Published February 2008 | Version v1
Journal article Metadata-only

Thermodynamic characteristics of sublimation of aluminum and indium complexes with tetraphenylporphine according to the high-temperature mass spectrometry data

Creators

  • 1. Ivanovskij Inst. GPS MChS Rossii, Ivanovo (Russian Federation)
  • 2. RAN, Inst. Khimii Rastvorov, Ivanovo (Russian Federation)
  • 3. Ivanovskij Gosudarstvennyj Khimiko-Tekhnologicheskij Univ., Ivanovo (Russian Federation)

Description

The thermodynamic characteristics of vaporization of meso-tetraphenylporphine complexes (X)MTPP (M = Al, In; X = Cl, OH; TPP is the meso-tetraphenylporphine H2TPP dianion) were studied by the Knudsen effusion method with mass spectrometric control of vapor composition. Chloride complexes sublimed as monomers over the temperature range 480-590 K. The hydroxo complex of aluminotetraphenylporphine was transferred into the gas phase in the form of the μ-oxo dimer. The temperature dependences of saturated vapor pressure were used to determine the enthalpies of sublimation of metalloporphyrins, which were found to be 203 ± 3.5 and 207 ± 6 kJ/mol for the chloride complexes of In and Al, respectively, and 206 ± 8 and 406 ± 40 kJ/mol for the monomer and μ-oxo dimer of (hydroxy)aluminum(III)porphyrin, respectively. The thermodynamic parameters of vaporization and the melting point of (OH)AlTPP were also determined (ΔvapH0 = 116 ± 6 kJ/mol, ΔvapS0 = 72 ± 11 J/(mol K), and Tm = 579 K). Composition-thermodynamic property correlations were analyzed for metalloporphyrins

Abstract (Russian)

Эффузионным методом Кнудсена с масс-спектрометрическим контролем состава пара изучена термодинамика процессов парообразования комплексов мезо-тетрафенилпорфина (Х)МТРР (М = Аl, In; X = Сl, ОН; ТРР = дианион мезо-тетрафенилпорфина Н2ТРР). Установлено, что в интервале температур 480-590 К хлоридные комплексы сублимируют в мономерной форме. Показано, что гидроксо-комплекс алюминийтетрафенилпорфина при 658-719 К переходит в газовую фазу в виде μ-оксо-димера. Из температурных зависимостей давления насыщенного пара определены энтальпии сублимации металлопорфиринов, равные (203 ± 3.5) и (207 ± 6) для хлоридных комплексов In и Аl и (206 ± 8) и (406 ± 40) кДж/моль для мономера и μ-оксо-димера (гидрокси)алюмин (III)порфирина соответственно, а также термодинамические параметры испарения и температура плавления (OH)AlTPP (ΔиспH0=(116 ± 6) кДж/моль, ΔиспS0=(72 ± 11) Дж/(моль К), Тпл=579 К). Приведен анализ корреляции состав - термодинамические свойства для металлопорфиринов

Additional details

Additional titles

Original title (Russian)
Термодинамика сублимации комплексов алюминия и индия с тетрафенилпорфином по данным высокотемпературной масс-спектрометрии

Publishing Information

Journal Title
Zhurnal Fizicheskoj Khimii
Journal Volume
82
Journal Issue
2
Journal Page Range
p. 216-220
ISSN
0044-4537
CODEN
ZFKHA9

INIS

Country of Publication
Russian Federation
Country of Input or Organization
Russian Federation
INIS RN
39097400
Subject category
S37: INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY;
Resource subtype / Literary indicator
Numerical Data
Descriptors DEI
CHLORIDES; EVAPORATION; EXPERIMENTAL DATA; HYDROXIDES; INDIUM COMPLEXES; PORPHYRINS; SUBLIMATION HEAT; TEMPERATURE DEPENDENCE; TEMPERATURE RANGE 0400-1000 K; VAPOR PRESSURE
Descriptors DEC
CARBOXYLIC ACIDS; CHLORINE COMPOUNDS; COMPLEXES; DATA; ENTHALPY; HALIDES; HALOGEN COMPOUNDS; HETEROCYCLIC ACIDS; HETEROCYCLIC COMPOUNDS; HYDROGEN COMPOUNDS; INFORMATION; NUMERICAL DATA; ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXYGEN COMPOUNDS; PHASE TRANSFORMATIONS; PHYSICAL PROPERTIES; TEMPERATURE RANGE; THERMODYNAMIC PROPERTIES; TRANSITION HEAT

Optional Information

Notes
15 refs., 3 figs., 3 tabs.