Isotope effects of simple fluids. Pressure-volume-temperature properties of C/sub 6/H/sub 6//C/sub 6/D/sub 6/, (CH/sub 3/)/sub 2/CO/(CD/sub 3/)/sub 2/CO, and CH/sub 3/OH/CH/sub 3/OD from 0. 1 MPa and 298 K to critical conditions or to 570 K and 6 MPa, whichever is less

Journal Article · Thu Nov 03 00:00:00 EST 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100333a045· OSTI ID:6259894

Kooner, Z S; Van Hook, W A

Vapor pressures, liquid compressibilities, expansivities, and molar volumes have been measured at high precision for perprotio- and perdeuteriobenzene and -acetone and for CH/sub 3/OH and CH/sub 3/OD, between room temperature and the critical temperature (or the temperature that corresponds to 6 x 10/sup 6/ Pa, whichever is lower). Vapor nonidealities, ..integral../sub 0//sup P/(V/sub v/ - RT/P) dP = ..integral../sub 0//sup P/..cap alpha../sub v/ dP, were measured for each compound and its isotopic isomer but only for samples of high vapor density. These various results, together with data from other laboratories for the CH/sub 4//CD/sub 4/ and H/sub 2/O/D/sub 2/O systems, are discussed in terms of the statistical theory of isotope effects in condensed phases. For each system investigated the sum, SUM = ln (P/degrees/'/P/degrees/) - (P/degrees/'V/degrees/' - P/degrees/v/degrees/)/RT + ..integral../sub 0//sup po'/ ..cap alpha../sub v/' dP - ..integral../sub 0//sup po'/ - ..cap alpha../sub v/' dP/RT, tends to zero within experimental precision in the critical region. This establishes that these samples of separated isotopes are in the congruent state when they are at identical temperatures and displaying their equilibrium molar volumes and vapor pressures. The high-temperature volumetric properties can be calculated from the vapor pressure and low-temperature molar volume isotope effects, provided the isotope effect on the coefficient of thermal expansion is available. That isotope effect is determined by anharmonicity in the vibrational part of the partition functions.

• Research Organization: Univ. of Tennessee, Knoxville (USA)
• OSTI ID: 6259894
• Journal Information: J. Phys. Chem.; (United States), Vol. 92:22
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETONE
ISOTOPE EFFECTS
BENZENE
DEUTERIUM COMPOUNDS
ETHANOL
EXPERIMENTAL DATA
HIGH TEMPERATURE
MEDIUM PRESSURE
MEDIUM TEMPERATURE
PRESSURE EFFECTS
TEMPERATURE EFFECTS
VAPOR PRESSURE
VOLUME
ALCOHOLS
AROMATICS
DATA
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
KETONES
NUMERICAL DATA
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
THERMODYNAMIC PROPERTIES
400202* - Isotope Effects
Isotope Exchange
& Isotope Separation