlation between common chromophoric functional groups and
the expected absorptions from ultraviolet spectrophotometry.13 Although not as informative as
infrared correlations, UV can often provide valuable qualitative information.

REFERENCES
1. Willard, H.H., Dean, J.A., Settle, F.A., and Merritt, L.L., Instrumental Methods of Analysis, 7th ed.,
Wadsworth Publishing Co., Belmont, CA, 1995.
2. Silverstein, R.M. and Webster, F.X., Spectrometric Identification of Organic Compounds, 6th ed.,
Wiley, New York, 1998.
3. Lambert, J.B., Shurvell, H.F., Lightner, D.A., Verbit, L., and Cooks, R.G., Organic Structural Spectroscopy, Prentice Hall, Upper Saddle River, NJ, 1998.

Copyright 2003 CRC Press, LLC

Chromophore
Ether
Thioether
Amine
Amide
Thiol
Disulfide
Bromide
Iodide
Nitrile
Acetylide
(alkyne)
Sulfone
Oxime
Azido
Alkene
Ketone
Thioketone
Esters
Aldehyde
Carboxyl
Sulfoxide
Nitro
Nitrite
Azo
Nitroso
Nitrate
Conjugated hydrocarbon
Conjugated
Conjugated
Conjugated
Conjugated

hydrocarbon
hydrocarbon
hydrocarbon
hydrocarbon

Conjugated hydrocarbon
Conjugated system

Copyright 2003 CRC Press, LLC

Functional Group

max, nm

max

O
S
NH2
CONH2
SH
SS
Br
I
CN
CC

185
194
195
<210
195
194
208
260
160
175180

1000
4600
2800

1400
5500
300
400

6000

SO2
NOH
>C=N
>C=C<
>C=O
>C=S
COOR
CHO
COOH
>SO
NO2
ONO
N=N
N=O
ONO2
(C=C)2
(acyclic)
(C=C)3
(C=C)4
(C=C)5
(C=C)2
(alicyclic)
C=CCC
C=CC=N

180
190
190
190
195
205
205
210
200210
210
210
220230
285400
302
270 (shoulder)
210230

5000
5000
8000
1000
Strong
50
Strong
5070
1500
Strong
10002000
325
100
12
21,000

260
300
330
230260

35,000
52,000
118,000
30008000

219
220

6500
23,000

max, nm

max

215

1600

255

400

270285

1830

280300

1118

3004000

10

max, nm

max

1573_C07.fm Page 313 Friday, November 14, 2003 5:12 PM

Correlation Table for Ultraviolet Active Functionalities

Chromophore
Conjugated system
Conjugated system
Benzene

Functional Group
C=CC=O
C=CNO2

max, nm
210250
229
184

max
10,00020,000
9500
46,700

Diphenyl

max, nm

max

202

6900

246

20,000

max, nm

max

300350

Weak

255

170

312

175

Naphthalene

220

112,000

275

5600

Anthracene

252

199,000

375

7900

174

80,000

195

6000

251

1700

227

37,000

270

3600

314

2750

218

80,000

266

4000

317

3500

Pyridine

Quinoline

N
Isoquinoline
N

Copyright 2003 CRC Press, LLC

1573_C07.fm Page 314 Friday, November 14, 2003 5:12 PM

Correlation Table for Ultraviolet Active Functionalities (continued)

1573_C07.fm Page 315 Friday, November 14, 2003 5:12 PM

WOODWARDS RULES FOR BATHOCHROMIC SHIFTS

Conjugated systems show bathochromic shifts in their * transition bands. Empirical methods
for predicting those shifts were originally formulated by Woodward, Fieser, and Fieser.l4 This
section includes the most important conjugated system rules.l5 The reader should consult references
5 and 6 for more details on how to apply the wavelength increment data.

REFERENCES
1. Woodward, R.B., Structure and the absorption spectra of ,-unsaturated ketones, J. Am. Chem. Soc.,
63, 1123, 1941.
2. Woodward, R.B., Structure and absorption spectra. III. Normal conjugated dienes, J. Am. Chem. Soc.,
64, 72, 1942.
3. Woodward, R.B., Structure and absorption spectra. IV. Further observations on ,-unsaturated
ketones, J. Am. Chem. Soc., 64, 76, 1942.
4. Fieser, L.F. and Fieser, M., Natural Products Related to Phenanthrene, Reinhold, New York, 1949.
5. Silverstein, R.M. and Webster, F.X., Spectrometric Identification of Organic Compounds, 6th ed.,
Wiley, New York, 1998.
6. Lambert, J.B., Shurvell, H.F., Lightner, D.A., Verbit, L., and Cooks, R.G., Organic Structural Spectroscopy, Prentice Hall, Upper Saddle River, NJ, 1998.

Rules of Diene Absorption

Base value for diene: 214 nm
Increments for (each) (in nm):
Heteroannular diene
Homoannular diene
Extra double bond
Alkyl substituent or ring residue
Exocyclic double bond
Polar groups:
OOCR
OR
SR
Halogen
NR2
Calculated

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+0
+39
+30
+5
+5
+0
+6
+30
+5
+60
= Total

1573_C07.fm Page 316 Friday, November 14, 2003 5:12 PM

Rules for Enone Absorptiona

C
O

Base value for acyclic (or six-membered) ,-unsaturated ketone: 215 nm

Base value for five-membered ,-unsaturated ketone:
202 nm
Base value for ,-unsaturated aldehydes:
210 nm
Base value for ,-unsaturated esters or carboxylic acids:
195 nm
Increments for (each) (in nm):
Heteroannular diene
+0
Homoannular diene
+39
Double bond
+30
Alkyl groups

+10

+12
and higher
+18
Polar groups:
OH

+35

+30

+50
OOCR
, , ,
+6
OR

+35

+30

+17

+31
SR

+85
Cl

+15

+12
Br

+25

+30
NR2

+95
Exocyclic double bond
+5
Calculated
a

= Total

Solvent corrections should be included. These are water (8), chloroform (+1),
dioxane (+5), ether (+7), hexane (+11), cyclohexane (+11). No correction for
methanol or ethanol.

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1573_C07.fm Page 317 Friday, November 14, 2003 5:12 PM

Rules for Monosubstituted

Benzene Derivatives

Rules for Disubstituted Benzene

Derivatives

Parent Chromophore (benzene): 250 nm

Parent Chromophore (benzene): 250 nm

Substituent

Increment

Substituent

4
4
0
16
16
16

R
COR
OH
OR
O
Cl
Br
NH2
NHCOCH3
NHCH3
N(CH3)2

+3
+3
+7
+7
+11
+0
+2
+13
+20

+20

+3
+3
+7
+7
+20
+0
+2
+13
+20

+20

+10
+10
+25
+25
+78 (variable)
+10
+15
+58
+45
+73
+85

R
COR
CHO
OH
OR
COOR

Note: R is an alkyl group, and the

substitution is on C6H5.

Note: R indicates an alkyl group.

Copyright 2003 CRC Press, LLC