IUPAC2004_Actin_March-23-04 Tuesday, 23 March 2004


Chemical Actinometry
(IUPAC Technical Report) Prepared for publication by H.J. Kuhn,1 S.E. Braslavsky,1 and R. Schmidt2

Max-Planck-Institut für Strahlenchemie, D-45413 Mülheim a.d.Ruhr, Germany
email: h.j.kuhn@t-online.de; braslavskys@mpi-muelheim.mpg.de


Institut für Physikalische und Theoretische Chemie, Universität Frankfurt, D-60054 Frankfurt/Main, Germany
email: r.schmidt@chemie.uni-frankfurt.de

Organic and Biomolecular Chemistry Division (III) Committee: President: Thomas T. Tidwell (1998-2003), Minoru Isobe (2002-2005); VicePresident: David StC. Black (1996-2003), Vadim T. Ivanov (1996-2005); Secretary: George M. Blackburn (2002-2005); Past President: Torbjörn Norin (1996-2003), Thomas 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




Abbreviations Symbols and Units Preface I. General Considerations on Chemical Actinometry II.1. Chemical Systems II. List of Actinometers II.1.1. Solid Phase and Microheterogeneous Phase II.1.2. Gas Phase II.1.3. Liquid Phase II.2. II.3. Electronic Devices Absolute Measurement of Incident Photon Flux by Means of Photodiodes

3 4-5 6 7- 9 10 - 38 10 - 37 10 - 13 13 - 16 17 - 37 37 - 38 38 - 40 40 - 46 46

III. Standard Liquid Phase Actinometric Procedures Appendix (additional references)

*In addition to the members of the IUPAC photochemistry commission (1985-1988), see first version in Pure & Appl. Chem. 61, 187-210, 1989), and Sub-Committee (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, R. Schrader, H.-P. Schuchmann, C. von Sonntag, R. Srinivasan, J. Theurich, L. Vincze, J. Wirz, H.E. Zimmerman and others. Members of the Photochemistry Commission (1998-2001) were: Chairmen: J.R. Bolton (Canada, 1996–9), R.G. Weiss (USA, 2000–1); Secretaries: R.G. Weiss (USA, 1998–9), J. Wirz (Switzerland, 2000–1); 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 Sub-Committee on Photochemistry (2001-2003): S.E. Braslavsky (Germany, Chairperson), A.U. AcuñaFernández (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 (Finnland), 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). 2

3 Abbreviations: AM = analytical method CA = chemical actinometer E = electronic device G = gas phase GC= gas chromatography HPLC = high pressure liquid chromatography IR = infra-red L = liquid phase LC = liquid chromatography PP = procedure, precautions, comments S = solid phase WR = wavelength range


4 SYMBOLS AND UNITS USED IN THIS DOCUMENT Common units are mentioned if different from SI base units Name absorbance (in general) at a particular wavelength λ absorption coefficient (decadic) absorption cross section

A = log ( P /P ) = -log T
Aλ = log ( Pλ0 /Pλ ) = -log Tλ
0 a λ = Aλ / l = (1/ l ) log ( Pλ /Pλ )

Symbol Aλ A a SI basea --- b --- b cm-1 cm2

Unit common

mol-1 dm3 cm-1 actinometric factor, see Sensitivity concentration fluence c frequency (linear) irradiance, c radiant power per unit area, incident from all directions. For a parallel and perpendicularly incident beam not scattered or reflected by the target or its surroundings fluence rate (E’) is an equivalent term. lifetime, the time needed for the concentration of an entity to decrease to 1/e of its original value molar (decadic) absorption coefficient mole of photons optical pathlength photon flux c,d number of photons per unit time photon fluence c number of photons per unit area photon fluence rate c applied to radiation falling from all directions photon irradiance c photon flux incident on a surface, identical to photon fluence rate for a parallel beam not scattered or reflected photon number pressure quantum yield quantum yield of charge carrier formation in a photodiode

σλ = (ελ/NA) ln 10 = 3.8236 x 10-21 ελ , with NA Avogadro constant and ελ in


c H’

E = dP/dS (with S the area) E

mol dm-3 = M J m-2 Hz W m-2



ελ = Αλ/(c l)

l Np or qp
H 'p

m2 mol-1 mol cm s-1 or mol s-1 e m-2 or mol m2e

dm3 mol-1 cm-1 = M-1 cm-1 einstein einstein s-1 e einstein m-2 e einstein m-2 s-1 e einstein m-2 s-1 e

Np = dQp / dt
H 'p = dQp /dS

E'p = d H 'p /dS


m-2 s-1 or mol m-2 s-1 e m-2 s-1 or mol m-2 s-1 e

Ep = dNp /dS


Qp p


number of events number of photons absorbed


1 Pa --- b



with ∆ελ the variation in the molar absorption coefficient at the observation wavelength S m2 mol-1 A W-1 K s --. According to IUPAC the symbol M should not be used with prefixes signifying multiples or submultiples.b dm3 mol-1 cm-1 Sλ.σ m-1 in vacuum ν = ν/c0 in a medium σ = 1/λ accepted prefixes may be used to signify decimal multiples and submultiples of SI basic units. photocurrent per watt of incident radiation temperature time transmittance wavelength wavenumber a b c Definition I = dP / dΩ P = dQ /dt Symbol Q H I P Unit J J m-2 W sr-1 W s τ0 = 1/ kr with kr the rate constant of the radiative step or the sum of rate constants for the radiative steps should there be more than one. Dimensionless quantity. the unit derived for the decadic molar absorption coefficient (ε ) used in this collection is dm3 mol-1 cm-1. in which case it is called the spectral quantity In photochemistry Φ is reserved for quantum yield. radiant energy per unit time radiative lifetime. The optical pathlengths (l) are usually in cm. This quantity can be defined at wavelength λ per unit wavelength interval.5 Name radiant energy radiant exposure c radiant intensity c radiant power. sensitivity of an actinometer sensitivity of a photodiode. The names. the lifetime of an excited molecular entity in the absence of radiationless transitions. Part 6: and carries the subindex λ d e Light and related electromagnetic radiations. If amount of photons is used. Consequently. τ0 S = Φλ ∆ελ . The unit of concentration (c) most commonly used is mol dm-3 (M) and we have used it in this collection. ISO 31-6:1992(E). 5 .w θ T = Pλ /Pλ 0 t T °C h m λ % ν% . units and symbols have been mainly taken from the ISO Handbook on Quantities and Units. rather powers of 10 should be used.

λ = N0. E. molecules changed. Murov. Some actinometers have been added whereas others have been deleted from the list with recommended procedures for their use. A. 1991. ISBN 0 471 92652 3.unibas. e.g. Presses Polytechniques Romandes. According to the "Glossary of Terms Used in Photochemistry" (IUPAC Recommendations 1996).M. The easiest case is for Nabs. Maurette. a calorimeter. light sources. J. λ) for which the quantum yield.. G. Braun. CRC Handbook of Organic Photochemistry (Scaiano.3. A chemical actinometer or dosimeter is a chemical system (fluid... principles of photochemistry. read Section I of this document and consult. Should this not be the case.ch/epa/ . 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 unit time [1]. provided that the absorbance Aλ is constant ± 10 % during the irradiation time. 2 Vols. Marcel Dekker. divided by the number of absorbed photons of that particular wavelength in the same period of time.L. Technologie Photochimique. Handbook of Photochemistry. of this document. M. J. Boca Raton 1989. 2nd Edition.λ for total absorption during the whole irradiation period.-T. John Wiley & Sons. the sections on gas-phase and solid state actinometers have been expanded. e. and reactors.. Calibration of an actinometer is done by applying a calibration lamp or by absolute measurement of irradiance (using.C. and a list of terms used is included. 68 (1996) 2223-2286. Chem. idem. Carmichael. 61 (1989) 187-210. or a photodiode).λ (1 – 10 –Aλ ). is accurately known. Photothermal methods are often used to calibrate actinometers in absolute terms. ed. a calibrated radiometer. For the most recent version of Glossary of Terms and Definitions Used in Photochemistry refer to: Verhoeven. 1986. The Photochemistry Commission (1998-2001) and subsequently the Sub-Committee on Photochemistry (from 2001) decided to update and expand the document. Chem.). and some procedures have been modified. The latter has been due to various reasons. Absolute measurement of incident irradiance (E in W m-2) or photon irradiance (Ep in quanta s-1 m-2 or einstein s1 m-2) or photon flux.g. Hug.. Φλ. gas.g. In particular. Determination of conversion to the products affords the total number of photons absorbed by the liquid or gas volume or solid surface which may have any form or geometry. as well as possible sources of error when performing actinometric measurements. Pure & Appl. 6 . CRC Press. New York 1993. A new version is under preparation. solid or in a microheterogeneous environment) that undergoes a light-induced reaction (at a certain wavelength. formed or destroyed.W. integration of the differential absorbance over time would be necessary. Oliveros.. e. Np (einstein s-1) using precalibrated photodiodes is described in section II.. S.6 Preface The first version of this list appeared in Pure Appl. Photochemical Technology. In some cases the actinometer reagent is no longer commercially available and in other cases the complexity of the procedure for the use or for the disposal of the waste does not justify the inclusion of the actinometer in a recommended list. The quantum yield of a photochemical reaction is defined as Φλ = the number of events. Lausanne. Since then.λ = N0. I..L. some methods have been improved. available at http://www. The terms related to radiation quantities have been made consistent with the International Organization for Standardization (ISO) recommendations. For details and references concerning radiometry and actinometry. Measuring the reaction rate allows the calculation of the absorbed photon flux (the incident photon flux is calculated from the relation Nabs.

1. The extent of this effect depends on the wavelength range in which the detector will be used. the response of which can be subject to changes. 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. The CAs offered in the present list meet the requirements mentioned above in various degrees. Direct spectrophotometric analysis is preferred. Disposal of the waste should be straightforward. 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. Consequently. Pros and cons of chemical actinometry In a chemical actinometer (CA) photochemical conversion is directly related to the number of photons absorbed because the chemical action of light means reversible or irreversible chemical change. provided that they are employed according to the recommended procedures. 7 . The system should display large sensitivity. The same is valid for thermopiles. of their properties such as spectra. General Considerations on Chemical Actinometry I. Quality marks of a chemical actinometer An established CA should meet the following requirements: The photochemical system should be simple and well studied. just by aging. depending on the intended experiment. consequently. A wide usable spectral range and wavelength-independent quantum yields are desired. The majority of physical detectors. The photoreaction must be reproducible under well-defined and easily controllable experimental conditions. The spectral sensitivity of the widespread silicium photodiodes is even altered without use. and precise performance. fast. Physical devices are often preferred to CAs for the case of simple irradiation geometries because of their easy. Chemical actinometry has been employed in photochemistry as a relatively simple and accurate method for radiation measurement since about 70 years [2]. semiconductors and electronic equipment. Quantum yields should be accurately known for a large number of wavelengths. these outstanding properties are inherent in only a small number of electrically calibrated radiometers (ECRs) available in a few highly equipped laboratories. like usual thermopiles. piezoelectric joulemeters or photodiodes are only secondary standards. occasional recalibration of radiation detectors against a standard is strongly recommended. The chemical components should be thermally stable to exclude complications due to dark reactions. These CAs have been proven reproducible and do not demand any recalibration. ECRs are special thermopiles [3] or piezoelectric radiometers [4. well established CAs lead to accurate absolute radiation measurements. which can be calibrated in an absolute manner by electrical substitution without the need of any standard.7 I. Due to the recent progress in the development of radiation detectors.e. I. Preferably it should be commercially available.. The actinometric material should be easy to synthesize and purify. destruction or buildup of molecules and. In contrast to the physical detectors. i. However. It is highly recommended to read the original literature on each actinometer prior to its use. Each system suffers also from disadvantages and a careful selection among the CAs is appropriate. The sensitivity of a joulemeter may decrease with use due to surface damage by high power radiation. An 18 % decrease in sensitivity at 300 nm in one year was reported to be a typical value [6]. physical devices furnished with a direct readout become more and more popular among photochemists for the measurement of radiation.5].2.

e. and to 0. I. Those CAs which have been investigated especially at high photon fluxes using laser excitation can be used as standards for this purpose [7].956 for CS2 (n = 1.R). At 250 nm (1 .R). PB = P/(1 .63). to 0.4. Only in this case.2. At 400 nm and 800 nm these values are higher by 0. At high laser powers most CAs will probably lose accuracy and sensitivity due to multiple photon processes occurring at high photon densities.959 for toluene (n = 1.29). the calibration by CAs is particularly easy since calibration at only one wavelength is sufficient.. I.. but also the spectral distribution of the irradiation source. photoreactors of the merry-goround type) CAs serve best for the purpose of absolute radiation measurement and are unrivalled by physical devices. Fields of application of chemical actinometry It is important to mention that chemical actinometry covers only the wavelength range up to 795 nm. the reflectance at the boundary between two materials of refractive indices n1 and n2 can be calculated through the Fresnel law: 2 ⎡n − n ⎤ R=⎢ 1 2⎥ ⎣ n1 + n2 ⎦ While entering a quartz sample cell the radiation passes the boundaries air/quartz and quartz/solution suffering reflections at each boundary.955 for 2.49). In the case of polychromatic irradiation conversion of photon flux to radiant power needs not only the knowledge of quantum yields and absorbances of the CA in the wavelength range considered. However. In any case. Photochemists using physical equipment for radiation measurements need standards for the occasional recalibration of their detectors. Assuming that the incident radiation strikes the sample surface at a right angle. For detectors with wavelength-independent response like thermopiles and joulemeters. A correction for the reflectance R should be performed in order to obtain the radiant power of the irradiation beam PB.g.3.0 = Np /(1 . a periodically repeated calibration by CAs at reduced laser power is an easy way of controlling the accuracy of the power meter.8 I. CAs are the first choice for this procedure. Potential errors in chemical actinometry The detailed description of the chemical system. R is approximately the sum of the reflection losses at both boundaries whereby the second contribution is smaller than the first. In photochemical experiments involving a complex irradiation geometry (e. Measurements of laser pulse energies can conveniently be done by joulemeters. or the photon flux of the irradiation beam Np. if linearity of the joulemeter readout is guaranteed.1.2-trifluoroethanol (n = 1.005 and 8 . only the wavelength dependence of the refractive index of quartz determines the wavelength dependence of R. Refractive index In this paragraph the discussion will be restricted to the case of monochromatic irradiation. the limitations and the possible sources of errors for each CA should be made explicit in every publication. a CA yields the radiant power P entering the sample cell. in photobiological and photochemical laboratories with less sophisticated equipment but where workers are experienced in chemical techniques. since a CA yields a photon rate or flux Np (photons or einstein s-1) entering the sample cell at a given wavelength.4. chemical actinometry is the standard procedure for radiation measurement. Consequently. In the following only general aspects are discussed. i.R) amounts to 0.

Photochemical quantum yields usually do not depend on temperature or only do so slightly. I. in laser beams. thus avoiding inhomogeneity problems during photoreaction. I. From the above estimation it follows that when comparing a photochemical system with a CA in different solvents an error of at most 0. Since in this case additional errors are introduced by light reflections and the necessary measurements of transmission during irradiation.4. each photon entering the actinometric solution causes chemical conversion with the same probability regardless of its energy. at the high photon flux met e. Absorption by photoproducts Ideally.4. Therefore.2. a mean value of 1 . I. Polychromatic quantum counters are 9 . this leading to a reduced conversion range. photon flux) can be expected. and possible competing dark reactions. The temperatureinduced changes in density lead to a corresponding change in concentration and consequently to an apparent change in chemical conversion. However. in the wavelength range of a particular CA photoproducts should not absorb. This difficulty should be considered with great care and extrapolation of the data to infinitely low conversion is recommended. respectively. Temperature may influence an actinometric system through the temperature dependency of the quantum yield.4.4. in some cases a large temperature variation of the possible dark reactions may take place. Deviations from this estimation are negligible for non-polarized 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 degrees [8]. This effect can easily be cancelled out by measuring the conversion at the temperature of CA calibration or by calculation using tabulated density values. I.R = 0.5. This arrangement is particularly advantageous for the case of high photon flux. Thus. these systems are unfavourable for the measurement of low levels of radiation. CAs exhibiting complete absorption of the radiation allow convenient measurement and easy evaluation and are thus preferred.5 % at most.007. the density of solvents.4 % will be introduced should the correction be omitted. This possible source of error is insufficiently discussed in the literature. actinometric measurements at temperatures different from the recommended range should be avoided. In this case.g. severe inhomogeneity problems arise.0 by introducing an additional error of 0. If photoproducts do absorb an inner filter will develop..4. Since at high absorbances the photoreaction occurs only in a very small reaction volume multiple photonic processes can be expected at high photon flux as often reported [7]. since the irradiated volume can be large. Temperature The influence of temperature variation has been investigated only for a small number of CAs. In this case a high dynamic range of the actinometric measurement (number of photons. Therefore. At high absorbance the penetration depth of irradiation is small.9 0.3.96 can be applied for the calculation of PB or of Np. which cannot be overcome even by effective stirring. Polychromatic quantum counters CAs with wavelength-independent quantum yields allow polychromatic quantum counting in the specified wavelength range provided complete absorption is maintained. Degree of absorption by the CA Some CAs are designed for incomplete absorption of the actinic light.

J. Systems that have fallen into discredit are given at the bottom of this list under the heading Disproved.S. J.N. In addition. however. Cook. W. J. 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. 3. 6. Chem. With chemical systems. 52 (1930) 3139-3152. W. Pure & Appl.1. All other systems appear to be not yet widely used and may be labelled under discussion.. Phys. Zuraw.2. List of Actinometers The present compilation lists chemical systems that have been shown suitable for the integration of incident light by chemical conversion.. and II. 3091-3094.4. B. 1. J.. Y. 4. G. Tetrahedron Lett.R. it is in general easier to mimic the experimental situation of the sample.. Velapoldi. Jr. A.1. Geist. Soc. H. F. Demas. is to use a total absorbing actinometer solution (see Section I. Braunschweig. 5. 7. Am. 10 . Applied Optics 12 (1973) 2532-2535.A. e. M. II. filters. pp. Wilkinson. J.1). Applied Optics 12 (1973) 2494-2500. Bischoff. Order in the following lists is with increasing wavelength range.F. Gardner.1. Zimmerman. Detlaf. Readers are encouraged to send complementary information. See the Abbreviations at the beginning of the document. Photochem. The same solvent and equal absorbances should be chosen for actinometry and reaction under study. II. and spatial arrangement of the reaction vessel. Soc.4). Chem. Optik 28 (1968/69) 183-189. Leighton. Jaworski.: Ito. J. 111 (1989) 7974-7989. R..J. J.g.. can be avoided without much effort.G.4. Emphasis is mainly on gas and liquid phase systems which photochemists are most frequently dealing with. etc.. Solid Phase and Microheterogeneous Phase Chemical Actinometers For solid-state quantum yield determination procedures cf. Forbes. some solid phase actinometers and convenient electronic devices are mentioned. 68 (1996) 2223-2286. without precautions). Chem. E. Verhoeven.. A: Chemistry 50 (1989) 141-145. 567. A recommended alternative (see Section I). however.J. Photobiol. R.L.E. A. References to section I.M. II. Corrections due to reflection losses at surfaces should be taken into account (see Section I. Chemical Systems Several physical methods for the calibration of light sources (see sections I. 2.J. K.R. J. 85 (1981) 2766-2771. corrections. Applied Optics 24 (1985) 1531-1534. and comments. Physik griffbereit. 1972.3) are known.A. surface. T. lenses. Bowman. especially for low photon densities at which multiphoton processes do not play a role.D. By choosing strictly identical experimental set-ups for standard and sample. Am. W. experimental errors due to differences in shape. II. Matsuura. 29 (1988) 3087-3090.W.. whenever possible.. Zalewski. Blevin. Chem.. Phelan. Vieweg und Sohn. 8.10 particularly accurate due to their wavelength-independent conversion yield.

Biological solar UV dosimeters. 37 (1983) 345-348.L.K. O. Chim. G. Photobiol. Photobiol. Gaspar. H.): J...J.H.11 For quantitative measurements in sol-gel materials see: Levy. P.R. Photobiol.. S.. Gurzadyan. e. Takayama.. Analyt. S01: Uracil photodimerization in polycrystalline thin layer. Y. Ch. Acta 318 (1995) 103-112. S02: DNA photodamaging. New York 1976. Young. Schulte-Frohlinde. Nikaido. ed. Biological UV dosimeter WR: > 250 nm. Davis. Rontó. Diffey... Rontó. UV-B radiation dosimeter in SDS microemulsions WR: 290– 320 nm.225-294. Vol. 2. P..5. S04: Thymine dimerization.J.g. Barnard. Photochem. Li. 3.. 64 (1996) 800-806. A. 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..al.. J.. therein. et. Chem. A. Johns. especially by Howard-Flanders. in: Photochemistry and Photobiology of Nucleic Acids. Y. Tate. Photobiol. Photochem. subtilis spores. Görner. G. Y. T.. Quintern. G. H. p. Photochem. 53 (1999). eds. e. Special issue on biological dosimetry of UV radiation (Fekete..G. B..g. Φ = 10−3 − 10−1 depending on [Thymine] and [SDS]/H2O ratio A TiO2 -sol based actinometer used to determine number of photons absorbed. cf. Horneck. some related “living dosimeters”: biofilm of Bac. D. on nylon membrane sealed in a polyethylene envelope. G. Gibbs. (193.recA-) with photodamage repair deficiency. Grof.Y. G. Ishigaki.1 (Wang. S03: 1-Ethyl-7-methyl-4-oxo-1.. Academic Press. Photochem. S.. 2. B: Biol. Radiation Research 141 (1995) 244-251 and refs. A. S. N. 31 (1980) 27-30. Phage T7 used as a calibration system. B: Biol. 254 nm). and refs... 55 (1992) 389-395. UV-A polyvinyl chloride film dosimeter WR: 280 – 360 nm AM: absorbance change at 330 nm PP: very preliminary batch-dependent data 1. therein. Yamashita. A.. Mater. WR: 254 – 330 nm AM: immunostaining with damage-specific monoclonal antibody [1] 1. Bücker. W. Photobiol.. D. 1 2 Fisher. Photochem. Huang.S. 11 . Photobiol.S.8-naphthyridine-3-carboxylic acid (nalidixic acid). AM: absorption spectrum 250 – 400 nm. 50 (1999)184-188.). L. special Escherichia coli bacteria strain K12 AB2480(uvrA.4-dihydro-1.E. Photochem. J.. AM: decrease of thymine absorption at 265 nm Che. U.. Eschweiler. H. 4. 9 (1997) 2666-2670.

. Rehim.N. Pitts. Photochem..L...J.S. Nakai. Chem. Photochem. Wong. Baum. KBr pellet. cf. Jr. S.C.J. G. J. GC 12 . Fleming. Bunce.8-dione (Diels-Alder adduct of 2. Hess. 46 (1987) 55-60. Photochem. Am. Φ = 1. Bunce.. Cowell. Am. Dreiman. J. C.A. Allen. J. L. cf.. 23 (1983) 219-231. Indian J. 4 (1965) 305-321.7-Dimethyl-1. Photobiol. Diffey. 14A (1976) 653-655..A. Jr. L31*. comparison of radiometric with actinometric measurements Some related UV-A and B dosimeter systems: polycarbonate plastic.J.. B.. G.06 AM: IR 1530 cm-1 (NO2 band disappearance) 1... also applicable in gas and liquid phase. J. M. Smith. Photobiol. Chem.5 ± 0.. 5. 90 (1968) 1106-1110.. B. Davis.F. Jr. Photochem. S08: 4a. J. Pitts. N. Lemke. E. J. Schuck. ferrioxalate.. C.8a-tetrahydro-1..N..S... 2.B. K. Roy.5-dimethylbenzoquinone and cyclopentadiene) photoisomerization in a dry silica matrix. J.S. Wan. WR: ≤ 315 nm AM: absorbance change at 300 nm (∆A300) 1. 34 (1989)1623-1629. A.5 (same in all phases) WR: 280 – 410 nm.N. S. R.A. Debrabandere. F. Photochem. A. Photobiol.0 (vs.. Gawad... Photobiol. 7.. J.A. Schuck. L22. Soc. 4. Leighton.. S06: o-Nitrobenzaldehyde → o-nitrosobenzoic acid photoisomerization. C. poly(methyl methacrylate). J.. E. Carter.A. for the measurement and penetration of UV radiation into marine water (see also L35. Photochem.. WR: 362 ± 5 nm.S.4. 34 (1981) 283-286. Fleischmann. F. A: Chemistry 64 (1992) 123-131.K... J.M..B.g. S07: Polysulfone UV-B film dosimeter. Φ ∼ 10-3 AM: absorbance at 420 nm 1. WR: 310 – 400 nm.J. Allen. Jacobs.. 69 (1999) 17S-18S.G. Montgomery. J. J. 86 (1964) 3606-3610. P. Quantitative erythemal effectiveness given vs. J. Soc.12 S05: Azoxybenzene → 2-hydroxyazobenzene.A.A. Oceanogr. Leermakers. Φ = 0.L. Photochem. Limnol. Irradiation apparatus described for adsorbed substances. J. fuchsin and sandolan yellow dyes in polyvinyl alcohol polymer. also in solution) AM: absorbance. Photobiol.K. T.K. 4. [5])..A.J. Φ = 0.D. 2. Wan. 50 (1989) 611-615. 34 (1986) 105-115. Photochem.. A.. S. Pitts. 2 (1934) 756-759.E. 3. Chem. P. 6. Phys.W. Photobiol.. Irradiance was measured using a vacuum thermopile. Stewart. E. E.R.W. Diffey.4a. 3. 2. Vesley. S. e. Fattah. N. ∆A300 mathematically correlates with the UV (300 nm) radiant exposure in kJ m-2. G. Tate. Chem. E. λ. Baertschi.4-methanonaphthalene-5. J. Das. poly(methyl methacrylate) block.. starting material disappearance and product appearance.M. Lucy. WR: 300 – 400 nm.A..J.

de Mayo. Ware. from 0.2.E. 1. 291-304) and Bercowitz.6 in the 75-105 nm region [1]. Opt. A. Samson. cf.4 . Photochemistry. J. 1.N. (Russian: Khim..44 ± 0.. M. 4. Φλ (ion) vary with λ. Jr. 32 (1996) 525-529. J. 19 (1985) 351-354.8 at 105 – 120 nm [3] AM: N2 analysis. extrapolation to zero pressure to correct for secondary ionization [1]. cf. WR: 366 – 436 nm. p. Φ = 2 x 10-5 AM: absorbance decrease at 420 nm Okabe. Schierholz.. Appl. Φ(∆n) ∼ 0. 2. P. Φ(Ν2) = 1. 34 (1981) 187-190. J. Soc. Wiley. S09: 2-(2-Quinolyl)-1. T. Bercowitz. Photochem. G01: Rare gases photoionization. The quantum yield of ionization. absolute photon fluences measured with a calibrated thermocouple.6 nm [3].N.. Onuki. K. 22 (1954) 1685-1687. 1(1959) 333-336. Space Sci. 21 (1987) 243-255. Gas Phase Chemical Actinometers For reviews on UV and vacuum UV actinometers. High Energy Chem. Vys. F.782. Φ(ion) = 1 at infinitely low pressure AM: He or Ne ion current measurement. 2. Appl. 2. Chem. Pitts.13 Lazare.98 in the 58-75 nm region and are 0.1 at moderate pressure near room temperature. Planet. Photobiol. G02: Nitrogen monoxide (NO) photoionization.R. Zelikoff. WR: 4. 21.2 nm. Physics Essays 13 (2000) 248-255. L. Groth. J. Shul'pyakov. H. 5 (1967) 391-396. H.66 to 0. 1. II..M. I.00 ± 0. Calvert.. 13 .05. J. 64 (1974) 47-54. Saito. N. Amer. Phys.Φ(Ν2Ο) = 1. J. Phys. PP: The use of the traditional name nitric oxide is not recommended by IUPAC G03*: Dinitrogen oxide (N2O) photolysis. 20 (1981) 4054-4058. Greiner. Plastic plates.R. 3. separation of N2 from NO and O2 or very accurate pressure measurement. Energ. pressure measurement PP: low absorbance at 150 – 170 nm (ε ≤ 30 dm3 mol-1 cm-1)..102.. 5. Sakai..R. Haddad. Opt. W. J. Φ(∆n) = Φ(Ν2) + Φ(Ο2 ) + Φ(NO) .M. New York 1966. J.A. Watanabe.M.18 at 123. A. 3. H. S. Gas-phase actinometry for UV and vacuum UV spectral regions.3-0. AM: ion yield by photocurrent measurement. Physics Essays 13 (2000) 248-255.G. H. Metrologia..O. W.M. WR: ≤ 134 nm . Aschenbrand. Pravilov. WR: 147 – 185 (138 – 210) nm. 47 (1967) 4373-4377. Φ(Ν2) = 1.1. Matsunaga. Pravilov. G. Chem. High Energy Chem. Bercowitz. J. Physics Essays 13 (2000) 248-255. Opt. The use of the traditional name nitrous oxide is not recommended by IUPAC.3-indanedione (quinophthalone) photofading.

. Photochemistry. 3. Phys. G04: Oxygen photolysis. Timmons. Scala. Br2 absorbance at 450 nm [3] 1.. Opt. New York 1978. Khan.A.. P. Pitts. 25 °C. Int. Pitts.782. Wiley. J. Wiley-Interscience..14 6.K. Jr.G.J. Φ(H2) = 0. P. M. J. cf. K. G08: Carbon dioxide photolysis. Wiley. Φ(CO) = 0. Kinet.782. cf. Potzinger. Phys. J. 2. Photochemistry.126. Φ(CO) = 0. L. Jr. G.C. WR: 170 – 255 nm. WR: 147. Jr.. WR: 147 nm. Photochemistry of Small Molecules. 2. 185 nm. 10 (1978) 1161-1166.. 13 (1971) 283-287. Davies. J. J. 56 (1966) 408-409. Kinet. Glasgow. Int. Driscoll.06 variable with λ AM: CO analysis. J. Amer.C. G. 2. New York 1966. A. Chem. P. 3 (1971) 269-282. independent of pressure. Φ = 1 (H2 or Br2) at 100 mm. 7 (1976) 389-398.. 52 (1970) 2790-2791. Dodge. Calvert. Chem..A. von Bünau. Mol. cf. Glasgow. 3.. p.N... J. G07: Trimethylamine photoionization. J. R. G. 27a (1972) 628-638... New York 1978. Phys. 14 . Φ (O3) = 2. oxygen formed must be separated PP: complex system with interferences by O3 and heterogeneous reactions on the walls 1. very precise Salomon.S. 2.G. Chem. 3. D. J. New York 1966. J. Wiley. WR: 147 nm. p. 4. Pitts.R. Heicklen. New York 1966.5 – 1. J. H. G09*: Hydrogen bromide photolysis. Photochem. Chem 76 (1972) 138-140. Z. AM: H2 analysis. P. Hg interferes. Wiley-Interscience. Magenheimer. L. Φ(ion) = 0. Powell. Okabe.. and temperature AM: H2 analysis. Photobiol. Photochemistry of Small Molecules.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. Photochem.38 AM: ion saturation current. WR: below 170 nm. McKellar.N. pressure measurement PP: care must be taken for λ > 180 nm [1] 1.B. p. Powell. p..N. D.S. Kinet. Chem. Potzinger. Phillips. A. 163. Photochemistry. wavelength. Calvert. 62 (1975) 1469-1472. Sethi.O. Soc. J. 10 (1978) 1161-1166. Chem. H. Okabe.97 ± 0. p. at low conversion (< 1 %) due to interference by product Br2..N. Warneck.127. Naturf. G06: Ethene photolysis. J.C.G. J.4.. G05: Hexafluoroacetone photolysis. J. Calvert. J. Sethi. J. D.782. WR: 130 – 190 nm.. Warneck. Int.F.R. G.05 AM: CO 1.

31 (1998) 1336-1342. Pitts.60 mm Hg. A. Karpov.B. 130 °C AM: GC or MS for CH4 and CO Horowitz. WR: 200 – 280 nm. cf.M. 300. 12 (1978) 468-469.I. de Staricco.B. p. Φ(CH4)/Φ(CO) = 2 at p(acetone) = 5 . 54 (1990) 181-186. G15*: Pentan-3-one photolysis. Roland. 2.. Φ(CO) = 1. Smirnova. Photochem. L. WR: 250 – 320 nm. L. Glicker. cf.. Phys. 3. Reaction Kinetics 2 (1964) 165-215. resp. 16 (1982) 331-333. Trans.N.. Jr.M..H. Photochemistry..P. 2. R.0 at ≥ 125 °C and ≤ 50 mm Hg AM: pressure measurement and GC (CO and CH4) after freezing down at –196 °C. WR: 254 nm. or Cl(CF2)3Cl .. J. D. 1 at 185 nm AM: CO measurement at liquid nitrogen temperature. and λ.M.G. WR: 285.02 ± 0. WR: 230 – 630 nm. Martin. New York 1966.E. G11: Nitrosyl chloride photolysis. Photochem.. E.782. Calvert. Pravilov. J. Φ(NO) ∼ 2. S. G13*: Acetone photolysis. 56 (1960) 1211-1224.0 ± 0.N.. simple pressure measurement for CO after freezing down at –196 °C G16: But-2-ene. Cundall. G14: Acetone/hydrogen chloride photolysis. J. New York 1978.E. p. New York 1966. Kozlov.G. Photochemistry of Small Molecules.0 AM: NO analysis 1. R. A. Willard. Phys. G12: Perfluoroglutaryl dichloride or 4-chloroperfluorobutanoyl chloride (stable intermediate product) photolysis. Calvert. PP: independent of total pressure. Staricco. Cundall..S. High Energy Chem. Pravilov. J.127.G. 3. Pitts. Chem.06. A. 15 . Photochemistry. T.. D: Appl. p. 313 nm. Cl(CF2)3COCl. H. Weibel.. J.. E. R.. Palmer. J. Wiley-Interscience. Photobiol.50 ± 0. Hg sensitized photoisomerization.15 2. Bolle. Progr. J. Phys. J. 40 (1964) 2999-3007. 1.782. R. WR: 232 – 270 nm or 240 – 270 nm. A. F.06 and 1. Faraday Soc. 91 (1987) 437-440. as G13. J. Jr.. High Energy Chem.G. AM: GC for CO..F.. Φ(CO) = 1. Phys. M. S. R. J. 37 (1987) 241-246. Anderson.. Vilesov.1 at 254 nm.R.03 ± 0. G10: Phosgene photolysis. Wiley. Wiley. Okabe. p(HCl) = 1 – 8 mm Hg. photon fluence. 2.02 at p ≥ 4 kPa AM: GC 1.W. Ryabov. Okabe. Φ(CO) = 1. Φ(cis→trans) = Φ(trans→cis) = 0.E. Chem. H.

Φ(CO) = 0. A: Chemistry 86 (1995) 9-14. 2. Chem. Φ(H2) = 0. study of perfluorosuccinic anhydride photolysis: Weibel. Chem. 60 (1986) 1105-1106 . Faraday Trans. H. Margreiter. p. Faraday Trans.. J. E. 265 nm. Soc.. J.16 3. E. Soc. Φ ∼ 30 -36 (chain length between 15 and 18. absolute measurement of radiant power with thermoelements) AM: Cl2 consumption 1..E. G19: Perfluoropropionic anhydride. WR: 254. A: Chemistry 49 (1989) 279-285. G20: Azomethane.24 at 26 °C. Chamberlain. E. independent of initial ClF pressure AM: Absorption at 210 nm of produced ClF3 Chebotarev. Chem. J. WR: 254. New York etc. 2.. Hg-sensitized photolysis. University of Alberta 1971. G21: Chlorine/hydrogen chain photoinitiation. physikal.29 at 200 °C AM: CO measurement 1. Chamberlain. Φ(CO) = 0. Y. J. Margreiter. De Maré.29 ± 0. Phys. Fourier transform infra-red (FTIR) spectroscopy. M. Angew. Russ.. 1978. fluence. Rousseau. Phys.A. K. Photobiol. Whittle. Chem. Abstr. 1. I 71 (1975) 1978-1990.. Sodeau. 16 . Φ(ClF3) = 1 at room temperature.R. Cremer. WR: 280 – 380 nm.H. Chem.Chem. E. J.R. Photochem. T. I 71 (1975) 1978-1990. Leipzig 199 (1952) 90-99.. Photochem. Z. Staricco. H. H. G17: Propane. WR: 270 – 410 nm: Φ(N2) = 1.C. for Cl2:O2 = 1:1. University of Alberta 1963. 0. Photochemistry of Small Molecules. 105 (1986) 87729c. 0. independent of temperature (24-164 °C). WR: 254 nm.581 at p = 40 kPa AM: pressure measurement 1.L. Photobiol. G22: Chlorine monofluoride. Cremer. and pressure AM: N2 must be isolated from the N2 + CH4 mixture Okabe. Pollock. 64 (1952) 427. WR: vacuum UV up to 320 nm. 2. de Staricco.A.. Dissertation. E. Whittle. Dissertation. G.. G. G. 265 nm. 25 (1974) 402-404.R. 2. E. Chem.02 at 25 °C. Lett.128. J. Wiley-Interscience. Termonia. Clemitshaw. G18: Perfluoroacetic anhydride.F. D.34 at 20 °C AM: CO measurement. N.

10 (1977) 59-145. Photochem. WR: 172 nm Xe-excimer source. D.02 M). cf. 7 (1976) 389-398. F.. L01: Water photohomolysis (OH radical production) in methanol (0. Photochem. Mol. Φ depends on the ethanol concentration. Schuchmann.05 in water AM: absorbance (HN3). C.. Phys..A. Bastian.44 [5] AM: trans-cyclooctene analysis (GC. 4.. G. 77 (1973) 1195-1198. Schuchmann. 5. P. 3. von Sonntag. Bastian. Photochem. Liquid Phase Chemical Actinometers For additional literature cf. 5. 2. A 102 (1998) 5551-5561.. J. DOC = dissolved organic carbon.34 ± 0. L03*: Ethanol photolysis (Farkas actinometer). W.. Chromatographia 7 (1974) 163-170. C. L04: Hydrogen azide (hydrazoic acid) photolysis. von Sonntag. Chem. Phys.-Y. EXPLOSIVE) was prepared in solution from NaN3 and HClO4 immediately prior to irradiation and no thermal decomposition was observed under the conditions applied Shapira. physikal.32. Schomburg. Saugy. NH2OH PP: HN3 (CAUTION.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. 69 (1970) 292-304. Phys. 39 (1984) 719-723. Weeke. Davies. J. Adam. Neuner. 4. J. the 254 nm Hg line is ineffective. Φ (trans→cis) = 0. formic acid. Heit. Braun. von Sonntag...04 AM: GC analysis of methanol degradation and products. 100 (1978) 7089-7091. Schomburg... Heit.K. Φ = 0. A..17 II. T. A 102 (1998) 5551-5561. WR: 200 – 260 nm. Schuchmann. N. F. G. Adv. 2. E.1 %). ibid 81 and refs. L02*: cis-Cyclooctene cis-trans photoisomerization. ethylene glycol. Z. Am.-P. J.M.-P. Chromatographia 7 (1974) 163-170.M. von Sonntag.3.. L02. Khan. calibration by cyclooctene actinometer.F. Ag complex) PP: the 254 nm Hg line is ineffective 1.42 ± 0. Oppenländer. Chem. 3. C.3 M) solution. Photobiol. 15 (1981) 159-162. L05: Glucose photolysis. H. G.4-DNPH. A. therein. 16 (1981) 289-295. Weeke. Saugy.00 ± 0. formaldehyde (2. R. no temperature dependence in the 15 – 40 °C range 1. Chem. H. 17 .1. WR: 185 nm: Φ(cis→trans) = 0..A. Srinivasan. A. Φ = 1. Appendix. WR: 172 nm (Xe-excimer source): Φ (cis→trans) = 0.02 in n-pentane (0. J..-P..-Y. Soc. Treinin. A. G. R. Photochem. A. H.O.. Chem. Srinivasan. Photochem. McKellar. K. G. WR: 185 nm. Ors. HPLC). A... J. F. E... Braun. Φ(H2) = 0. J. Neuner. N2.2 – 0. Phillips. C. J. P. Chem.

Parker.120. Benítez. a non-irradiated blank). R. Creation and Detection of the Excited State (Ware. J. W. 1972. J. p. G. Chem. 1. Fernández Sevilla. Calif. Res.P. PP: Take care to dispose of the uranium waste in accordance with the legal regulations. ed. J.) 4 (1976) 140.. Hatchard. 15..D. Photochemistry. Albizzati. Chem. Lippman. . 4.A.). Res. Soc. 6. 8. González. Forbes. Heidt. Leighton. J.H. J. p. Eng. C. Bracket. Alfano. New York. the C2O4-2 concentration of the blank. Molina Grima.. F. A. Chem. ed. de Mayo. 13. Jr. Taylor. Sánchez Mirón. F.G. F. K. Rao. Calvert.. W.F. E. J. I. G. J.F.305. Dekker.G.91 ± 0.N...M. Pitts. Turse. or GC (pH dependency [7. 21. J. Soc... Ind.N. 74 (1970) 1876-1882.H. Murov.M. A220 (1953) 104-116.. F. D. Pitts. Eaton. T. Am. (1949) 1233-1237. p.. Wiley. 67 (1963) 2501-2503.K. method depends critically on Ce(IV) concentration which should not be less than that of. Porter. H2C2O4 ⎯⎯⎯→ H2O + CO2 + CO WR: 200 – 500 nm: Φ ∼ 0. J. Margerum. Y.... PP: use of commercial Ce(IV) sulfate for titration of non-photolysed C2O4-2 is not recommended because ammonium nitrate impurities may limit the stability of the standardised solution. 2. R. Φ ∼ 0.A. W. Parker.. 77 (1955) 5499-5501..M. H.13. W.. Chem.. L07: 4-(Dimethylamino)-α-[4-(dimethylamino)phenyl]-α-phenylbenzeneacetonitrile (malachite green leucocyanide) photoionization in slightly acidified ethanol WR: 225 – 289 nm (especially useful for very low fluences).H. [12].D. L. R. Volman. 14.. L06*: Uranyl oxalate photolysis.L. 12. 52 (1930) 3139-3152. Am.P. 91. J. Chem. C.D. in: Analytical Photochemistry and Photochemical Analysis. (Fitzgerald. D. 3. Chem. Smith. Seed.. Chisti. Anal. K. 28 (1994) 2095-2100. Dekker. 9. J. Roy.L. 2nd ed. Appl. 10 min) of photolysed solution with Ce(IV) sulfate in H2SO4 (vs.R.J. D. 787.. Acero.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. Chem.. H. For the preparation of Ce(IV) cf. Tregay. Am.R. C. Brim. Middleton. G. Soc. Rossetti.H.01 (determined by using a thermopile for absolute measurement of fluences) 18 hν 10. Thesis. and not higher than twice. New York 1966.5 – 0.G.. Proc.. 84 (1962) 2011-2012.J... P. Phys. Chem.F. 37 (1998) 3592-3601. Am. Beltrán-Heredia. New York 1971. Soc.A.33 in 5 % aqueous solution AM: absorbance of malonaldehyde/2-methylindole complex at 555 nm Datta. Smith. P. J. 1993. C. A235 (1956) 518-536. Taylor. sect.10]) for CO.A. CO2 .(London). New York. J. Phycology 12 (2000) 385-394. E. Forbes. Proc.. 16. Jr. 17. Soc.N. J. 86 (1964) 5095-5098. Fly. J. O.W. (London). Chem.. Soc. Phys. S. Φ = 0.A. 55 (1933) 4459-4466.18 WR: 200 – 300 nm. 5. Wat. Volman.. 14A (1976) 122-123. J. J. p. Jr. Institute of Technol. Roy.. 7. G. G. Indian J. Soc... Ph. Shizuka. Handbook of Photochemistry. 11..S. Am..S. Dekker. Discher. García Camacho. Chem.

Kogelschatz... Photobiol. Mark. Photochem.. P. B: Biol. J. on paper: Chalkley. Roczn.. Soc. J. von Sonntag. 3.169-224 in: Photochemistry and Photobiology of Nucleic Acids. 63 (1996) 143-153. G.. J.6].. Photobiol. 0..N. Photobiol. Photochem. 8 (1997) 901-909. HPLC PP: (1 – 1. 9. Fisher. 19 . W. 91-115 in: Analytical Photochemistry and Photochemical Analysis (Fitzgerald. S.. Leighton. Environm.019 (254 nm. Applied Surface Science 109/110 (1997) 482-486 – Chem. Nikogosyan.1 (Wang. Getoff. Φλ = 0. 5. L. Leighton. R.L. 5 (1990) 413-427. M. Academic Press. Chem. 91-115. J. 61 (1939) 2299-2301. 5. [8]).. 123 (1997) 1142-1149.G. Φλ ca. C.. PP: care should be taken to avoid product accumulation. 2. in: Analytical Photochemistry and Photochemical Analysis (Fitzgerald.. W.M. A. J. G.M. Phys.019 [1. Abstr. 10 (1991) 91-110. polarography. C. Φλ = 0. 4. 7. J. P. 74 (1952) 2101-2103.016 (280 nm). ed.034 (doubtful.044 (193 nm. Soc. turbidimetry. Görner. Khoroshilova. 62 (1940) 1879-1880. 42 (1952) 387-392. Nagashiro. Nohr. Sol-Gel.019 (248 nm). 6. Photobiol. New York 1971. Makita. 10. Grabowska. J.-P. MacDonald. Vol.. Schuchmann.S.. L08: Chloroacetic acid photohydrolysis. Darby. Am..G.. 13 (1979) 101-105.19 AM: absorbance at 620 nm 1.-Y. A: Chemistry 79 (1994) 141-149. [4. K. Am. Photobiol. Rechen. R.B. Johns. Taylor. Chem.G. 25 °C. [5]). Gurzadyan.L. Photochem. Esrom.A.. Photochem. 2 (1963) 419-434. ed).A. H. Schuchmann. J. Photochem. 2. Photochem. [9]). D.W.V. B: Biol. R. H. Photobiol. 5. Ch. AM: absorbance of uridine at 262 nm (chromophore loss). J.G. H.31 at 254 nm (vs.027. 8] at shorter λ (193 nm) are ascribed to additional ionization pathways and to dimerization reactions at higher concentrations.A. Smith. Johns. 6 (1967) 757-767. Ar [8]). H. fluence measured with a calibrated joulemeter).. H.J. 0. p. Fisher. Ar. 2. Photobiol. p. temperature coefficient +0. J. Φλ = 0. Kemula..G. other actinometers). Φλ = 0. K.N. applied to 222 nm excimer lamp. ed. 60 (1994) 323-332. Görner.A. 0.J. I. Chem. Taylor..E. J. H.ion specific electrode 1. 0. 5... Neumann-Spallart. 6] refer to chromophore-loss due to photohydration. Φλ = 0. Amer. J. WR: ≤ 270 nm. E. higher values [5. H. conditions not given. no effect of oxygen at 254 nm. Am. J. G.017 (238 nm). 4. Boyd.018 (254 nm. New York 1971. H. Sc. Zhang. H.017 (265 nm).G. Photochem. Φλ = 0. Cl. G.5) x 10-4 – 10-5 M neutral aqueous solution. Soc.. Eng..-P. H.4. 4.Y. H. Chemii 29 (1955) 834-838. 3. Techn. Dekker.C. J. LeBlanc. 0. [8]. von Sonntag. Radiat. p. G. Φλ = 0. New York 1976. Thomas. Gurzadyan. AM: product formation by potentiometry. 126256881/19. Dekker. Opt. L. Soc. J. H. in thin films: Nakazumi.032 (193 nm laser.B.J. J. Görner. N. Setlow.. R. 8. Calvert.). U. Swenson. 1. Φλ = 0. 3. Water SRT-Aqua 41 (1992) 67-74.). J. Linden. L09*: Uridine (1-ß-D-ribofuranosyluracil) photohydration in H2O WR: 216 – 280 nm.018 (216 nm laser. Chem..009/°C in aqueous solution.

J. Am.1 (Wang. Vol. O.J. in: Photochemistry and Photobiology of Nucleic Acids.. Numao. EPA Newsletter 29 (1987) 45-46. Gauglitz. J. L11*: Azobenzene [also called Actinochrome 2R (245/440)] photoisomerization (reusable).Y. different for the two bands. emission at 375 nm) of product 1-deazapurin-2-one or 1-methyl analog. Water Res.15 (± 0. thermal cis → trans regeneration at 60 °C possible. N. 20 .035) in n-hexane: Siampiringue. G. Photochem.. 7. 37 (1987) 185-188. Chem. U. Gauglitz. WR: 250 – 310 nm. Drabek. J. Photochem.48 in CH3OH. (0. Al-Nakib.01 – 0. 30 (1979) 317-318.14 in CH3OH. Poskocil.0005 AM: absorbance at 266 nm 1. 0. Paik. Yonemitsu. Nießner.H. Ch. Cepciansky. 10 (1991) 91-110. conversion limit 20 % (total absorption). 5. R. Hubig. Tetrahedron Lett. Listy 78 (1984) 94-98. ed).0134 ± 0. p.0147 (280 nm) at 0.4 – 0.. Φλ = 0.37 ± 0. Johns. S. New York 1976. 0. Davies. Photobiol. Soc. Photochem. 3. A. G.-Y. Photochem. 265.35 ± 0. T. no side products. Φ(cis→trans) = 0. 15 (1981) 255-257. P.O.55 in isooctane.0016. N. Φ(average) = 0.1 – 0. Persy. H. 4. 2. (0. Guyot.0007 in water (254 nm). 2.5-b]pyridine 4-oxide) or 1-methyl-1-deazapurine 3-oxide (6-methyl-imidazo[4.01 M phosphate buffer. 4.40 ± 0. G. 29 (1995) 2125-2137.G. and 310 nm. also applicable for lasers 1. Hubig.44 ± 0. G. S. G. L.. WR: 240 – 280 nm. B: Biol.. R.0111 (248 nm). T. Hamada. Academic Press. Hubig. 5 (1976) 41-47. S. J.20 L10: 1.0139 ± 0. I.40 ± 0. N. 0.-J. Chem. Chem. S. Φ(trans→cis) = 0.02) at 250. 295. pH 7. Gauglitz.3-Dimethyluracil photohydration in aqueous solution. J. 254. S. R. G. quality is sufficient. no wavelength dependence of Φ for the trans → cis reaction. 57 (1993) 380-382. G.0140 (240 nm)....035) in THF or 20 % ethanol/water. J. 80 (1958) 3528-3531..030) in cyclohexane. 0...A.0130 ± 0. Photobiol. J.24 in isooctane. Weil. S about 103 dm3 mol-1 cm-1..2 in methanol or isooctane. Sellin. L. Zimmerman. at 6 x 10-5 M: Φ(average) = 0. Photochem. Φ(trans→ cis) = 0. WR: 230 – 460 nm.025) in methanol.169-224.5. 139 (1984) 237-246. L12: 1-Deazapurine 3-oxide (imidazo[4. 3.. F. 1 mM solutions in 10 mM phosphate buffer... J. Φ = 0. HPLC PP: 6.9 mM in 0. PP: Quantum yields for the cis → trans reaction at 313 nm in various solvents were redetermined Φ = (0. Monti.4. Görner. (0. AM: absorbance at 358 nm. Rahn. (0. 30 (1985) 121-125. J. Photochem. Blaney. Phys. 0. Chow. (1977) 1661-1164. H.. H. 8. 6. Z..030) in acetonitrile. 0. application to polychromatic radiation (medium pressure Hg-arc plus filter solutions): Gahr. Photobiol. Bortolus. reproducibility better than 2 %. R.13 – 0.5b]pyridine 4-oxide) fluorogenic photorearrangement.4 x⋅10-4 M in CH3OH. Gauglitz. 280.. Φ(cis→trans) = 0. Fisher. Photochem. no temperature dependence.0138 (265 nm). commercial p.J. Wirz.. G. AM: fluorometric estimation (excitation at 340 nm.

Can. Schuchmann. M. J. 70 (1999) 314-318. 3. 1.1M borate buffer pH 4..1-Diphenylsilacyclobutane photolysis.5 + 0. Photochem. Organometallics 15 (1996) 2246-2253.. Rahn. Cserti. N2O bubbling (electron scavenger). L14: Potassium iodide in dinitrogen oxide (N2O)-saturated aqueous solution. 21 . 2..M. gradual decrease (1-2 % per hour) of triiodide.J. Bradaric.C. 78 (2003) 146152. 77 (1999) 1136-1147.H. However.15 M KI in 0. lack of oxygen leads to lower Φ values. G.02 (determined against a calibrated radiometer [3]) at 20. 1. M. AM: pH measurement and/or titration. C. C. Kerst. R.1 M tert-butanol. G. Kryschi.015θ. Rahn. Schuchmann. W. Φλ increases at λ < 254 nm and decreases at λ > 254 nm [3]. 2. standard deviation < ± 5 %.. L17: 1. Leigh. WR: 254 nm. Boukherroub. R. WR: 254 nm. R. M. J. 3. or irradiation under pH monitoring up to the equivalence point (consumption of pre-added base sodium borate).21 ± 0.. H.. C. H.235 at 25 °C in aqueous solution. O. C.O.25.-P.-P.01 M borate buffer at pH 9. temperature (θ) dependence = +0. M.J. J.O. C. P. J.N. P. von Sonntag.J. Shaw.. Chem. besides ethene) 1. PP: freshly prepared oxygenated actinometer solution: 10 mM K2S2O8 and 0. von Sonntag..6 M iodide and 0. Bolton. Bradaric... Photobiol. exact calibration of pH instrument necessary in the 2 – 5 range. E. Photobiol.N. working range 10 – 25 °C.O. Photochem. at other temperatures (θ): Φ = 1. Photobiol. W. Φ = 0.. H. L15: Potassium iodide/potassium iodate in aqueous solution. system developed for use in waterworks. Photochem.03 in deoxygenated methanolic hexane AM: GC analysis of diphenylmethoxymethylsilane (trapping of primary product 1.1-diphenylsilene. independent of photon irradiance between 5 x 10-6 – 2 x 10-5 einstein m-2 s-1...J. no bubbling necessary. of iodide at 300 nm PP: 0.-P.-S. von Sonntag. PP: The use of the traditional name nitrous oxide is not recommended by IUPAC. R.. R.2 at 20 °C (H+ production). 58 (1993) 874-880. C. K.. R.21 L13*: Potassium peroxodisulfate/tert-butyl alcohol in oxygen-saturated aqueous solution.R. C.1 M potassium iodate (electron scavenger) in 0. Φ = 1. Lykke. Φ = 0. but note concentration and temperature dependence.3-Cycloheptadiene photoisomerisation. Goren. Water SRTAqua 41 (1992) 75-81. J. L16: 1. Photobiol. J. Mark. Mark. Xu.004 (θ-25) [°C] AM: absorbance at 352 nm of triiodide PP: 0. WR: 254 nm. Photobiol.. 2..73 ± 0.7 °C AM: absorbance at 352 nm of triiodide ion. Banisch. A: Chemistry 55 (1990) 157-168. Miller. Rahn. Φ = 0. Rahn.... G. Schuchmann..N.I. Schuchmann. tert-butanol is essential (no other alcohol). Schuchmann. S.8 ± 0.O.. Water SRT-Aqua 39 (1990) 309-313. WR: 254 nm. I. Photochem.. Hoyer. J.. erratum: ibid 66 (1997) 885. Leigh.R. above 25 °C higher Φ values due to thermal decomposition of the peroxo salt. 66 (1997) 450-455.. Schmeisser. Photochem.L. only basic laboratory equipment required. Stephan. Schuchmann. Piecha.. Mark.

Takamuku. Y.4-dimethoxy-6-(2-hydroxyphenyl)-s-triazine (besides 4-OH isomer) . Yonemitsu. Actinometric use of the reverse reaction [3] is no longer recommended by the authors.P. F. all at 23 ± 2 °C AM: absorbance at 572 nm PP: temperature coefficient +0.. O. WR: 254 nm. W. S05 22 . since there are more convenient systems available for this wavelength region.R.48 ± 0.15 ± 0. Harris. K. R. 37 (1983) 587-591.12 ± 0. Murata. Photochem. solutions recover on exposure to sunlight behind a 455 nm cut-off filter and may be reused ∼ 100 times without loss in accuracy. Photochem. 25 (1984) 489-499..2 %/ °C. Tetrahedron Lett.-D. 1. Shizuka. Yamaguchi. Brauer.27 ± 0. S = (7770 ± 200) dm3 mol-1 cm-1 (253 – 302 nm). respectively. Majer. J. K. Sλ = 7050. 2. 3. and 334 nm.J. Chem.3.E.2. Hamada. Schmidt. Willard.. G. Brauer. Brauer. no effect of oxygen AM: absorbance at 331 nm of product 2. Schmidt. Simons. K.. L21: 8H. Schmidt. Photochem. Φ = 0. 6740. 2. G. Takamuku. A: Chemistry 60 (1991) 207-214.16-dione [heterocoerdianthrone endoperoxide. Hubig. WR: 248 – 334 nm for the dissociation.01 in methylcyclohexane. 2. Am. T. 20 (1982) 335-340. N. continuous irradiation or 266 nm laser flashes (< 1017 photons per pulse). Brauer. Yamaguchi. S. Photobiol... Soc. H.. Schmidt..29 ± 0. Φ = 0. Photochem.4-Tetraphenylcyclobutane (TPCB) photocycloreversion. Shizuka. (1977) 1661-1664. Takamuku. Comes. S. Photochem. Adv. H.-D. R... J. In solid phase cf.. Schnabel. continuous irradiation or 266 nm laser flashes (< 1017 photons per pulse).. Photobiol. R.12b-Epidioxydibenzo[a. G..0 AM: radiochemical 1. 76 (1954) 4678-4687. J. Jesse. L22: Azoxybenzene ⇒ 2-hydroxyazobenzene photorearrangement. also called Actinochrome 1R (248/334)] photoreversible photodissociation. W. S.-D.-D. S. 313.01 in ethanol and 0. the compound is no longer commercially available. Murata. Lett. 11 (1979) 49-52. J.01 in dichloromethane (2 x 10-3 M) independent of λ between 253 and 302 nm.. J.. and 4630 dm3 mol-1 cm-1 at 248. Φ = 1. 2 (1964) 137-181.. J. R. L20: 2. L19: 1. Gauglitz. Φ = 0. 4. H.16H-4b. Photochem.01 in n-butyl chloride or methylcyclohexane (MCH) AM: absorbance at 295 nm (trans-stilbene) PP: no effect of temperature (270 – 310 K. A: Chemistry 60 (1991) 207-214. H.01 in ethanol AM: absorbance at 246 nm Numao. 160 (1989) 8-12..22 WR: 254 nm. J. Chem. Y. Φ = 0.4-Dimethoxy-6-phenoxy-s-triazine (DMPT) photo-Fries rearrangement WR: 250 – 270 nm. Unfortunately. L18: Iodomethane photoexchange with 132I2. Photochem. Beck.. MCH) or dissolved oxygen (MCH) 1..j]perylene-8. WR: 250 – 270 nm. Photobiol. Phys. suitable as polychromatic quantum counter. J. H. conversion limit ≤ 1 %. Drews. J. H...M.

Ar or O2.23 ± 0. 67 (1994) 1762-1764. P.1 x 10-3 (254 nm.01 (366 nm).10 ± 0.4 %. Perbet.. Pizzocaro. O2 . Soc. J. Academic Press.0085 (aerated). Chem.. 1. WR: 254 – 300 nm. 2. Kajiura.. Photochem.. Chem. Mizuno.23 (313 nm). Bull.. G. Gauglitz.. 2 x 10-5 M. Marinari. J. 0. Lemaire. G.. in acidic THF (99. 101 (1979) 2982-2996. Boule. 193 nm laser and 254 nm continuous irradiation: Gurzadyan.W. Chem.0029 (deoxygenated). J. general dependence on concentration..-M. 0. Mitchener. L. 36 (1987) 11-26. 739 (1970) 84-94. D.21 (334 nm). strong effects of solvent and acidity. wavelength. Stier. [2] Not recommended as a reliable actinometer. Photochem.. negligible effect of oxygen. Saltiel.. F. J. 2. ed. [2] 1. N. Φ = 0. Matsushima.C.23 WR: 250 – 350 nm: Φ ∼ 0.. [2]) AM: absorbance at 260 nm PP: 4 x 10-5 M aqueous solution.01 AM: absorbance. J. Charlton. Bunce. L23: 3-(2-Hydroxyphenyl)-2-propenoic acid (o-coumaric acid dianion) photoisomerization in aqueous solution cis → trans reaction WR: 254 – 300 nm: Φ(cis→trans) = 0. cf. Am. in: Rearrangements in Ground and Excited States (de Mayo.-L. fluorescence at 492 nm PP: Not recommended as a reliable actinometer. Vaish. 23 . thermal bleaching of photoproduct at 50 oC. S. 2. Lemaire. 2. quantum yields depend on stilbene substitution and solvent AM: absorbance. 313 – 400 nm: Φ(cis→trans) = 0. M. 1. and pH. AM: absorbance near 450 nm PP: 0. 39 (1984) 531-533. Rivera. T. Chang.. J. Phys. L24: Adenine photolysis.. Suzuki.D. L25: 2-Hydroxy-4'-(dimethylamino)chalcone to 4'-(dimethylamino)flavylium ion photoconversion. J.05 trans → cis reaction WR: 254 – 300 and 350 – 400 nm: Φ(trans→cis) = 0. Mauser. G..5 % purity) solution.52 ± 0.. N. and counterion (Cl-) concentration. G. water content of THF well below 0. P.05. J. no photoreversion.75 ± 0. cf. 5 mM p-toluenesulphonic acid (necessary for ring closure). Φ (chromophore loss) ≈ 0. water decreases quantum yield. J.0027 – 0.L. Photobiol. Chem. M. H. Saltiel. Photobiol. Photobiol. Görner. 75 (1978) 1096-1104. Soc. 0.. J. R. Liebigs Ann. Morioka. 60 (1994) 323-332. 66 (1989) 1049-1051. H.0 mM chalcone. 0.. 1. Chim. student experiment.. oxygen.P. Φλ = 0. Megarity. Photochem. 2. GC 1. J. R. A. Jpn. WR: 254 – 366 nm. J..16 (254 nm) at 20 °C.J. C. L26: Stilbenes cis → trans photoisomerization. Photochem. LaMarre. [1]. H. Guyot. Educ. E. A: Chemistry 109 (1997) 91-94.. no temperature dependence up to at least 45 °C. A.0081 – 0.075 – 10. Matsushima.) 3.02 in ethanol. strong dependence on pH.G. WR: 254 – 366 nm.. Coulangeon. Muarakami. moderately dependent on λ AM: absorbance at 458 nm in ethanolic KOH PP: no concentration dependence.

.O.2-Dimethoxy-4-nitrobenzene → 2-methoxy-5-nitrophenolate anion. Ho.L. Chem. G.R. PP: See however. P. Chem.. E. Adv. H. 33 (1986) 237-255. EPA Newsletter 26 (1986) 23-25. Weeks. L. temperature (θ) coefficient ∆Φ/∆θ = 0. Chem. no significant dependence on air. Hwang. G. 69 (1957) 579-599. H2O2 consumption 1.03 (20 °C) in 3 M H2SO4. 3. 130 259437. conversion limit about 20 %. Chem. F. 2. AM: absorbance at 360 – 390 nm.-M. Mvula. Ber.. 78 (1956) 1278-1279. Su.6 – 0. Ho.. J. p 25-90. A: Chemistry 41 (1988) 293-298. J..05.R. Paris. C. K. Chem. Hildenbrand. 1 (1996) 170-178.0029 ± 0. (0. Folcher. J. WR: 254 – 405 nm. I. Chem. T.. J. J. I.. cf. PP: Take care to dispose of the uranium waste in accordance with current legal regulations. von Bünau. von Sonntag. 4. J. Eur. J. 3. J. Esrom. R.0095/ °C AM: O2 volumetric. H. L28: p-Benzoquinone photoreduction in aqueous solution. Adv. AM: transient absorption at 430 nm (flash photolysis) of p-benzosemiquinone radical anion. Oxid..2). pH 7.. Kuhn. Nicole. C. Photobiol. Chim... 78 (1956) 1273-1278. Bolton. Duguet. Defoin-Straatmann. Schenck.J. A. A: Chemisry 48 (1989) 435-446. J.. for primary Φ of Η2Ο2 decomposition: cf. von Sonntag. photohydrolysis..-I. Lipczynska-Kochany. Sci. J. J. EPR 1. Bunsenges. Φ = 0. 92 (1988) 6208-6219. Phys. E.. Nouv. J. Oxid.116 ± 0. K. Boyd. Am. Kuhn. Photochem. 90 (1986) 6270-6274. Kuzmic.5 M aqueous KOH) AM: absorbance of product 2-methoxy-5-nitrophenolate anion 1. Am. 2. Görner. Φ = 0. M... 2. Photochem. Saito. Φ = 1. Coll. M. Dore. Angew. J.J..L. Bonnel. potentiometry. 24 . Görner.. concentration or radiant power.. Ononye.S. J. Pavlickova. Chem. G. 4. H.O.R.. M. Photochem.-Y. T. Hildenbrand. Matheson. L27: 1. Lipczynska-Kochany. NMR PP: moderately dependent on λ.. Zhang. Soucek. Soc.002 (0. 24 (1990) 157-168. E. T. referred to in: Schenck.. Technol.. E. Czech.. WR: 260 – 380 nm.J.L. Defoin. Kuhn.24 New York 1980.W. Bittersmann.8 in acidic acetonitrile-water (3:1 v/v) solution.47 ± 0. photorheological effects in micellar solution: Wolff. Technol. Reproducibility better than ± 0. DeLaat. H.I. T. Abstr. WR: 254 – 365 nm (applied to 308 nm XeCl-excimer lamp. J.30 ± 0. J. J. A. 7 (1983) 703-709.0007/ °C. J. 138-139 (1999) 315-319 – Chem. H. 51 (1986) 368-374. 1 (1996) 170-178. J. T. H. 2. T. 1. 88 (1984) 1199-1208 Ho. Phys. Dainton. Surf. Phys. 3. Schmidt. Soc. Φ = 0.S.P. Bolton.. ref. 4. Haubold.-C. W. correction for product benzaldehyde content at λobs ≤ 370 nm is necessary. Chem.. F. L30: Hydrogen peroxide photolysis sensitized by uranyl sulfate. freshly recrystallized acid should be used. WR: 250 – 450 nm. Appl.3 –1) 10-3 M in 5 x 10-3 M phosphate buffer.. L29: Phenylglyoxylic acid photodecarboxylation.04. 10 (2004) 440-451. temperature coefficient +0. Photobiol.. Bolton. HPLC. Kreft. strongly dependent on pH and water content..136 mM in 0. Comm. E. J. A. G. Water Res.. not to be used above 45 °C. D. Defoin..

K.25 L31*: Potassium tris(oxalato)ferrate(III) (potassium iron(III) oxalate. Calvert. Schonberg.22. Bridge. Apparatus for the measurement of quantum yields and rates of photochemical reactions. 2nd ed.A new sensitive chemical actinometer. Phys.E. H. Handbook of Photochemistry. 30 (1958) 922928. Weiss. H. Analytical methods and techniques for actinometry. Proc. make sure that there is total absorption. Taylor.W.C. WR: 250 – 500 nm.9 AM: absorbance at 510 nm of Fe(II)-1.H. complexation should be done immediately after irradiation. Schnieper. Photochem. K3[Fe(C2O4)3]⋅3H2O) photoreduction (Hatchard-Parker actinometer). Wolf. Lee. J. C. Soc.. phenanthroline solution is sensitive to UV (fluorescent room lights) and should be stored in the dark. Roy. 9.. Elsevier.20 M solutions have been used. Dekker. Amsterdam 1968. 80 (1976) 24342435. 59 (1955) 783-788. E. (Fitzgerald. J.. Dekker. 12.J. (London). Baxendale. A. 6. S. Bricker.. A220 (1953) 104-116. Jr. Absolute quantum yields for the photolysis of some aqueous chromium(III) complexes. 3 (1972) 387-394. Wrighton. A warning on its correct use. 6 (1967) 321-329. 8. C. III. Anal. 0.N. S. H. Chem. Wegner. Parker. New York 1971. p. Soc. Adamson..299-313. Chem. J. Measurement of reaction quantum yields. Chemical actinometry in the long wavelength visible region. B. (London). Photochemistry. p. Photoluminescence of Solutions.S. recrystallized from water is stable in the dark..M. J.E. Pitts. 25 . Chem. de Mayo. Chem. 88 (1966) 394-404. (1971) 2081-2082.R. N. 7. p. K. II. A modification to the ferrioxalate actinometer. C. Demas.. 40 (1964) 519-523.N. New York 1966. Ferrioxalate actinometry. Kurien. C. Potassium ferrioxalate as a standard chemical actinometer. ed. P. test for the linearity of the results with irradiation time.D. 783. J. 4. Photobiol. New York 1973. J. Parker. Seliger. commonly called ferrioxalate actinometer. J. complete complexation takes about an hour. Photochemistry of complex ions. 1. Hatchard.S. J. part I: Parker. Φ = 1. Stability of Fe(II) in ferrioxalate solutions... Proc. 10.. S.A. 91-115. 208-214. PP: In view of the numerous different and often contradictory observations and recommendations given in the literature concerning the adequate use of this actinometer it is suggested that publications contain a short but unequivocal indication as to which experimental conditions have been applied. 5. Bowman.A. p. 3. A235 (1956) 518-536.. no problems at 60 °C without deoxygenation. add irradiated solution to pre-mixed buffer-phenanthroline solution. ed. J.) 4 (1976) 139-216. K. W.A. 13. Chem.L. Phys. Roy. Creation and Detection of the Excited State. Phys.A.33]. pure solid green K3[Fe(C2O4)3]⋅3H2O. in case of high conversion there may not be sufficient phenanthroline to complex all Fe(II). sufficient stirring is essential.13. Soc. Quantum yield of ferrioxalate actinometer. J. 1993. M. Mol. for use with lasers [19.. sect. P. C. only freshly prepared and mixed solutions should be used. Shizuka. Wiley. Soc. J. Witz. p. (Ware.. 2..10-phenanthroline complex in buffered acidic solution PP: See [36] for possible wavelength dependence in the 240-280 nm range.006 – 0. Bohning. Am. in Analytical Photochemistry and Photochemical Analysis. The most widely accepted standard actinometer. 14.H. 11. Photoreduction of ferric compounds in aqueous solutions. Photometric determinations of Vanadium and Chromium. PP: all work must be done under dark red light. Photochem.. H. Murov.P. Chem.25 – 0.A. J. 119.). W.G.

Demas. Benedix. Abstr..-T. 32.L. n = 1 – 3. P. 3 (1982) 101-111. Chem. Errors in ferrioxalate actinometry.. Educ. 19.M. Chem. p. M. Photobiol.. Vincze.. A: Chemistry 123 (1999) 7-13. Fischer.26 15. Chem. Chichester. M. Individual quantum yields of (Fe3+OXn2-Hm)+• complexes in aqueous acidic solutions (OX2. Namasivayam. Photobiol. Actinometry of an excimer laser with a ferrioxalate chemical actinometer. 21. C. J. Ali... R. H.M. Chim. Connolly. 55 (1983) 2428-2429.. The ferrioxalate actinometer: A lecture demonstration. J. 33.. Measuring the pulse energy of a nitrogen laser with a potassium ferrioxalate actinometer. Acta 53 (1981) L59-L60. Braun.≡ C2O42-. H. Phys. Mol. E.. 34 (1981)145-146. Appl. L. Reza Kenkyu 19 (1991) 247-253 – Chem.D. 30. J. 11 (1979) 69-71.D. Izumi. Photobiol. Boschmann. Unwin. Nicodem. Photochem. Lykke. 20. Zalewski.S. Vitz.. D. J. H.E. Ulrich.L. Maurette. Rahn. Technologie Photochimique. E.. (actinometry in an ESR tube). J. Spin-trapping as a tool for quantum yield determinations in radical forming processes. 34. Chem.A. C. J. 25. Timpe. 35. Y. M. J. Goren.D. G.. Causton. Photochem.1). at longer wavelengths. EPA Newsletter 21 (1984) 33-34. Determination of the quantum yield of the ferrioxalate actinometer with electrically calibrated radiometers. Modern chemical actinometry. 17. EPA Newsletter 19 (1983) 49-53.M. Photochem. Kemp. J.H. Environ. Phys. W. J. Bolton. Bowman. Eng. Velapoldi.R. Stefan. J. V. 26. et al. J. Thomas. Langford.R.. W.C. Shaw. integrating sphere assembly. Hennig. S.A. J.A. O. Aquilera.. 21 (1983) 189-193. L. D. A photochemical light meter suitable for ecological survey.. Photochem.R. 51 (1980) 5204-5206. M. Gafney. C. H. 29.W. in an EPR flat cell).. 100 (1996) 4127-4134. 24. 27. a firstyear chemistry experiment. G.-S. E. The use of 0. 1991. Papp. Kirk. Sun. R.. S. Oliveros.. Photochemical Technology.. Agnew. 26 . Adams. Photobiol. Gruter. Anal. Ferreira. A. L. 31. 22. Ferrioxalate actinometry. T. Photochemical reactions of tris(oxalato)iron (III). Gauglitz. 115 193378/18.O. Moore. Presses Polytechniques Romandes.F. D. M. Determination of the quantum yield for the photochemical generation of hydroxyl radicals in TiO2 suspensions (heterogeneous soln. A: Chemistry 61 (1991) 77-89. Cabral. Inorgan. Wolfenden. Zur Synthese und Photolyse von Trisphenanthrolinium-trisoxalato-eisen(III) und seiner Eignung als Aktinometersubstanz. Figuera. 23. 78 (2003) 146-152.V. 28. Chem. A. E. Tobar. Gellender.M. 85 (1981) 2766-2771. P.D.96.D.. J. Wavelength and temperature dependence in the photolysis of the chemical actinometer. Z. J. J. Photochem. 57 (1980) 314-315. E.. 36 (1987) 289-296. p 77-81. 18. m = 0. Plant. P. Nicodem. Meyer. actin. Standardization of the potassium ferrioxalate actinometer over the temperature range 5 – 80 °C.. A convenient irradiation cell for ferrioxalate actinometry. Photochem.D. T. Photochem. Casadavell.. Acta Oecolog. E. Lausanne 1986..N.R. Fernández. A. Baker. potassium trisoxalatoferrate(III)... Flow actinometry in a thin film reactor: modeling and measurements. 36. E. Sorensen.. 17 (1977) 114-115.F. J.Q.. Educ.H.I.E.. Chem. John Wiley & Sons Ltd..15 M potassium ferrioxalate as a chemical actinometer. A.. A.. 8 (1977) 213-238..P..N. Quantum yield of the iodide/iodate actinometer: dependence of wavelength and concentration (possible wavelength dependence of the ferrioxalate actinometer in the 240-280 nm range). J.J. Photochem...-J. 58 (1981) 655. Oecol. D. E.. Use of the potassium ferrioxalate actinometer below 254 nm. idem. 16. A. 113 (1987) 612-627. Harris. S. Holubov.R. Bolton.. 43 .D. Potassium ferrioxalate as chemical actinometer in ultraviolet reactors. Vincze. Phys. K.

Shestra. Ref. 9. Photobiol..Z. volumetric PP: slight dependence of Φobs on 2. ZnTPP in toluene and other solvents): Romashov. 27... T. J.R. K. Chem.. Kawai. McBride. Bonneau. J. Demas. J. C. 347 nm: (benzophenone-4-carboxylate in aqueous solution): Hurley. R. Land. Int. J. J.. Hoffman.. Chemistry.R. R. Elsevier. J. 2. 28 (1978) 277-281.K. 6. Demas. Chim. Harris.html#browse_access L33: 2... p.. 5. naphthalene in cyclohexane) Bensasson. J.J. Chem. 12 (1978) 132-134.K.S High Energy Chem.3-Dimethylbut-2-ene. Photochem. Photochem. A. Goldschmidt. 353 nm (all-trans-retinal in hexane): Bensasson. C. R. WR: 265 – 532 nm in various solvents (depending on the substance used) AM: transient absorbance 1. Chem. H. 308 nm: (benzophenone-4-carboxylate in aqueous solution): von Sonntag. 63 (1991) 289-299. G.. 7. 1975.. Soc.. E. Yu. J.. 308 nm . Carmichael. Yagi.. Φ = 0. Treinin. Truscott. Molar absorption coefficients of transient species in solution. J. WR: 280 – 560 nm. 2. 117 (1995) 10871-10878. Methods for the analysis of transient absorbance data. 3. Photobiol. 337 nm (benzophenone-4-carboxylate in aqueous solution): Marciniak. J..L.N. Hug. L. Kajii. sensitized photooxygenation. Phys. C. H. cf..I. Hug. G... J. Photochem.. Proc. Hurley.A. Amsterdam. Photochem.nd.edu/browse_compil. Phys.. Am. Photobiol. G. Land. N..). Truscott. Phys.L. A: Chemistry 70 (1993) 29-33. Carmichael.76 ± 0.N. Photochem. Sun.03 with methanolic Ru(bpy)32+ chloride and 2. in the presence of O2 in a sealed cuvette AM: O2 consumption... (Joussot-Dubien.G. Harris. I. 80 (1976) 2248-2253. R. and Biophysics. Y. 28 (1978) 277-281. see: http://www. Data 15 (1986) 1-250. Phys. Kh.W. Photochem. Chem. R. Y. Bonneau.... G..477-484. A: Chemistry 116 (1998) 179-185. A. Takatori. 4. Linschitz.27 L32*: Laser pulse actinometry via standard transients.P.G. ed. 69 (1997) 979-992. E. 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 Method applied for the analytical determination of I2 reducing substances 27 . A. E. Andrzejewska.W.K. Chem.E. R. cf. Soc. Goldschmidt. I. I.. McGimpsey. Zuberbühler. benzoins): García. Photobiol. Smith..P.L. A: Chemistry 126 (1999)1-5. 265 nm (anthracene in hexane.3-dimethyl-2-butene concentration and oxygen pressure 1.J.W. Pure Appl. Redmond.J.. 8. Meet. 355 nm. J. N. J. Sinai. H.rcdc. 347 nm (benzophenone. in: Lasers in Physics. Bagdasar'yan. Hug. Wirz.G. M. J.3-dimethyl-2-butene as acceptor. T. 10. K. McBride. A: Chemistry 112 (1998) 21-28. Chem.V. Pure Appl. E. Linschitz. E. Photobiol.. Photochem. 38 (1983) 9-14. Obi. Shibuya... E.. 355 nm (benzophenone. A. 92 (1988) 5151-5159. R. 532 nm [Ru(bpy)3 2+ in aqueous solutions and polar organic solvents]: Yoshimura. Especially designed for high-power pulse and cw lasers... W. B. Kiryukhin. Photobiol. Kochevar. Photobiol. J.D.

Φ = 0. Hammond. Chem.. L36: Sodium nitrate/ benzoic acid in aqueous solution. 77 (2000) 900-902.. J. Pérez-Ruiz.00152 ± 0. Am.. insensitive to room lights. 3. J. Photobiol. relative method. Foss.410 nm. Hernández-Córdoba. Pitts. S.M. confirmed against ferrioxalate actinometer (L31*). J. for the determination of quantum yields by conductimetry.5 at 308 nm.. Photobiol. J. for the determination of solar UV radiation and penetration in waters. New York 1973. G. Photobiol. Knolle. Murov. Vernon.307. Baertschi.A. 3.13. Chem. Chem. S. Allen.. J. 4.. extremely sensitive (10-9 einstein still detectable) 1. 84 (1962) 1368-1371. 4.E.. J. J. Allen. Chem...P.28 Sánchez-Pedreño. H. Jara. G.C. Limnol. 6. Micheau. S.M. Braun. PP: strong wavelength and temperature dependence.00003 (formation of phydroxybenzoic acid) AM: HPLC analysis (with absorbance and fluorescence detection) of salicylic acid and m/p-hydroxybenzoic acid or batch fluorescence (λexc = 305.M.. Chem. Phys. J. L37: Benzophenone/benzhydrol photoreduction in benzene. A: Chemistry 101 (1996) 89-103. 2. F. Levy.K. sect.00004 (scavenging product salicylic acid). Lavabre. 38 (1993) 703-705. Dekker.G. Analyt. Schuchmann. J. Photobiol. Lucy. Willett. Handbook of Photochemistry. C. C. Cabrera. T.S.5 in acetone and Cl2CH2. Oceanogr. J.J. Photobiol. Morales. Wan. Korth.A. Soc. Moore. Dreiman. von Sonntag. Photochem.. A.. IR NO2 band disappearance 1. p. Chim. J.S. 69 (1999) 17S-18S. Photochem. Moore. the pH of the solution serves as a measure of the degree of photoisomerization.M. von Sonntag. 21 (1995) 837-859. Int..5 x 10 -3 M sodium bicarbonate solution at pH 7. J. Leighton. Soc. P... AM: GC. Borderie. 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. J. M. G.. 172 nm cf.-G. C. M...2. Am. M. Acta 104 (1979) 397402.C. when the reaction is carried out in the presence of NaOH. WR: 300 – 390 nm. 28 .L. 3.. A: Chemistry 56 (1991) 13-23. Intermed. D. Φ = 0. Laplante. W. p. R. Air Water Pollut.. Photochem. J.: González. Photochem.P. Φ = 0.. S06). 1993. no pre-determined Φ AM: differential absorbance 1. S. R. R.00105 ± 0. Kleber. LC. 70 (1999) 319-328. Photochem. D. J.J. Ed. 2.. 2nd ed.125.. Hites.. K. independent of temperature. 5. Same Φ in all phases (cf. J. 2 (1934) 756-759. J. Jr.P. H. Φλ = 0. K.L. Res.M. 290-410 nm : Jankowski. also: Mark.A. L35: o-Nitrobenzaldehyde → o-nitrosobenzoic acid photoisomerization. WR: 300 .N. 83 (1961) 2789-2794. W. W. Mopper. cf. G. WR: 305 – 320 nm.W.-P.. Ketchum.. B. A: Chemistry 136 (2000) 133-139. 2. Martínez-Lozano.. 9 (1965) 595-600.

R.K. Amrein.24 (in benzene. L40: Valerophenone photolysis. Kemppainen.. Amrein. besides cyclobutanols 1. J.A. P. Wan. Soc. Publ. L42: trans-2-Nitrocinnamaldehyde photoisomerization. Albini.. HPLC. Abstr. Oral commun. Jr..03 (only acetophenone formation) AM: GC. Chem. sect. Φ = 0.. J. CO. Cavrini. 2. W. A. Phys.075 (cyclobutanol)..J. Coulson. Ballardini. Bovina... De Filippis.E. V. P..J. A. Wagner. Wolf. Φ = 0. 365 nm. L.. L43: Penta-1. Pavia. Chimia 28 (1974) 185-188. Scaiano. Dekker. D. K. J. Φ = 0. Soc. J.33 (2-hexanone consumed) in pentane solution AM: GC 1.126. H..3-diene photoisomerization sensitized by benzophenone.-R. J.. 94 (1972) 7495-7499. Johnston. Φ = 0. Schaffner. W.22 (acetone). 2.25 (propene). Chem. 0. p. Φ = 0. Chem. Handbook of Photochemistry. WR: 313 nm. Chim.S. WR: 313 nm. Photochem. Photostability of Drugs. Chem. products isopropylbenzene. 1997.29 L38: Hexan-2-one photolysis.15 AM: absorbance at 440 nm. K. E. Spec. M. 3. H. G. J.. Baum. 88 (1966) 4511-4513.J. ferrioxalate.M. Soc. Chem. J.N.C. P.309. New York 1973. secondary products besides the cis-isomer upon prolonged irradiation 1. Soc.13. Φ(cis→trans) = 0. L31*. cf. Gao.A. Küntzel. Yang. Tetrahedron Lett. 2nd Intern. J.. Gloor. L. W. Leermakers. J. N. 2. Photobiol.. HPLC PP: 0.04 (cleavage plus cyclization). Wagner.55. Φ = 0. Vesley. 2nd ed. 110 (1988) 511-517. Bovina E.. 130 43207.. Miller. Zepp. Schuck. Wintgens. (1968) 5385-5388. 102 (1998) 5716-5723..44 29 .D.G. Chimia 28 (1974) 185-188.. Φ(trans→cis) = 0. et al.35 in benzene. K. Schaffner. used as actinometer) AM: GC. Hess. 4 (1965) 305-321. products acetophenone and ethene Pitts. no wavelength or temperature effect (25-40 °C).R.Chem. L39: Butyrophenone photoelimination. Am.C. E.. 0.. A. WR: 313 nm.65 ± 0. 2. 366 nm. p. 290-330 nm: in aqueous solution Φ ∼ 0. besides cyclobutanols and 1-phenylcyclopentanol PP: no effect of pH between 4 and 7 1. Am.J.14-16. p. Sept. Gloor. 225 (Drugs: Photochemistry and Photostability) (1998) 305-316 . L41: 2-Methyl-2-phenylpropanal photolysis.L. R. Schaffner..83 in isooctane AM: GC. Italy. S.. Acta 54 (1971) 868-897. E. 4. 3.98 ± 0.7489-7494. Meet.L. WR: 313. V. WR: 313 nm.5 % methanolic solution (A > 2).. EPA Newsletter 61 (1997) 85-86. Am.30 – 0. Murov. 0. Gumz. Helv. products: acetophenone and propene. P.. H. 1993. WR: 313 nm.

Aberchrome 540 is no longer commercially available 1. Hayata.. degassing desirable while not essential. Polym. L45*: Fulgide reversible photocyclization: (E)-[1-(2. Johnston. M.20 in toluene solution (5 x 10-3 – 10-2 M).T. 3 (1971) 193-200.7a-pentamethylbenzo[b]furan-5. linearly dependent on λ. 2. Φ = 0. PVA and others: Rappon.G. 0. Glaze. J. 1993. Photochem. H. Dekker. 1214 dm3 mol-1 cm-1 at 343 nm.13. Amsterdam. 189 (1988) 2503-2512.. R. (1981) 71-73. in toluene [10e]). 591-594. V. J. J. Soc. Photochem. [6. Syvitski.J. R. Ito. 0. Eur.073 (436 nm). Gill. kinetics of photodecolouration in polymer films. G. n-hexane [10e]) WR: back reaction 435 – 535 nm. J.g. M. 7. sect. Kurita.. Photochem. cf. 63 (1990) 1607-1610. Mol. L44: Cyclohexa-1. New York 1973. Handbook of Photochemistry. Chuenarm. Perkin Trans. J. Bouas-Laurent. Murov. precision ± 3 %.. Bhaovibul. the E → Z photoisomerization. Chem. J. H. 2nd ed.. H.254.0594 (494 nm).310. USA Patent 9/719. G.L. Whittal. therefore.F. p. Langan.C. eds.30 AM: GC 1. reuse of the actinometer solution after photoreversion is strongly discouraged. Perkin Trans. Syvitski. Soc. Sλ = 487 dm3 mol-1 cm-1 at 494 nm. Deblauwe. Φ = 0. n-hexane [10e]) AM: absorbance at 494 nm (ε494 = 8200 dm3 mol-1 cm-1) or at 343 nm (ε343 = 6077 dm3 mol-1 cm-1) PP: reproducibility ± 1 %. in: Photochromism.T. WR: 313. Soc.4.G. Elsevier. probably caused by side processes (e. Heller. Heller.. Sλ = 1640 dm3 mol-1 cm-1 at 494 nm. (1978) Brit.5-dimethyl-3-furyl)ethylidene](isopropylidene)succinic anhydride (Aberchrome 540) 2. 2 (1992). 27 (1991) 365-370 . V.. 5. PP: Unfortunately. L.. in toluene or ethylacetate [10e])..7. Hammond.. H.7. p. Vesley.18 (365 nm. Duggal. details concerning bleaching reaction: cf. Molecules and Systems (Dürr. A. Φλ = 0. S.0470 (546 nm).. Am.3-diene. 5 (1973) 367-369..P... J.11 (436 nm. Smets G.7a-dihydro- Φ = 0.R. Soc. Bull. I. A.J. EPA Newsletter Oct. Y. Makromol..10]). Heller. PP: while Aberchrome 540 is a widely used actinometer.G. Ind. 9.. sensitized photodimerization. M. H.F. Chem. H.6-dicarboxylic anhydride (Aberchrome 540P). Φ = 0. H.. no conversion limit. Mol. Whittal.. A.. 7. J. other solvents possible. Patent 7/1464603. R. 193.R. other authors [10e] see only negligible amounts of Z isomer and suggest other causes (ring opening). Chem. p.09 (436 nm. at the same time recommending a stringent recalibration. Φ = 0. 30 . A: Chemistry 94 (1996) 243-247.G. Scaiano. H.467-492. Chem. PMMA. in ethylacetate [10e]). 366 nm: Φ = 0. J.).97 in benzene AM: GC Vesley. Chem.T. 3.. J. 6. Rappon. but only small A changes necessary. 128. quantum yields of E → Z and Z → E isomerization and E-cyclization and back reaction in various solvents and polymers: Yokoyama. 8. G.S. Syvitski. Langan. Φ = 0. Ch.. (1981) 341-343. 1990. H. O. there is a controversy about decreased quantum yields after repeated use [10]. Chem. WR: 310 – 375 nm (reversible with white light).. 2. Jpn. solvent effects on bleaching: Rappon. 9.20 (365 nm. polystyrene. 110 (1988) 511-517. use in one and two-laser experiments: Wintgens. Photobiol.06 (436 nm. Heller. Y.

2. Creation and Detection of the Excited State (Ware.R. New York.2 ± 1..A. 10871-10878. G. C. Arnold.. 66 (1993) 330-333. R. J. J. Wegner. reply: Heller..5) dm3 mol-1 cm-1 [4] AM: absorbance at 450 nm of Fe(III) thiocyanate complex {ε = (3400 ± 200) dm3 mol-1 cm-1[7] . reproducibility ± 2 %. W. Photobiol. 66 (1989) 605-608.273 at 750 nm [4]. Chem.. 117 (1995) L46: Potassium diamminetetrakis(thiocyanato-N) chromate (potassium reineckate. 12. note: diff. Y. Commonly called Reinecke’s salt actinometer. X. H. J. 0. EPA Newsletter 47 (1993) 42-43. 10. Prog. 10e. 10d. E. 7.7 x 10-3 M in air-saturated Freon 113 Uvasol Merck AM: absorbance at 324 nm 31 . R..3 ± 2. K. Martuszewski. D. no significant dependence on fluence.. H.). A: Chemistry 88 (1995) 31-34. Bilski.F. P. Adamson. Φ ~ 0. A. A. J. Marty. G..310 at 416 nm... Görgens. Redmond.R. Am.282 at 545 nm. Kochevar. J. Gauglitz) Tübingen 1980. J. P. cf. Blazejowski. A.10-Dimethylanthracene self-sensitized photooxygenation. Critical discussion: 10a. Polym. J.7) dm3 mol-1 cm-1.-F.. I. precision ± 5 %.. PP: This actinometer is not recommended due to its large error and cumbersome handling 1. 5.. 0. 1. J. Photobiol.7 ± 2.. Am.. J.270 at 577 and 585 nm. H. Bull. de Mayo. Biotechnol. 0. Photochem. Creation and Detection of the Excited State (Ware. Gros. cf. WR: 334 – 395 nm.S.N.) 4 (1976) 139-216. McGimpsey. Soc.. G. Analyst 114 (1989) 739-741. Chem. photokinetics: Guo. Z. R.335 at 366 nm. E. Demas.. 28 (1992) 399-403.31 Chuenarm.-B. Wang.E. Matsushima. 0. Szychlinski. J. Boule.. Bull. 13 (1997) 408-415. Dekker. García. New quantum yields: Uhlmann.H. Kaneko. ε452 = (36. Experim. 11.A.291 at 316 nm. ed. Photobiol. 0. 4. Chem. 0.. electronic substituent effects on quantum yields: Tomoda.W.. Chem. J. 0. Diplomarbeit (G.5 dm3 mol-1 cm-1 at 520 nm. 3. improved preparation of Reinecke’s salt. Eur.. Hubig.311 at 452 nm. W.271 at 676 nm. P. Soc. ε392 = (96. New York.: Scaiano. Dekker.R. Photochem. L47*: 9. Photochem. from [1]} PP: Φλ = 0.388 at 350 nm.. e.g. J.. ε520 = (110. only slightly dependent on temperature. laser actinometry. A. E. K[Cr(NH3)2(CNS)4]) photoaquation in dilute acidic solution. S. thermal dark reaction. 88 (1966) 394-404. Tang. WR: 316 – 750 nm: Φλ ∼ 0. the commercially available salt must be carefully recrystallized in the dark from water below 80 °C to limit thermal aquation. P. Searle. J.F. Soc. Hänsel. temperature dependence is related to pH.3 dependent on λ. McGimpsey. Pilichowski. 98 (1994) 5431-5434. Chem. 0.. Gauglitz. ed. G. W.W. Böttcher. J. 0. Tsuboi. P. table below. Educ.C. Boule.316 at 392 nm... Jpn. W. only weak red light ≥ 750 nm is admitted. Sλ = 30.G.6. Shizuka. House. Song. G. EPA Newsletter 47 (1993) 44. 0. A: Chemistry. application to biophotoreactor: Cornet.299 at 504 nm.. 6.G. 0. 98 (1996) 45-49.G. 0. Physik 35 (1987) 201-212.. J...276 at 600 nm. A: Chemistry 71 (1993) 51-53. conversion should not exceed 10 %.284 at 713 nm. H. in basic solution thermal aquation (substitution) becomes a major problem. Techn. 4 (1976) 1-62. 0.302 at 735 nm.286 at 520 nm. B.3) dm3 mol-1 cm-1. 10b. Phys. 0. A. 10c. Smith.E. Pilichowski. J.

Anal. 64 (1992) 134-137. 425 – Chem. A.01 (334 nm). Z. K.F. Φλ = 0. 4.6. Japan. Am. Rau. Bunsenges. System several times reusable. Soc. Photobiol. PP: 2 x 10-4 M CdCl2 subphase. 0.32 Sλ = standard deviation standard λ irrad /nm Φλ ε324 / dm3 mol-1 cm-1 Φλ deviation 334 350 365 380 395 627 642 611 651 616 ±8 ±9 ± 10 ± 10 ±9 0.017 ± 0. Liu. Methodol.. Schuster. T.05 (405 nm). Org. Morigaki..1 ± 0.13 ± 0.F. Suitable for photon irradiance < 10-8 einstein cm-2 s-1.022 at 350 nm in 95 % ethanol AM: absorbance at ≥ 500 nm 32 . 1992. pp. Proc.5 – 2... Hashimoto. K. A. Chem.12 ± 0.01 (340 nm). R. Z. H. 3. A.595 0. Morigaki.016 ± 0. 123 097468/08. Hashimoto. direct reading of the Faradaic charge (Coulomb meter) or the cathodic saturation current gives irradiance (after calibration against ferrioxalate. Liu.. Sensors Actuators B.2. Ber..). WR: 350 nm. 97 (1993) 860-864. Hashimoto.5) x 10-3 M ABD. Hashimoto. Chem. H.02 (365 nm). Photochem.. A: Chemistry 65 (1992) 285-292. L49: 3. Photobiol. 1. 13-14 (1993) 226-229. commercially available SnO2 glass (10 Ω lateral resistance) pretreated with 50 % v/v hot sulfuric acid.566 0. React.. Int.7-tetraazaspiro[4.. Abstr. Liu.. Brauer. Kyoto 1991 (Shono. Liu. L48: 4-Octyl-4´-[(5-carboxypentyl)oxy]azobenzene (ABD) trans → cis photoisomerization in an assembled monolayer film (Langmuir-Blodgett technique) coated on electrode. Phys. L31*).3.-D. Mod.581 0. Photochem. Tokyo. WR: 345 nm AM: CD Blume. Fujishima. For the determination of molar ellipticity or the degree of circularly polarized light. (1....6-diene photolysis in n-hexane. Fujishima.1'-Azoxynaphthalene. Z. A.8.014 ± 0. Morigaki. O. 98 (1976) 6583-6586.. J. K. 0. Fujishima.-J. AM: in situ selective electrochemical reduction of cis-ABD.7 %) with different glass substrates. WR: 334 – 405 nm. K... suitable as quantum counter.4]nona-1.11 ± 0. Chem. K.. R.. L50: 1. reproducibility problems (< ± 1. J. 2. Symp.F. 0. J.015 ± 0. negligible dark reaction. Adick.8-Tetramethyl-1. Φ = 0. Org. Schmidt. K. H.571 ± 0. A: Chemistry 45 (1988) 89-96. Z. Kodansha.015 PP: conversion limit ∼ 20 %. For actinometry with circularly polarized light. Fujishima.603 0. ed. irradiation times of only few seconds. independent of photon flux 10-7 – 10-9 einstein s-1. K.-F. K. Synth. Morigaki.

Φ = 0.J. 405. W. Sandrini. L54: Tris(2.4. 1. Bolletta. Photobiol.00116 ± 0. Φ = 0. insensitive to room lights. 22 (1982) 153-157. L56: Degradation of 2. photocurrent depends on quencher concentration AM: reading of photocurrent PP: calibration against ferrioxalate.2.. limited scavenging.J. C.00004 (scavenging product salicylic acid). Photochem. M. Kleber... D. G. J.. Φ(trans→cis) = 0. 7 (1977) 355-357.4'-Tetraisopropylazobenzene. T. Montgomery. V. there is a slow dark reaction. 436 nm Lingamurthy. photocurrent depends on quencher and its concentration AM: reading of photocurrent Dressick.. R.5 x 10-3 M sodium bicarbonate solution at pH 7. A.G. Photochem... 34 (1986) 105-115. S.2'-bipyridine)ruthenium(II)* irreversible electron transfer quenching in an electrochemical cell.6-tetramethyl-4-oxo-1-piperidyloxyl. S = 16600 dm3 mol-1 cm-1 AM: absorbance at 450 nm PP: Φ depends on pH and peroxodisulfate concentration.112 ± 0. 405.J. Chim. J.6. Photochem. PP: strong λ and temperature dependence. WR: 350 – 450 nm. Chem.. 70 (1999) 319-328. D. B.J. 436 nm. L52: Riboflavin* irreversible reductive quenching by Na2EDTA in aqueous medium in a photoelectrochemical cell.. EPA Newsletter 31 (1987) 13-33.. or TAN. F.04 in heptane AM: absorbance at 365 nm Frank. L55: Tris(2. Bhanumathi.2'.3 in argon-saturated aqueous solution (1. Maestri. Stewart. J. J.. Debrabandere. WR: 360 – 580 nm. Durham.. Schulte-Frohlinde. mixtures should not be stored.B.R. K. E.J. H. WR: 366.. L53: Sodium nitrite/ benzoic acid in aqueous solution. Photobiol.E.S. WR: 360 – 380 nm. J. A: Chemistry 68 (1992) 395-399.33 PP: more pronounced spectral shift from reactant to product than with azoxybenzene (L22) but more difficult to prepare Bunce. Φ = 1. B.. Juris. at 366. Gauglitz. Görner. by photoproduced hematoporphyrin anion 33 . Acta 44 (1980) L175-L176. WR: 350 – 390 nm. Isr.4 x 10−4 M Ru(bpy)32+ and 2 x 10-3 M potassium peroxodisulfate. 2.J. Lemke.00187 ± 0. Kuhn. 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. Jacobs. J. M. G. L31*. Inorg. K. Photochem.. but extremely sensitive (10-9 einstein still detectable) Jankowski.J. Mopper. Meyer. L51: 2. D..2'-bipyridine)ruthenium(II) oxidation upon photolysis in the presence of peroxodisulfate. H. N. pH ∼ 5). Nakai. Therefore. Sethuram.. Absorption must be measured immediately after irradiation because of a reverse dark reaction.2.00005 (phydroxybenzoic acid) AM: HPLC analysis (with absorbance and fluorescence detection) of salicylic acid and m/p-hydroxybenzoic acid or batch fluorescence (λexc = 305..

48 in aqueous solution AM: absorbance at about 376 nm 1. Waldmann..020 ± 0.. independent of λ AM: EPR measurement of radical production Moan.753 0. J..7. Acta 22 (1956) 175-182.74 with pheophytin or pheophorbid as sensitizers in pyridine AM: O2 consumption. A. in air-saturated Freon 113 Uvasol Merck (1. G.. Behrmann. L59: Thiourea photooxidation.018 ± 0. Biophys.. Φ = (4. O.6-dicarboxylic anhydride (Aberchrome 999P) reversed photocyclization. suitable as polychromatic quantum counter Adick.759 0. Φ ~ 0.763 0. 2.7.12-Diphenylnaphthacene self-sensitized photooxygenation.. H. AM: absorbance at 383 nm Sλ = standard deviation standard λ irrad /nm Φλ ε383 / dm3 mol-1 cm-1 Φλ deviation 405 436 450 475 490 500 666 662 670 671 657 644 ± 12 ± 11 ± 12 ± 12 ± 13 ± 13 0. 25 (1977) 208-214. L57*: 5. D. L60: 4. Brauer.7a-tetramethyl-2-phenyl-7.018 ± 0. table below. Biochem. WR: 435 – 640 nm. manometric 1. J..7a-dihydro-benzo[b]thiophene-5. 0. Photochem. L58: p-(Diethylamino)benzenediazonium tetrafluoroborate (DEAD) photolysis. W.-Mater.. Schocken. Pinot de Moira. Signalaufz.1 ± 0. 0. Photobiol.-J. B. WR: 405 – 500 nm. Ortmann.0351 at 436 nm. Wold. negligible dark reaction. Warburg. Sci.6 x 10-3 M). WR: 420 – 660 nm.018 ± 0.-D. Actinometry in an EPR cavity. Kemp. Baumann. 30 (1979) 623-624. T.J.98 with ethyl chlorophyllide. Photochem.. J. cf.. J.2).0240 at 546 nm. Φλ = 0.34 radicals in buffered aqueous solutions. 2.018 PP: conversion limit ∼ 30 %. Cox.767 0. Schwartz. Arch. WR: 366 .. WR: 405 nm. Biochim. Φ = 0. Photobiol. A: Chemistry 45 (1988) 89-96. Photogr. 546 nm. 405.769 0. H. M. 21 (1949) 363-369.75. H. R. 34 . K. Hovik. Schmidt.738 ± 0.1 M amine and borax buffer (pH 9.. linear dependence of Φ on λ. Sλ = 288 dm3 mol-1 cm-1 at 546 nm.R. P. V. E. 11 (1983) 385-394.0210 at 575 nm in toluene.2) 10-3 in 0. H. Payne. Jahnke.016 ± 0. Φ = 0. Φ ∼ 0.

. H. Phys. 7.. Φ = 0.05) x 10-2 (in methanol) AM: HPLC of cis-isomer (401 nm) PP: strong dependence on solvent polarity. 2.10 AM: precipitation of the unreacted complex as the perchlorate salt and determination of chromium in the supernatant. J.. 3970 dm3 mol-1 cm-1 at 1000. Ber. 2000. R.G. A: Chemistry 69 (1993) 351-356.. Bunsenges.. 25 (1984) 489-499. solutions stable at –15 °C for at most 3 months. Glaze. Φ ∼ 0. Φ = (2. no side products. Dissertation Frankfurt 1980. Dissertation Tübingen 1984. WR: 475 – 610 nm. Photobiol. beware of light absorption by cis-isomer traces below 410 nm. WR: 488 nm. S = (4080 ± 90) dm3 mol-1 cm-1 at sea level (S = 4030.P. Harris. 6. isomer equilibrium stable in the dark.. H. PP: Unfortunately. S. 5. 1.. WR: 462 nm at continuous and 532 nm at ns laser photolysis. Marguet.J. G. Soc.22 ± 0.C. R. Adamson. C. Mialocq. Bruce. Chim.. Adick. (1985) 957-961.W. J.-D. 38 (1983) 527-531. irreversible. A: Chemistry 45 (1988) 89-96. I.-D. R. 1. Adamson. 4. S.. reversible (photocyclization) on exposure to 366 nm. Photobiol. suitable as polychromatic quantum counter.. reproducibility better than ± 1 %. H.o]perylene (meso-diphenylhelianthrene. W. Soc. L63: 7. Gauglitz.. Brauer. R.-J. no thermal reversion. WR: 452 – 735 nm. S.16-Diphenyldibenzo[a. no conversion limit. no dependence on λ. Schmidt. A.. J. independent of concentration. Photochem. L61: Hexakis(urea)chromium(III) chloride.09 – 0. Brauer.. W. Photobiol.35 AM: absorbance at 546 nm (ε546 = 12000 dm3 mol-1 cm-1) PP: reproducibility ± 0.5 %. S. Φ = 0. G. 35 . Schmidt. Photochem. 37 (1983) 595-598. Whittal. 2. Strydom. PP: Unfortunately. L64: Cobalt(III) acidoammines photolysis in aqueous solutions. Chem. Φ ∼ 10-4 – 5 x 10-3 at 25°C AM: NH3 release and halide aquation. Chem.. Photobiol. Schmidt..G.. A. for similar compounds cf. H. Ann.M. 2 (1947) 844-873. Brauer.W. Johncock.A. Drews. Chem. this actinometer is no longer commercially available. H. or Actinochrome N (475/610) ) self-sensitized photooxygenation . S. R. Am. 90 (1986) 813-819. X. Heller. absorbance at 625 nm Pribush.224 ± 0. insensitive to oxygen.N. [Cr(urea)6]Cl3 photoaquation. H. 88 (1966) 394-404. 96 (1974) 3027-3032.-D. A. Poon.. respectively) AM: absorbance at 429 nm PP: conversion limit ∼ 10 %. H. Wegner. Perkin Trans.004 in air-saturated toluene (10-3 M) independent of λ. A. and 3000 m altitude. Chem.-D. Am. L62: 4-Dicyanomethylene-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran (DCM) trans → cis photoisomerization.. R.. Schmidt. Photochem. J. Brauer. E. 3. Oliver. J. Sauvage. J. Photochem. private communication by Heller.A. Hubig. Acs. Photochem. Actinochrome is no longer commercially available.K. 4000. Hubig.. Armand. P.02 (in CHCl3). C. Schmidt. Reuse of the solution not recommended because some degradation takes place during recolouring. Soc. J.28 ± 0. J.E.

H.3'-hexamethylindotricarbocyanine iodide (HITC). L66: 7. ∆ε405 = ε405 (MDH) .0452 0.003 ± 0.0017 ± 0. 1.. Brauer. 7.0018 0.ε405 (MDHPO) Sλ = standard deviation standard λ irrad /nm Φλ ∆ε405 / dm mol cm-1 3 -1 Φλ deviation 670 680 685 695 700 705 710 818 780 769 772 780 796 809 ± 19 ± 18 ± 18 18 17 17 17 36 0. MDH) photooxygenation. Photochem.5 x 10-11 –10-9 einstein s-1.3.003 PP: contribution to initial absorbance at 405 nm by MB (0.36 L65: 7. WR: 610 – 670 nm. Photobiol. AM: change in absorbance at 405 nm of endoperoxide. Φ ∼ 0.0427 0. Adick. table below (halfwidth of monochromatic light 6 nm). at 22 ± 2 °C. MDH) photooxygenation sensitized by methylene blue (MB) .109 0.106 ± 0. AM: change in absorbance at 405 nm of endoperoxide. R. WR: 670 – 795 nm.106 0. H. table below (halfwidth of monochromatic light 6 nm).0431 0.0447 ± 0. variation of oxygen concentration has no influence.0440 0. A: Chemistry 49 (1989) 311-316.-J.003 ± 0. cf.0019 0.6 x 10-4 M MDH.16-Diphenyldibenzo[a.o]perylene (meso-diphenylhelianthrene.0017 ± 0.114 0. A > 3.0018 0.o]perylene (meso-diphenylhelianthrene. 10-4 M MDH.2 x 10-5 M HITC in air-saturated CHCl3 solution.. bleaching of MB is negligible. suitable for polychromatic radiation.003 ± 0.ε405 (MDHPO) Sλ = standard deviation standard λ irrad /nm Φλ ∆ε405 / dm3 mol-1 cm-1 Φλ deviation 610 620 633 * 654 670 * (He-Ne laser) 2062 1972 1918 1918 1919 ± 39 ± 38 ± 38 ± 36 ± 35 0.1'. 8 x 10-5 M MB.1 in air-saturated CHCl3 solution.3'. J. Φ independent of concentration and photon flux = 1. cf.035) and MDH (0.0016 0. ∆ε405 = ε405 (MDH) .165).003 ± 0.04 . Schmidt. Φ ~ 0. sensitized by 1.-D.3.106 0. suitable for polychromatic radiation.0431 0.0425 0.16-Diphenyldibenzo[a.0016 .

Two independent studies advised against the use of this system because of complex stoichiometry. 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.. Φ independent of photon flux in the range 5 x 10-11 – 5 x 10-10 einstein s-1.0016 0. The instruments allow to apply a preset amount of quanta to the sample and account for changes of the power of the light source and of the absorbance of the sample. D. 10] are designed to measure and integrate the amount of light absorbed by the sample during irradiation. P. Schmidt. H. Minn. G. counted and displayed. Integrating electronic actinometers of the "Quantacount" type [E06.. Soc.37 720 730 745 755 770 780 795 810 781 738 716 680 678 678 17 16 15 15 15 14 14 0. K.01 1. no significant dark reaction in the cold. Chem. (1974) 565. Chem. Filipescu.. WR: 290 – 370 nm.0375 0. F. Disproved: L67: Decafluorobenzophenone photoreduction in 2-propanol. H. Soc. Photochem. Sci. (1970) 1413. E01: UV light integrator as photochemical monitor.3) and HITC (0. J.g. decrease of oxygen concentration of 20 % decreases quantum yields by only 2 %. Registration of the absorbance [E06] or taking a complete absorption spectrum [E10] are comfortable additional options allowing to monitor the photochemical conversion. R. Comm. II.60 ± 0. 3. Margaretha. 4 (1975) 309-312. A: Chemistry 54 (1990) 27-30. or during. J.0408 0. Gauglitz. E02: Calibrated thermopile for continuous measurement of light absorption during irradiation.2. J. and dependence on fluence: 2. Rhodamine B) and photodiodes (or photoelements or photomultipliers) the two light beams produce voltages that are electrically matched.-D.R. Dickinson. Gloor.0375 0. Chem. By means of a chemical quantum counter (e. For that purpose. Pinion.0016 0.-J.25).0448 0.W.. Chem. Φ = 0. Photochem.0016 0. J. λ-dependent Φ. U. R. Schaffner. Comm. J. J. largely independent of the absorbance. Photobiol.0014 0. the entering monochromatic light is split into a sample beam and a reference beam. Kölle.0396 0.. During irradiation the difference in radiant power before and behind the sample is continuously computed and converted into a frequency [E06] which is integrated.. J. Yip.. a photochemical reaction (the quantum yield of which is of interest) are rather cumbersome to perform with traditional methods of chemical actinometry. Brauer. 37 .P. 43 (1966) 758-759..0014 PP: contribution to initial absorbance at 405 nm by MB (0.0014 0. Adick. Instr.0018 0. 07. Electronic Devices Radiant power measurements before and after. N.0376 0.0432 0.L.

Instr.L.. D. E04: Physical light integrator.578 nm (Rhodamine B as quantum counter.560 nm is detected by a photodiode Davidson.. G. G.. Absolute Measurement of Incident Photon Flux by Means of Photodiodes Photodiodes are used for the detection of electromagnetic radiation in the ultraviolet. Signalaufz. H. Yguerabide. H.. E08: Luminescent quantum counters. E03: Photon irradiance monitor consisting of a Rhodamin B solution and a photomultiplier. 717-722. the emission at 420 . 6 (1967) 321-329. Garland Encyclopedias in the History of Science. E05: Digital quantum dose integrator with memory. Kuhn. Cutler.P. Chimia 28 (1974) 185-188. 34 (1981) 287-296. Schultze. Z.. 24 (1984) 20-21. Kofsky. Weigt. p.N. T. H. 5 (1973) 223-229.. photodiodes) 1. W. Vogel. 2. Photobiol. Schaffner. 8 (1977) 379-389. J. E09: MgWO4 phosphor photoelectronic UV-B dosimeter for microcomputer read-out. Baumann.) Vol.. ibid. 25b (1970) 330-331. J..N. 39 (1968) 1048-1052. J. J. Photochem. E06*: Electronically integrating actinometer. Z.B. Sci. photoelements) 1.. R. Naturf. Rev. Chem.G. Demas. E10*: Integrating electronic actinometer with automatic UV/VIS monitoring. 15 in: Instruments of Science. Garland Publ. Goldsmith. Mol. G. Schaarschmidt. K.. W.-R.-Mater. Inc. H. H.. Waldmann. R. Chem. T. K. 1.E. Photochem. An Historical Encyclopedia (Bud.. Analyt. Behrmann. Fitzgerald.. Photochem. Kyziol. Actinometer. Ortmann. WR: UV-B.P. Fanghänel. Photobiol.J. Demas.. Mol. eds. Warner. K. ISBN 0-8153-1561-9. Instrumentation 5 (1973/74) 283-290.. Gloor. 51 (1979) 712-717. 2. J. V. WR: 254 .. 2. 2. New York 1998. Jahnke.J.. H. II. E. D. Behrmann. Amrein. WR: 365 – 578 nm (Rhodamine B as fluorescent converter. and infra-red range. J. K. J. Photochem. Sluder.. Schnieper.J.R.A.. I. H.3. Bohning. E07*: Electronic actinometer with photomultipliers. which rapidly recombines in the absence 38 . visible. Each photon which is absorbed in the semiconductor material leads to excitation into the conduction band and produces one electron-hole-pair. Weiss. Taylor.. Chem. P. Zimmerman..38 Wolf. Their basic principle rests on the photoelectric effect. 11 (1983) 385-394. B.

which amounts to about 30 % for uncoated Si.44 x 10-5 einstein s-1A-1 between 450 and 1000 nm.hamamatsu. Such measurements have been performed in photochemical investigations [1] and in the calibration of several chemical actinometers [2]. Therefore. the charge of 72180 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 Sλ. one einstein has the energy Eλ = 0. As shown above.05 between 450 and 1000 nm. Thus. a photodiode may be used as a detector for the absolute determination of the photon flux of monochromatic radiation. Some mass produced Si photodiodes show direct proportionality of Sλ. Photodiodes can be used as polychromatic quantum counters in this wavelength range. the output voltage U equals the product of photocurrent Ip and the resistance Rf of the feed-back resistor: U = Ip⋅Rf. Therefore. After proper calibration with an external standard. before (at shorter wavelengths than the optimum one) and behind (at longer wavelengths) the p-n diffusion layer. with λ given in m.W = 8. By multiplying Sλ.066 x 105 λ A W-1 with λ in m. Sλ.W with λ holds true. the mean apparent quantum yield of charge carrier formation of the S2387 diode including reflection loss amounts to Φc = 0..e in einstein s-1 A-1 is then Sλ.e by the measured photocurrent Ip the desired photon flux at the wavelength λ in einstein s-1 is readily obtained.e. The relative Sλ. The needed diode sensitivity Sλ. i. i.W Eλ )-1. when only moderate 39 . When an outside electrical connection between both sides of the junction is made. Due to the wavelength dependence of the absorption coefficient of the semiconductor material. Thus. however.W data plotted vs. The fit follows the relation S’λ. The sensitivity of the semiconductor at a given wavelength λ is given in photocurrent (amperes) per watt of incident radiation. Φc is in good approximation constant in this range as indicated in Figure 1. absorption of radiation can also occur in the layers where the separation of electrons and holes is less effective. Sλ.82 x 105 x λ A W-1. leading to the maximum possible sensitivity Sλ.44 x 10-5 einstein s-1A-1 in practically the whole visible wavelength range and even in the NIR. With Eλ = NA hc/λ.e = ( Sλ. The deviation of the linear fit from the data is smaller than 12 % between 430 and 1000 nm.pdf).e = 1. Hamamatsu S2387).e.e is the conversion factor transforming the photocurrent to the number of photons of wavelength λ striking the diode per unit time. indicating a constant value of Φc (e. The main process reducing the sensitivity of Si photodiodes in the visible range is the reflection of the incident light at the planar surface. electrons and holes are very effectively separated by the strong local electric field. However. The determination of the quantum yield of the 1940 nm b → a emission of singlet molecular oxygen was performed with an InAs photodiode. Φc = 1 means that the charge of 96485 A s is produced by the energy Eλ = 0. the flowing photoinduced current can be measured with high precision using an operational amplifier.. Precise investigations of Si photodiodes have shown that the quantum yield Φc of electron-hole-pair formation is actually unity for radiation of wavelengths for which absorption takes place in the p-n junction [3]. the quantum yield of charge carrier formation Φc of the diode is constant. In actinometry.W with λ in a broad range of the visible spectrum.39 of an electric field.72 ± 0. Hereby.066 x 105 x λ A W-1 holds true in the absence of reflection loss for Φc = 1. it is important to have diode sensitivities related to photon flux (Np) rather than to radiant power. Linear least squares fitting between 290 and 895 nm with fixed zero intercept results in the straight line in Figure 1. if the absorption takes place in the depletion region of the p-n junction of the diode.W in A W-1. and even < 7 % between 450 and 1000 nm.W = 8. for which Φc was constant from 1100 to 2700 nm according to the data sheets of the manufacturer [4]. For the wavelength region where direct proportionality of Sλ. this cheap Si-photodiode may be used as a polychromatic quantum counter of constant sensitivity Sλ. λ in Figure 1 have been extracted from the S2387data sheet (URL:http://www.de/assets/pdf/parts_S/S2387-1010R.e = 1.1196/λ J for λ in m.1196/λ J of one einstein of absorbed photons. Sλ.W = 5. g.

and H. Section II.W / A W wavelength / nm Figure 1 Other detectors (Si. other photodiodes of the same type.. Photobiol.44 A volume of 2 . Zalewski. Appl.3 0. W.-P. 99 (1995) 15919-15924.2 0. C.1. H. HgCdTe) may also be used for absolute radiation measurements in the near and middle IR range. Photochemical set-up: Drews.-D. a chemical actinometer or vs. Phys. A. A gas-tight cell assembly is necessary.. F. (submitted by R. R. 3. R. Photochem. M. Standard Liquid Phase Actinometric Procedures (For references and more data cf.lasercomponents. Ge. Φ(trans→cis) = 0. Schmidt.. 0. Ge. 38 (1983) 527-531. Quantum yield of electron-hole-pair formation of a Si photodiode: Geis. Schuchmann) WR: 185 nm. Even though 40 .. Photobiol.. Opt. Judson.-D. Determination of the quantum yield of the 1940 nm b → a emission of singlet oxygen: Schmidt. 6 (1976/77) 391-403. J. 4. Schaefer. Acs. However.1 0. EG & G Optoelectronics. InAs. Φ(cis→trans) = 0. Photochem. J. A. Chem. it is strongly recommended to occasionally calibrate the photodiode vs. Laser Components GmbH. Bodesheim. References to section II. InAs. HgCdTe): Infrared Detector 1998. 19 (1980) 3795-3799.. URL: http://www. H.de III. total absorption) containing nonane as a GC standard are 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. Photochem. above) L02*: cis-Cyclooctene cis → trans photoisomerization.-D.4 0.6 0.40 accuracy is required. Spectral sensitivity of other semiconductor devices (Si.3.. R.. which have been kept in the dark for reference purposes.3.. Schmidt. von Sonntag. H. 1.W with λ is fulfilled for several semiconductor devices [5]. 37 (1983) 587-591.4 cm3 of a solution of cis-cyclooctene in pentane (2 x 10-2 M. Brauer. 2. E. Srinivasan. Brauer. R. Schmidt. Calibration of chemical actinometers: Brauer.34. R. 5. J. since the condition of direct proportionality of Sλ.5 0.0 300 400 500 600 700 800 900 1000 -1 Sλ.

3.6 The chemical reaction used is the photodecomposition of oxalic acid. ε (trans) = 6000 dm3 mol-1 cm-1.5 M. from a solution of uranyl oxalate. Section II. there is total absorption at concentrations ≥ 0.4 2 .[cis ]∞ ([cis ] . The product-collecting procedure is the same as the purging procedure. ε (cis) = 8500 dm3 mol-1 cm-1. A gas-tight cell assembly is necessary.ε (trans ) ε (cis ) .5. references in L02.5 – 0. H2C2O4.6 x 1016 s-1 (cross section 2 .[cis ]o ) + ( [cis ]o + [cis ]∞ ) ln ε (trans ) ε (trans ) [cis ]o . is photoisomerized back to the cis compound (side reactions are very minor).[cis ]∞ [cis] is the time-dependent cis-cyclooctene concentration. L03*: Ethanol photolysis (Farkas actinometer). and H.4 cm2) at 185 nm.1. NA = Avogadro constant . Alfano) WR: 200 – 500 nm. Eaton. For details and an alternative graphical method of evaluation cf. Schuchmann) WR: 185 nm. [cis]∞/[cis]o is close to 0.4 cm2 ) at 185 nm to be easily measurable by gas chromatography. Subscript o indicates zero conversion and ∞ refers to the stationary state ([trans]∞/[cis]∞ ∼ 1). (submitted by C. It is recommended to stir the solution during purging.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. The conversion after 1 min of irradiation is easily measurable by gas chromatography at a photon flux of about 1. 41 . trans-cyclooctene. L06*: Uranyl oxalate photolysis. Np. (D. It is recommended to stir the solution during purging and irradiation by a Teflon-coated bar magnet. Enough hydrogen is produced after one min excitation with a photon flux of about 2 x 1016 s-1 (cross section 2 . O. the GC determination requires calibration. it may lead to relative longer wavelengths chargetransfer absorption involving the solvent.F.41 oxygen is not expected to interfere with the isomerization reaction. irradiation. Φ(H2) = 0. Hydrogen is stripped from the sample directly into the gas chromatograph by the carrier gas. and stripping by a Teflon-coated bar magnet.ε (trans ) [cis ] . Φ = 0. The hydrogen quantum yield depends on the concentration of ethanol. This actinometer involves a system where the product. The number of absorbed photons per sample volume per unit time. As usual. The irradiation is performed at room temperature. von Sonntag C. t = irradiation time. is calculated from N p [cis ]o f([cis ]) Φ (trans → cis ) =t N A [cis ]∞ where f([cis]) is given by the expression f([cis ]) = ε ( cis ) .-P.

0 dm3 in the dark. Ceric sulfate is prepared from ammonium hexanitratocerate according to the procedure by Smith and Fly (L06*.42 H2C2O4 ⎯⎯⎯→ H2O + CO2 + CO After irradiation the non-reacted C2O4-2 is titrated with Ce(IV) with a solution of ceric sulfate.41 x 103 dm3 mol-1 cm-1.2 N H2SO4 in a 1.999. The precipitate is then dissolved in hot 2 N sulfuric acid (125 cm3) and washed into a 1. The factor 2 in the denominator results from the stoichiometric factor in the titration reaction. The concentration of Ce(IV) is then adjusted until it is slightly larger than twice the (molar) concentration of oxalate in the actinometer solution. The solution is cooled and brought to approximately 950 cm3. The solutions are then incubated at 80 °C for 10 min and allowed to cool in the dark. this factor depends on irradiation wavelength and pathlength). usually 1 cm). since it is contaminated by ammonium nitrate which limits the stability of standardized cerium solutions. Vflask2 = volume of the reaction flask 2 (recommended 0. Procedure: After irradiation of two 3. 1. [14]). primary standard grade) are dissolved in 0. Valiq = volume of the measured aliquot (recommended 1 cm3). following the reaction: 2 Ce(IV) + C2O4-2 → 2 Ce(III) + 2 CO2 Preparation of solutions: 0. The resulting precipitate is washed with six portions of water (25 cm3 each) until neutral to pH paper.2 N H2SO4 and diluted to 1. The oxalate photodecomposition quantum yields (Φλ) are: 42 . PP: The use of commercial ceric sulfate is not recommended.011 x 10-3 M in uranyl ion.004 x 10-3 M in oxalate dianion and 1.67262 g disodium oxalate (Na2C2O4. ε320 = molar absorption coefficient of cerium(IV) at 320.0 nm ( l = pathlength. The Ce(IV) concentration is then determined spectrophotometrically by dilution of an aliquot and measurement of the absorbance at 320.0 cm3 volumetric flask 2.42478 g uranyl sulfate (UO2SO4) and 0. Calculations: The photon flux Np/einstein s-1 entering the sample cell is given by: hν Np = Virrad ∆A Vflask2 2 t Φ f l ε 320 Valiq with Virrad = volume of irradiated actinometer solution (recommended 3 cm3). The solution is 5.0 cm3 H2SO4 (2 N) are added and the solution brought to the mark with water.0 cm3 aliquots of actinometer solution. The decadic molar absorption coefficient of Ce(IV) at 320 nm is ε320 = 5.0 dm3 volumetric flask 1.01 dm3).0 nm. Store in the dark.5 g (NH4)2Ce(NO3)6 are dissolved in 15 cm3 water and treated with 100 cm3 15 N NH4OH. f = fraction of incident actinometric light absorbed by actinometer solution (0. Approximately 5.0 cm cell. Φ = quantum yield of oxalate loss. 0.0 cm3 of the standard Ce(IV) solution and 1.0 cm3 aliquot is pipetted into a 10. a 1. as follows. The absorbance difference between sample and non-irradiated blank (∆Α ) is determined at 320.0 nm vs. t = time of irradiation. Both irradiated samples and non-irradiated blanks are treated in this way.

The photolyzed solution is then concentrated under vacuum and the sulfate may be crystallized and recrystallized after adding sulfuric acid. The sensitivity of the method is only half of that of the conventional ferrioxalate procedure (L31*.49 0. Efficient stirring of the solution is essential in all cases. L06*).60 0.4 x 10-4 M methanol solution of azobenzene.61# λ /nm 254 265 278 302 313 Φλ 0.58 The marked (#) values in the table are interpolations from the other data (after Leighton and Forbes [1]. is measured at 358 nm. (submitted by G. For this purpose the used actinometric solutions are collected and photolyzed until complete oxidation of the oxalate.56 λ /nm 335 366 405 436 Φλ 0. Gauglitz) WR: 230 – 460 nm. PP: Take care to dispose of the uranium waste in accordance with the current legal regulations.61 0. A value of A358 ca. where ∆A358 is the change in absorbance at 43 .58# 0.30) and the final value should be A358 < 0. The actinometry (as above) then starts at the photostationary state (A358 ∼ 0. largely because ε of Ce(IV) at the analysing wavelength is only half that of the phenanthroline-Fe(II) complex used in the analysis during the ferrioxalate procedure).02 and the final value should be kept between 0.43 λ /nm 208 237 243 245 248 Φλ 0.58 0. only radiation ≥ 500 nm is to be admitted to the sample. Except during irradiation. Φ(trans→cis) = 0. Φ(cis→trans) = 0. S = 130 – 3900 mol-1 dm3 cm-1 Wavelength range 245-266 nm: The solution is pre-irradiated at 313 nm. Wavelength range 350 – 440 nm: There is no total absorption in this range. Wavelength range 270-340 nm: The absorbance A of a 6.9.48 0. Considerable care must be exercised when using the uranyl oxalate actinometer. For the range 375 – 440 nm.48. a pre-irradiated solution is used and the procedure starts at the photostationary state.1 is recommended.85 and 0. L11*: Azobenzene [Actinochrome 2R (245/440)] photoisomerization (reusable). 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 non-irradiated blank.57 0.53 0. Each irradiation period should cause a change in A358 of about 0. stored in the dark (see below). The uranyl may be recovered as sulfate. For regeneration a sealed cell should be stored in the dark or irradiated at 254 nm. 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.45. Irradiation and observation wavelengths should be the same. 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. the results will be meaningless.58 0.56 0. Evaluation: For the range 245-340 nm the following formula is used.60# 0. and Brackett and Forbes [2].14. Comments: The procedure discussed here is an improved version of one due to Pitts.

Total absorption at the desired irradiation λ and optical pathlength is recommended. photoreduction (HatchardParker actinometer. but should be determined for each lamp/filter combination at the irradiation wavelengths. 10 cm3 conc. The graphical method uses the expression EP = τ Q×t . where Q = [Φ(trans→cis) ⋅ ε(trans) + Φ(cis→trans) ⋅ ε(cis)] 1000. K3[Fe(C2O4)3]⋅3H2O). The latter is done with the aid of a computer. Hubig) WR: 250 – 500 nm.8. S = 13900 – 9990 dm3 mol-1 cm-1 All procedures should be done under red safe-light. the photon irradiance. Np. Ideally. entering the sample cell is given by EP = Fλ ⋅ ∆A358 / t in einstein cm-2 s-1. t.44 358 nm and t is the irradiation time in seconds.63⋅10-6 5. Thus. dried at 45 °C and kept in the dark. ε510 = 11100 dm3 mol1 cm-1). Conversion should not exceed 5 %. is the pseudo total quantum yield. An absorption spectrum of the solution is taken. commonly called ferrioxalate actinometer). A 0.10-phenanthroline solution (store in the dark !) and 0..4 – 1. EP. 1 M FeCl3 solution. or 0. 1. A510 should be within the range 0. Q values are independent of time and concentration. Φ = 1.g.947 g of the crystals in 100 cm3 H2SO4 (1 N) and dilution with distilled water to 1 dm3. Gauglitz and S.9. Green crystals of K3[Fe(C2O4)3]⋅3H2O are prepared by mixing 3 vol. the photoreaction should be made in a cuvette of the same dimensions as that used for the actinometer.006. in einstein s-1 44 .012.006 M solution is prepared by dissolving 2.30⋅10-6 4. 0.60⋅10-6 4.3]). τ is taken from calibration graphs of the timedependent absorbance vs. The photon flux.5 cm3 buffer (stock solution: 82 g NaC2H5CO2.30⋅10-6 3. λirrad/nm 245 280 302 313 334 Fλ / einstein cm-2 2. The factors Fλ are given in the table below.5 M K2C2O4 with 1 vol. A reference is prepared in the same way except that it has not been irradiated. L11* [2. Both solutions are kept in the dark (about an hour) until full colour development is achieved.1 % 1. with ε at the irradiation wavelength. For the range 350 – 440 nm graphical or arithmetical kinetic evaluation methods have to be used (cf. 0. E. 3 cm3 (V1) of the solution are irradiated under efficient stirring. recrystallized three times from warm water. H2SO4. 1 cm3 (V2) of the irradiated solution is given into a 10 cm3 (V3) volumetric flask containing a mixture of 4 cm3 0. L31*: Potassium tris(oxalato)ferrate(III) (potassium iron(III) oxalate. and the absorbance difference between the two samples is measured at 510 nm (1 cm optical pathlength (l). It is essential that the irradiation time measurement (electronic shutter) as well as the pipetting is done very precisely. diluted to 1 dm3 with distilled water) which is then diluted to the mark with distilled water.25 – 0.15 M (≥ 405 nm) solutions can be used for actinometry.60⋅10-6 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 (einstein s-1) is desired. (Submitted by G. They are listed in the literature.

[10e].20 M) at 514 nm. Φ = 0. A magnetic stirrer is recommended. periodical fluctuations in radiation power may not be "seen" during the rather short irradiation periods.375 nm.7 × 10-3 M solution of 9. 1. Aberchrome 540 is no longer commercially available.15 M solution. 1. ε494 = 8200 dm3 mol-1 cm-1.01 M) at 458 nm. L45*: Fulgide reversible photocyclization: (E)-[1-(2. (submitted by H. The coloured form is reversed with white light. Schmidt) WR: 334 – 395 nm.10-Dimethylanthracene self-sensitized photooxygenation.45 entering the sample cell is given by: NP = ∆A V1 10-3 V3 Φλ ε 510 V2 l t where t is in seconds. It is essential that the solution absorbs all radiation falling upon it.93 (0.G. entering the sample cell.20 from 310 .g. to be calculated from 7. (submitted by R.2.5-dimethyl-3-furyl)ethylidene](isopropylidene)succinic anhydride (Aberchrome 540) 2. Unfortunately. After irradiation in a 1 cm cell (l) and mixing. Care should be taken to prevent the magnetic stirrer from entering the light beam.006 M) for the wavelength range 254 – 366 nm.15. L47*: 9.e.7a-dihydro- NP = ∆A V Φ ε 494 l t where V = irradiated volume in dm3.7.4.10-dimethylanthracene in air-saturated Freon 113 (molar absorption coefficient ε324 = 1080 mol-1 dm3 cm-1) of initial absorbance A324 = 1. At room temperature Φλ = 1.6-dicarboxylic anhydride (Aberchrome 540P).11 (0. Heller) WR: 310 – 375 nm. In this case the value of the photon flux must be divided by the fraction of absorbed light at the irradiation wavelength.583 ± 0.7. Φ = 0. 3 cm3 ) of this solution is pipetted into a cuvette and the absorbance (if any) at 494 nm is noted. (1-10-A). There is no total absorption above 450 nm even in 0. An accurately measured volume (e. 1. S = (629 ± 17) dm3 mol-1 cm-1 A defined volume of a 1.8 (optical pathlength l = 1 cm) is filled into a 45 .14 at 405 nm. but the precautions listed above should be obeyed. S = 1640 dm3 mol-1 cm-1 A ca. i.20 – 1. PP: Re-use of the actinometer solution after photoreversion is strongly discouraged). The increase in absorbance (∆Α494) enables the photon flux. 5 x 10-3 M solution is prepared by dissolving 25 mg Aberchrome 540 in 20 cm3 toluene. Np in einstein s-1. the absorbance at 494 nm is measured.12 (0. The procedure described in Murov's Handbook of Photochemistry (L31*[12]) is also recommended. and 0. PP: due to its high S-value L31* is not really an integrative system.006 M) at 436 nm. Φ = 0.08 (0. Φλ = 1.08 M) at 488 nm. For recent quantum yields cf. t = time in seconds.7a-pentamethylbenzo[b]furan -5.26 (0. The stirred solution is then irradiated for a known period.

R. Appendix Additional references concerning practical problems as well as kinetic and theoretical aspects of quantum yield calculation: 1.575 g cm-3). The solution completely absorbs the incident radiation in the useful wavelength range 405 – 520 nm.1.12-Diphenylnaphthacene self-sensitized photooxygenation. Φ = 0.583 ± 0. S = (662 ± 13) dm3 mol-1 cm-1 A defined volume of a 1.. The conversion should not exceed 30 %.L. Radiation of λ < 435 nm should be completely avoided during preparation and handling of the solution.. Np (einstein s-1) entering the sample cell is calculated by using the absolute value of the absorbance decrease at 383 nm upon irradiation (∆A383) and the following equation NP = ∆ A383 V ε 383 Φ t l with t = irradiation time in seconds. Schläfer.C.758 ± 0. L57*: 5. Only yellow or red light ≥ 560 nm may be used during preparation and handling of the solution.E.758 ± 0. H. Ber. V = volume of the solution in dm3 (density = 1. Am.1. Hahn. Chem.46 spectrophotometric cell equipped with a magnetic stirring bar. Zimmerman. (submitted by R. The photon flux.016. Soc.. The system is suited as a polychromatic quantum counter independent of wavelength with S = ε383 ⋅ Φ = (662 ± 13) dm3 mol-1 cm-1 and Φ = 0. H. Morrison.C. The conversion should not exceed 20 %.. The photon flux. During irradiation stirring is essential.3. O.015. 46 . Nikolaiski. The solution completely absorbs the incident radiation in the wavelength range 334 – 395 nm. The system is suited as a polychromatic quantum counter independent of wavelength with ε324 ⋅ Φ = (629 ± 17) dm3 mol-1 cm-1 and Φ = 0. H. Phys. Schmidt) WR: 405 – 500 nm.3. Values of S = ε324 ⋅ Φ at particular irradiation wavelengths are given under L47* in section II. M. Values of S = ε383 ⋅ Φ at particular rradiation wavelengths are given under L57* in section II. 2. V = volume of the solution in dm3 (density = 1. J. 87 (1965) 1138-1140. Chem. Wani.4 (optical pathlength l = 1 cm) is filled into a spectrophotometric cell equipped with a magnetic stirring bar. Kling. E.575 g cm-3).12-diphenylnaphthacene in air-saturated Freon 113 (molar absorption coefficient ε383 = 873 dm3 mol-1 cm-1) of initial absorbance A383 = 1. Np (in einstein s-1) entering the sample cell is calculated by using the absolute value of the absorbance decrease at 324 nm upon irradiation (∆A324) and the following equation NP = ∆ A324 V ε 324 Φ t l with t = irradiation time in seconds. 67 (1963) 883-892. Bunsenges.16.6 × 10-3 M solution of 5. During irradiation stirring is essential..

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