Atmosphere equilibrium with

Water in contact with either the atmosphere or carbonate-bearing sediments contains dissolved or free CO2 that exists in equilibrium with gaseous CO2 and the aqueous carbonate species H2CO3, HCO3A and. The concentration of free... 

Equilibrium moisture content of a solid is particularly important in drying because it represents the limiting moisture content for given conditions of humidity and temperature. If the material is dried to a moisture content less than it normally possesses in equilibrium with atmospheric air, it will return to its equilibrium value on storage unless special precautions are taken. 

The charging process is affected by atmospheric moisture only to the extent that the moisture comes to equilibrium with the contacting surfaces. 

PRESSURE SYSTEM Defined in the Pressure System Safety Regulations 2000 as a system containing one or more pressure vessels of rigid construction, any associated pipework and protective devices the pipework with its protective devices to which a transportable gas container is, or is intended to be, connected or a pipeline and its protective devices which contains or is liable to contain a relevant fluid, but does not include a transportable gas container. Here relevant fluid is steam any fluid or mixture of fluids which is at a pressure of >0.5 bar above atmospheric pressure, and which fluid or a mixture of fluids is a gas, or a liquid which would have a vapour pressure of >0.5 bar above atmospheric pressure when in equilibrium with its vapour at either tlie actual temperature of the liquid or 17.5°C or a gas dissolved under pressure in a solvent contained in a porous substance at ambient temperamre and which could be released from the solvent with the application of heat. 

Kotas [3] has drawn a distinction between the environmental state, called the dead state by Haywood [1], in which reactants and products (each at po. To) are in restricted thermal and mechanical equilibrium with the environment and the truly or completely dead state , in which they are also in chemical equilibrium, with partial pressures (/)j) the same as those of the atmosphere. Kotas defines the chemical exergy as the sum of the maximum work obtained from the reaction with components atpo. To, [—AGo], and work extraction and delivery terms. The delivery work term is Yk k kJo ln(fo/pt), where Pii is a partial pressure, and is positive. The extraction work is also Yk kRkTo n(po/Pk) but is negative. 

Phosphorus (like C and S) exists in many allotropic modifications which reflect the variety of ways of achieving catenation. At least five crystalline polymorphs are known and there are also several amorphous or vitreous forms (see Fig. 12.3). All forms, however, melt to give the same liquid which consists of symmetrical P4 tetrahedral molecules, P-P 225 pm. The same molecular form exists in the gas phase (P-P 221pm), but at high temperatures (above 800°C) and low pressures P4 is in equilibrium with the diatomic form P=P (189.5 pm). At atmospheric pressure, dissociation of P4 into 2P2 reaches 50% at 1800°C and dissociation of P2 into 2P reaches 50% at 2800°. 

Soluble corrosion products may increase corrosion rates in two ways. Firstly, they may increase the conductivity of the electrolyte solution and thereby decrease internal resistance of the corrosion cells. Secondly, they may act hygroscopically to form solutions at humidities at and above that in equilibrium with the saturated solution (Table 2.7). The fogging of nickel in SO2-containing atmospheres, due to the formation of hygroscopic nickel sulphate, exemplifies this type of behaviour. However, whether the corrosion products are soluble or insoluble, protective or non-protective, the... 

Capillary condensation The vapour pressure above a concave meniscus of water is less than that in equilibrium with a plane water surface. It is therefore possible for moisture to condense in narrow capillaries from an atmosphere of less than 100% r.h. 

Chemical condensation This occurs when soluble corrosion products or atmospheric contaminants are present on the metal surface. When the humidity exceeds that in equilibrium with a saturated solution of the soluble species, a solution, initially saturated, is formed until equilibrium is established with the ambient humidity. The contaminants have already been detailed and of the corrosion products, obviously sulphates, chlorides and carbonates are most important in this context. However, in some cases there is a lack of reliable data on the vapour pressure exerted by saturated solutions of likely corrosion products. The useful data was summarised in Table 2.7. 

Sea water of normal salinity, in equilibrium with the atmosphere, has the following oxygen contents (compare Table 2.14) ... 

The obvious method of reducing corrosion in fused salts is to choose a system in which either the metal can come to equilibrium with the melt, or else truly protective passivity can be attained. In most cases in industry neither of these alternatives is used. In fact, fused salt baths are usually operated in air atmosphere, and the problem is the prevention of excessive corrosion. This can be done in two ways, (a) by reducing rates of ingress of oxidising species (mainly O2 and H2O) from the atmosphere, and rates of their diffusion in the melts, and (b) by keeping the oxidising power (redox potential) of the melt low by making periodic additions to the bath. 

Table 21.21 Oxygen dissolved in sea-water in equilibrium with a normal atmosphere (101 325 N m" ) of air saturated with water vapour ...

Table 21.22 Saturated solubilities of atmospheric gases in sea-water at various temperatures Concentrations of oxygen, nitrogen and carbon dioxide in equilibrium with 1 atm (lOI 325 N m ) of designated gas...

It is necessary to draw attention to the variable pH of water which may be encountered in quantitative analysis. Water in equilibrium with the normal atmosphere which contains 0.03 per cent by volume of carbon dioxide has a pH of about 5.7 very carefully prepared conductivity water has a pH close to 7 water saturated with carbon dioxide under a pressure of one atmosphere has a pH of about 3.7 at 25 °C. The analyst may therefore be dealing, according to the conditions that prevail in the laboratory, with water having a pH between the two extremes pH 3.7 and pH 7. Hence for indicators which show their alkaline colours at pH values above 4.5, the effect of carbon dioxide introduced during a titration, either from the atmosphere or from the titrating solutions, must be seriously considered. This subject is discussed again later (Section 10.12). 

Rain in equilibrium with atmospheric C02, but uncontaminated by industrial emissions, should have a pH of 5.7. However, atmospheric pollution from burning fossil fuels has resulted in acid rain of pH as low as 3.5 (24). If this condition continues for a long time, it may lead to a change in groundwater composition, which may considerably change the migration of plutonium in nature. 

In a packed column, operating at approximately atmospheric pressure and 295 K, a 10% ammonia-air mixture is scrubbed with water and the concentration of ammonia is reduced to 0.1%. If the whole of the resistance to mass transfer may be regarded as lying within a thin laminar film on the gas side of the gas-liquid interface, derive from first principles an expression for the rate of absorption at any position in the column. At some intermediate point where the ammonia concentration in the gas phase has been reduced to 5%. the partial pressure of ammonia in equilibrium with the aqueous solution is 660 N/nr and the transfer rate is ]0 3 kmol/m2s. What is the thickness of the hypothetical gas film if the diffusivity of ammonia in air is 0.24 cm2/s ... 

The greenhouse effect is a natural phenomenon whereby the earth s atmosphere is more transparent to solar radiation than terrestrial infixed radiation (emitted by the earth s surface and atmosphere). Consequently, the planet s mean surface temperature is about 33 K higher than the planet s radiative equilibrium temperature (the temperature at which the earth comes into equilibrium with the energy received from the sun). 

In the case of CO2 one must consider the hydrated form (H2CO3) and the non-hydrated form, C02(aq). This latter form is in equilibrium with the atmosphere ... 

As discussed in Chapter 6, water forms strong hydrogen bonds and these lead to a number of important features of its atmospheric behavior. All three phases of water exist in the atmosphere, and the condensed phases can exist in equilibrium with the gas phase. The equilibria between these phases is summarized by the phase diagram for water. Fig. 7-9. 

In the ocean, inert gas concentrations tend to follow the temperature solubility dependence closely. This suggests that water parcels obtain their gas signatures when they are at the seasur-face close to equilibrium with the atmosphere at ambient temperature. 

Ripening seeds, except where they are enclosed in fleshy fruit, lose water until their water content is in equilibrium with atmospheric humidity and at this stage they contain 5-20% water. The water contents of some seeds can be reduced still further with no adverse effects on viability, rather this can enhance their survival in the dried state (Roberts, 1973). The longevity of seeds in this anhydrobiotic state can be prodigious, lasting for several hundred years (Priestley Posthumus, 1982). 

With a sparingly soluble gas a much higher partial pressure of that gas is in equilibrium with a solution of a given concentration than is the case with a highly soluble gas. Exposure of a solution to any atmosphere will lead to the take-up, or release, of gas until equilibrium is eventually attained. 

A vapor pressure is the pressure exerted by a gas in equilibrium with its condensed phase. When this equilibrium has been reached, the gas is saturated with that particular vapor. Notice in Table 5A that at 25 °C the atmosphere is saturated with water vapor when the partial pressure of H2 O is 23.756 torr. At this pressure, the molecular density of H2 O in the gas phase is sufficient to make the rate of condensation equal to the rate of evaporation. Any attempt to add more water molecules to the gas phase results in condensation to hold the partial pressure of H2 O fixed at 23.756 torr. 

The Earth s atmosphere contains 78% N2,21% O2, and minor amounts of other gases, including CO2 (0.0325%). Determine the concentrations of N2, O2, and CO2 in water at equilibrium with the Earth s... 

Each gas establishes its own dynamic equilibrium with water. The concentration depends on the partial pressure of the gas in the atmosphere and on the value of its Henry s law constant at 25 °C. Recall from Chapter 5 that the partial pressure of any gas in a mixture is given by the mole fraction (X multiplied by total pressure. 

C12-0011. What are the concentrations of these gases in water at equilibrium with the atmosphere at 30 °C ... 

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