VOLUME CONTRACTION Subject

In discussing Fig. 4.1 we noted that the apparent location of Tg is dependent on the time allowed for the specific volume measurements. Volume contractions occur for a long time below Tg The lower the temperature, the longer it takes to reach an equilibrium volume. It is the equilibrium volume which should be used in the representation summarized by Fig. 4.15. In actual practice, what is often done is to allow a convenient and standardized time between changing the temperature and reading the volume. Instead of directly tackling the rate of collapse of free volume, we shall approach this subject empirically, using a property which we have previously described in terms of free volume, namely, viscosity. 

The drying protoplast will be subjected to tension as the result of volume contraction and its adherence to the cell wall. Early observations (Steinbrick, 1900) on desiccation tolerant species showed that the protoplasm does not separate from the wall, but rather that it folds and cavities develop in the wall. Where there are thick-walled cells, localised separation of the plasmalemma from the wall may occur. It seems unlikely, however, that rupture of the plasmalemma normally occurs during desiccation. A more subtle form of membrane damage may arise from dehydration-induced conformational changes. Certainly it is relatively easy to demonstrate that dehydrated membranes exhibit a loss of functional integrity... 

The variation of the unit cell parameters versus temperature is reported in Figure 2. For the as-synthesized sample, at room temperature, the cell parameter are a=7.5675, b=l 8.1187, c=26.0605 A and the cell volume is 3573.2 A3. In the first step of heating (T <120 °C) only small variation of the cell parameters are shown. The volume variation is mostly due to the c parameter shortening, since it is the most subjected to temperature induced modifications. Between 120 and 360 °C a remains almost constant, c decreases of 0.1%, while b slightly increase-up to 215 °C- and subsequently regains its initial value. The combination of these variations leads an inflection in the volume contraction, slowing down its decrease. Above 390 °C the cell volume remains almost constant and only minor variations in the parameters are observed. The final values obtained after the refinement at 715 °C accounted a variation of -0.25, +0.07, -0.77 and -0.95% for a, b, c and V respectively. The minor variation of the cell parameters above 450 °C indicates that at this temperature the dehydration process is almost fulfilled. The TG curve in flowing air shows that the total mass variation of the as-synthesized phase is 15.8%. Dehydration process is almost fulfilled at about 500 °C above this temperature only... 

Reduction in volume (volume contraction) values typically lie between 0.2% and 2%, subject to plastics grades processed... 

C is a reduction factor since the gas which passes at a high velocity through the orifice, is subject to a volume contraction downstream of the orifice ( vena contracta ). 

Meters are accurate within close limits as legislation demands. However, gas is metered on a volume basis rather than a mass basis and is thus subject to variation with temperature and pressure. The Imperial Standard Conditions are 60°F, 30inHg, saturated (15.56°C, 1913.7405 mbar, saturated). Gas Tariff sales are not normally corrected, but sales on a contract basis are. Correction may be for pressure only on a fixed factor basis based on Boyle s Law or, for larger loads, over 190,000 therms per annum for both temperature and pressure using electronic (formerly mechanical) correctors. For high pressures, the compressibility factor Z may also be relevant. The current generation of correctors corrects for pressure on an absolute basis taking into account barometric pressure. 

Dilatometer Basically it is a pyrometer equipped with instruments to study density as a function of temperature and/or time. It can measure the thermal expansion or contraction of solids or liquids. They also study polymerization reactions it can measure the contraction in volume of unsaturated compounds. It basically is a technique in which a dimension of a material under negligible load is measured as a function of temperature while it is subjected to a controlled temperature program. 

The techniques used for handling various materials depend on their physical states as well as their chemical properties. While it is comparatively easy to handle liquids and solids, it is not as convenient to measure out a quantity of a gas. Fortunately, except under rather extreme conditions, all gases have similar physical properties, and the chemical identity of the substance does not influence those properties. For example, all gases expand when they are heated in a nonrigid container and contract when they are cooled or subjected to increased pressure. They readily diffuse through other gases. Any quantity of gas will occupy the entire volume of its container, regardless of the size of the container. 

This inward attraction causes the surface to diminish in area, because the surface molecules are continually moving inwards more rapidly than others move outwards to take their places the number. of molecules in the surface is therefore continually diminishing, and the contraction of the surface continues until the maximum possible number of molecules are in the interior, i.e. until the surface is the smallest possible for a given volume, subject to the external conditions or forces acting on the drop. 

After many experiments with chemical reactions in which gases are involved w ere carried out, it was recognized about a hundred years ago that equal volumes of different gases contain the same number of molecules. This statement, together xvith the quantitative expression Of the fact that gases expand in volume vhen they are heated and contract in volume when they are subjected to increased pressure, constitutes the gas laws, which will be treated in Chapter 8. 

In 104 healthy men (mean age 29 years, weight 60 kg) who took tafenoquine for malaria prophylaxis (loading dose 400 mg/day for 3 days followed by 400 mg/month in 5 consecutive months) age and weight affected the apparent volume of distribution, and subjects who contracted malaria had higher clearance rates (3). The population estimate of the first-order absorption half-life was 1.0 hour, clearance was 3.20 1/hour, volume of distribution was 1820 liters, and half-life was 16.4 days. 

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