Title: “A new method to measure partial molar volumes of

binary gas mixtures”

Authors: P. A. Russell, B. A. Buffham, G. Mason, K. Hellgardt

 developed as a by-product of modification of an experiment for

measuring the gradient of viscosity with composition of gas mixtures at
low temperatures (emphasize non-ideal conditions) and provides direct
measurement of molar volume with more accurate results
 Perturbation viscometer: differential capillary viscometer (which
acts as a highly sensitive flowmeter) that measures logarithmic
viscosity gradient of the viscosity-composition curve for gas mixtures
and designed to run at temperatures going down to -30C to
accentuate non-ideal behavior of the gas mixture.
 Binary mixture: helium and pentafluoroethane (Suva-125) at 23C
and 1.11 bar (absolute)

EXPERIMENTAL PROCESS:
 Gas mixture has a composition flows at a molar flow rate M
passing through valve 2, ambient temperature delay line, cold delay
line, then finally to measuring capillary (main flow)

 Valve 1 is set to deliver another gas flow of composition to valve

2, where it goes straight to the purge stream at the same conditions
as the main experimental flow ( ).
 Valves 1 and 2 are switched simultaneously; the gas in the transfer
line is pushed in the main flow causing an increase in flow without a
change in composition

 The gas in the transfer line is pushed as a “slug” of gas (about one-
minute duration) in to the main flow, causing the composition of the
main flow to change to .
THEORY:
 Pressure drop across the measuring capillary

Poiseiulle equation for laminar flow:

 Conventional method of partial molar volume determination

- Density measurements

- Redlich-Kister equation:

 Flow Ratio:

 Change in flow due to perturbation

 Change in flow due to mixing

 Mass balance across the perturbation valve

 Molar volume-composition curve

 Partial molar volume: pure component perturbation flows:

Pure A added to main flow of composition

Pure B added to main flow of composition

Change of molar volume due to mixing:

 Small perturbation flow rates:

 Large perturbation flow rates:

EXPERIMENTAL RESULTS:
 Two sets of data were reported:
o Small perturbation flows at 0.1 nominal mole fraction intervals
across the composition range
o Large perturbation flows of each pure gas
 Both data sets show remarkable agreement
 Data sets lie within range of values predicted using the Redlich-
Kwong and Soave-Redlich-Kwong equations of state.
 Perturbation flow of helium was added to- then removed from- a
HFC-125 main gas flow.

P0  P1 : due to increase in flow when perturbation is added

P1  P2 : volume change on mixing of the two gas flows
P2  P3 : change in thermal expansivity of gas in cold block
P3  P4 : increase in viscosity due to increase in helium mole fraction
P4  P5 : decrease in flow when perturbation is removed
P5  P6 : change in thermal expansivity of gas in cold block
P6  P7 : decrease in viscosity due to decrease in helium mole fraction
 FIFTEENTH SYMPOSIUM ON
THERMOPHYSICAL PROPERTIES
Boulder, CO, USA

June 22 - 27, 2003

Organized by

 National Institute of Standards and Technology

 Committee on Thermophysical Properties
Heat Transfer Division
American Society of Mechanical Engineers

http://symp15.nist.gov/