Volume contraction 1.29

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 principal mechanism of the hypotensive effect of diuretics (qv) is salt and fluid depletion, leading to reduction in blood volume (200,240). Acute effects lead to a decrease in cardiac output and an increase in total peripheral resistance. However, during chronic adrninistration, cardiac output and blood volume return toward normal and total peripheral resistance decreases to below pretreatment values. As a result, the blood pressure falls. The usual reduction in blood volume is about 5%. A certain degree of sustained blood volume contraction has to occur before the blood pressure decreases. The usual decrease in blood pressure achieved using a diuretic is about 20/10 mm Hg (2.7/1.3 kPa) (systoHc/diastoHc pressures. 

Estimate the percentage volume contraction due to solidification in pure copper. Use the following data = 1083°C density of solid copper at 20°C = 8.96 Mg m ... 

Much of the interest in ring-opening polymerizations stems from the fact that the polymers formed may have lower densities than the monomers from which they are derived (i.e. volume expansion may accompany polymerization).168-171 This is in marked contrast with conventional polymerizations which typically involve a nett volume contraction. Such polymerizations are therefore of particular interest in adhesive, mold filling, and other applications where volume... 

Rare-earth ions inserted in the tetraborides have the 34- oxidation state, except for CeB4 and YbB4 (see Fig. 2). The abnormal volume contraction for the CeB4 unit cell can be explained by the presence of some Ce ions . Recoilless y-ray emission spectra and magnetic measurements indicate that ytterbium in YbB4 has an intermediate valence state as in YbAl3... 

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... 

Glass transition temperature (Tg), measured by means of dynamic mechanical analysis (DMA) of E-plastomers has been measured in binary blends of iPP and E-plastomer. These studies indicate some depression in the Tg in the binary, but incompatible, blends compared to the Tg of the corresponding neat E-plastomer. This is attributed to thermally induced internal stress resulting from differential volume contraction of the two phases during cooling from the melt. The temperature dependence of the specific volume of the blend components was determined by PVT measurement of temperatures between 30°C and 270°C and extrapolated to the elastomer Tg at —50°C. 

For preparation of solvent mixtures, the single solvents should be measured out separately and then properly mixed in a vessel with a ground glass stopper (avoidance of volume contraction and measuring errors). 

Note 285 mL (Vex) results from 200 mL of acetone and 100 mL of GPC eluting mixture minus 15 mL caused by volume contraction and by loss of acetone in the aqueous phase. 

SIADH (should distinguish between cerebral salt-wasting syndrome in which patients are volume-contracted)... 

The kidney is unable to adjust to abrupt changes in sodium intake in patients with severe CKD. Therefore, patients should be advised to refrain from adding salt to their diet, but should not restrict sodium intake. Changes in sodium intake should occur slowly over a period of several days to allow adequate time for the kidney to adjust urinary sodium content. Sodium restriction produces a negative sodium balance, which causes fluid excretion to restore sodium balance. The resulting volume contraction can decrease perfusion of the kidney and hasten the decline in GFR. Saline-containing intravenous (IV) solutions should be used cautiously in patients with CKD because the salt load may precipitate volume overload. 

It has to be noticed that no isothermal volume contraction on cooling or volume expansion on heating is associated with Tg, contrary to crystallisation or melting. The latter is a true first-order transition exhibiting a discontinuity in... 

Most probable positions of the chains are determined by the use of a characteristic vector r. This vector is representative of an average network chain of N links (the average links per chain). It deforms affinely whereas the actual network chains might not, and its value depends only upon network deformation. Crystallization leaves r essentially unaltered since the miniscule volume contraction brought about by crystallization can be ignored. But real network chains are severely displaced by crystallization. These displacements, however, must be compatible with the immutability of r. So in a sense, the characteristic vector r limits the configurational variations of the chains to those consistent with a fixed network shape and size at a given deformation. 

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... 

While for the as-synthesized sample, after the fulfilling of dehydration, no further volume variation is observed, for the exchanged phase after the ammonia release, the cell volume contraction rate quickly increases leading to a final volume decrease of 3.82%. This could be the consequence of the larger voids left in the channels of the latter phase, where, only protons are left in the channels of the dehydrate NH4-form. 

Change in dimensions of an unvulcanised rubber (calendered sheet or extruded section) on cooling from the processing temperature. Also the volume contraction of a moulded rubber product on cooling from vulcanising temperature. See Coefficient of Thermal Expansion (Volumej. Shrinking... 

Intuitively, one would expect a volume contraction on forming a strongly bonded compound from the elements. Indeed, Richards 190, 191) regarded heats of formation as heats of compression. The fractional volume contraction, AV = (molecular volume - 2 atomic vol-ume)/2(atomic volume), has been related to formation heats for NaCl or CsCl type structures 151). Even nonpolar compounds in the condensed state cohere in close-packed arrays. The packing density of difluorine, derived from the ratio of the van der Waals envelope to the molecular volume, is especially low, and a larger contraction would be expected for fluorides than for other halides. This approach has yet to be systematically examined. 

Compensation with inert gas to offset volume contraction... 

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