Pure Appl. Chem., Vol. 76, No. 12, pp. 2105–2146, 2004.

© 2004 IUPAC
INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY
ORGANIC AND BIOMOLECULAR CHEMISTRY DIVISION *
SUBCOMMITTEE ON PHOTOCHEMISTRY**

CHEMICAL ACTINOMETRY
(IUPAC Technical Report)
Prepared for publication by
H. J. KUHN1, S. E. BRASLAVSKY1,‡, AND R. SCHMIDT2
1Max-Planck-Institut für Bioanorganische Chemie (formerly
Ruhr, Germany; 2Institut für Physikalische und Theoretische

Strahlenchemie), D−45413 Mülheim a.d.
Chemie, Universität Frankfurt, D−60054
Frankfurt/Main, Germany

*Membership of the Organic and Biomolecular Chemistry Division during the final preparation of this report
(2002–2003) was as follows:
President: T. T. Tidwell (1998–2003), M. Isobe (2002–2005); Vice President: D. StC. Black (1996–2003), V. T.
Ivanov (1996–2005); Secretary: G. M. Blackburn (2002–2005); Past President: T. Norin (1996–2003),
T. T. Tidwell (1998–2005) (initial date indicates the first time elected as Division member). The list of the other
members of the Division can be found in <http://www.iupac.org/divisions/III/members.html>.
In addition to the members of the IUPAC Photochemistry Commission (1985–1988), see first version in Pure Appl.
Chem. 61, 187–210 (1989), and Subcommittee (2001–2003), the following colleagues kindly supplied literature,
special information, helpful comments, and discussions which are gratefully acknowledged: O. M. Alfano, D.
Brämert, A. M. Braun, N. J. Bunce, D. De Keukeleire, H. Deinert, J. N. Demas, D. F. Eaton, G. Gauglitz, H. Görner,
G. G. Gurzadyan, G. Guyot, H. G. Heller, W. E. Klotzbücher, G. Koç-Weier, D. Kreft, J. J. McCullough, E.
Oliveros, P. Potzinger, W. H. Powell, A. Rizzi, R. Schrader, H.-P. Schuchmann, C. von Sonntag, R. Srinivasan, J.
Theurich, L. Vincze, J. Wirz, H. E. Zimmerman.
Members of the Photochemistry Commission (1998–2001) were: Chairmen: J. R. Bolton (Canada, 1996–1999),
R. G. Weiss (USA, 2000–2001); Secretaries: R. G. Weiss (USA, 1998–1999), J. Wirz (Switzerland, 2000–2001);
Titular Members: J. R. Bolton (Canada), S. E. Braslavsky (Germany), H. Bouas-Laurent (France), R. G. Weiss
(USA), J. Wirz (Switzerland); Associate Members: A. U. Acuña–Fernández (Spain), H. Masuhara (Japan);
National Representatives: F. C. De Schryver (Belgium), Y. Eichen (Israel), M. G. Neumann (Brazil), T. Bérczes
(Hungary), S. J. Formosinho (Portugal), A. Horvath (Hungary), S. Içli (Turkey), B. S. Martineigh (South Africa),
G. Pandey (India), F. H. Quina (Brazil), S. C. Shim (Korea), P. Hrdlovic (Slovakia), C.-H. Tung (China), C.
Wentrup (Australia), I. Willner (Israel), Y. Yagci (Turkey).
**Members of the Subcommittee on Photochemistry (2001–2003): S. E. Braslavsky (Germany, Chairperson), A.
U. Acuña–Fernández (Spain), G. A. Argüello (Argentina), T. D. Z. Atvars (Brazil), R. Bonneau (France), A. M.
Braun (Germany), A. Chibisov (Russia), K. Ghiggino (Australia), H. Lemmetyinen (Finland), H. Miyasaka
(Japan), D. C. Neckers (USA), J. Niytrai (Hungary), M. Olivucci (Italy), D. Phillips (UK), R. O. Rahn (USA), N.
Serpone (Canada), R. Schmehl (USA), M. Terazima (Japan), S. Wu (China).
‡Corresponding

author: E-mail: braslavskys@mpi-muelheim.mpg.de

Republication or reproduction of this report or its storage and/or dissemination by electronic means is permitted without the
need for formal IUPAC permission on condition that an acknowledgment, with full reference to the source, along with use of the
copyright symbol ©, the name IUPAC, and the year of publication, are prominently visible. Publication of a translation into
another language is subject to the additional condition of prior approval from the relevant IUPAC National Adhering
Organization.

2105

H. J. KUHN et al.

2106

Chemical actinometry
(IUPAC Technical Report)
Abstract: This document updates the first version of the IUPAC technical report on
“Chemical actinometers” published in Pure Appl. Chem. 61, 187–210 (1989).
Since then, some methods have been improved, procedures have been modified,
and new substances have been proposed as chemical actinometers. An actinometer
is a chemical system or a physical device by which the number of photons in a
beam absorbed into the defined space of a chemical reactor can be determined integrally or per time. This compilation includes chemical actinometers for the gas,
solid, microheterogeneous, and liquid phases, as well as for the use with pulsed
lasers for the measurement of transient absorbances, including the quantum yield
of phototransformation, as well as the literature for each of the actinometers. The
actinometers listed are for the use in the wavelength range from the UV to the red
region of the spectrum. A set of recommended standard procedures is also given.
Advantages and disadvantages are discussed regarding the use of chemical actinometers vs. electronic devices for the measurement of the number of photons absorbed. Procedures for the absolute measurement of incident photon flux by means
of photodiodes are also discussed.
CONTENTS
ABBREVIATIONS
QUANTITIES, SYMBOLS, AND UNITS
PREFACE
1.
GENERAL CONSIDERATIONS ON CHEMICAL ACTINOMETRY
1.1
Pros and cons of chemical actinometry
1.2
Quality marks of a chemical actinometer
1.3
Fields of application of chemical actinometry
1.4
Potential errors in chemical actinometry
1.4.1
Refractive index
1.4.2
Temperature
1.4.3
Absorption by photoproducts
1.4.4
Degree of absorption by the chemical actinometer
1.4.5
Polychromatic quantum counters
2.
LIST OF ACTINOMETERS
2.1
Chemical systems
2.1.1
Solid- and microheterogeneous-phase chemical actinometers
2.1.2
Gas-phase chemical actinometers
2.1.3
Liquid-phase chemical actinometers
2.2
Electronic devices
2.3
Absolute measurement of incident photon flux by means of photodiodes
3.
STANDARD LIQUID-PHASE ACTINOMETRIC PROCEDURES
APPENDIX

© 2004 IUPAC, Pure and Applied Chemistry 76, 2105–2146

2107

Chemical actinometry
ABBREVIATIONS
AM
CA
E
G
GC
HPLC
IR
L
LC
PP
S
WR

analytical method
chemical actinometer
electronic device
gas phase
gas chromatography
high-pressure liquid chromatography
infrared
liquid phase
liquid chromatography
procedure, precautions, comments
solid phase
wavelength range

QUANTITIES, SYMBOLS, AND UNITS
Name

Symbol

Definition
lg(P0/P)

absorbance (decadic)
absorption coefficient
linear decadic
molar decadic
absorption cross-section
actinometric factor
amount of photons
amount concentration
area
Avogadro constant
electric current
fluence
frequency (linear)
irradiance, intensity
(radiant flux received)
lifetime
optical pathlength
photon fluence
photon fluence rate
photon flux, amount basis
photon flux, number basis
photon irradiance
photon number
pressure
quantum yield

A, A10

A=

a
ε
σ

a = A10/l
ε = a/c = A10/cl
σ = (ε/NA)ln 10
See sensitivity

of charge carrier formation
in a photodiode
radiant energy
radiant exposure
radiant intensity
radiant power, radiant energy
per time

Φc

np
c
S
NA
i
H'
ν
E

τ
l
Hp'
Ep'
qn,p
qp
Ep
Np
p
Φ

Q
I
P

= –lg T

c = n/V
NA = 6.022 141 5 × 1023 mol–1
H' = ∫E' dt
ν = c/λ
E = dP/dS
c(t = τ) = c(t = 0)/e
Hp' = dNp/dS
Ep' = dHp/dt
qn,p = qp/NA
dNp/dt
Ep = dqp/dS
Np = np NA

Φ = (number of events)/
(number of photons absorbed)
∫λ Qλ dλ
See fluence
I = dP/dΩ
P = dQ/dt

SI units

Notes

1

1

m–1
m2 mol–1
m2

2
3
4

mol
mol m–3
m2
mol–1
A
J m–2
Hz
W m–2

5
6

s
m
m–2
m–2 s–1
mol s–1
s–1
m–2 s–1
1
Pa
1

7
8

9
9
10
9, 11
9, 12

J
W sr–1
W

13

(continues on next page)

© 2004 IUPAC, Pure and Applied Chemistry 76, 2105–2146

H. J. KUHN et al.

2108
Table (Continued).
Name

Symbol

radiative lifetime
rate constant for radiative step
refractive index
sensitivity
of an actinometer

τ0
kr
n

of a photodiode
solid angle
spectral fluence (in terms
of wavelength)
speed of light
in vacuum
in a medium
temperature, Celsius
temperature, thermodynamic
time
transmittance
volume
wavelength
wavenumber

Definition

τ0 = 1/kr
n = c0/c

Spd

Sac(λ) = Φ (λ) ε(λobs)
or Sac(λ) = Φ (λ) ∆ε (λobs)
Spd = Ipd /P


H'λ

Ω = S/r2
H'λ = dH'/dλ

c0
c
θ
T
t
T
V
λ

ν

c0 = 299 792 458 m s–1
c = c0/n
θ/°C = T /K – 273.15

Sac

T = P/P0

ν = ν/c0 = 1/n λ

SI units

Notes

s
s–1
1
m2 mol–1

14

A W–1
= V–1
sr, 1
J m–3

15

m s–1
m s–1
°C
K
s
1
m3
m
m–1

16
17

1

Notes
1.
2.
3.
4.
5.
6.
7.
8.
9.

10.
11.
12.
13.
14.

15.
16.

If losses from reflection, scattering, and luminescence are neglected, T = P/P0 = I/I0, where superscript 0 indicates incident radiant energy and no superscript transmitted radiant energy.
In spectroscopy, usually defined in terms of the spectral radiant power, Pλ = dP(λ)/dλ.
Numerical values are often quoted in mol–1 dm3 cm–1. Note the lack of compactness in using two submultiples of length.
In spectroscopy, the net cross-section resulting from the sum of effects due to absorption and induced emission. A conversion equation in common units is σ/cm2 = (3.823 6 × 10–21/mol) × (ε/dm3 cm–1 mol–1).
Amount of photons is often given in the non-SI unit einstein = mol.
The usual units are mol dm–3 or mol l–1 or submultiples. Commonly, the non-SI unit M (small cap) is used
as an abbreviation for mol dm–3.
2002 value [1].
For a parallel and normally incident beam, a synonym is radiant exposure. When applied to the total radiant energy incident from all directions, the symbol H′ is used.
These quantities, defined on a number basis, can be expressed on a chemical amount basis by dividing by
the Avogadro constant, e.g., photon flux (chemical amount basis) = qp/NA. If distinction needs to be made
between quantities based on chemical amount and number, then symbols such as qn,p and qp can be used.
A common unit is einstein s–1. A term not in accordance with the usual definition of flux [2].
As defined in [4] (see also [5]); called photon flux in [3], a term not in accordance with the usual definition
of flux [2].
Equivalent to photon fluence rate for a parallel beam not scattered or reflected.
Definition from [2]; synonymous with radiant energy power, radiant energy flux defined in [3].
λ is the excitation wavelength, and λobs is the observation wavelength which may be the same as or differ
from the former. The first definition corresponds to the case in which the actinometer does not absorb at λobs,
whereas the second definition corresponds to the case in which the actinometer absorbs at λobs. Common
units are dm3 mol–1 cm–1.
Related to qn,p by qn,p = [λ/(NA h c Spd)] ipd with ipd the electric current of the photodiode.
The stearadian is an SI supplementary unit, but is dimensionless, so has SI unit 1.

© 2004 IUPAC, Pure and Applied Chemistry 76, 2105–2146

D. J. prepared for publication by I. Kallay. e. Homann. some methods have been improved.. Some actinometers have been added. terms from which are included in [5]. gas. photon fluence. Units and Symbols in Physical Chemistry (the ‘Green Book’). and units given in [2. A chemical actinometer or dosimeter is a chemical system (fluid. Chem. McNaught and A. IUPAC Recommendations. which may have any form or geometry. λ) for which the quantum yield. Verhoeven (2nd ed. Blackwell Science. formed. 60. or a photodiode). Switzerland (1992). © 2004 IUPAC. or in a microheterogeneous environment) that undergoes a light-induced reaction (at a certain wavelength. Quantities. UK (1997). PREFACE The first version of this document appeared in Pure Appl. the actinometer reagent is no longer commercially available. Should this not be the case. Oxford. N. The quantum yield of a photochemical reaction is defined as Φ(λ) = the number of events. IUPAC Organic Chemistry Division.g. Chem. The Photochemistry Commission (1998–2001) and subsequently the Subcommittee on Photochemistry (from 2001) decided to update and expand the document. λ) = qo(λ) for total absorption during the whole irradiation period. 61. molecules changed. The latter has been due to various reasons. Mills. 2nd ed.). 3. photon flux. The incident photon flux qpo is calculated from the relation qp(abs. Houk (1st ed. K. integration of the differential absorbance over time would be necessary. λ) = qpo(λ) (1–10–A(λ)). K. Pure Appl. Part 6: Light and related electromagnetic radiations. Commission on Photochemistry. is accurately known. Cvitaš.. provided that the decadic absorbance A(λ) is constant ±10 % during the irradiation time. 1055 (1996). symbols. Measuring the reaction rate allows the calculation of the absorbed photon flux. and a list of terms used is included. and some procedures have been modified. Determination of conversion to the products affords the total number of photons absorbed by the liquid or gas volume or solid surface.). a calibrated radiometer. 4. ISO 31–6:1992(E).g. and in other cases. see below). In some cases. E. Pure and Applied Chemistry 76. 187–210 (1989). compiled by A. an actinometer is a chemical system or a physical device by which the number of photons in a beam absorbed into the defined space of a chemical reactor can be determined integrally or per time.3]. e. 2105–2146 . a calorimeter. Kuchitsu. 2nd ed.. solid. Analogous quantities relative to frequency or to wavenumber may also be defined. Oxford.).nist. and are slightly modified from those in [4]. W. Calibration of an actinometer is done by applying a calibration lamp or by absolute measurement of irradiance (using. Blackwell Science. whereas others have been deleted from the list with recommended procedures for their use. 2. the sections on gas-phase and solid-state actinometers have been expanded. ISO. IUPAC. In particular.. Since then. Compendium of Chemical Terminology. divided by the number of absorbed photons of that particular wavelength in the same period of time. <http://physics. Braslavsky. or destroyed. Entries in the table are consistent with terminology. The terms related to radiation quantities have been made consistent with the International Organization for Standardization (ISO) recommendations. N. UK (1993). Photothermal methods are often used to calibrate actinometers in absolute terms. T. Wilkinson. References for Table 1: 1. Glossary of Terms Used in Photochemistry (2nd ed. prepared for publication by S. According to the “Glossary of terms used in photochemistry” (IUPAC Recommendations 1996.Chemical actinometry 17. The easiest case is for qp(abs. Φ(λ). the complexity of the procedure for the use or disposal of the waste does not justify the inclusion of the actinometer in a recommended list. 2109 Other physical quantities X such as irradiance. Geneva. Handbook on Quantities and Units. and radiant intensity may be used to derive the corresponding “spectral” quantity (relative to wavelength) by Xλ = dX/dλ. 5. K.gov/constants> IUPAC. photon fluence rate.

2223–2286 (1996). • • A. 2nd ed. ECRs are special thermopiles [3] or piezoelectric radiometers [4.. these outstanding properties are inherent in only a small number of electrically calibrated radiometers (ECRs) available in a few highly equipped laboratories. light sources. New York (1993). J. Hug. photochemical conversion is directly related to the number of photons absorbed because the chemical action of light means reversible or irreversible chemical change. I. E. L. Scaiano (Ed. semiconductors. or photodiodes are only secondary standards. L. Absolute measurement of incident irradiance.1 Pros and cons of chemical actinometry In a chemical actinometer (CA). CRC Handbook of Organic Photochemistry. using precalibrated photodiodes is described in Section 2. Handbook of Photochemistry. John Wiley. Visually unnoticeable damage of photodiodes occurs during exposure to high irradiation levels (generally more than 10 mW cm–2 for silicon photodiodes in continuous wave experiments) resulting in an irreversible decrease of sensitivity and severe inhomogeneities in the surface. physical devices furnished with a direct readout become more and more popular among photochemists for the measurement of radiation.. The spectral sensitivity of the widespread silicon photodiodes is even altered without use. principles of photochemistry. New York (1991).). © 2004 IUPAC. 68. W. However.. Maurette. Boca Raton (1989). Pure Appl. like usual thermopiles. Chem. refer to: • J. In contrast to the physical detectors. and electronic equipment. GENERAL CONSIDERATIONS ON CHEMICAL ACTINOMETRY 1. available at <http://www. Ep/s–1 m–2 or Εn. read Section 1 of this document and consult. A new version is in preparation. CRC Press. ch/epa/>. of their properties such as spectra. Physical devices are often preferred to CAs for the case of simple irradiation geometries because of their easy. e. The majority of physical detectors. M. 1. Pure and Applied Chemistry 76. J.. destruction or buildup of molecules and. E/W m–2 or photon irradiance. Murov. C.g. occasional recalibration of radiation detectors against a standard is strongly recommended. idem. provided that they are employed according to the recommended procedures. 2 vols. The sensitivity of a joulemeter may decrease with use due to surface damage by high-power radiation. consequently. 2105–2146 . piezoelectric joulemeters. Presses Polytechniques Romandes. and precise performance. Marcel Dekker.-T. Lausanne (1986). For the most recent version of “Glossary of terms and definitions used in photochemistry”. i.e. Oliveros.5]. fast. well-established CAs lead to accurate absolute radiation measurements. Braun. the response of which can be subject to changes. S. Owing to the recent progress in the development of radiation detectors. Verhoeven.p/einstein s–1 m–2 or photon flux.3 of this document. just by aging. G. Chemical actinometry has been employed for about 70 years in photochemistry as a relatively simple and accurate method for radiation measurement [2]. KUHN et al.p/einstein s–1. Technologie Photochimique. These CAs have been proven reproducible and do not demand any recalibration. The same is valid for thermopiles. as well as possible sources of error when performing actinometric measurements. For details and references concerning radiometry and actinometry. qn.unibas. An 18 % decrease in sensitivity at 300 nm in one year was reported to be a typical value [6]. Carmichael. Photochemical Technology. M.2110 H. Consequently. and reactors. which can be calibrated in an absolute manner by electrical substitution without the need of any standard. The extent of this effect depends on the wavelength range in which the detector will be used.

a CA yields the radiant power P entering the sample cell.p/einstein s–1. The CAs offered in the present list meet the requirements mentioned above in various degrees. The actinometric material should be easy to synthesize and purify. or photon flux. The chemical components should be thermally stable to exclude complications due to dark reactions. In the following section. 1. conversion of photon flux to radiant power needs © 2004 IUPAC. the calibration by CAs is particularly easy since calibration at only one wavelength is sufficient. qp/s–1. Quantum yields should be accurately known for a large number of wavelengths.1 Refractive index In this paragraph.g. However. and a careful selection among the CAs is appropriate. Photochemists using physical equipment for radiation measurements need standards for the occasional recalibration of their detectors.4. depending on the intended experiment. Fields of application of chemical actinometry It is important to mention that chemical actinometry covers only the wavelength range up to 795 nm. number basis. CAs are the first choice for this procedure. qn. CAs serve best for the purpose of absolute radiation measurement and are unrivalled by physical devices. entering the sample cell at a given wavelength. Direct spectrophotometric analysis is preferred. it should be commercially available. 2105–2146 . At high laser powers. Reading the original literature on each actinometer prior to its use is highly recommended. Only in this case. Measurements of laser pulse energies can conveniently be done by joulemeters. Each system suffers also from disadvantages. photoreactors of the merry-go-round type).4 Potential errors in chemical actinometry The detailed description of the chemical system and the limitations and possible sources of errors for each CA should be made explicit in every publication. most CAs will probably lose accuracy and sensitivity due to multiple photon processes occurring at high photon densities. Disposal of the waste should be straightforward. the discussion will be restricted to the case of monochromatic irradiation. Those CAs that have been investigated especially at high photon fluxes using laser excitation can be used as standards for this purpose [7]. amount basis. For detectors with wavelength-independent response like thermopiles and joulemeters.Chemical actinometry 1. A wide usable spectral range and wavelength-independent quantum yields are desired. The system should display large sensitivity. In any case. In photochemical experiments involving a complex irradiation geometry (e. Pure and Applied Chemistry 76.3 The photochemical system should be simple and well studied. a periodically repeated calibration by CAs at reduced laser power is an easy way of controlling the accuracy of the power meter. 1. The photoreaction must be reproducible under well-defined and easily controllable experimental conditions. only general aspects are discussed. since a CA yields a photon flux. chemical actinometry is the standard procedure for radiation measurement. The handling of the photochemical system and the evaluation of the number of photons absorbed should be simple and straightforward. The analytical methods should be simple. In the case of polychromatic irradiation. in photobiological and photochemical laboratories with less sophisticated equipment but where workers are experienced in chemical techniques. if linearity of the joulemeter readout is guaranteed. Preferably.2 2111 Quality marks of a chemical actinometer An established CA should meet the following requirements: • • • • • • • 1..

Photochemical quantum yields usually do not depend on temperature or only do so slightly.2 Temperature The influence of temperature variation has been investigated for only a small number of CAs. However.e.49). and to 0. 2112 not only the knowledge of quantum yields and absorbances of the CA in the wavelength range considered.H.96 can be applied for the calculation of Pb or of Np. actinometric measurements at temperatures different from the recommended range should be avoided.2–trifluoroethanol [2. At 250 nm (1 – R) amounts to 0. whereby the second contribution is smaller than the first. Assuming that the incident radiation strikes the sample surface at a right angle. If photoproducts do absorb.4.2–trifluoroethan-1-ol] (n = 1. 2105–2146 . photoproducts should not absorb. At 400 and 800 nm.5 % at most. additional errors are introduced by light reflections and the necessary measurements of transmission during irradiation. 1. This arrangement is particularly advantageous for the case of high photon flux.959 for toluene (n = 1.3 Absorption by photoproducts Ideally. 1.4 % will be introduced should the correction be omitted. Deviations from this estimation are negligible for nonpolarized as well as polarized radiation as long as the angle of the incident radiation with respect to the plane of the sample lies between 70 and 90° [8]. © 2004 IUPAC. In this case. in the wavelength range of a particular CA. in some cases a large temperature variation of the possible dark reactions may take place.0 by introducing an additional error of 0. respectively. The temperature-induced changes in density lead to a corresponding change in concentration and consequently to an apparent change in chemical conversion. This difficulty should be considered with great care.956 for CS2 (n = 1.2.005 and 0.955 for 2.007. the reflectance at the boundary between two materials of refractive indices n1 and n2 can be calculated through the Fresnel law: n − n  R= 1 2  n1 + n2  2 While entering a quartz sample cell. a mean value of (1 – R) = 0. This effect can easily be cancelled out by measuring the conversion at the temperature of CA calibration or by calculation using tabulated density values. since the irradiated volume can be large. i. and possible competing dark reactions. Since in this case. J. to 0.4 Degree of absorption by the chemical actinometer Some CAs are designed for incomplete absorption of the actinic light. leading to a reduced conversion range. these systems are unfavorable for the measurement of low levels of radiation. the radiation passes the boundaries air/quartz and quartz/solution suffering reflections at each boundary. Pure and Applied Chemistry 76. an inner filter will develop. the density of solvents.. Thus. KUHN et al. but also the spectral distribution of the irradiation source. Therefore. these values are higher by 0. it follows that when comparing a photochemical system with a CA in different solvents an error of at most 0. From the above estimation.4. R is approximately the sum of the reflection losses at both boundaries.4.29). Pb = P/(1 – R). 1. A correction for the reflectance R should be performed in order to obtain the radiant power of the irradiation beam Pb. a high dynamic range of the actinometric measurement (number of photons. photon flux) can be expected.63).2. thus avoiding inhomogeneity problems during photoreaction. and extrapolation of the data to infinitely low conversion is recommended. only the wavelength dependence of the refractive index of quartz determines the wavelength dependence of R. Consequently. Temperature may influence an actinometric system through the temperature dependency of the quantum yield.

7. 567. W. however. severe inhomogeneity problems arise. In addition. Physik griffbereit. 2. R. it is in general easier to mimic the experimental situation of the sample. W. Soc. Zalewski. Appl. Am. F. Readers are encouraged to send complementary information. Opt. whenever possible. In this case. E.and liquid-phase systems which photochemists are most frequently dealing with. R. References to Section 1: 1. Pure Appl. 2. 2532–2535 (1973). Actinometric systems or procedures marked by an asterisk (* = well established) in the following list have been used over years by different authors in several laboratories and can thus be recommended (not necessarily. J. 2766–2771 (1981). J. Systematic IUPAC names are given in square brackets where applicable. 3. Polychromatic quantum counters are particularly accurate due to their wavelength-independent conversion yield. 68. LIST OF ACTINOMETERS The present compilation lists chemical systems that have been shown suitable for the integration of incident light by chemical conversion. and A. without precautions). which cannot be overcome even by effective stirring. experimental errors due to differences in shape.Chemical actinometry 2113 CAs exhibiting complete absorption of the radiation allow convenient measurement and easy evaluation and are thus preferred. Emphasis is mainly on gas. 12. With chemical systems.5 Polychromatic quantum counters CAs with wavelength-independent quantum yields allow polychromatic quantum counting in the specified wavelength range provided complete absorption is maintained. Forbes. 2. lenses. Appl. R. Chem. Geist and W. M. p. J. surface. A.2. B. Optik 28.3) are known. 2. S.g. 12. Opt. The same solvent and equal absorbances should be chosen for actinometry and reaction under study. 2223–2286 (1996). Cook. however. By choosing strictly identical experimental set-ups for standard and sample. Opt. D. 183–189 (1968/69).4. multiple photonic processes can be expected at high photon flux as often reported [7]. Systems that have fallen into discredit are given at the bottom of this list under the heading Disproved. Phys. Detlaf. Since at high absorbances the photoreaction occurs only in a very small reaction volume. Leighton and G. Braunschweig (1972). J. especially for low © 2004 IUPAC. etc. 4. Phelan. Blevin. Vieweg und Sohn. J.1 Chemical systems Several physical methods for the calibration of light sources (see Sections 1. Jr. can be avoided without much effort. Chem. L. 6. J. Verhoeven. 52. and comments. Chem.1).4. 85. filters. Gardner and F. Demas. A recommended alternative. J. Wilkinson. corrections. at the high photon flux met (e. and spatial arrangement of the reaction vessel. the penetration depth of irradiation is small. 1531–1534 (1985). Note carefully that names of chemicals are given usually as common names that appear in the relevant publications. Therefore. J. Bischoff. W. Corrections due to reflection losses at surfaces should be taken into account (see Section 1.. Pure and Applied Chemistry 76. 2494–2500 (1973). Velapoldi. A. This possible source of error is insufficiently discussed in the literature. G. 8. N. 24. Jaworski and A. 3139–3152 (1930). and 2. 5. R. K. each photon entering the actinometric solution causes chemical conversion with the same probability regardless of its energy. 2105–2146 . Appl. 1. in laser beams). All other systems appear to be not yet widely used and may be labelled under discussion. At high absorbance. Bowman. some solid-phase actinometers and convenient electronic devices are mentioned.

Vol. 225–294. Chap. G. photon densities at which multiphoton processes do not play a role.4). Tate. J. Photobiol. In Photochemistry and Photobiology of Nucleic Acids. A. Yamashita. J. Diffey. B 50. especially by P. 141–145 (1989). 1. Tetrahedron Lett. Chem. 2.g. Special Escherichia coli bacteria strain K12 AB2480 (uvrA– recA–) with photodamage repair deficiency (193. Grof. Photochem. Rontó. Photochem.4-dihydro-1. 2. Ito and T. Fekete and G. Photobiol. N... Rad. J. Am. Biofilm of Bacilus subtilis spores. E. Gaspar. Soc. Special issue on biological dosimetry of UV radiation. Eschweiler. Takayama. S03: 1-Ethyl-7-methyl-4-oxo-1. 64. Zuraw. S01: Uracil photodimerization in polycrystalline thin layer Biological UV dosimeter WR: >250 nm AM: absorption spectrum 250–400 nm Phage T7 used as a calibration system 1. J. © 2004 IUPAC. therein. and refs. Wang (Ed. 5. e. 37. pp. H. Schulte–Frohlinde.. 27–30 (1980).. 29. J. cf. some related “living dosimeters”: 2. B. Fisher and H. See the Abbreviations at the beginning of the document. The references given below in the area of solid-state chemical and biological dosimetry are not meant to cover this vast field as a whole but to give just some selected entry keys.8-naphthyridine-3-carboxylic acid (nalidixic acid) UV-A polyvinyl chloride film dosimeter WR: 280–360 nm AM: absorbance change at 330 nm PP: very preliminary batch-dependent data 1. Academic Press. Photobiol. Order in the following lists is with increasing wavelength range. J. 3091–3094 (1988). 345–348 (1983).g. G. S02: DNA photodamaging. Chem. 3. L. Rontó (Eds. Matsuura. on nylon membrane sealed in a polyethylene envelope Biological solar UV dosimeters WR: 254–330 nm AM: immunostaining with damage-specific monoclonal antibody [1] 1.4. Photobiol. U. S. T. Davis. 2. therein. e. 4. Photochem.). Bücker. For quantitative measurements in sol-gel materials. 3087–3090. New York (1976). Research 141. L. S. Y. Ishigaki. K.. 389–395 (1992). Johns. 55. is to use a totally absorbing actinometer solution (see Section 1. Mater. 111. Photochem. Pure and Applied Chemistry 76.1.2114 H. H. Görner. S. Howard-Flanders et al. Horneck. Photobiol. Levy. see: D. Photochem. G. Y. Quintern. O. 244–251 (1995) and refs. KUHN et al. Nikaido. G. Photobiol. e. Photobiol. 800–806 (1996). Zimmerman and M.: Y. E. H. Photochem. B 53 (1999). 184–188 (1999). D.. 9. 2105–2146 . J.).1 Solid. Young. G. R. A. P. J. 31.g. 254 nm). A 50. Gibbs and A. A. Photochem. 2666–2670 (1997). 7974–7989 (1989).and microheterogeneous-phase chemical actinometers For solid-state quantum yield determination procedures cf. Gurzadyan.

C. Y. starting material disappearance and product appearance. Gawad. B. Davis. Photochem. M. J. N. Barnard. Photobiol. 34. Jr. 1623–1629 (1989). G. 2. 34. J. Tate. A. Carter. S06: o-Nitrobenzaldehyde → o-nitrosobenzoic acid photoisomerization WR: 310–400 nm. C. J. P. Lazare. 105–115 (1986). 3. Photochem. Soc. T. J. Photobiol. Vesley. Some related UV-A and B dosimeter systems: polycarbonate plastic.4. 219–231 (1983). J. 611–615 (1989). Photochem. Jr. J. W. Nakai. S. e. Photochem. 103–112 (1995). Acta 318. 7. 2. J.5 (same in all phases) WR: 280–410 nm. Li. E. Fuchsin and sandolan yellow dyes in polyvinyl alcohol polymer. Debrabandere. Jr. Chem. S. Das. J. B. L22 WR: 300–400 nm. P. A. J. Φ = 10–3–10–1 depending on [Thymine] and [SDS]/[H2O] ratio A TiO2-sol-based actinometer used to determine number of photons absorbed AM: decrease of thymine absorption at 265 nm 1. W.4-methanonaphthalene-5. Chem. Chem. A. Fleming. F. G. 4. J. 123–131 (1992). 756–759 (1934). N. G. Wong.5 ± 0. KBr pellet. Pitts. 3606–3610 (1964). 1106–1110 (1968). A. Ind. Am. Wan. J. A. 46. D. 305–321 (1965). W. Analyt. C. Fattah. Pure and Applied Chemistry 76. K.. Photochem. Cowell and J.. Allen. Fleischmann. E. E. 653–655 (1976). S. Quantitative erythemal effectiveness given vs. J. J. K. W. Φ = 0. Roy and S. Y. Chim. Φ ~ 10–3 AM: absorbance at 420 nm 1. 2. E. GC 1. Photochem. S.4a. L. 55–60 (1987). S. Photochem. B. A.g. S07: Polysulfone UV-B film dosimeter WR: ≤315 nm AM: absorbance change at 300 nm 1. [5]). Φ = 1. G. L31*. Bunce and J. Leermakers. A. Schuck. 50. Photochem. Stewart.Chemical actinometry 2115 S04: Thymine dimerization UV-B radiation dosimeter in SDS microemulsions WR: 290–320 nm. 2. J.8-dione] photoisomerization in a dry silica matrix Irradiation apparatus described for adsorbed substances WR: 362 ± 5 nm. λ. J. Ware. H. 6. Also applicable in gas and liquid phase. 90. S08: Diels–Alder adduct of 2. C. 4. A. Phys. de Mayo. Irradiance was measured using a vacuum thermopile. R. 69. 14A. Pitts. 34. A. J. E. 2105–2146 . S05: Azoxybenzene → 2-hydroxyazobenzene. J. E. 4. Photochem.7-dimethyl-1. N. Baum. Photobiol. 86. S. 34. R.06 AM: IR 1530 cm–1 (NO2 band disappearance) 1. Photobiol. S. A. N. for the measurement and penetration of UV radiation into marine water (see also L35. J. Lemke. N. J. Photobiol. S. Limnol. Leighton and F. Hess. ∆A(300 nm) mathematically correlates with the UV (300 nm) radiant exposure H/J m–2. S. 283–286 (1981). Am. K. Photobiol. Wan. Oceanogr. © 2004 IUPAC. Diffey.0 (vs. cf. poly(methyl methacrylate). Smith. K. 5. A. Montgomery. Huang. ferrioxalate. P. Schuck. B. A 64. Φ = 0. Pitts. J. Allen. L. comparison of radiometric with actinometric measurements. Che. Lucy. 187–190 (1981). 3. M. 17S–18S (1999). J. also in solution) AM: absorbance. 23. R. Rehim. cf.. Dreiman. Chem. Soc.8atetrahydro-1. L.5-dimethylbenzoquinone and cyclopentadiene [4a. F. A. S. Diffey.. Baertschi. Photobiol. Bunce. Jacobs. poly(methyl methacrylate) block. M.

Physics Essays 13. A. M. 2. Saito and H. Pravilov. Heicklen. Metrologia 32. separation of N2 from NO and O2 or very accurate pressure measurement The use of the traditional name nitrous oxide is not recommended by IUPAC. from 0. Photochemistry. M. Phys. 21. Appl. High Energy Chem. M. “The quantum yield of ionization”. 333–336 (1959). J. W. J. 291–304 (1987)] and J. Zelikoff and L. 2. J. Kinet. J. New York (1966). G. N. “Gas-phase actinometry for UV and vacuum UV spectral regions”. Am. E. F. 6. Chem. N. Bercowitz. S09: Quinonaphthalone [2-(2-quinolyl)indane-1. Φ = 2 × 10–5 AM: absorbance decrease at 420 nm 1. J. Φ(∆n) ~ 0. Okabe. ion) vary with λ. M. Shul’pyakov. Physics Essays 13. Photobiol. Φ(Ν2) = 1. 3. Soc.1 at moderate pressure near room temperature. 4.0 at low conversions and fast flow systems AM: absorbance at 353 nm of iodine–iodide complex (formed from the produced ozone bubbled through a KI solution) 1. Opt. Jr. 525–529 (1996). 283–287 (1971). 21. Appl. M. PP: The use of the traditional name nitric oxide is not recommended by IUPAC. G01: Rare gases photoionization WR: 4. J. High Energy Chem.6 in the 75–105 nm region [1] AM: ion yield by photocurrent measurement. Pitts. John Wiley. H.2116 H. R. Space Sci. Energ.1. 782. 47–54 (1974). H. Φ(ion) = 1 at infinitely low pressure AM: He or Ne ion current measurement.2 Gas-phase chemical actinometers For reviews on UV and vacuum UV actinometers. N. Chem. 2. Greiner. 1685–1687 (1954). Bercowitz. Φ(λ. 64. 47. A. G02: Nitrogen monoxide (NO) photoionization WR: ≤134 nm. C. Φ(Ν2) = 1. 782. Calvert and J. 351–354 (1985). 243–255 (1987) [Russian: Khim. extrapolation to zero pressure to correct for secondary ionization [1] 1. Dodge and J. Pravilov and I. Chem. Opt. 2. K.66 to 0. 1. Photochem. J. New York (1966). 1. 5. 13. Bercowitz. Vys. 248–255 (2000). N. Phys. Photochemistry.18 at 123. 391–396 (1967). Jr. Onuki. absolute photon fluences measured with a calibrated thermocouple 1. Schierholz.05.3–0. Planet. Calvert and J. KUHN et al. 248–255 (2000). Pitts. Samson and G. G. 3. Pure and Applied Chemistry 76. J. Driscoll and P. N. 2105–2146 . O. Φ(O3) = 2. 269–282 (1971). 2. Groth and H. Sakai. R.00 ± 0. John Wiley. J.3-dione] photofading Plastic plates WR: 366–436 nm. p. T. p.6 nm [3]. G04: Oxygen photolysis WR: 130–190 nm. 19. 5. cf.4–102.2 nm. J. 248–255 (2000). Opt.8 at 105–120 nm [3] AM: N2 analysis.44 ± 0. M. G03*: Dinitrogen oxide (N2O) photolysis WR: 147–185 (138–210) nm. Matsunaga. A. Watanabe. J. 20. Haddad. cf. Φ(∆n) = Φ(Ν2) + Φ(Ο2) + Φ(NO) – Φ(Ν2Ο) = 1. Int. 4054–4058 (1981). Warneck. Physics Essays 13. pressure measurement PP: low absorbance at 150–170 nm (ε ≤ 30 dm3 mol–1 cm–1). cf.98 in the 58–75 nm region and are 0. 3. Aschenbrand. 4373–4377 (1967). © 2004 IUPAC. 22.

R. 1161–1166 (1978). G. Roland. Am. Photochemistry of Small Molecules. New York (1978).Chemical actinometry 2117 3. H. 76. 2. 408–409 (1966). Naturforsch. p. 138–140 (1972). P. Glasgow and P. 2790–2791 (1970). 2105–2146 . Pitts. pressure measurement PP: care must be taken for λ > 180 nm [1] 1. 62. 2. Pure and Applied Chemistry 76.97 ± 0. J. 1336–1342 (1998). L. wavelength. R. Int.1 at 254 nm. John Wiley. O. J. Opt. R. Magenheimer and R. P. N. G.5–1. Phys. Calvert and J. New York (1966). G10: Phosgene photolysis WR: 200–280 nm. Phys. Okabe. J. Kinet. 628–638 (1972).38 AM: ion saturation current. K. McKellar. A. 1161–1166 (1978). Chem. Timmons. Glicker and H. Photochemistry. p. Int. J. Φ(ion) = 0. 1469–1472 (1975). oxygen formed must be separated PP: complex system with interferences by O3 and heterogeneous reactions on the walls 1. 3. J. B. cf. Φ(CO) = 0. 2. 10. R. Sethi. Chem. Pitts. Wiley-Interscience. Phillips. K. Soc. 782. 2999–3007 (1964). Phys. D. G. 389–398 (1976). Okabe. M. C. Wiley-Interscience. J. G06: Ethene photolysis WR: 147. Okabe. J. Powell and D. independent of pressure.4. Phys. Scala. Phys. 3. M. 2. 7. 4. Photochemistry of Small Molecules. 27a. cf.0 ± 0. very precise 1. G. Z. Phys. D: Appl. Potzinger. 56. Chem. G09*: Hydrogen bromide photolysis WR: 170–255 nm. p. L. Willard. Bolle. J. A. H. 126. Br2 absorbance at 450 nm [3] 1. 185 nm. Sethi. S. A. Kinet. C. Φ = 1 (H2 or Br2) at 100 mm. Khan. 782. John Wiley. W. Glasgow. G05: Hexafluoroacetone photolysis WR: 147 nm. Jr. Warneck. J. F. 31. Photochemistry. G08: Carbon dioxide photolysis WR: below 170 nm. S. J. Anderson. Calvert and J. Potzinger. Chem. 437–440 (1987). Chem. S.06 variable with λ AM: CO analysis. von Bünau. Chem. Φ(CO) = 0. G07: Trimethylamine photoionization WR: 147 nm. Davies. J. p. Salomon and A. Photochem. J. at low conversion (<1 %) due to interference by product Br2 AM: H2 analysis. Powell and D. 10. New York (1966). Martin and J. Phys. 127. New York (1978). 91. 163. p. N. Wiley-Interscience. P. New York (1978). 1 at 185 nm AM: CO measurement at liquid nitrogen temperature 1. G. G. J. 2. and temperature AM: H2 analysis. Φ(CO) = 1. Φ(H2) = 0. J. 40. 3. Chem. Hg interferes. Jr. Photochemistry of Small Molecules. E.05 AM: CO 1. Okabe. Mol. 127. 25 °C. © 2004 IUPAC. H. R. 52.

R. 0. Chamberlain and E. A..4. Photobiol. AM: GC for CO. A. Vilesov. Φ(CO) = 0. A 86. New York (1966). A. T. Φ(CO) = 0. Phys. 37. R. 331–333 (1982). G15*: Pentan-3-one photolysis As G13. 56. 3. photon fluence. 2. 54. Clemitshaw and J. R. Cl(CF2)3COCl.2. University of Alberta (1971). Kinet. Pitts. 130 °C AM: GC or MS for CH4 and CO 1. Y. 16. 782. B. 402–404 (1974). F. E. F. Jr. and λ 1. Φ(CO) = 1.29 ± 0. 2.0 AM: NO analysis 1. Smirnova. p.. 181–186 (1990). 0. De Maré. simple pressure measurement for CO after freezing down at –196 °C G16: But-2-ene. L.2118 H. Photobiol. Fourier transform infrared (FTIR) spectroscopy 1. R. S. Pure and Applied Chemistry 76.34 at 20 °C AM: CO measurement. 265 nm. N. Photochem. M. E. J. Φ(CO) = 1. G11: Nitrosyl chloride photolysis WR: 230–630 nm. N. cf. Pitts. 468–469 (1978). 9–14 (1995).0 at ≥125 °C and ≤50 mm Hg AM: pressure measurement and GC (CO and CH4) after freezing down at –196 °C 1. C. Soc. G19: Perfluoropropionic anhydride WR: 254. Dissertation. Palmer. Faraday Soc. 165–215 (1964).02 at p ≥ 4 kPa AM: GC 1. p(HCl) = 1–8 mm Hg. J.50 ± 0. Photochemistry. Termonia and G. E. Φ(H2) = 0. J. Ryabov. High Energy Chem. Staricco. Calvert and J. 25. G14: Acetone/hydrogen chloride photolysis WR: 285.06 and 1. 2. A. Φ(CH4)/Φ(CO) = 2 at p(acetone) = 5–60 mm Hg. New York (1966). 241–246 (1987). G. 265 nm. John Wiley. E. B. Weibel. Rousseau. React. G. p. resp. Kozlov. Pollock.4-hexafluorobutanoyl chloride] (stable intermediate product) photolysis WR: 232–270 nm or 240–270 nm. High Energy Chem. Hg-sensitized photolysis WR: 254 nm. L. Φ(NO) ~ 2. 12.03 ± 0. M. Cundall.3. Whittle. Photochemistry. Photochem. J. Pravilov.02 ± 0. Karpov. G17: Propane. Hg-sensitized photoisomerization WR: 254 nm.3.581 at p = 40 kPa AM: pressure measurement 1. Cundall and T. Trans. de Staricco. Dissertation. Prog. D. KUHN et al. 2. J. 3. Horowitz. Faraday Trans. I. L. or Cl(CF2)3Cl PP: independent of total pressure. Jr. G18: Perfluoroacetic anhydride WR: 254. Φ(cis → trans) = Φ(trans → cis) = 0. Chem. Pravilov and S. G. 782. 1211–1224 (1960). G. G13*: Acetone photolysis WR: 250–320 nm. K. Lett. G. R. 2.06. Photochem. J. 300.29 at 200 °C AM: CO measurement © 2004 IUPAC. 1 71. H.02 at 25 °C. M. A. 1978–1990 (1975).24 at 26 °C. J. Sodeau. cf. 2105–2146 . Calvert and J. G12: Perfluoroglutaryl dichloride [4-chloro-2. John Wiley. 313 nm. Chem. University of Alberta (1963).

Staricco. von Sonntag. 1978–1990 (1975). G20: Azomethane WR: 270–410 nm: Φ(N2) = 1.-P. Abstr. cf. 100. 64.. A 102. Ag complex) PP: The 254 nm Hg line is ineffective. E. independent of temperature (24–164 °C).34 ± 0. Z. E. A. J. absolute measurement of radiant power with thermoelements) AM: Cl2 consumption 1. 3. New York (1978). 4. Soc. G22: Chlorine monofluoride WR: vacuum UV up to 320 nm. Chem. J. R. Bastian. Φ(H2) = 0. Φ (trans → cis) = 0. 5551–5561 (1998). formic acid. the 254 nm Hg line is ineffective.4-(dinitrophenyl)hydrazine]. fluence. Phys. © 2004 IUPAC. Srinivasan. cf. 5. E. G.04 AM: GC analysis of methanol degradation and products. 90–99 (1952). Margreiter. A. Adam and T.-Y. HPLC). Neuner. M. H. Wiley-Interscience. Heit. Chem. Faraday Trans.3 M) solution WR: 172 nm Xe-excimer source. G. for Cl2:O2 = 1:1. G21: Chlorine/hydrogen chain photoinitiation WR: 280–380 nm. L02*: cis-Cyclooctene cis–trans photoisomerization WR: 185 nm: Φ(cis → trans) = 0. Photobiol. Phys. 39. Phys. Φ depends on the ethanol concentration. independent of initial ClF pressure AM: Absorption at 210 nm of produced ClF3 1. DOC = dissolved organic carbon. Chamberlain and E. ethylene glycol. A 102. 2105–2146 . Chebotarev. de Staricco. L01: Water photohomolysis (OH radical production) in methanol (0. Photobiol. 279–285 (1989). Srinivasan and J. H. Braun. L03*: Ethanol photolysis (Farkas actinometer) WR: 185 nm. Schomburg. Cremer and H. Φ = 0. Photochem. Φ ~ 30–36 (chain length between 15 and 18. Chem. no temperature dependence in the 15–40 °C range. 1 71.02 M). A. 2. G. E. 15. 2. Study of perfluorosuccinic anhydride photolysis: D. Margreiter.44 [5] AM: trans-cyclooctene analysis (GC. 2. Whittle. Photochem. Chem. 5551–5561 (1998). Okabe.1 %). F. R. A. Heit. Cremer and H. E. Pure and Applied Chemistry 76. calibration by cyclooctene actinometer. M. 163–170 (1974). Weibel. J. WR: 172 nm (Xe-excimer source): Φ(cis → trans) = 0. 1105–1106 (1986). Weeke. L02 1. 2. Soc. Photochemistry of Small Molecules. P. 427 (1952). J. F. G. 7089–7091 (1978). J. Chem. Oppenländer.3 Liquid-phase chemical actinometers For additional literature.4 in 5 M aqueous solution AM: H2 analysis (GC) PP: Solution must be free of H atom scavengers like O2 and acetaldehyde which implies low conversions (≤0. Appendix.2–0. 159–162 (1981). Neuner. p. 60.Chemical actinometry 2119 1.4-DNPH [2. J. Saugy. (Leipzig) 199. Chem.1. Schuchmann. R. Saugy.. Chem. Angew.32. Braun. A. C.42 ± 0.02 in n-pentane (0. J. Am. A 49. A. E.-Y. 105. and pressure AM: N2 must be isolated from the N2 + CH4 mixture 1. formaldehyde (2. Photochem. H. Ors. 1. Chem. 128. Russ. Φ(ClF3) = 1 at room temperature. W. 87729c (1986). N. Chromatographia 7. Phys. 719–723 (1984). P.

Jr. Proc. G. Phys. 15. A. Am. R. Turse. Chem. Phys. Pitts. Middleton. S. 86. Fitzgerald (Ed. M. Chem. J. 52. González. Leighton and G. K. Lippman. G. [12]. 77. Soc. H. 787. C. Murov. Volman. A. N. Forbes. L05: Glucose photolysis WR: 200–300 nm. K. 1233–1237 (1949). NH2OH PP: HN3 (CAUTION. Forbes. 2501–2503 (1963). Beltrán–Heredia. thesis. J. 81 and refs. J. Phys.05 in water AM: absorbance (HN3). Discher. California Institute of Technology (1972). A. Marcel Dekker. 11. A235. A. or GC (pH dependency [7. Eaton. 3. R. 84. 10. J. Tregay. H. Parker. therein. p. 10. ibid. de Mayo and H. Anal.. 5. Proc. 6. and not higher than twice. 1. Volman and J. P.00 ± 0. D. New York (1993). 3139–3152 (1930). Brim. 12. Pitts. McKellar. K.). (London). Chem. Schuchmann. J. Ind. Chem. Taylor. W. S. Ph. F. 59–145 (1977). Khan. H. Creation and Detection of the Excited State. J. Jr. 140. von Sonntag and H. © 2004 IUPAC. Soc. 120. 2105–2146 . Pure and Applied Chemistry 76. 104–116 (1953). Schuchmann and C. R. N. J. 5. Chem. E. Mol. Treinin. J. Weeke. Bracket and G. W. Chem. F. Fly. S. N. John Wiley. Seed. For the preparation of Ce(IV) cf. 305. Φ = 1. Photochem. A. Margerum. L06*: Uranyl oxalate [dioxouranium(VI) oxalate] photolysis hν H 2 C2O4 → H 2O + CO2 + CO WR: 200–500 nm: Φ ~ 0. R.5–0. 122–123 (1976). 5499–5501 (1955). 7. T. J.D. G. Chem. O. 14A. 2120 1. 13. D. L. H. Acero. J. Taylor. Smith and W. and no thermal decomposition was observed under the conditions applied. J. 91. 9. 74. P. Schomburg.33 in 5 % aqueous solution AM: absorbance of malonaldehyde/2-methylindole complex at 555 nm 1.-P. Smith. C. Φ ~ 0. 389–398 (1976). K. 8. 4. Calvert and J. Chem. J. Jr. 77. New York (1976). P. Adv. 2095–2100 (1994). G. F. Marcel Dekker. 2011–2012 (1962). Am. Soc. Chromatographia 7. J. P. 13. Am. Ware (Ed. F.6 in acidic aqueous solution AM: KMnO4 titration (rather insensitive at low conversion [9]) or absorbance at 320 nm of Ce(IV) after incubation (80 °C. 1195–1198 (1973). 7. 16. Photochem. F. 2. Shizuka. method depends critically on Ce(IV) concentration which should not be less than that of. D. New York (1966). Shapira and A. In Analytical Photochemistry and Photochemical Analysis. L. 28. J. 67. 2. Soc. 10 min) of photolyzed solution with cerium(IV) sulfate in H2SO4 (vs. Sect. F. 14. Phillips. A. Chem. Rao. Porter and D. p. N. Davies. 2nd ed. F. C. 3. Benítez. EXPLOSIVE) was prepared in solution from NaN3 and HClO4 immediately prior to irradiation. Photochem. Am. C. 4. Marcel Dekker. L.) 4. W. KUHN et al. 4459–4466 (1933). 69. J. Datta and K. 289–295 (1981).-P. R. Soc. L04: Hydrogen azide (hydrazoic acid) photolysis WR: 200–260 nm. von Sonntag. J. J. a nonirradiated blank). Chem. Z. Parker. 163–170 (1974). 1876–1882 (1970). F. Chem. (London) A220. H.10]) for CO. Water Res. 1.. W. p. R. 292–304 (1970). Soc. 5095–5098 (1964). G.H. J. Am. D. Bastian. 518–536 (1956). I. Soc. C. New York (1971). Hatchard and C. 55. R. F. J. J. N2. Handbook of Photochemistry. G. CO2 PP: Use of commercial Ce(IV) sulfate for titration of nonphotolyzed C2O42– is not recommended because ammonium nitrate impurities may limit the stability of the standardized solution. A. Phys. Heidt. von Sonntag. the C2O42– concentration of the blank. Photochemistry. G. 21. p.

Thomas. 2. L07: Malachite green leucocyanide (4-dimethylamino)-α-[4-(dimethylamino)phenyl]-α-phenylbenzeneacetonitrile [2. Johns. M. Soc. J. 323–332 (1994). Johns. Nikogosyan. 1. Smith. Φ(λ) = 0. Leighton.016 (280 nm). G. Photochem. 4. Ar [5]).-P. B. Photochem. Alfano. HPLC PP: (1–1.034 (doubtful. 25 °C. 143–153 (1996).). 757–767 (1967).017 (265 nm). A 79. pp. Wang (Ed. A. Water SRT–Aqua 41. Schuchmann.).009/°C in aqueous solution AM: product formation by potentiometry. J. V. 61. H. Am. Fitzgerald (Ed. L. A. von Sonntag and H. In Photochemistry and Photobiology of Nucleic Acids. 91–115. Soc. Kogelschatz. Technol. Photobiol. Nagashiro. H. 413–427 (1990). Makita. M. Leighton. Photochem. 2. O.-Gel. 101–105 (1979). E.019 [1. Vol. applied to 222-nm excimer lamp [9]). 0.. Φ(λ) = 0. J. 67–74 (1992). García Camacho.2-bis(4-dimethylamino)phenyl]-2-phenylacetonitrile] photoionization in slightly acidified ethanol WR: 225–289 nm (especially useful for very low fluences).6] refer to chromophore loss due to photohydration.. B 5. Gurzadyan and H. Am. New York (1976). Φ(λ) ca. Taylor. 1. J. © 2004 IUPAC. no effect of oxygen at 254 nm. Chap. Chem. Görner. In thin films: H. Rossetti. 91–110 (1991). 6. H. F. 4. 2299–2301 (1939). J. 0. J. A. N. H. Fitzgerald (Ed. G. Rechen. turbidimetry.). Chem. Photochem. 62.Chemical actinometry 2121 16. In Analytical Photochemistry and Photochemical Analysis. G. 42. B 10. Marcel Dekker. Chalkley. A.8] at shorter λ (193 nm) are ascribed to additional ionization pathways and to dimerization reactions at higher concentrations. J. J. P. Chem. Y. Ind. 2105–2146 . E. Calvert and H. J. 2. R. LeBlanc. J. L08: Chloroacetic acid photohydrolysis WR: ≤270 nm. 1. 2. Pure and Applied Chemistry 76. C. Photobiol..019 (254 nm. Photobiol. 37. Photobiol. Görner. Appl.31 at 254 nm (vs. J.017 (238 nm). Soc. Fernández Sevilla. A. M. 141–149 (1994). Khoroshilova. J. Y. Setlow. Radiat. W. 6. 1879–1880 (1940).5) × 10–4–10–5 M neutral aqueous solution. Sci. D. C.018 (254 nm [8]. G. Chem. Swenson and R. 63. Getoff. 74. 5. Photochem. J. Taylor.6]). Sol. New York (1971). MacDonald. Φ(λ) = 0. Chemii 29. Φ(λ) = 0. 60. other actinometers). Photobiol. PP: Care should be taken to avoid product accumulation. 3. Neumann-Spallart and N. H. pp. conditions not given. Gurzadyan and H. Photochem. E. Phycol. 13. L09*: Uridine (1-β-D-ribofuranosyluracil) photohydration in H2O WR: 216–280 nm. Nohr. Am. G. 3592–3601 (1998). Cl– ion-specific electrode 1. J. Photochem. C. Φ(λ) = 0. 419–434 (1963). 5. Nakazumi. R. N. temperature coefficient + 0. Roczn. J. 834–838 (1955). Görner. 12. Phys. J. Albizzati. Fisher and H. 901–909 (1997).5. J. Am. 385–394 (2000). Φ(λ) = 0.027. Φ = 0. U. G. Kemula and A. von Sonntag. K. Res. Ar [8]) AM: absorbance of uridine at 262 nm (chromophore loss). 387–392 (1952). G. 2101–2103 (1952). Fisher. E. Mark. S. M. Φ(λ) = 0.032 (193 nm laser. Marcel Dekker. G. Opt. 7. D. Chem. R. P. On paper: L.01 (determined by using a thermopile for absolute measurement of fluences) AM: absorbance at 620 nm 1. J. Soc. fluence measured with a calibrated joulemeter). W. H. J. polarography. Schuchmann. M. Photobiol. L. In Analytical Photochemistry and Photochemical Analysis. 0. higher values [5. New York (1971). S. 4. G. [4. G. pp. 0.-P. PP: Take care to dispose of the uranium waste in accordance with the legal regulations. 2. Molina Grima. G. Sánchez Mirón.91 ± 0. Chisti. 3. 17.044 (193 nm. 169–224. 8. 8. 0. B. 3. Eng.019 (248 nm). Φ(λ) = 0.018 (216-nm laser [8]). Grabowska. Academic Press. 91–115. Photobiol.

G. 139.0016. R. Chow. Chap. pH 7. Bortolus.01–0.37 ± 0. J. © 2004 IUPAC.0138 (265 nm). L. 29. R.40 ± 0. 91–110 (1991). Φ = 0. (0. H. Zimmerman. thermal cis → trans regeneration at 60 °C possible. G. 4. Z. 121–125 (1985). J. S. 482–486 (1997).24 in isooctane. 57.).0147 (280 nm) at 0. R. commercial p. J.0134 ± 0. Chem. 123. Rahn and H. Water Res.5.4trimethylpentane] different for the two bands. quality is sufficient. G. Blaney. J. L. EPA Newslett. 0.3-Dimethyluracil photohydration in aqueous solution WR: 240–280 nm. 15. N. 295. Chem. 2105–2146 . I. Surf. Abstr. Φ(cis → trans) = 0. Gauglitz and S. Sellin. 80. Φ(average) = 0. 7. reproducibility better than 2 %. Photobiol. Gahr. Gauglitz and S. Al-Nakib.48 in CH3OH. U. Nießner.35 ± 0. T. Φ(trans → cis) = 0. Boyd. J. 1142–1149 (1997). Numao. 0. Photochem. Fisher and H. and 310 nm AM: fluorometric estimation (excitation at 340 nm. 109/110. (0.5-b]pyridine 4-oxide] or 1-methyl-1-deazapurine N(3)-oxide [6-methylimidazo[4. P.4 × 10–4 M in CH3OH. Photobiol. L10: 1.0111 (248 nm). Photochem. 3. Phys. Appl. 1 mM solutions in 10 mM phosphate buffer. 37. 9. Siampiringue.0005 AM: absorbance at 266 nm 1.0007 in water (254 nm). Am. Görner. Gauglitz.-Y. L. 5.13–0. 30. Tetrahedron Lett.-J. no side products. J.0140 (240 nm). Chem. Sci. G. F. J. 2.14 in CH3OH. Davies. 317–318 (1979). K. Photochem. pp. O. 1.-Y.5-b]pyridine 4-oxide] fluorogenic photorearrangement WR: 250–310 nm.035) in THF or 20 % ethanol/water. 45–46 (1987). In Photochemistry and Photobiology of Nucleic Acids.025) in methanol. Application to polychromatic radiation (medium pressure Hg-arc plus filter solutions): A. PP: Quantum yields for the cis → trans reaction at 313 nm in various solvents were redetermined: Φ = (0. Hamada. 9. emission at 375 nm) of product 1-deazapurin-2-one or 1-methyl analog 1. N. J.9 × 10–3 M in 10–2 M phosphate buffer. Φ(cis → trans) = 0.0139 ± 0. T. Gauglitz and S. at 6 × 10–5 M. 5. 29. Hubig. Wirz. Monti. 2. 0. Φ(average) = 0.2 in methanol or isooctane [2.55 in isooctane. KUHN et al.2122 H. Persy and J. Pure and Applied Chemistry 76. Photochem. G. W. (0. Environ. Linden and J. H. 3528–3531 (1958). 0. 10. J. Drabek. G. I. Φ(trans → cis) = 0. S. 185–188 (1987). Yonemitsu. G.030) in cyclohexane. no wavelength dependence of Φ for the trans → cis reaction. 1661–1164 (1977). J. Soc. New York (1976). (0. J. HPLC PP: 6. Photochem. Φ(λ) = 0. G. O. Chem. 0.4–0. Cepciansky. G. no temperature dependence. Photochem. Darby. 30. N.40 ± 0. Hubig.44 ± 0. 380–382 (1993). 169–224. L12: 1-Deazapurine N(3)-oxide [imidazo[4. 41–47 (1976). 237–246 (1984). B 10. 2125–2137 (1995).. 280. Guyot. J.1–0. Vol. H. 4. 94–98 (1984). 255–257 (1981).2. 0. Esrom. Academic Press. also applicable for lasers 1. Johns. R. 6. Weil.02) at 250. 4.15 (±0. Zhang. Hubig. J. Y. Sac about 103 dm3 mol–1 cm–1 AM: absorbance at 358 nm. Photobiol. Poskocil. Wang (Ed. L11*: Azobenzene {Actinochrome 2R (245/440)} [diazenediyldibenzene] photoisomerization (reusable) WR: 230–460 nm.030) in acetonitrile. 126–256881/19. 265. 254. 3.0130 ± 0. Photochem. Listy 78.A. Paik. Eng. conversion limit 20 % (total absorption).035) in n-hexane: 8. G.

78. J. 2246–2253 (1996). Mark. 1. only basic laboratory equipment required. C. C.25. Φ = 0. Hoyer. Organometallics 15.235 at 25 °C in aqueous solution.. PP: The use of the traditional name nitrous oxide is not recommended by IUPAC. H. Kryschi. L14: Potassium iodide in dinitrogen oxide (N2O)-saturated aqueous solution WR: 254 nm. 66. 2. M. Φ = 0. Φ = 0. H. Rahn. R. 2. Bradaric. C.5 + 0.1–Diphenylsilacyclobutane photolysis WR: 254 nm. Can. M. Schuchmann. R. J. M. N. 309–313 (1990). J.03 in deoxygenated methanolic hexane AM: GC analysis of diphenylmethoxymethylsilane (trapping of primary product 1. Shaw. von Sonntag. R. 75–81 (1992). J. O. Mark. R. N2O bubbling (electron scavenger). Rahn. C. H. Schuchmann. N.15 M KI in 0.7 °C AM: absorbance at 352 nm of triiodide ion. 1. I. J. von Sonntag.Chemical actinometry 2123 L13*: Potassium peroxodisulfate/tert-butyl alcohol [2-methylpropan-2-ol] in oxygen-saturated aqueous solution WR: 254 nm. I. Water SRT–Aqua 41. Stephan.21 ± 0. Bradaric. Goren. Bolton. M. Boukherroub. R. O. besides ethene) 1.1 M borate buffer pH 4. R. 77. 1136–1147 (1999). Photobiol.73 ± 0. 2105–2146 .1 M potassium iodate (electron scavenger) in 0. Cserti.004 (θ – 25) [°C] AM: absorbance at 352 nm of triiodide PP: 0.2 at 20 °C (H+ production). 3. © 2004 IUPAC. 2. 450–455 (1997). Photochem. von Sonntag. O. E. 3. Φ = 1. C. of iodide at 300 nm PP: 0. J. Photochem. Schuchmann. L16: 1. Leigh. A 55. exact calibration of pH instrument necessary in the 2–5 range.-S. lack of oxygen leads to lower Φ values. G. tert-butanol is essential (no other alcohol). but note concentration and temperature dependence. J. J. 146–152 (2003). C. Rahn. standard deviation < ± 5 %. Photobiol. O. G. Photobiol. Schuchmann. at other temperatures (θ): Φ = 1. Schuchmann. 70. K. Photobiol. Schmeisser. Rahn. 1.6 M iodide and 0.01 M borate buffer at pH 9. Φ(λ) increases at λ < 254 nm and decreases at λ > 254 nm [3]. Miller. P. N. gradual decrease (1–2 % per hour) of triiodide. J.015θ.-P. Leigh. working range 10–25 °C. 58. M. or irradiation under pH monitoring up to the equivalence point (consumption of preadded base sodium borate) PP: freshly prepared oxygenated actinometer solution: 10 × 10–3 M K2S2O8 and 0. Chem. H.1-diphenylsilene. 885 (1997). Lykke. Photochem. L15: Potassium iodide/potassium iodate in aqueous solution WR: 254 nm. Photochem.-P. Photobiol. temperature (θ) dependence = +0. Banisch. C. 157–168 (1990). 314–318 (1999). O.8 ± 0. erratum: ibid 66. no bubbling necessary. Photochem. L. C.p between 5 × 10–6 – 2 × 10–5 einstein m–2 s–1 AM: pH measurement and/or titration. Xu. G. J.-P. W.1 M tert-butanol. R. 874–880 (1993). W. However. J. independent of photon irradiance En. Schuchmann. Piecha. Water SRT–Aqua 39. system developed for use in waterworks. S. Pure and Applied Chemistry 76.02 (determined against a calibrated radiometer [3]) at 20. Kerst. above 25 °C apparently higher Φ values due to thermal decomposition of the peroxo salt. R. P. Mark.

Simons. Schmidt. J. L22: Azoxybenzene [diphenyldiazene oxide] → 2-hydroxyazobenzene [2-(phenyldiazenyl)phenol] photorearrangement In solid phase. 313..2 %/°C. H.-D. 37.15 ± 0. cf. Φ = 0. 207–214 (1991). Φ = 1. H. G. 2. S05 WR: 250–350 nm: Φ ~ 0. Photobiol. Drews. Pure and Applied Chemistry 76. L21* Heterocoerdianthrone endoperoxide {Actinochrome 1R (248/334)} [4b. Y.0 AM: radiochemical 1. Schmidt. Photochem. 1661–1664 (1977). respectively. T. 25. R. 489–499 (1984). Schnabel. W. H. J. L19: 1.2124 H.2. 6740. J. H. solutions recover on exposure to sunlight behind a 455 nm cut-off filter and may be reused ~100 times without loss in accuracy. since there are more convenient systems available for this wavelength region. L18: Iodomethane photoexchange with 132I2 WR: 254 nm. Photochem. S.-D. P.29 ± 0. 587–591 (1983). J. Photochem.. Am. Photobiol. S. KUHN et al.3. G. M. Photochem. Murata.4-dimethoxy-6-(2-hydroxyphenyl)-s-triazine (besides 4-OH isomer) 1. J. L17: Cyclohepta-1. Photobiol. R. moderately dependent on λ AM: absorbance at 458 nm in ethanolic KOH PP: no concentration dependence. conversion limit ≤ 1 %. Brauer.16-dione] photoreversible photodissociation WR: 248–334 nm for the dissociation. 76.01 in ethanol AM: absorbance at 246 nm 1. Chem. Yamaguchi. 2. Takamuku.4-Dimethoxy-6-phenoxy-s-triazine (DMPT) photo-Fries rearrangement WR: 250–270 nm.Yonemitsu. 2105–2146 . Photochem. Gauglitz. all at 23 ± 2 °C AM: absorbance at 572 nm PP: temperature coefficient + 0.01 in methylcyclohexane.01 in ethanol and 0. Harris and J. and 334 nm. R. K. 49–52 (1979). J. Sac(λ) = 7050. Adv. K. Photochem. Hamada.-D. 335–340 (1982). Φ = 0. 207–214 (1991). R.-D. 2. Beck.48 ± 0. K. Y. 2. O. Chem. Lett. and 4630 dm3 mol–1 cm–1 at 248. J. Murata. Φ = 0. continuous irradiation or 266 nm laser flashes (<1017 photons per pulse). Takamuku. no effect of oxygen AM: absorbance at 331 nm of product 2. Phys. A 60. W. L20: 2. Majer and J. E. Photochem. S. Actinometric use of the reverse reaction [3] is no longer recommended by the authors. Brauer. G. The compound is no longer commercially available. A 60. Jesse.12 ± 0.12b-Epidioxydibenzo[a. 1. 3.01 in 1-chlorobutane or methylcyclohexane (MCH) AM: absorbance at 295 nm (trans-stilbene) PP: no effect of temperature (270–310 K. Shizuka. Willard. Φ = 0.02 in ethanol. 4. S. suitable as polychromatic quantum counter.4-Tetraphenylcyclobutane (TPCB) photocycloreversion WR: 250–270 nm. 137–181 (1964). Tetrahedron Lett. 4678–4687 (1954). Numao. Schmidt. Schmidt and H. Sac = (7770 ± 200) dm3 mol–1 cm–1 (253–302 nm).j]perylene-8. J.01 in dichloromethane (2 × 10–3 M) independent of λ between 253 and 302 nm. continuous irradiation or 266 nm laser flashes (<1017 photons per pulse). 11. 20. N. Brauer. Takamuku. H. MCH) or dissolved oxygen (MCH) 1. Yamaguchi. 8–12 (1989). Comes. Shizuka.27 ± 0. J. no temperature dependence up to at least 45 °C © 2004 IUPAC. Brauer and R. Hubig.3-diene photoisomerization WR: 254 nm. F. J. Soc. 160.

1199–1208 (1984). 1049–1051 (1989). J. O2. 91–94 (1997). Chem. 1–117 (1995). L24: Adenine photolysis WR: 254–300 nm. Phys. C. Chem. D. no photoreversion. © 2004 IUPAC.0027–0. Academic Press. Marinari. P. L. cf. Morioka. Ar or O2. A 41. von Bünau (Eds. Am.Chemical actinometry 2125 1. Lemaire.) 3. G. 66.-M. Mauser. 2105–2146 .23 ± 0. 2. N.. cf. GC 1. Photobiol.-I.52 ± 0. general dependence on concentration. Ho. H. Ber. J. J. and counterion (Cl–) concentration 1. N. 1762–1764 (1994). 313–400 nm: Φ(cis → trans) = 0. A 109.-L. Hwang.0085 (aerated). L25: 2-Hydroxy-4′-(dimethylamino)chalcone [1-[4-(dimethylamino)phenyl]-3-(2-hydroxyphenyl)prop-2-en-1-one] to 4′-(dimethylamino)flavylium ion photoconversion WR: 254–366 nm. 75.0081–0. negligible effect of oxygen 1. oxygen. 2. J. 101. 293–298 (1988). Kuhn. In Rearrangements in Ground and Excited States. Pizzocaro. Photochem. J. P. J. S. 5. 2982–2996 (1979). Chim. A. quantum yields depend on stilbene substitution and solvent AM: absorbance. C. 739. Boule.01 AM: absorbance. Bull. Photochem. D. Soc. G. 60.10 ± 0. 67. D. 0. Stier. Chem.4 %. thermal bleaching of photoproduct at 50 °C. J. cf. Matsushima. 193 nm laser and 254 nm continuous irradiation: G. 3. 19. H. F. J. Görner. T. water content of THF well below 0. Gurzadyan and H. Megarity. Chem. J. Photochem. 11–26 (1987). [2]) AM: absorbance at 260 nm PP: 4 × 10–5 M aqueous solution. Soc. Suzuki. Lemaire. New York (1980). Liebigs Ann. J.). Photobiol. H. Phys. Chem. LaMarre.1 × 10–3 (254 nm. Chang. 2. Mizuno. strong dependence on pH. 0. H. H. C. J. wavelength. Φ(λ) = 0. 0. Gauglitz. L23: 3-(2-Hydroxyphenyl)-2-propenoic acid [prop-2-enoic acid] (o-coumaric acid dianion) photoisomerization in aqueous solution cis → trans reaction WR: 254–300 nm: Φ(cis → trans) = 0. Photobiol. 84–94 (1970). Mitchener.0029 (deoxygenated). E. Φ = 0. water decreases quantum yield.-L.16 (254 nm) at 20 °C.23 (313 nm). Charlton. T. M. student experiment [1]. Vaish. Guyot.05 trans → cis reaction WR: 254–300 and 350–400 nm: Φ(trans → cis) = 0. 1. Pure and Applied Chemistry 76. 531–533 (1984). Volman. J. Görner and H. T. P. 2 × 10–5 M [2] Not recommended as a reliable actinometer. Φ (chromophore loss) ≈ 0. 25–90. J. Perbet. Photochem. de Mayo (Ed. Photochem. Saltiel. 0. Saltiel and J. Adv.-C. pp. Görner. D. M. Muarakami. 1096–1104 (1978).075–10) × 10 –3 M chalcone. Rivera. W. 5 × 10–3 M p-toluenesulfonic acid [4-methylbenzenesulfonic acid] (necessary for ring closure). 323–332 (1994)..05. Neckers. 88.5 % purity) solution AM: absorbance near 450 nm PP: (0. J. 2. R. Coulangeon.21 (334 nm). strong effects of solvent and acidity. Su. C. R: Matsushima. Educ. Photobiol.01 (366 nm). 2. T. Bunsen-Ges. Photochem. G. Jpn. Kajiura. in acidic THF (99. For quantum yields. G. 4. 39. A.75 ± 0. 36. Bunce. fluorescence at 492 nm PP: Not recommended as a reliable actinometer. L26: Stilbenes cis → trans photoisomerization WR: 254–366 nm. and pH [2].-M.

A 48.47 ± 0. I. For primary Φ of Η2Ο2 decomposition: cf.5 M aqueous KOH) AM: absorbance of product 2-methoxy-5-nitrophenolate 1. P.3–1) 10–3 M in 5 × 10–3 M phosphate buffer AM: transient absorption at 430 nm (flash photolysis) of p-benzosemiquinone radical anion. L31*: Potassium ferrioxalate. 368–374 (1986). 703–709 (1983). L28: p-Benzoquinone photoreduction in aqueous solution WR: 260–380 nm. Soc. Czech. Matheson. I. DeLaat. 259437. Φ = 0. Mvula. Bolton. I. Bonnel. M. H. Soucek. J. 78. Am. 440–451 (2004). von Sonntag. K3[Fe(C2O4)3]3H2O [potassium tris(oxalato)ferrate(III) trihydrate] photoreduction (Hatchard–Parker actinometer). Photochem. Am.-Y. Kuhn and H. E. Chem.002 (0. C. F. Chem. The most widely accepted standard actinometer. L27: 1. Φ = 0. 130. Water Res. K. Dainton.2126 H. Lipczynska-Kochany. 78. EPR 1. W. R. 3. L. Esrom. 24. photohydrolysis WR: 254–365 nm (applied to 308 nm XeCl-excimer lamp. 23–25 (1986). 237–255 (1986).136 mM in 0. 2. J. Hildenbrand. 10. Ononye and J. Saito. 33. Appl. 7. 4. J. Defoin-Straatmann. Kuhn.04.10-phenanthroline)iron(II)] in buffered acidic solution © 2004 IUPAC. S.0007/°C. R. M. L. 2. Φ = 0. Duguet. Sci. 3. J. Eur.. J. Chem. Photorheological effects in micellar solution: T.05. J. Commun. Collect. J. Weeks and M. Chem.25–0. Technol. E. H. (0. Reproducibility better than ±0. J. 90. D. no significant dependence on air. Haubold. commonly called ferrioxalate actinometer. NMR PP: moderately dependent on λ. Ho. 2.30 ± 0. A. strongly dependent on pH and water content. Chem. Photochem. Kreft. Chem. Oxid. Oxid. PP: Take care to dispose of the uranium waste in accordance with current legal regulations. J. Bolton. cf. O. Referred to in: G. 6208–6219 (1988).10-phenanthroline complex [tris(1. E. Defoin and H. KUHN et al. 51. 579–599 (1957). 1278–1279 (1956). WR: 250–500 nm. A. 1273–1278 (1956). correction for product benzaldehyde content at λobs ≤ 370 nm is necessary. J. T. Surf. Bittersmann. Görner. temperature coefficient +0. K. 6270–6274 (1986). Abstr. pH 7. Schmidt. 157–168 (1990). J. H2O2 consumption 1. J. Hildenbrand. von Sonntag. A. O. T.116 ± 0. Phys. C. 1. Photobiol.0029 ± 0. 4. Φ = 1. Angew. Φ = 1. F. Chem. J. L30: Hydrogen peroxide photolysis sensitized by uranyl sulfate [dioxouranium(VI) sulfate] WR: 250–450 nm. J. Paris. Bolton. however. S. J. 1. Wolff. Dore.0095/°C AM: O2 volumetric. 170–178 (1996). 315–319 (1999).8 in acidic acetonitrile–water (3:1 v/v) solution AM: absorbance at 360–390 nm. 69. R. PP: See. concentration or radiant power. G. Technol. E. L. Ho. [2]). Pure and Applied Chemistry 76. Kuzmic. Nicole. J. Pavlickova. 1.03 (20 °C) in 3 M H2SO4. Boyd. Adv.9 AM: absorbance at 510 nm of Fe(II)-1. Folcher. H. G. Schenck and W. not to be used above 45 °C. 2105–2146 . G. R. J. Chim. potentiometry. 2. Kuhn. 170–178 (1996). Nouv. Soc. 92. HPLC. Phys. L. J. Adv. temperature (θ) coefficient ∆Φ/∆θ = 0. E. Defoin. J. von Bünau. Lipczynska-Kochany.2-Dimethoxy-4-nitrobenzene → 2-methoxy-5-nitrophenolate. Chem. Schenck. P. 138–139. conversion limit about 20 %. J. 26. Zhang. 435–446 (1989). freshly recrystallized acid should be used. L29: Phenylglyoxylic acid photodecarboxylation WR: 254–405 nm. J.6–0. J. EPA Newslett.

Bridge. M. Chem. 69–71 (1979). H. 104–116 (1953). Fitzgerald (Ed. G. J. 24. 18. 783–788 (1955). EPA Newslett. 114–115 (1977). J. Chem. J. Marcel Dekker. Shizuka. 13. Educ. Am. 21. 321–329 (1967). 58. pp. 27. idem. pp. Parker. Gauglitz. there may not be sufficient phenanthroline to complex all Fe(II). C. Pure and Applied Chemistry 76. Phys. Wolfenden. Chem. Photochem. 16. P. 1. New York (1971).33]. M. S.). Soc. Photobiol. Appl. J. Nicodem and O. Phys. Schonberg. M.20) M solutions have been used.-T. add irradiated solution to premixed buffer–phenanthroline solution. Z. complexation should be done immediately after irradiation. N. Agnew. 59. F. E. (0. Cabral. D. J. N. 28. 55. Hatchard and C. Baxendale and N. H. 17. E. W. 2428–2429 (1983). New York (1966). J. Phys. Bowman and J. J. N. Gellender. Inorgan. 9. Soc. Parker. Chim. J. 13. K. Oliveros. M.Chemical actinometry 2127 PP: See [36] for possible wavelength dependence in the 240–280 nm range. E. E. Soc. R. D. 208–214. Holubov. J. Mol. Chem. A. 299–313. D. H. J. 20. Ferreira. W. 15. P. 101–111 (1982). Kirk and C. Marcel Dekker. 88. sufficient stirring is essential. 519–523 (1964). 145–146 (1981). 387–394 (1972). 189–193 (1983). P. A. Presses Polytechniques Romandes. C. 213–238 (1977). Hennig. Wrighton and S. J. J. 5. Nicodem. Photochem. EPA Newslett. M. H. N. Photochem. 139–216 (1976). part I: C. Sect. 394–404 (1966). Photobiol. Soc. Witz. 49–53 (1983). 2105–2146 . E. A. A. F. 2. A. C. W. E. C. 77–81. J. Chem. Demas. E. Causton. A. Boschmann. 29. 922–928 (1958). 26. J. “Analytical methods and techniques for actinometry”. 11. A. in case of high conversion. Photoluminescence of Solutions.006–0. 3. Photochem. Phys. J. A. Acta 53. 518–536 (1956). K. Weiss. Wolf. Photochemistry. Demas. J. R. Jr. L. Wegner and A. 8. 21. S. J. recrystallized from water is stable in the dark. no problems at 60 °C without deoxygenation. D. Murov. G. Technologie Photochimique. John Wiley. J. 4. 2434–2435 (1976). Baker. 2081–2082 (1971). PP: In view of the numerous different and often contradictory observations and recommendations given in the literature concerning the adequate use of this actinometer. 11. 314–315 (1980). 655 (1981). M. Creation and Detection of the Excited State. it is suggested that publications contain a short but unequivocal indication as to which experimental conditions have been applied. Zalewski. John Wiley. Bowman. make sure that there is total absorption. Bricker and S.) 4. 80. 51. R. 2766–2771 (1981). pp. 10. Chem. 30. W. 14. P. “Measurement of reaction quantum yields”.. H. Thomas. 5204–5206 (1980). 43–96. C. D. 6. 6. Chem. Chichester (1991). S. A. Aquilera. p. 3. D. phenanthroline solution is sensitive to UV (fluorescent room lights) and should be stored in the dark. J. Lee and H. 91–115. Vitz and E. Gafney. L. for use with lasers [19. New York (1993). E. L59–L60 (1981). only freshly prepared and mixed solutions should be used. Anal. Meyer. Elsevier. pure solid green K3[Fe(C2O4)3]3H2O. pp. complete complexation takes about an hour. Maurette. Adamson. Schnieper. Langford and C. Fernández. D. Ware (Ed. E. H. Mol. 2nd ed. Casadavell. Figuera. Calvert and J. 34. test for the linearity of the results with irradiation time. Photochem. J. 57. 8. Plant. Chem. London A220. London A235. Anal. Q. B. 783. J. 17. D. 3. Parker. Velapoldi. R. K. in Analytical Photochemistry and Photochemical Analysis. 22. H. Handbook of Photochemistry. Kurien. H. S. Phys. 25. Namasivayam. Chem. PP: All work must be done under dark red light. Bohning. A. 12. Tobar. Braun. 19. © 2004 IUPAC. 85. Photochem. 33–34 (1984). Benedix. Seliger. D. V. Photochemical Technology. 7. 40. M. Proc. W. A. Oecol. Gruter. A. Connolly and T. A. Proc. C. Chem. Amsterdam (1968). Taylor. H. Lausanne (1986). R. 19. pp. Acta Oecolog. 21. Chem. E. M. Fischer. P. 23. E.22. Pitts. Educ. de Mayo and H. M. A.

Chem. 80.76 ± 0.-J. Chem. 265 nm (anthracene in hexane. J. E. 98–103 (2003) (microelectrochemical actinometer). Photobiol. R. 277–281 (1978). 9. © 2004 IUPAC. 353 nm (all-trans-retinal in hexane): R. Demas. Photochem. Yoshimura. 5. Andrzejewska. L. W. Vincze and S. 7–13 (1999) (flow actinometer).2128 H. Yagi. S. Φ = 0. T. G. and Biophysics. J. N. R. Hug. 247–253 (1991). 146–152 (2003). J. H. Y. W. R. I. Phys. Zuberbühler. sensitized photooxygenation Especially designed for high-power pulse and cw lasers WR: 280–560 nm. J. G. J. ZnTPP in toluene and other solvents): L. Harris. 35. Bensasson. Z. L. Lykke. 2. W. Goren. 117. P. 28. R. Treinin. Elsevier. T. 2 (2). M. In Lasers in Physics. M. N. E. L. 100.nd. K. 10871–10878 (1995). Environ. S. J. I. 30. J. Carmichael. Bolton. 28. V. Smith. Moore. H. Photochem. N. J. 38. 612–627 (1987). I. L. T. 289–299 (1991). Goldschmidt. Sun and J. D. 77–89 (1991) (actinometry in an EPR tube). High Energy Chem. 132–134 (1978). Stefan. Unwin.edu/browse_compil. P. Sinai. Rahn. Yu. Sun.. E. Ref. T. Kochevar. Data 15. K. Phys. Linschitz. I. J. 9–14 (1983). J. Ali. KUHN et al. J. J. Bonneau. G. Reza Kenkyu 19. Romashov. J. 12. 2105–2146 . 1–5 (1999). Takatori. Pure and Applied Chemistry 76.3-dimethyl-2-butene as acceptor. See: <http://www. N. 337 nm (benzophenone-4-carboxylate in aqueous solution): B. Shestra. 477–484. Harris. Photochem. R. Photochem. Photobiol. Marciniak. P. Izumi. Soc. A 123. A 70.03 with methanolic Ru(bpy)32+ chloride and 2. Amsterdam (1975). Papp. Meet. Kemp. Joussot-Dubien (Ed. Vincze. 31. Chemistry. 61. Y. Am.. Land. in the presence of O2 in a sealed cuvette AM: O2 consumption. 179–185 (1998). Photobiol. A. Photochem. J. S. L. Bolton. Hug.rcdc. 63. volumetric PP: slight dependence of Φobs on 2. L. M. Photochem. Photochem. 29–33 (1993). Shibuya. L33: 2. Bensasson. P. Photobiol. J. Kajii. Unwin. 4. G. W. A 126. E. cf.. Hug. Carmichael and G. Redmond.. benzoins): C. J. 979–992 (1997). Sorensen. R. Kawai. Photobiol. L32*: Laser pulse actinometry via standard transients WR: 265–532 nm in various solvents (depending on the substance used) AM: transient absorbance 1. J. H. J. Truscott. Kiryukhin. E. G. A 116. Photobiol. García. 1–250 (1986). J. 3. 21–28 (1998). Hoffman. Goldschmidt. Bagdasar’yan. Eng. D. 4127–4134 (1996) (EPR flat cell). A 112. Proc. K. 5151–5159 (1988). K. Photochem. Soc. Obi. 308 nm. E. 34. G. 277–281 (1978). R. J. Land. McGimpsey. R. McBride. 33. Int. S. R. 37. D. G. Photobiol. Ahmed. Ulrich. 308 nm: (benzophenone-4-carboxylate in aqueous solution): J. O. Y. Fonseca. 32. Wirz. Photochem. 2. 78. J. Harris.). A: Chem. Chem. C. 347 nm (benzophenone-4-carboxylate in aqueous solution): J. 289–296 (1987). H. Linschitz. Hurley. K. R. K. Photochem. Bonneau. M. P. Demas. 355 nm. D. Chem. 347 nm (benzophenone. Timpe. McBride. 7. C. Kemp. 532 nm [Ru(bpy)3 2+ in aqueous solutions and polar organic solvents]: A. Photobiol. 8. 36. E. Phys. Shaw. J. Photochem. Chem. 355 nm (benzophenone. A.3-dimethyl-2-butene concentration and oxygen pressure 1. R.. 113. Hurley. Chem. 115 193378/18. J. L. Adams. J. Pure Appl. naphthalene in cyclohexane): R. J. R. V. Abstr. pp. 69. 27. Pure Appl.3-Dimethylbut-2-ene. cf. 10. 6. R. K. Phys. A. W.html#browse_access>. Photobiol. E. I. Photochem.-S. A. 92. 36. 2248–2253 (1976). Chem. Phys. S. Photobiol Sci. Photobiol. Chim. Truscott. Chem. von Sonntag.

Chem. 2. Am. confirmed against ferrioxalate actinometer (L31*). von Sonntag and W. Same Φ in all phases (cf. 397–402 (1979). Photochem. Hammond. Marcel Dekker. S. T. Oceanogr. D. 4. 133–139 (2000)..00152 ± 0. Micheau.-P. Handbook of Photochemistry. 9. C. J. G. Mark. p.5 at 308 nm. A. H. New York (1993). 595–600 (1965). L35: o-Nitrobenzaldehyde → o-nitrosobenzoic acid photoisomerization WR: 300–410 nm. J. also: G. Jr. Knolle. J.5 × 10–3 M sodium bicarbonate solution at pH 7. Res. Moore and M. 3. Jara. 89–103 (1996). K. C. Int. Photobiol. C. 2nd ed.00004 (scavenging product salicylic acid). Schuchmann.Chemical actinometry 2129 L34: Iodide photooxidation in aerated aqueous buffered solution WR: Rose Bengal sensitization AM: amperometric detection of I2 or redox titration of iodine PP: Efficiency of I2 formation depends on pH and temperature. Foss. Cabrera. S. 2. S.2 PP: strong wavelength and temperature dependence. Chem. R. 2. 4. Air Water Pollut. B. 2105–2146 . P. 837–859 (1995). Braun. von Sonntag. extremely sensitive (10–9 einstein still detectable) 1. Limnol. Pure and Applied Chemistry 76. Chem. 172 nm: cf. J. Photobiol. J. Photochem. 38.. P. G. 307. IR NO2 band disappearance 1. Φ = 0. C. L37: Benzophenone/benzhydrol [diphenylmethanol] photoreduction in benzene WR: 300–390 nm. S. H. M. 69. W. 17S–18S (1999). Martínez-Lozano. K. 5. 1368–1371 (1962). Sect. Borderie. Hites. Phys. Soc. 77. Photochem. A 101. Chem. Leighton and F. Lucy. 13. J. Wan. Intermed. independent of temperature. K.: M. L. R. L. Photobiol. the pH of the solution serves as a measure of the degree of photoisomerization. 319–328 (1999). Anal. for the determination of solar UV radiation and penetration in waters. S06) AM: GC. Photobiol. Soc. W. LC. 13–23 (1991). Ketchum. J. J. Kleber. Chem. 2. A. Ed. Laplante. J. Dreiman. Mopper. no predetermined Φ AM: differential absorbance 1. W. 70. Photochem. J. J. P. E. Chim. cf. for the determination of quantum yields by conductimetry. when the reaction is carried out in the presence of NaOH. A 136. Moore. G. Sánchez–Pedreño. insensitive to room lights. 83. D.00105 ± 0. Baertschi. G..00003 (formation of p-hydroxybenzoic acid) AM: HPLC analysis (with absorbance and fluorescence detection) of salicylic acid and m/p-hydroxybenzoic acid or batch fluorescence (λexc = 305 nm. A 56. Am. S. 290–410 nm: J. J.. relative method. J. J. M. Photochem. Allen. 3. Jankowski. Willett and R. 21. Pitts. Φ = 0. Acta 104. Pérez-Ruiz. Φ = 0. M. P. λem = 410 nm) of salicylic acid (without HPLC) PP: 10–2 M sodium nitrate and 10–3 M benzoic acid (OH radical trap) in air-saturated 2. Hernández-Córdoba. Levy. Method applied for the analytical determination of I2 reducing substances 1. A. 6. Allen. M. Vernon. 84.-G. © 2004 IUPAC. Korth. J. M. L36: Sodium nitrate/benzoic acid in aqueous solution WR: 305–320 nm. 3. Lavabre. 703–705 (1993). Φ(λ) = 0. C. 756–759 (1934).. Morales. J. 900–902 (2000). M. J. N. S.5 in acetone and CH2Cl2. J. González and A. 2789–2794 (1961). Photobiol. Murov.

Wagner. 4511–4513 (1966). Pure and Applied Chemistry 76. Am. 2nd ed. besides cyclobutanols and 1-phenylcyclopentanol PP: no effect of pH between 4 and 7 1. 310. 2. Amrein. 3. J. G. L42: trans-2-Nitrocinnamaldehyde [trans-3-(2-nitrophenyl)prop-2-en-al] photoisomerization WR: 313 nm. J. Φ = 0. Φ(trans → cis) = 0. 365 nm. M. Helv. Abstr. 13. 290–330 nm: in aqueous solution Φ ~ 0. E. 1997. Bovina. Vesley. V. Wintgens. Albini. products: acetophenone and propene. S. 511–517 (1988). S. S.55. Cavrini. L31*. p. Italy. Kemppainen. A. 366 nm. Marcel Dekker. Soc. J. products acetophenone and ethene 1. E. Chem.65 ± 0. Φ = 0. 0. Chem. L39: Butyrophenone [1-phenylbutan-1-one] photoelimination WR: 313 nm. Marcel Dekker. 2nd Intern. C. H. A. N. J. Scaiano. J. CO. 2nd ed. 2105–2146 . 2. WR: 313 nm. Chimia 28.075 (cyclobutanol). Murov.30–0. Spec. Phys.. ferrioxalate. P. Tetrahedron Lett. Photobiol. 2. 0. Zepp. Handbook of Photochemistry. 43207. HPLC PP: 0. Φ = 0.03 (only acetophenone formation) AM: GC. Wan. Am.35 in benzene. Pitts.. 94. Pavia. New York (1993) 2. Schuck. EPA Newslett. J. 185–188 (1974). D. L38: Hexan-2-one photolysis WR: 313 nm. P. © 2004 IUPAC. 85–86 (1997). 5716–5723 (1998). L43: Penta-1. 185–188 (1974). L.22 (acetone). C. 4. 5385–5388 (1968). Schaffner. Photochem. K. Soc. K. oral commun. 0. Chem. Chim.98 ± 0. Gumz. HPLC. J. 2.. L40: Valerophenone [1-phenylpentan-1-one] photolysis WR: 313 nm. Am. 193–200 (1971). Acta 54. Gao. Schaffner. P. Vesley. 13.44 AM: GC 1. Wolf. 3. W. V. Φ = 0. G. 305–321 (1965). J. Photostability of Drugs. 225 (Drugs: Photochemistry and Photostability) 305–316 (1998). Sect. 4. J. secondary products besides the cis-isomer upon prolonged irradiation 1. L41: 2-Methyl-2-phenylpropanal photolysis. Johnston. P. Chem. W. R. Meet. Baum.24 (in benzene. besides cyclobutanols 1.3-diene photoisomerization sensitized by benzophenone WR: 313. Sect. Chimia 28. 7489–7494. R. Bovina et al. Leermakers. used as actinometer) AM: GC.04 (cleavage plus cyclization).15 AM: absorbance at 440 nm. D. K. R. Chem. cf. L. M.2130 H. Handbook of Photochemistry. p. Yang.. L. 61. 14–16 Sept. KUHN et al. Amrein. Chem. Jr. Wagner and A. A 102. Gloor.–R. A. New York (1993).83 in isooctane AM: GC. F. Φ(cis → trans) = 0. J. no wavelength or temperature effect (25–40 °C). Photochem. W. Mol. Miller.33 (2-hexanone consumed) in pentane solution AM: GC 1. 88.. 7495–7499 (1972). J. 309. Hess. 110. K. Soc. J. De Filippis. E. 130.5 % methanolic solution (A > 2). L. Gloor. Φ = 0. 3. Murov. Publ. E. H. L. Soc.25 (propene). Ballardini. J. Schaffner. 868–897 (1971). K. Coulson and N. G. E. Φ = 0. Küntzel. J. products isopropylbenzene.

Makromol. other solvents possible. Smets. 10b. in toluene [10e]). A.7. Hayata. Critical discussion: 10a. R. 3. Φ(λ) = 0. 243–247 (1996). Rappon and R. sensitized photodimerization WR: 313. T. Kaneko. J. Bull. J. Eur. Am. Gauglitz. at the same time recommending a stringent recalibration. 63. 4.3-diene. V.0594 (494 nm).7. Elsevier.g.S. Chem. Electronic substituent effects on quantum yields: A. 6. Whittal. C. 7. 1. Amsterdam (1990). 193 (1978). X. U. other authors [10e] see only negligible amounts of Z isomer and suggest other causes (ring opening). there is a controversy about decreased quantum yields after repeated use [10]. Deblauwe and G. H. 31–34 (1995). Chap. but only small A changes necessary PP: Aberchrome 540 is a widely used actinometer.254.. Tomoda. Jpn. 66. Chem. 467–492. A. A 88. 5. Use in one. Guo. P. H. In Photochromism.18 (365 nm. Patent 7/1464603. J. New quantum yields: E. Rappon.0470 (546 nm). Heller. 8. Soc. Jpn.7a-dihydro-2.7a-pentamethylbenzo[b]furan-5. G. Heller. Duggal.Chemical actinometry 2131 L44: Cyclohexa-1. 47. Vesley and G. linearly dependent on λ. Tang. EPA Newslett. Wang. 2503–2512 (1988). Chem. T. Photochem. Soc.09 (436 nm. 2105–2146 . F. Whittal. Matsushima. 1607–1610 (1990). EPA Newslett. Gill. J. 399–403 (1992). Kurita. Rappon. J. 366 nm: Φ = 0. Polym. 44 (1993). R. Syvitski. H. Pure and Applied Chemistry 76. J. Perkin Trans. J. However. Photobiol. F. Soc. Photochem. 28. J. 2. Yokoyama. A. 42–43 (1993). 47. P.97 in benzene AM: GC 1. Photobiol. A 98. Sac(λ) = 487 dm3 mol–1 cm–1 at 494 nm. H. pp. Photobiol. Photochem. Brit. in toluene or ethylacetate [10e]). 5. Reply: H. Y. reuse of the actinometer solution after photoreversion is strongly discouraged.4. Chem. Mol. Chem. degassing desirable while not essential. precision ±3 %. F. Photochem. Y. cf. Ind. [6. Quantum yields of E → Z and Z → E isomerization and E–cyclization and back reaction in various solvents and polymers: Y. Soc. Glaze. Scaiano. © 2004 IUPAC. J. Syvitski. Chem. Pilichowski. L. therefore. Langan.6-dicarboxylic anhydride] WR: 310–375 nm (reversible with white light). 330–333 (1993).20 in toluene solution (5 × 10–3–10–2 M). Φ = 0. PMMA. Photokinetics: Z. Chuenarm. Uhlmann and G. G. G. Johnston. Molecules and Systems. O. G.. S. 511–517 (1988). 1 341–343 (1981). 189. Bull. A. 71–73 (1981). Tsuboi. Details concerning bleaching reaction: cf.5-dimethyl-3-furyl)ethylidene](isopropylidene)succinic anhydride]   Aberchrome 540P [7. Polym. H.and two-laser experiments: V. n-hexane [10e]) WR: back reaction 435–535 nm.. solvent effects on bleaching: M. J. Eur. Perkin Trans. Φ = 0. 0. Song. polystyrene.. Pilichowski. H. L45*: Fulgide reversible photocyclization: Aberchrome 540 [(E)-[1-(2. Soc. 45–49 (1996). Patent 9/719. in ethylacetate [10e]).20 (365 nm.10]). M. R. 9. Heller and J. Chem. 1214 dm3 mol–1 cm–1 at 343 nm. J. 9. J. Φ = 0. H. Oct. P. PVA. R. Kinetics of photodecolouration in polymer films. 10d. Ito. Boule and J. Langan. Wintgens. Bouas-Laurent (Eds.073 (436 nm). G. the E → Z photoisomerization. and others: M.. 367–369 (1973). Heller and J. H. Hammond. no conversion limit. n-hexane [10e]) AM: absorbance at 494 nm [ε (494 nm) = 8200 dm3 mol–1 cm–1] or at 343 nm [ε (343 nm) = 6077 dm3 mol–1 cm–1] PP: reproducibility ±1 %. 51–53 (1993). Bhaovibul. 10e. J. G. Syvitski. A. 110. Φ = 0.06 (436 nm. probably caused by side processes (e. 27.11 (436 nm. Photochem. Heller. G. Dürr and H. R. Φ = 0. Photobiol. 0. A 94. 365–370 (1991). H.). 2 591–594 (1992). Φ = 0. 10c. T. Boule and J. Chuenarm. EPA Newslett.. PP: Aberchrome 540 is no longer commercially available. A 71. Sac(λ) = 1640 dm3 mol–1 cm–1 at 494 nm. J.

7) dm3 mol–1 cm–1. A.581 0.7 × 10–3 M in air-saturated Freon 113 Uvasol Merck AM: absorbance at 324 nm λ/nm 334 350 365 380 395 Sac(λ) = Φ(λ) ε(324 nm)/ dm3 mol–1 cm–1 Standard deviation ± Φ(λ) Standard deviation ± 627 642 611 651 616 8 9 10 10 9 0. temperature dependence is related to pH. thermal dark reaction. New York (1976). 0.10-Dimethylanthracene self-sensitized photooxygenation WR: 334–395 nm. P. Exp. 201–212 (1987). H. McGimpsey. W.388 (350 nm). 0. 0. I. Soc. precision ±5 %. Marcel Dekker. J. Demas. McGimpsey. J.: J.-D. Gros. 0. Blazejowski. In Creation and Detection of the Excited State. suitable as polychromatic actinometer 1.316 (392 nm). Wegner and A. Phys. J. S. Ware (Ed. negligible dark reaction. 605–608 (1989).311 (452 nm). House. Photochem. J. 4.335 (366 nm). W.6 (cf. Diplomarbeit (G. A. 0. Schmidt. 0. K[Cr(NH3)2(CNS)4] [potassium diaminetetrakis(thiocyanato-N) chromate] photoaquation in dilute acidic solution. cf. 0. L46: Potassium reineckate.016 0. Soc.302 (735 nm). Marty. A. thermal aquation (substitution) becomes a major problem.5) dm3 mol–1 cm–1 [4] AM: absorbance at 450 nm of iron(III) thiocyanate complex {ε = (3400 ± 200) dm3 mol–1 cm–1[7]. J. 4. R. Redmond. E. 89–96 (1988). 739–741 (1989). 0. R.7 ± 2.566 0.015 PP: conversion limit ~20 %. 12. 2. application to biophotoreactor: J.) 4. 2105–2146 . PP: This actinometer is not recommended due to its large error and cumbersome handling. table below for the exact Φ(λ) values. E. K. Am. 5431–5434 (1994). W.595 0. L47*: 9. pp. Chem. Böttcher.. Chem. Educ. 66. Biotechnol.-B. 139–216. G. 10871–10878 (1995). the commercially available salt must be carefully recrystallized in the dark from water below 80 °C to limit thermal aquation. 408–415 (1997). ε(520 nm) = (110. Arnold. KUHN et al. 1.3 ± 2. Kochevar. E. reproducibility ±2 %. 98. J. J. Physik 35.3) dm3 mol–1 cm–1. R. Brauer. J. 0. Szychlinski. H. C. In Creation and Detection of the Excited State. 0.284 (713 nm). G. Sac(λ) = 30. R. de Mayo and P. only weak red light ≥ 750 nm is admitted.273 (750 nm) [4].015 0. Searle. Gauglitz) Tübingen (1980). Prog. R. G. 117. Am.310 (416 nm). Martuszewski. 88. H. J. 0. New York (1976). W. Smith. Bilski.g. Ware (Ed.270 (577 and 585 nm). W. Hubig.603 0. J. D. García.014 0.5 dm3 mol–1 cm–1 at 520 nm. H. Görgens. Hänsel. only slightly dependent on temperature.571 0. Photobiol.). Marcel Dekker.2 ± 1. C. Adamson. 0. 1–62. H. 2132 11. 0.291 (316 nm). P.-J. B. R.3 dependent on λ. independent of photon flux 10–7–10–9 einstein s–1. no significant dependence on fluence. ε(392 nm) = (96.H.286 (520 nm). Techn. 394–404 (1966). depending on the excitation wavelength λ) 1. note: diff. Cornet. N. Shizuka. A 45.271 (676 nm). Laser actinometry. G. © 2004 IUPAC.017 0. Commonly called Reinecke’s salt actinometer. Analyst 114.282 (545 nm). 7. 5. 13. S. G.299 (504 nm). Bull.-F. Improved preparation of Reinecke’s salt. Φ ~ 0. e. in basic solution. Adick. ε(542 nm) = (36. conversion should not exceed 10 %. Pure and Applied Chemistry 76. Chem. from [1]} PP: Φ(λ) = 0. 6. E. W. WR: 316–750 nm: Φ(λ) ~ 0. 0. pp.276 (600 nm). 3. Chem. Scaiano.

Org. commercially available SnO2 glass (10 Ω lateral resistance) pretreated with 50 % v/v hot sulfuric acid. 395–399 (1992). Jacobs.8-Tetramethyl-1. Hashimoto. Φ(λ) = 0. J. 64. 0. Org. Mod.1'-(diazene-1. © 2004 IUPAC.. Phys. Photobiol. Frank and G. Symp. Hashimoto. J. Hashimoto. Proc.8.5–2. p. Photochem. R. 4. C. Photochem. Fujishima. 860–864 (1993). photocurrent depends on quencher concentration AM: reading of photocurrent PP: calibration against ferrioxalate. 1. Lingamurthy.Chemical actinometry 2133 L48: Azo dye ABD [6-{4-[(4-octylphenyl)diazenyl]phenoxy}hexanoic acid] trans → cis photoisomerization in an assembled monolayer film (Langmuir–Blodgett technique) coated on electrode WR: 334–405 nm. L49: 3. Photochem. Actuators. 1. Schuster. Liu.2. Morigaki. K. 0. J. irradiation times of only few seconds. K. L52: Riboflavin irreversible reductive quenching by Na2EDTA in aqueous medium in a photoelectrochemical cell WR: 350–450 nm. A. 97. E. G. 285–292 (1992). H. Sens. A. Chem.04 in heptane AM: absorbance at 365 nm 1. V.2-diyl)bis [2.13 ± 0. K. A. N. T. Fujishima.4-bis(2-methylpropyl)benzene] WR: 350–390 nm.7-tetraazaspiro[4.022 at 350 nm in 95 % ethanol AM: absorbance at ≥500 nm PP: more pronounced spectral shift from reactant to product than with azoxybenzene (L22) but more difficult to prepare 1.112 ± 0. React. R. Int. Chem. K. Φ = 0. R. Z. direct reading of the Faradaic charge (Coulomb meter) or the cathodic saturation current gives irradiance (after calibration against ferrioxalate. L51: 2. Bunce. 436 nm 1.4'-Tetraisopropylazobenzene [bis-(2. Suitable for < 10–8 einstein cm–2 s–1. Morigaki. Z. Shono (Ed. Kyoto 1991. Z. K.6. A. Z. B.. Kodansha. Gauglitz. at 366.5) × 10–3 M ABD. Lemke.-F. 105–115 (1986). Morigaki. Synth. L50: 1.3.12 ± 0.-F.2'. 097468/08. reproducibility problems (< ± 1. Methodol. WR: 345 nm AM: CD 1. Fujishima. O. Debrabandere. 6583–6586 (1976).7 %) with different glass substrates.1 ± 0. Bhanumathi. 355–357 (1977). Hashimoto.4]nona-1. K. 2.02 (365 nm). Pure and Applied Chemistry 76.4. 7. Stewart.-F. L31*. Bunsen-Ges. K. Soc.11 ± 0. K. A 65. 2105–2146 . For the determination of molar ellipticity or the degree of circularly polarized light. J. Tokyo (1992). S. Sethuram. Liu.-F. Blume. J. J. Am. Photobiol. Chem. Chem. L31*) PP: 2 × 10–4 M CdCl2 subphase (1. Photochem.1'-(diazene-1. Anal. Montgomery.01 (340 nm). B 13–14. G.1'-Azoxynaphthalene [di-(1-naphthyl)diazene oxide. System several times reusable. 1. 134–137 (1992). 3..01 (334 nm).4-isopropylphenyl)diazene. Φ(trans → cis) = 0.6-diene photolysis in hexane For actinometry with circularly polarized light. Rau.). 0.05 (405 nm) AM: in situ selective electrochemical reduction of cis-ABD.2-diyl)dinaphthalene oxide] WR: 350 nm. S. Morigaki. 226–229 (1993). Fujishima. J. 34. M. E. Ber. Liu. A 68. 405. Nakai. 98. Abstr. Liu. B. 123. J. 425. K.

Φ ~ 0. Meyer. Hovik.753 0. Durham. Maestri. E. mixtures should not be stored. Bolletta.2). A.763 0. independent of λ AM: EPR measurement of radical production 1. J.75 (cf. B. Photochem.769 0.001 16 ± 0. Φ = (4. Mopper.759 0. J. WR: 360–580 nm.000 04 (scavenging product salicylic acid [p-hydroxybenzoic acid]). λem = 410 nm) of salicylic acid (without HPLC) PP: 10–3 M sodium nitrite and 10–3 M benzoic acid (OH radical trap) in air-saturated 2. photocurrent depends on quencher and its concentration AM: reading of photocurrent 1. Photobiol. J.1 M ionic strength amine and borax buffer (pH 9. 70. Photochem.2 PP: strong λ and temperature dependence.767 0. Isr. Sandrini. T. J. in air-saturated Freon 113 Uvasol Merck (1. Dressick. Juris. insensitive to room lights. J. M. H. KUHN et al. J.6 × 10–3 M) AM: absorbance at 383 nm λ/nm 405 436 450 475 490 500 Sac(λ) = Φ(λ) ε(383 nm)/ dm3 mol–1 cm–1 Standard deviation ± Φ(λ) Standard deviation ± 666 662 670 671 657 644 12 11 12 12 13 13 0. D. 623–624 (1979). 13–33 (1987). L54: Tris(2. Jankowski. Chim. Kuhn.2'-bipyridine)ruthenium(II) oxidation upon photolysis in the presence of peroxodisulfate WR: 366. L175–L176 (1980). J.000 05 AM: HPLC analysis (with absorbance and fluorescence detection) of salicylic acid and m/p-hydroxybenzoic acid or batch fluorescence (λexc = 305. 30. D. 405. there is a slow dark reaction. Chem. Pure and Applied Chemistry 76. but extremely sensitive (10–9 einstein still detectable) 1.020 0.6-tetramethyl-4-oxo-1-piperidinyloxyl (TAN) by photoproduced hematoporphyrin anion radicals in buffered aqueous solutions.018 © 2004 IUPAC. limited scavenging. Therefore. F. D. Sac = 16 600 dm3 mol–1 cm–1 AM: absorbance at 450 nm PP: Φ depends on pH and peroxodisulfate concentration.018 0. L57*: 5. table below for the Φ(λ) values depending on the excitation wavelength λ). 22. 405. Absorption must be measured immediately after irradiation because of a reverse dark reaction.6. H. Kleber. 2105–2146 .016 0.5 × 10–3 M sodium hydrogencarbonate solution at pH 7. Actinometry in an EPR cavity.H. J.2'–bipyridine)ruthenium(II) irreversible electron transfer quenching in an electrochemical cell. J. 2134 L53: Sodium nitrite/benzoic acid in aqueous solution WR: 360–380 nm. 546 nm. Φ = 0. 31. EPA Newslett. WR: 366.3 in argon-saturated aqueous solution (1.018 0.4 × 10–4 M Ru(bpy)32+ and 2 × 10–3 M potassium peroxydisulfate [µ-peroxo-bis(trioxysulfate)(2-)].12–Diphenylnaphthacene self-sensitized photooxygenation WR: 405–500 nm.2) 10–3 in 0.001 87 ± 0. Görner. Acta 44.1 ± 0. 436 nm. Moan. L56: Degradation of 2. Φ = 1. 2. L55: Tris(2. Φ = 0. 1.738 0. B. Schulte-Frohlinde. Inorg. pH ~ 5).018 0.2. W. 153–157 (1982). Photobiol. Wold. K. 319–328 (1999).

L59: Thiourea photooxidation WR: 420–660 nm. Schocken.7a-tetramethyl-2-phenyl-7. Harris. Armand. isomer equilibrium stable in the dark. Chem. Photochem. O.7. 175–182 (1956). Pure and Applied Chemistry 76.09–0.05) × 10–2 (in methanol) AM: HPLC of cis-isomer (401 nm) PP: strong dependence on solvent polarity. 1 957–961 (1985).-D. 11. J. 363–369 (1949). no conversion limit. Brauer. Strydom. J. 2.0240 (546 nm).. Johncock. J. linear dependence of Φ on λ. 2105–2146 . © 2004 IUPAC. H. A. Cox. reuse of the solution not recommended because some degradation takes place during recoloring 1. P. P. Heller. P.7.28 ± 0. Biophys. N. Photobiol. 394–404 (1966). L60: 4. Adick. 21. Mialocq. Kemp.0351 (436 nm). 351–356 (1993). suitable as polychromatic quantum counter 1.48 in aqueous solution AM: absorbance at about 376 nm 1. Biochem.74 with pheophytin or pheophorbide as sensitizers in pyridine AM: O2 consumption. G. E. Acta 22. Baumann.10 AM: precipitation of the unreacted complex as the perchlorate salt and determination of chromium in the supernatant 1.7a-dihydro-benzo[b]thiophene-5. J. J. A 45. Photochem. Arch. H. Φ = 0.Chemical actinometry 2135 PP: conversion limit ~30 %. A. W. 2. insensitive to oxygen 1. Schwartz. T. S. C. Sci. K. H.. Oliver. Heller. 88. M. Behrmann. 2. Am. R. W. G. negligible dark reaction. Pinot de Moira.-Mater. 0. Marguet. 208–214 (1977). manometric 1. Soc. H. J. Ortmann. Photobiol. cf. Whittal. L61: Hexakis(urea)chromium(III) chloride. A 69. Private communication by H. J. Biochim. Waldmann. Perkin Trans.98 with ethyl chlorophyllide [chlorophyllide ethyl ester]. Signalaufz..5 %. E.0210 (575) nm in toluene. W. Φ ~ 0. L62: 4-Dicyanomethylene-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran (DCM) [2-(2-{2-[4-(dimethylamino)phenyl]ethen-1-yl}-6-methyl-4H-pyran-4-ylidine)propanedinitrile] trans → cis photoisomerization WR: 462 nm at continuous and 532 nm at ns laser photolysis. 25. Payne. Φ = (2. Φ = 0. no thermal reversion. 385–394 (1983). L58: p-(Diethylamino)benzenediazonium tetrafluoroborate (DEAD) photolysis WR: 405 nm. G. independent of concentration. Jahnke. S. R. 89–96 (1988). Schmidt. Adamson. J. H. reversible (photocyclization) on exposure to 366 nm. Photogr. D.22 ± 0. Φ = 0. S. Glaze. 0. A.6-dicarboxylic anhydride (Aberchrome 999P) reversed photocyclization WR: 435–640 nm. For similar compounds. beware of light absorption by cis-isomer traces below 410 nm. Soc. Φ(λ) = 0. Φ ~ 0. Sac(λ) = 288 dm3 mol–1 cm–1 at 546 nm AM: absorbance at 546 nm [ε(546 nm) = 12 000 dm3 mol–1 cm–1] PP: reproducibility ±0. Wegner and A. Warburg and V. PP: This actinometer is no longer commercially available.02 (in CHCl3). J.-J. J. [Cr(urea)6]Cl3 photoaquation WR: 452–735 nm. X. Chem.

Φ is independent of concentration and photon flux = 1. 3. Dissertation Frankfurt (Main) (1980). S. 595–598 (1983). Sauvage. J. reproducibility better than ±1 %. C. H. H. A.o]perylene (meso-diphenylhelianthrene. Am.-D. table below for the Φ(λ) values as a function of the excitation wavelength λ (halfwidth of monochromatic light: 6 nm). A. 25. J. Pure and Applied Chemistry 76. PP: Actinochrome is no longer commercially available. L64: Cobalt(III) amines photolysis in aqueous solutions WR: 488 nm. K.106 0. Schmidt. Photochem. Photobiol. Pribush. solutions stable at –15 °C for at most 3 months 1. Bruce. A > 3. MDH) photooxygenation. 2136 L63*: 7. W. Adamson. Photochem.106 0. Photochem. A 49. and 3000 m altitude. Chim. Photobiol. Phys. Hubig. pH-dependent AM: NH3 release and halide aquation. Φ ~ 10–4 – 5 × 10–3 at 25 °C. R. suitable for polychromatic radiation AM: change in absorbance at 405 nm of endoperoxide. R.003 0. Acs.-J. 89–96 (1988).H.. C. bleaching of MB is negligible 1. Ber. MDH) photooxygenation sensitized by methylene blue (MB) WR: 610–670 nm.16-Diphenyldibenzo[a. cf.003 *(He–Ne laser) PP: contribution to initial absorbance at 405 nm by MB (0. Schmidt. 844–873 (1947). Schmidt.004 in air-saturated toluene (10–3 M) independent of λ.109 0. S. R.3. Chem. 38. Φ = 0. Adick. 90. 37. Schmidt.3-trimethylindoline-2-ylidine)heptadienylium iodide] (HITC) © 2004 IUPAC.003 0. Chem. 5. 3970 dm3 mol–1 cm–1 at 1000. 527–531 (1983). Brauer.114 0. Gauglitz.035) and MDH (0.. irreversible. MDHPO) λ/nm S(λ) = Φ(λ) ∆ε(405 nm)/ dm3 mol–1 cm–1 Standard deviation ± Φ(λ) Standard deviation ± 610 620 633* 654 670 2062 1972 1918 1918 1919 39 38 38 36 35 0. Poon. Brauer.3. Photobiol. absorbance at 625 nm 1.16-Diphenyldibenzo[a. Photochem. H. 10–4 M MDH. H.3'. suitable as polychromatic quantum counter.-D.224 ± 0. R. Photochem. L66: 7. Dissertation Tübingen (1984).1'. respectively) AM: absorbance at 429 nm PP: conversion limit ~10 %. 2.1 in air-saturated CHCl3 solution. 2105–2146 . G.-D. Brauer. L65: 7.-D. 6.165). Brauer.7-bis-(1.106 0. at 22 ± 2 °C. 4. Φ ~ 0. Ann. no dependence on λ. J.5 × 10–11–10–9 einstein s–1. G. 813–819 (1986). KUHN et al.-J. M. J. 2000.o]perylene [meso-diphenylhelianthrene] {Actinochrome N (475/610)} self-sensitized photooxygenation WR: 475–610 nm. 8 × 10–5 M MB. Soc.o]perylene (meso-diphenylhelianthrene. Adick. J. Sac = (4080 ± 90) dm3 mol–1 cm–1 at sea level (Sac= 4030. 311–316 (1989).-D. H. 4000. H. R.003 0.16-Diphenyldibenzo[a. Drews. A. 7.3'-hexamethylindotricarbocyanine iodide [1. sensitized by 1. no side products. 2.3. Bunsen-Ges. A 45. R. variation of oxygen concentration has no influence. Schmidt and H. 3027–3032 (1974). Hubig. Brauer. MDH) – ε(405 nm. Photobiol. 489–499 (1984). Schmidt. W. R.003 0. 96. ∆ε(405 nm) = ε(405 nm.

P. Chem. F. Adick.04 . counted.0431 0. 1. By means of a chemical quantum counter (e. Pure and Applied Chemistry 76. 1413 (1970). suitable for polychromatic radiation AM: change in absorbance at 405 nm of endoperoxide. Gauglitz and U. P. MDHPO) λ/nm S(λ) = Φ(λ) ∆ε(405 nm)/ dm3 mol–1 cm–1 Standard deviation ± Φ(λ) Standard deviation ± 670 680 685 695 700 705 710 720 730 745 755 770 780 795 818 780 769 772 780 796 809 810 781 738 716 680 678 678 19 18 18 18 17 17 17 17 16 15 15 15 14 14 0. Schmidt. decrease of oxygen concentration of 20 % decreases quantum yields by only 2 %.2 Electronic devices Radiant power measurements before and after. 2105–2146 . G.. Φ = 0. Rhodamine B) and photodiodes (or photoelements or photomultipliers) the two light beams produce voltages that are electrically matched. Kölle.0447 0. ∆ε(405) = ε(405. J. largely independent of the absorbance. The instruments allow the application of a preset amount of quanta to the sample and account for changes © 2004 IUPAC. Commun.0016 0.g.0452 0. Chem. H.0440 0.2 × 10–5 M HITC in air-saturated CHCl3 solution. J. R. 7.0016 0. A 54. cf. a photochemical reaction (the quantum yield of which is of interest) are rather cumbersome to perform with traditional methods of chemical actinometry.. Filipescu. table below for the Φ(λ) values as a function of the excitation wavelength λ (half-width of monochromatic light 6 nm).2137 Chemical actinometry WR: 670–795 nm.0408 0. no significant dark reaction in the cold 1. Margaretha. Commun.0016 0.0014 PP: contribution to initial absorbance at 405 nm by MB (0.0017 0. or during. Integrating electronic actinometers of the “Quantacount” type [E06. and displayed.0376 0. Brauer.60 ± 0. Soc.0425 0.0018 0.-J. the entering monochromatic light is split into a sample beam and a reference beam.-D. For that purpose. 3.0016 0. J. Photochem.0014 0.0431 0. K. and dependence on fluence: 2. Gloor.25). 2. λ-dependent Φ. E10] are designed to measure and integrate the amount of light absorbed by the sample during irradiation. During irradiation the difference in radiant power before and behind the sample is continuously computed and converted into a frequency [E06].0018 0. Φ independent of photon flux in the range 5 × 10–11 – 5 × 10–10 einstein s–1. which is integrated. J. 4.0375 0. J. Φ ~ 0. 565 (1974). 309–312 (1975).0018 0.3) and HITC (0. Two independent studies advised against the use of this system because of complex stoichiometry. Disproved: L67: Decafluorobenzophenone photoreduction in propan-2-ol WR: 290–370 nm.6 × 10–4 M MDH. Chem.01 1.0014 0. Photochem. MDH) – ε(405..0448 0.0427 0.0375 0.0019 0. N. E07.0017 0. 27–30 (1990). L. Pinion. Schaffner. Photobiol..0016 0.0432 0.0396 0. Soc. J. H. Chem. Minn.

2105–2146 . G. In Instruments of Science. Photochem. A. E04: Physical light integrator 1. Anal. G. 1048–1052 (1968). E. New York (1998). 15. An Historical Encyclopedia. Rev. Weiss. H. T. Schaffner. W. W. Each photon which is absorbed in © 2004 IUPAC. 51. J. 2. K. 223–229 (1973).-R. D. Davidson. Instrum. Kuhn. Bohning. P. Cutler. Garland Encyclopedias in the History of Science. 330–331 (1970). R. Photobiol. 287–296 (1981). Photochem. N. P. Fitzgerald. 5. B. R. Garland Publ. 8. Jahnke. of the power of the light source and of the absorbance of the sample. 758–759 (1966). J. Taylor and J. J. 2. Zimmerman. Z. L. Warner (Eds. 11. J. Vol. 2. P. E02: Calibrated thermopile for continuous measurement of light absorption during irradiation 1. J.-Mater. I. 34. Naturforsch. E05: Digital quantum dose integrator with memory 1. 39. Gloor. H. Inc. J. photoelements) 1. Waldmann. Yip and D. E09: MgWO4 phosphor photoelectronic UV-B dosimeter for microcomputer read-out WR: UV-B. Chem. K. Wolf. E03: Photon irradiance monitor consisting of a Rhodamin B solution and a photomultiplier 1. 379–389 (1977).3 Absolute measurement of incident photon flux by means of photodiodes Photodiodes are used for the detection of electromagnetic radiation in the ultraviolet. 5. 283–290 (1973/74). Dickinson. Signalaufz. Instrum. Photochem. Schaarschmidt. photodiodes) 1. Kofsky. Pure and Applied Chemistry 76. Chimia 28. Mol. 43. H. Amrein. The complete optical and electronic set-up has to be calibrated by chemical or physical means (see Preface) determining the einstein per count relationship for the desired wavelengths. N. p. W. the emission at 420–560 nm is detected by a photodiode 1. Kyziol. K. Demas. Behrmann. Z. 185–188 (1974). Schultze and H. Bud and D. Goldsmith. Registration of the absorbance [E06] or taking a complete absorption spectrum [E10] are comfortable additional options allowing the monitoring of the photochemical conversion. visible. Chem. Fanghänel. Demas. E10*: Integrating electronic actinometer with automatic UV/VIS monitoring WR: 365–578 nm (Rhodamine B as fluorescent converter. Vogel. Their basic principle rests on the photoelectric effect. H. E01: UV light integrator as photochemical monitor 1. 2. R. T.. 6.). 717–722. H. Sci. and infrared range. Baumann. G. R. 712–717 (1979). H. KUHN et al. B. R. Sci. J. Weigt. J. Behrmann. J. V. 2. Instrum. Yguerabide. Schnieper. 20–21(1984). E. 321–329 (1967). 24. ibid. Sluder. Ortmann. Photobiol. Chem. G. 385–394 (1983). Photochem. Mol. E07*: Electronic actinometer with photomultipliers 1. K. J. 25b. E08: Luminescent quantum counters 1. J.2138 H. E06*: Electronically integrating actinometer WR: 254–578 nm (Rhodamine B as quantum counter.

e. and the resistance Rf of the feedback resistor: U = ipd Rf.g. the flowing photoinduced current can be measured with high precision using an operational amplifier. other photodiodes of the same type. By multiplying Sn(λ) by the measured photocurrent ipd the desired photon flux/einstein s–1 at wavelength λ is readily obtained. The relative Spd(λ) data plotted vs. which have been kept in the dark for reference purposes. Hereby. Therefore.e. indicating a constant value of Φc (e.72 ± 0. λ in Fig.066 × 105 λ/m. Therefore.119 586 m/λ of one einstein of absorbed photons. For the wavelength region where direct proportionality of Spd(λ) with λ holds true. which amounts to about 30 % for uncoated Si. Hamamatsu S2387). one einstein has the energy E(λ)/J = 0. Φc is in good approximation constant in this range as indicated in Fig. Thus. 1. In actinometry. Thus. it is strongly recommended to occasionally calibrate the photodiode vs. Owing to the wavelength dependence of the absorption coefficient of the semiconductor material.Chemical actinometry 2139 the semiconductor material leads to excitation into the conduction band and produces one electron-holepair. leading to the maximum possible sensitivity Spd(λ)/A W–1 = 8.. i.. Some mass-produced Si photodiodes show direct proportionality of Spd(λ) with λ in a broad range of the visible spectrum. Φc = 1 means that the charge of 96 485 Å is produced by the energy E(λ)/J = 0. The needed diode sensitivity is Sn(λ)/(einstein s–1 A–1) = [Spd(λ) E(λ)]–1. © 2004 IUPAC. Precise investigations of Si photodiodes have shown that the quantum yield Φc of electron-holepair formation is actually unity for radiation of wavelengths for which absorption takes place in the p–n junction [3]. 2105–2146 . As shown above. Linear least-squares fitting between 290 and 895 nm with fixed zero intercept results in the straight line in Fig. 1.pdf>).44 × 10–5 in practically the whole visible wavelength range and even in the NIR. After proper calibration with an external standard. The determination of the quantum yield of the 1940 nm b → a emission of singlet molecular oxygen was performed with an InAs photodiode. it is important to have diode sensitivities related to photon flux (qn. When an outside electrical connection between both sides of the junction is made. The sensitivity of the semiconductor at a given wavelength λ is given in photocurrent (A) per watt of incident radiation.44 × 10–5 between 450 and 1000 nm. Pure and Applied Chemistry 76. electrons and holes are very effectively separated by the strong local electric field. a chemical actinometer or vs. However. if the absorption takes place in the depletion region of the p–n junction of the diode.066 × 105 λ/m holds true in the absence of reflection loss for Φc = 1. which rapidly recombines in the absence of an electric field.82 × 105 λ/m. 1 have been extracted from the S2387 data sheet (<http://www. with a constant Φc from 1100 to 2700 nm according to the data sheets of the manufacturer [4]. when only moderate accuracy is required.. The main process reducing the sensitivity of Si photodiodes in the visible range is the reflection of the incident light at the planar surface. Photodiodes can be used as polychromatic quantum counters in this wavelength range. the output voltage U equals the product of photocurrent ipd.05 between 450 and 1000 nm. absorption of radiation can also occur in the layers where the separation of electrons and holes is less effective. a photodiode may be used as a detector for the absolute determination of the photon flux of monochromatic radiation. this cheap Si-photodiode may be used as a polychromatic quantum counter of constant sensitivity Sn(λ)/einstein s–1A–1 = 1. i. Spd(λ)/A W–1.p) rather than to radiant power.de/assets/pdf/parts_S/S2387-1010R. the mean apparent quantum yield of charge carrier formation of the S2387 diode including reflection loss amounts to Φc = 0. Such measurements have been performed in photochemical investigations [1] and in the calibration of several chemical actinometers [2]. the charge of 72 180 A s is produced by the incidence of one einstein onto the surface of the S2387 photodiode in this wavelength range resulting in the constant sensitivity Sn(λ)/einstein s–1A–1 = 1. before (at shorter wavelengths than the optimum one) and behind (at longer wavelengths) the p–n diffusion layer. With E(λ) = NA h c/λ. However.119 586 m/λ.hamamatsu. Spd(λ)/A W–1 = 8. The deviation of the linear fit from the data is smaller than 12 % between 430 and 1000 nm. the quantum yield of charge carrier formation Φc of the diode is constant. however. and even <7 % between 450 and 1000 nm. The fit follows the relation S′pd(λ)/ A W–1 = 5.

38.1. Schaefer. Photochem. 2. Zalewski. 587–591 (1983). Photochem. Phys. InAs. The irradiation is performed at room temperature. Opt. Even though oxygen is not expected to interfere with the isomerization reaction. References to Section 2. A.6 × 1016 s–1 (cross-section 2–4 cm2) at 185 nm.34.-P. CdHgTe) may also be used for absolute radiation measurements in the near and middle IR range. 391–403 (1976/77). H. since the condition of direct proportionality of Spd(λ) with λ is fulfilled for several semiconductor devices [5]. This actinometer involves a system where the product. F. Drews. R.) L02*: cis-Cyclooctene cis → trans photoisomerization (submitted by R. Laser Components GmbH. 2105–2146 . 99. 6.-D. Ge. Determination of the quantum yield of the 1940 nm b → a emission of singlet oxygen: R. 3795–3799 (1980). Schmidt. 37. Brauer. Brauer and R. HgCdTe): Infrared Detector 1998. Fig. Ge. total absorption) containing nonane as a GC standard is placed in a suprasil cell and deaerated by purging with a gentle stream of oxygen-free argon while the sample is kept cold to minimize solvent evaporation. is photoisomerized back to the cis compound (side reactions are very minor). The conversion after 1 min of irradiation is easily measurable by gas chromatography at a photon flux of about 1. E. Chem. 527–531 (1983). Srinivasan. 5. STANDARD LIQUID-PHASE ACTINOMETRIC PROCEDURES (For references and more data.-D.3. URL: <http://www. A. it may lead to relatively longer wavelengths charge-transfer absorption involving the solvent. J. Section 2. Photochemical set-up: W. Schmidt. Spectral sensitivity of other semiconductor devices (Si. Calibration of chemical actinometers: H. EG & G Optoelectronics. Schuchmann) WR: 185 nm. InAs. 3. trans-cyclooctene. Schmidt. Φ(trans → cis) = 0. 3. R. cf. 19. H. 15919–15924 (1995). Photochem. The number of photons Np absorbed per sample volume V and unit time t.lasercomponents. above. Judson.2140 H. Schmidt and M.3: 1. Quantum yield of electron-hole-pair formation of a Si photodiode: J. J. Geis. and H. Brauer. Appl. Φ(cis → trans) = 0. Acs. Pure and Applied Chemistry 76. 1 Other detectors (Si. A gas-tight cell assembly is necessary. KUHN et al.de>.-D. R. J. Photobiol. Photobiol. It is recommended to stir the solution during purging and irradiation by a Teflon-coated bar magnet. 4. Bodesheim. von Sonntag.44 A volume of 2–4 cm3 of a solution of cis-cyclooctene in pentane (2 × 10–2 M. is calculated from © 2004 IUPAC. C.

as follows.672 62 g disodium oxalate (Na2C2O4. the nonreacted C2O4–2 is titrated with a solution of Ce(IV) sulfate. ε (trans) = 6000 dm3 mol–1 cm–1.-P. It is recommended to stir the solution during purging. The Ce(IV) concentration is then determined spectrophotometrically by dilution © 2004 IUPAC. L03*: Ethanol photolysis (Farkas actinometer) (submitted by C. 2105–2146 . For details and an alternative graphical method of evaluation. Approximately 5. The hydrogen quantum yield depends on the concentration of ethanol. A gas-tight cell assembly is necessary. irradiation.5 M.5–0.4 2–4 cm3 of a 5 M aqueous solution of pure ethanol (free of acetaldehyde and oxygen) are placed in a suprasil cell and purged with a gentle stream of oxygen-free argon while the sample is kept cold in order to minimize evaporation.6 The chemical reaction used is the photodecomposition of oxalic acid. and stripping by a Teflon-coated bar magnet. NA = Avogadro constant. following the reaction: 2Ce(IV) + C2O4–2 → 2 Ce(III) + 2CO2 Preparation of solutions: 0. Alfano) WR: 200–500 nm. Subscript o indicates zero conversion and ∞ refers to the stationary state ([trans]∞/[cis]∞ ~ 1). Eaton and O.3. t = irradiation time. As usual. there is total absorption at concentrations ≥0. [cis]∞/[cis]o is close to 0.004 × 10–3 M in oxalate dianion and 1. the GC determination requires calibration. The precipitate is then dissolved in hot 1 M sulfuric acid (125 cm3) and washed into a 1. Pure and Applied Chemistry 76.5 g (NH4)2Ce(NO3)6 are dissolved in 15 cm3 water and treated with 100 cm3 15 M NH4OH. references in L02. Φ = 0. Section 2.011 × 10–3 M in uranyl ion.1. Store in the dark. H2C2O4.1 M H2SO4 and diluted to 1.5.0 dm3 volumetric flask 1. The resulting precipitate is washed with six portions of water (25 cm3 each) until neutral to pH paper. F.42478 g uranyl sulfate (UO2SO4) and 0. from a solution of uranyl oxalate. primary standard grade) are dissolved in 0. cf. ε (cis) = 8500 dm3 mol–1 cm–1. von Sonntag and H. hν H 2 C2O4 → H 2O + CO2 + CO After irradiation.0 dm3 in the dark. Φ(H2) = 0. The solution is cooled and brought to approximately 950 cm3.Chemical actinometry 2141 N p [cis]o f ([cis]) Φ (trans → cis) =– t N A V t [cis]∞ where f([cis]) is given by the expression ε (cis) – ε (trans) ([cis] – [cis]o ) + ε (trans) [cis] – [cis]∞ ε (cis) – ε (trans) [cis]∞ ) ln + ( [cis]o + ε (trans) [cis]o – [cis]∞ f ([cis]) = [cis] is the time-dependent cis-cyclooctene concentration. The product-collecting procedure is the same as the purging procedure. Ce(IV) sulfate is prepared from ammonium hexanitratocerate according to the procedure by Smith and Fly (L06* [14]). The solution is 5. Enough hydrogen is produced after 1 min excitation with a photon flux (number basis) of about 2 × 1016 s–1 (cross-section 2–4 cm2) at 185 nm to be easily measurable by gas chromatography. L06*: Uranyl oxalate [dioxouranium(VI) oxalate] photolysis (submitted by D. Hydrogen is stripped from the sample directly into the gas chromatograph by the carrier gas. Schuchmann) WR: 185 nm.

and one should always check the integrity of freshly prepared solutions by comparing photon flux measured by uranyl oxalate actinometry to that obtained using ferrioxalate actinometry at a wavelength at which quantum yields are known for both systems.56 0. this factor depends on irradiation wavelength and pathlength). The decadic molar absorption coefficient of Ce(IV) at 320 nm is ε(320 nm) = 5.0 nm vs. Both irradiated samples and nonirradiated blanks are treated in this way. 1. and l/cm is the pathlength. KUHN et al.58 0. ∆Α(320 nm) is the absorbance difference between sample and nonirradiated blank.p = Virrad ∆A V flask2 2 Φ ( λ ) f ε (320 nm) Valiq l t with Virrad = volume of irradiated actinometer solution (recommended 3 cm3).0-cm3 aliquots of actinometer solution. PP: The use of commercial Ce(IV) sulfate is not recommended. L06*). Pure and Applied Chemistry 76. 2105–2146 . Φ = quantum yield of oxalate loss.999.01 dm3).57 0. largely because of Ce(IV) at the analyzing wavelength is only half that of the phenanthroline-Fe(II) complex used in the analysis during the ferrioxalate procedure].0 cm3 of the standard Ce(IV) solution and 1. ε(320 nm) = molar absorption coefficient of Ce(IV). Comments: The procedure discussed here is an improved version of one due to Pitts.53 0. Valiq = volume of the measured aliquot (recommended 1 cm3). The sensitivity of the method is only half of that of the conventional ferrioxalate procedure [L31*.p/einstein s–1 entering the sample cell is given by: qn . The factor 2 in the denominator results from the stoichiometric factor in the titration reaction.60# 0.1 M H2SO4 in a 1. Considerable care must be exercised when using the uranyl oxalate actinometer.58# 0.58 The marked (#) values in the table are interpolations from the other data (after Leighton and Forbes [1]. and the solution is brought to the mark with water. The oxalate photodecomposition quantum yields [Φ(λ)] are: λ/nm Φ(λ) 208 237 243 245 248 0. 0. J.61# λ/nm Φ(λ) 254 265 278 302 313 0. qn. a 1.56 λ/nm Φ(λ) 335 366 405 436 0.0-cm3 volumetric flask 2.H. f = fraction of incident actinometric light absorbed by actinometer solution (0. if the concentration is significantly greater than twice the oxalate concentration of the blank then the absorbances measured for the blank and irradiated samples will be so large as to render invalid differential absorption techniques.60 0. © 2004 IUPAC.58 0. since it is contaminated by ammonium nitrate which limits the stability of standardized cerium solutions. and Brackett and Forbes [2]. the results will be meaningless. amount basis.0 cm3 H2SO4 (1 M) are added. 2142 of an aliquot and measurement of the absorbance at 320.49 0.0-cm3 aliquot is pipetted into a 10. t = irradiation time. The solutions are then incubated at 80 °C for 10 min and allowed to cool in the dark.0-cm cell. Procedure: After irradiation of two 3.61 0. Vflask2 = volume of the reaction flask 2 (recommended 0. Calculations: The photon flux. The concentration of Ce(IV) is then adjusted until it is slightly larger than twice the (molar) concentration of oxalate in the actinometer solution.48 0. The success of this method also depends critically on the concentration of Ce(IV): if the concentration is less than that required to oxidize all the oxalate in the nonirradiated blank.41 × 103 dm3 mol–1 cm–1.

02 and the final value should be kept between 0. graphical or arithmetical kinetic evaluation methods have to be used (cf. Pure and Applied Chemistry 76. a preirradiated solution is used and the procedure starts at the photostationary state. Each irradiation period should cause a change in A(358 nm) of about 0. but should be determined for each lamp/filter combination at the irradiation wavelengths.trans) + Φ(cis → trans) ε(λ. with C = [Φ(trans → cis) ε(λ. For the range 375–440 nm.p/einstein s–1) is desired. Evaluation: For the range 245–340 nm. t. Φ(trans → cis) = 0.45.6010–6 4. For this purpose.30] and the final value should be A(358 nm) < 0. Wavelength range 270–340 nm: The absorbance A of a 6. Wavelength range 350–440 nm: There is no total absorption in this range. PP: Take care to dispose of the uranium waste in accordance with the current legal regulations. Φ(cis → trans) = 0. Gauglitz and S. the photon irradiance (in amount basis) entering the sample cell is EP/einstein cm–2 s–1 = F(λ) ∆A(358 nm)/t. the following formula is used. Irradiation and observation wavelengths should be the same.3]). stored in the dark (see below).6310–6 5. 1 is recommended. photoreduction (Hatchard–Parker actinometer. Sac = 13 900 – 9990 dm3 mol–1 cm–1 © 2004 IUPAC. The latter is done with the aid of a computer.85 and 0. Hubig) WR: 250–500 nm. Ideally. The graphical method uses the expresτ . C values are independent of time and concentration. the pseudo total sion EP = C— t quantum yield and ε at the irradiation wavelength. L11*: Azobenzene {Actinochrome 2R (245/440)} photoisomerization (reusable) (submitted by G. the used actinometric solutions are collected and photolyzed until complete oxidation of the oxalate.9. Φ = 1. The photolyzed solution is then concentrated under vacuum and the sulfate may be crystallized and recrystallized after adding sulfuric acid.14. 2105–2146 .4 × 10–4 M methanol solution of azobenzene.cis)] 1000. Sac = 130–3900 mol–1 dm3 cm–1 Wavelength range 245–266 nm: The solution is preirradiated at 313 nm.Chemical actinometry 2143 The uranyl may be recovered as sulfate. For the range 350–440 nm. L11* [2. Gauglitz) WR: 230–460 nm.3010–6 3. Thus. commonly called ferrioxalate actinometer) (submitted by G. λ/nm 245 280 302 313 334 F(λ)/ einstein cm–2 2. The lifetime τ is taken from calibration graphs of the time-dependent absorbance vs. The actinometry (as above) then starts at the photostationary state [A(358 nm) ~ 0. where ∆A(358 nm) is the change in absorbance at 358 nm and t/s = irradiation time.6010–6 The ratios of the irradiated volumes as well as of the front areas of actinometric and reaction cell have to be taken into consideration in case the photon flux (qn.3010–6 4. The factors F(λ) are given in the table below.48. only radiation ≥ 500 nm is to be admitted to the sample. a sealed cell should be stored in the dark or irradiated at 254 nm.9. A value of A(358 nm) ca. Except during irradiation. They are listed in the literature. is measured at 358 nm. L31*: Iron(III) potassium oxalate trihydrate [potassium tris(oxalato)ferrate(III) trihydrate] K3[Fe(C2O4)3]3H2O). the photoreaction should be made in a cuvette of the same dimensions as that used for the actinometer.25 – 0. For regeneration. Efficient stirring of the solution is essential in all cases.

20 from 310–375 nm. 2144 All procedures should be done under red safe-light. Pure and Applied Chemistry 76. The photon flux. Heller) WR: 310–375 nm.20–1. or 0.006 M) at 436 nm. A 0. the value of the photon flux must be divided by the fraction of absorbed light at the irradiation wavelength (1–10–A). Φ(λ) = 1. 3 cm3) of this solution is pipetted into a cuvette and the absorbance (if any) at 494 nm is noted. 1 cm3 (V2) of the irradiated solution is given into a 10 cm3 (V3) volumetric flask containing a mixture of 4 cm3 0. A reference is prepared in the same way except that it has not been irradiated.4–1. Care should be taken to prevent the magnetic stirrer from entering the light beam.01 M) at 458 nm.012. G.006 M solution is prepared by dissolving 2. PP: Reuse of the actinometer solution after photoreversion is strongly discouraged. 1. A(510 nm) should be within the range 0. 0.15 M (≥405 nm) solutions can be used for actinometry.14 at 405 nm..7a-dihydro-2. For recent quantum yields cf. J.4. ε(510 nm) = 11 100 dm3 mol–1 cm–1]. and 0. H2SO4. dried at 45 °C and kept in the dark. At room temperature Φ(λ) = 1. The colored form is reversed with white light. After irradiation in a l = 1 cm cell and mixing. Sac = 1640 dm3 mol–1 cm–1 A ca.08 M) at 488 nm.5-dimethyl-3-furyl)ethyl→ Aberchrome 540P [7. In this case. amount basis. entering the sample cell is given by (in coherent SI units): ∆A V1 V3 qn.8.12 (0. There is no total absorption above 450 nm even in 0. The procedure described in Murov’s Handbook of Photochemistry (L31*[12]) is also recommended.2. t = time. Green crystals of K3[Fe(C2O4)3]3H2O are prepared by mixing 3 vol 1.947 g of the crystals in 100 cm3 H2SO4 (0. qn. 1.7.5 cm3 buffer (stock solution: 82 g NaC2H5CO2. Φ = 0. but the precautions listed above should be obeyed.08 (0. entering the sample cell with qn. A magnetic stirrer is recommended.15 M solution. L31* is not really an integrative system. [10e]. © 2004 IUPAC. For example. Both solutions are kept in the dark (about an hour) until full color development is achieved. and the absorbance difference between the two samples is measured at 510 nm [optical pathlength l = 1 cm.93 (0.1 % 1.5 M K2C2O4 with 1 vol 1 M FeCl3 solution. It is essential that the solution absorbs all radiation falling upon it. 0.7.g. Conversion should not exceed 5 %. It is essential that the irradiation time measurement (electronic shutter) as well as the pipetting is done very precisely. i. L45*: Fulgide reversible photocyclization: Aberchrome 540 [(E)-[1-(2. An absorption spectrum of the solution is taken. amount basis. Aberchrome 540 is no longer commercially available. The increase in ∆Α(494 nm) enables the calculation of the photon flux.006.e. 10 cm3 conc.6-dicarboxylic anhydride] (submitted by H. periodical fluctuations in radiation power may not be “seen” during the rather short irradiation periods. The stirred solution is then irradiated for a known period. 1.006 M) for the wavelength range 254–366 nm.p/einstein s–1 . recrystallized three times from warm water. ε(494 nm) = 8200 dm3 mol–1 cm–1.H. 2105–2146 .11 (0. 3 cm3 (V1) of the solution are irradiated under efficient stirring.26 (0. diluted to 1 dm3 with distilled water) which is then diluted to the mark with distilled water.7a-pentamethylidene](isopropylidene)succinic anhydride] ← benzo[b]furan-5. Total absorption at the desired irradiation λ and optical pathlength is recommended. An accurately measured volume (e. PP: Owing to its high Sac-value.5 M) and dilution with distilled water to 1 dm3.p/einstein s–1.p = ∆A(494 nm) V Φ ε (494 nm) l t where V = irradiated volume. the absorbance at 494 nm is measured.p = Φ (λ ) ε (510 nm) V2 l t with t = irradiation time. qn. Φ = 0. KUHN et al.. 5 × 10–3 M solution is prepared by dissolving 25 mg Aberchrome 540 in 20 cm3 toluene.20 M) at 514 nm.10-phenanthroline solution (store in the dark!) and 0.

Am. Jones and K. V = volume of the solution (density = 1.6 × 10–3 M solution of 5. 8. stirring is essential. R. 87. The conversion should not exceed 30 %. C. Mauser. Schmidt) WR: 334–395 nm.016. qn. Wani. H. 67.3.583 ± 0. 3704–3706 (1967).p/einstein s–1. 2105–2146 . During irradiation.583 ± 0. 3. E. Radiation of λ < 435 nm should be completely avoided during preparation and handling of the solution.12-Diphenylnaphthacene self-sensitized photooxygenation (submitted by R. The photon flux. amount basis. amount basis. S. The system is suited as a polychromatic quantum counter independent of wavelength with a mean value Φ(λ) ε (324 nm) = (629 ± 17) dm3 mol–1 cm–1 and Φ(λ) = 0.15.1. Ber. Salisbury. Hahn. Formale Kinetik. Chem. Bunsen-Ges.758 ± 0.3. 2. entering the sample cell is calculated by using the absolute value of the absorbance decrease ∆A(383 nm) upon irradiation and the following equation qn. © 2004 IUPAC. L. V = volume of the solution (density = 1.4 (optical pathlength l = 1 cm) is filled into a spectrophotometric cell equipped with a magnetic stirring bar.p = ∆A(383 nm) V Φ ( λ ) ε (383 nm) l t with t = irradiation time. Only yellow or red light ≥ 560 nm may be used during preparation and handling of the solution. E. The system is suited as a polychromatic quantum counter independent of wavelength with a mean value Sac = Φ(λ) ε(383 nm) = (662 ± 13) dm3 mol–1 cm–1 and Φ(λ) = 0. H. Morrison. Photobiol. E. Φ = 0. The conversion should not exceed 20 %.1.7 × 10–3 M solution of 9. APPENDIX Additional references concerning practical problems as well as kinetic and theoretical aspects of quantum yield calculation: 1. L57*: 5. Photochem. 71. Values of Sac = Φ(λ) ε (383 nm) at particular irradiation wavelengths are given under L57* in Section 2.Chemical actinometry 2145 L47*: 9. 1138–1140 (1965). C. J. Zimmerman. Chem. The solution completely absorbs the incident radiation in the useful wavelength range 405–520 nm. Johns. Schmidt) WR: 405–500 nm. 6. Values of Sac = Φ(λ) ε (324 nm) at particular irradiation wavelengths are given under L47* in Section 2.p = ∆A(324 nm) V Φ( λ ) ε (324 nm) t l with t = irradiation time. The photon flux. 883–892 (1963). H. Kling. The solution completely absorbs the incident radiation in the wavelength range 334–395 nm.015.575 g cm–3). H.575 g cm–3). Chem. Düsseldorf (1974). Φ = 0. Phys.16. Soc.758 ± 0. Bertelsmann Universitätsverlag. Sac = (629 ± 17) dm3 mol–1 cm–1 A defined volume of a 1.12-diphenylnaphthacene in air-saturated Freon 113 (molar absorption coefficient ε (383 nm) = 873 dm3 mol–1 cm–1) of initial absorbance A(383 nm) = 1. Schläfer. 547–563 (1968). Photochem. J. stirring is essential.8 (optical pathlength l = 1 cm) is filled into a spectrophotometric cell equipped with a magnetic stirring bar. Sac = (662 ± 13) dm3 mol–1 cm–1 A defined volume of a 1. M. 435–445 (1972).p/einstein s–1. During irradiation. 16. Phys.10-Dimethylanthracene self-sensitized photooxygenation (submitted by R. entering the sample cell is calculated by using the absolute value of the absorbance decrease ∆A(324 nm) and the following equation qn. O. 4. H. Pure and Applied Chemistry 76. H. qn.10-dimethylanthracene in air-saturated Freon 113 (molar absorption coefficient ε (324 nm) = 1080 mol–1 dm3 cm–1) of initial absorbance A(324 nm) = 1. Nikolaiski. 5. Fischer. E. Photobiol.

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