Reaction volume of water formation detected by time-resolved photoacoustics: Photoinduced proton transfer between o-nitrobenzaldehyde and hydroxyls in water

被引:44
作者
Bonetti, G
Vecli, A
Viappiani, C
机构
[1] UNIV PARMA,DIPARTIMENTO FIS,I-43100 PARMA,ITALY
[2] UNIV PARMA,IST NAZL FIS MAT,I-43100 PARMA,ITALY
关键词
D O I
10.1016/S0009-2614(97)00291-1
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The structural volume changes accompanying light-induced proton transfer reactions in aqueous solutions. of o-nitrobenzaldehyde have been investigated using time-resolved photoacoustics. The solvation of the newly formed ions is accompanied by a contraction of the medium of about -5.2 +/- 0.2 ml/mol, At a pH above 9.5, the formation of water molecules leads to an expansion of 24.5 +/- 0.4 ml/mol. The apparent rate constant for the protonation of hydroxyls is k = (4.9 +/- 0.4) X 10(10) M-1 s(-1). This is the first direct time-resolved measurement of the extent of the structural volume changes accompanying water formation.
引用
收藏
页码:268 / 273
页数:6
相关论文
共 32 条
[1]   ACTIVATION AND REACTION VOLUMES IN SOLUTION [J].
ASANO, T ;
LENOBLE, J .
CHEMICAL REVIEWS, 1978, 78 (04) :407-489
[2]   LASER PHOTOLYSIS OF 2,6-DINITROTOLUENE IN SOLUTION [J].
ATHERTON, SJ ;
CRAIG, BB .
CHEMICAL PHYSICS LETTERS, 1986, 127 (01) :7-12
[3]  
ATKINS PW, 1989, PHYSICAL CHEM
[4]   TIME-RESOLVED PHOTOTHERMAL AND PHOTOACOUSTIC METHODS APPLIED TO PHOTOINDUCED PROCESSES IN SOLUTION [J].
BRASLAVSKY, SE ;
HEIBEL, GE .
CHEMICAL REVIEWS, 1992, 92 (06) :1381-1410
[5]   FAST CHANGES OF ENTHALPY AND VOLUME ON FLASH EXCITATION OF CHROMATIUM CHROMATOPHORES [J].
CALLIS, JB ;
GOUTERMAN, M ;
PARSON, WW .
BIOCHIMICA ET BIOPHYSICA ACTA, 1972, 267 (02) :348-+
[6]  
Drude P., 1894, Z PHYS CHEM, V15, P79, DOI DOI 10.1515/ZPCH-1894-1506
[7]   Photoacoustic evaluation of volume and entropy changes in energy and electron transfer. Triplet state porphyrin with oxygen and naphthoquinone-2-sulfonate [J].
Feitelson, J ;
Mauzerall, D .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (18) :7698-7703
[8]  
GENSCH T, 1996, IN PRESS J PHYS CHEM
[9]   PHOTOCHEMISTRY OF ORTHO-NITROBENZALDEHYDE AND RELATED STUDIES [J].
GEORGE, MV ;
SCAIANO, JC .
JOURNAL OF PHYSICAL CHEMISTRY, 1980, 84 (05) :492-495
[10]   THE DYNAMIC ASPECTS OF PROTON-TRANSFER PROCESSES [J].
GUTMAN, M ;
NACHLIEL, E .
BIOCHIMICA ET BIOPHYSICA ACTA, 1990, 1015 (03) :391-414