The Water Activity

A variety of methods have been devised to stabilize shales. The most successful method uses an oil or synthetic mud that avoids direct contact between the shale and the emulsified water. However, preventing direct contact does not prevent water uptake by the shale, because the organic phase forms a semipermeable membrane on the surface of the wellbore between the emulsified water in the mud and the water in the shale. Depending on the activity of the water, it can be drawn into the shale (activity lower in the shale) or into the mud (activity higher in the shale) (95—97). This osmotic effect is favorable when water is drawn out of the shale thus the aqueous phase of the oil or synthetic mud is maintained at a low water activity by a dding a salt, either sodium chloride or more commonly, calcium chloride. The salt concentration is carried somewhat above the concentration required to balance the water activity in the shale to ensure water movement into the mud. 

Addition of a salt can transform the shale by cation exchange to a less sensitive form of clay, or reduce the osmotic swelling effect by reducing the water activity in the mud below that which occurs in the shale. These effects depend on the salt concentration and the nature of the cation. Salts containing sodium, potassium, calcium, magnesium, and ammonium ions ate used to varying degrees. 

Other factors also impact the type of crystals formed upon cooling of hot soap. Water activity or moisture content contribute to the final crystal state as a result of the different phases containing different levels of hydration. Any additive that changes the water activity changes the crystallization pathway. For example, the addition of salt reduces the water activity of the mixture and pushes the equiUbrium state toward the lower moisture crystal stmcture. Additionally, the replacement of sodium with other counter cations influences the crystallization. For example, the replacement of sodium with potassium drives toward the formation of 5-phase. 

The rate of aspartame degradation in dry mixes is more dependent on the water activity than on the temperature (23). In dry mixes, aspartame may also engage ia Maillard reactions with the aldehyde moieties of flavoting agents, resulting ia the loss of sweetness and flavor. Use of the corresponding acetals of the flavor compounds to avoid this reaction has been reported (24). 

In this process the addition of water vapor to the sweep stream can be controlled so that the water activity of the gas phase equals that of the beverage. When this occurs, there is no transport of water across the membrane. The water content of both the beverage feed and the sweep stream is kept constant. These conditions must be maintained for optimum alcohol reduction. The pervaporation system controls the feed, membrane, airstream moisture level, and ethanol recovery functions. An operational system has been developed (13). 

The increase at low acid concentrations is due to catalysis the decrease at high acid concentrations is due to reduction in the water activity. 

When either the organic solvent or the ionic liquid is used as pure solvent, proper control over the water content, or rather the water activity, is of crucial importance, as a minimum amount is necessary to maintain the enzyme s activity. For ionic liquids, a reaction can be operated at constant water activity by use of the same methods as established for organic solvents [17]. [BMIM][PFg] or [BMIM][(CF3S02)2N], for example, may be used as pure solvents and in biphasic systems. Water-miscible ionic liquids, such as [BMIM][BF4] or [MMIM][MeS04], can be used in the second case. 

To maintain enzymatic activity a minimal amount of water has to be present, best described by the water activity. However, water present in the reaction system may cause hydrolysis of some ionic liquids. 

Further studies of Pseudomonas sp. lipase revealed a strong influence of the water content of the reaction medium (Entry 20) [48]. To be able to compare the enzyme activity and selectivity as a function of the water present in solvents of different polarities, it is necessary to use the water activity (a ) in these solvents. We used the... 

The commercial samples of pectins mainly used as food additives represent modified forms of the natural polymers due to the conditions of extraction. Nevertheless, it is usually recognized two categories of pectins the high methoxyl pectins (HM) with a degree of methylation DM>50% forming gels at low pH in presence of saccharose to reduce the water activity and the low methoxyl pectins (LM with DM<50%) forming gel in presence of calcium [4]. 

The availability of water, i.e. the water activity, in a material is of great importance for its biological and biochemical properties. It depends both on the water content, and significantly on the nature of the structural bond of water molecules, in other words, how strongly they are retained by the matrix. Thus, for similar water contents, when determined by Karl Fischer titration, quite different water activities may be obtained for different materials. This is of paramount importance for RM stability. 

Figure 2.4 shows the equilibrium relationships of biological materials between the water content and the water activity, at constant temperatures and pressures. These data were first published in 1971, but did not find much attention in the RM field until now. At equilibrium the water activity is related to the relative humidity cp of the surrounding atmosphere (Equation 2.3) where p is the equihbrium water vapor pressure exerted by the biological material and po the equilibriiun vapor pressure of pure water at the same temperature. 

Thus, in the observation of the drying process of biological materials, the water activity is at least as valuable as the water content of a material. As water activity measurements are complete in about 3 min, they represent a useful tool for control of the drying process. 

BCR CRM 402 Trace Elements in White Clover 0, = 0.456 at 2i.r°C w.c. = 7.52 0.04%. Despite its relatively high value, the water activity is still in the range for long-term stability and major differences in the water content as a consequence of sorption processes are not to be expected. This is supported by the fact that no spoilage has been observed, even though the production was in 1987. 

BCR RM 40 Wholemeal Wheat Flour a <0.03 w.c. = 1.70 + 0.04 %. It is important to note that this material is likely to have handling problems due to its hygroscopic behavior. The water activity is in the range where the monomolecular surface layer of water may be removed. Thus, deterioration of the lipids is hkely to occur during storage. 

These examples illustrate that, for many materials, the water content can be relatively high without leading to any material instability dmring shelf life, which depends on the water-bonding capacity of the material. When water is strongly retained, the water activity and thus the amount of free water will be low. It must be mentioned that this is quite contradictory to some former and still presently reported assumptions that the water content of CRMs should generally not exceed a rather low value, e.g. around 3 % for long-term stability of RMs. 

For protonation-dehydration processes, such as trityl cation formation from triphenylcarbinols, equation (24), the water activity has to be included if the formulation of the activity coefficient ratio term is to be the same as that in equation (7), which it should be if linearity in X is to be expected see equation (25). The excess acidity expression in this case becomes equation (26) this is a slightly different formulation from that used previously for these processes,36 the one given here being more rigorous. Molarity-based water activities must be used, or else the standard states for all the species in equation (26) will not be the same, see above. For consistency this means that all values of p/fR listed in the literature will have to have 1.743 added to them, since at present the custom... 

Now a very useful feature of the excess acidity method comes into play likely nucleophiles or bases can be tested by subtracting their log activities or concentrations from the left-hand side of equations (59) and (60), and the species reacting with SH+ is uniquely identified when linearity of the result against X is achieved.145,161 For instance, subtraction of twice the water activity is required to attain linearity in ester hydrolysis processes such as equation (42), as shown in Fig. 11 for methyl benzoate41 and ethyl benzoate.210 The water activities given in Table 3 were used. The parameters of the lines in Fig. 11, obtained by curve-fitting, are methyl benzoate, slope 0.921 + 0.010, intercept... 

In contrast to the above, other reactions have been found to require base assistance by water in the rate-determining step, i.e. the water activity does appear in the rate law. The mechanism formulated for the condensation of acetaldehyde in sulfuric acid is given in equation (63), following on from the enolization of Scheme 7, subsequent dehydration to crotonaldehyde occurring as shown in Scheme 8. The ky k2, k3 and k 3 steps shown were all studied.246... 

This term is normally abbreviated to ERH. The ERH is deduced by extrapolating the weight loss values over a range of water activities greater and lesser than that of the product. Where the two lines intersect lies the water activity of the product. This extremely tedious and time consuming method has largely been superseded by instruments that measure the water activity directly. The ERH still has practical importance since it indicates the conditions under which the product can be stored without deterioration. 

As an example, Cauvain and Young give figures for the water activity of the components of savoury pies such as pork pies as pastry (0.24), jelly (0.99), and filling (0.98).4 The jelly and the filling clearly have nearly matched water activities so migration is unlikely to be a problem. 

There are two ways of preventing this problem, the first is to modify the high water activity material or provide a barrier layer the second is to decrease the water activity of the material that is in contact. Examples of this sort of problem are ice cream in contact with a wafer, caramel in contact with a wafer and the filling and the pastry of an apple pie. 

In practice, to maintain the right texture of a bakery product the water activity has to remain low. Therefore, the only way of matching the water activity of the two components is to lower the water activity of the other component. 

Traditionally, butter was made by allowing cream to separate from the milk by standing the milk in shallow pans. The cream is then churned to produce a water in oil emulsion. Typically butter contains 15% of water. Butter is normally made either sweet cream or lactic, also known as cultured, and with or without added salt. Lactic butter is made by adding a culture, usually a mixture of Streptococcus cremoris, S. diacetylactis and Betacoccus cremoris. The culture produces lactic acid as well as various flavouring compounds, e.g. diacetyl, which is commonly present at around 3 ppm. As well as any flavour effect the lactic acid inhibits any undesirable microbiological activity in the aqueous phase of the butter. Sweet cream butter has no such culture added but 1.5 to 3% of salt is normally added. This inhibits microbiological problems by reducing the water activity of the aqueous phase. It is perfectly possible to make salted lactic butter or unsalted sweet cream butter if required. In the UK most butter is sweet cream while in continental Europe most butter is lactic. 

Drying out can be prevented in one of two ways, either by packaging or by lowering the water activity of the product. Starch retrograda-tion can be inhibited by using a starch complexing emulsifier with or without the addition of fat. Mould growth is inhibited by a low water activity. 

Notably, low water activity only inhibits mould growth. Most bakery products leave the oven in a sterile condition, any mould contamination is subsequent to baking. The effect of a low water activity is that the osmotic pressure is such that no mould spores can reproduce. Thus the product is safe unless the water activity rises locally. 

There is a practice of making holes in this sort of cake and pouring in spirits such as whisky, brandy or rum. While this may be done to enhance the flavour it will almost certainly improve the keeping properties. The alcoholic mixture will not only reduce the water activity as ethanol has considerable mould inhibitory and antibacterial properties. 

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