Values of chemical potential
Soil water management and irrigation practices largely depend on a timely and accurate characterization of temporal and spatial soil moisture dynamics in the root zone. Consequently, measurements and detailed information about soil water sorption, water content, behavior, and potential are required. In that concern, water vapor adsorption is an important phenomenon in arid and semi-arid regions, as well as in dry periods of tropical soils. Therefore, quantifying adsorption is important for agricultural water management, surface energy balance studies, ecological studies, and remote sensing investigations (changes in surface soil moisture content will affect land surface properties such as albedo, emissivity, and thermal inertia). The vapor pressure and isothermal adsorption of water vapor can be used to predict soil moisture adsorption capacity (Wa), specific surface area, and hydro-physical properties of arid soils such as in Egypt and in the tropical soils in Ecuador. Theory of adsorption of water vapor on soil particles is developed among the mono-molecular and poly-molecular adsorption with respect to Brunauer, Emmett, and Teller (BET) theory. Data of soil-water adsorption (W%) at different relative vapor pressures (P/Po) can be obtained for the soils, where the W% values are increased with increasing P/Po in general. The highest values of water adsorption capacity (Wa), specific surface area (S), and other hygro-physical properties such as adsorbed layers and maximum hygroscopic water are observed in the clay depths of soil profiles, while the lowest values can be found in coarse textured soils (sandy and sandy loam soils profiles). Two equations were assumed: (1) to predict P/Po at water adsorption capacity (Wa) and (2) to apply Wa in prediction of soil moisture retention, i.e., ψ (W) function at pF < 4.5.
- Water adsorption capacity
- vapor pressure isotherm
- soil hydro-physical properties
- specific surface area
- poly-molecular adsorption
- soil wetting
The depletion in irrigation water in arid and semi-arid regions, as well as in some tropical zones, may be due to the discharge scarcity of water resources in dry periods at which the high temperature and dry weather supports to more evapotranspiration. In that concern, water vapor is adsorbed from the atmosphere by a thin layer of top soil where the amounts of adsorbed water can be considerable, up to 70% of daily evaporation depending on water vapor amount, pressure, and temperature [20, 17, 1].
Adsorbed water on soil surface layer can be caused not only by vapor adsorption but also by dew deposition. Dew deposition is a phenomenon recorded for most soil and climate types . It occurs with decreasing the temperature, particularly during the night, when dew point is reached and it results in a discernible wetting of the surface.
The vapor pressure and isothermal adsorption of water vapor is used to predict soil moisture adsorption capacity (
2. Water vapor pressure
According to the kinetic theory, molecules in a liquid are in continuous motion reflecting their thermal energy. Occasionally, one or another of the molecules absorbs sufficient momentum to leap out of the liquid into the atmosphere above it. The relative movement rates of molecules depend upon the concentration of vapor in the atmosphere relative to its concentration at a state of equilibrium (i.e., when the movement in both directions of water and air is equal). An atmosphere that is at equilibrium with a body of pure water that is at atmospheric pressure is considered to be saturated with water vapor; the partial pressure of the vapor in such an atmosphere is called the saturation (or equilibrium) vapor pressure. The vapor pressure at equilibrium with any body of water depends upon the physical condition of the water (pressure and temperature) and its chemical condition (solutes), but does not depend on the absolute or relative quantity of liquid or gas in the system . The saturation vapor pressure increases with increasing temperature. If the temperature range is not too wide, the dependence of saturation vapor pressure on temperature is expressible by the equation:
3. Atmospheric humidity
Air humidity is expressed by either absolute humidity, which is known by estimation of the amount of water vapor already existing in unit volumes of air, or relative humidity, which is estimated as a percentage of the amount water vapor already existing in unit volumes of air and the amount of water required for the steam to satisfy this volume of air at the same temperature. Generally, the water vapor percentage change from one place to another is less significant in desert areas due to the lack of water, as well as in the polar regions where it is much colder and there is less evaporation and less possibility of the air to bear the water vapor; while water vapor is higher in the air in warm, rainy, and tropical regions . On the other hand, the water vapor density decreases with height greater than the density of the main constituent gases of the air, i.e., when rising from 1.5 to 2 km above sea level, water vapor density is less twice than that of atmospheric layer in contact with the surface of the earth, and vanish at altitudes of more than 10–15 km . In general, at all times and at different temperatures a part of water vapor remains in a gaseous phase even with predominance of condensation in the air. Therefore, water vapor is considered as one of the air gases component, and has a significant pressure like the rest of the gases in the atmosphere. This pressure (P) is linked to the quantity water vapor (Q) by the relationship :
where α represents volumetric expansion coefficient of air (α = 0.004), and T is air temperature. From the relationship, it is clear that Q = P when the temperature rises to 15oC, and thus relative humidity can be expressed in terms water vapor pressure rather than mass (quantity), i.e, relative humidity = actual pressure (P)/pressure saturated (P0).The difference between saturated vapor pressure and actual vapor pressure is represented in the lack of air humidity, which is known as lack of saturation (or saturation deficit). The lack of saturation is equal to zero at the dew point, which means that the air could not carry other amounts of water vapor. The dew point can be obtained when the temperature is reduced to the degree at which the condensation of water vapor begins, and then the saturation pressure is reached. Thus, relative humidity can be expressed as a percentage of the saturated water vapor pressure at the dew point (i.e., at the temperature of condensation) to the saturated water vapor pressure at normal temperature. Thus, it is clear that the saturation of the air with water vapor is directly influenced by air temperature degree.
4. Water vapor and soil humidity
Water vapor either reaches the soil from the atmosphere or is formed in the soil by the evaporation of water. The migration of water vapor in soil depends not only on the difference of vapor pressure in different sites, but also on the capacity of soil particle surfaces to attract and absorb the molecules of vapor.
However, soil water contains solutes—mainly electrolytic salts—in highly variable concentrations. Since the vapor pressure of electrolytic solutions is lower than that of pure water, accordingly, soil water also has a lower vapor pressure even when the soil is saturated. In an unsaturated soil, the capillary and adsorptive effects further lower the potential and the vapor pressure.
A distinction should be made between
On contact of soil particles with water vapor, electro-molecular force of interactions are formed that strongly attract dipoles of water to the surface of mineral particles; and the greater the unit surface area of the particles, the larger the number of water molecules in a bonded state.
5. Soil moisture films and adsorption capacity
The electro-molecular force is very strong, as much as several hundreds of mega-Pascal (MPa) for the first layer of bonded (adsorbed) molecules of water at the surface of particles. In the layers of water, the 1–3 rows of molecules that are closest to the mineral particle surface are firmly immobile adsorbed water or the so-called
Amer  studied the molecules layers of the adsorbed films and proved that the three layers of adsorbed water can be expressed in term of soil moisture adsorption capacity (Wa) in the following form:
The property of moisture adsorption capacity (
The moisture adsorption capacity (
6. Adsorption isotherms and BET theory
The relationship between vapor pressure and moisture content is difficult to be deduced by means of thermodynamics but can be obtained experimentally or from theories of soil moisture involving the molecular structure of the water films, whereas, soil sample is maintained in equilibrium with an atmosphere of water vapor, a thin film of moisture is adsorbed on the external surface of the soil particles. So the water vapor adsorption isotherms (at 25oC) on dried soil particles can be determined gravimetrically using different saturated salt solutions that have specific relative water vapour pressure (P/Po) value for each solution. Table 1 shows the values of P/Po for some saturated solutions of salts and also the corresponded chemical potential or its equivalent pressure at 25oC .
The vapor adsorption isotherms, specific surface area, moisture adsorption capacity, and hygroscopic parameters of soil have been found to be correlated with soil physical properties such as texture, cohesion, clay percentage, clay minerals, cation exchange capacity, water retention, and permeability. Figure 1 shows the water vapor adsorption isotherms for sandy soils, located at Mláky II near Sekule Bratislava (southwest Slovakia).
On the other hand, Figure 2 shows the adsorption isotherms for the clay minerals. However, a number of theories have been proposed to explain the observed relation between the vapor pressure and moisture content of a soil. The most widely used theory is from Brunauer, Emmett, and Teller , whereas they derived what has come to be known as the BET equation based on multilayer adsorption theory. In the BET theory, the explanation proposed for sigmoid type isotherm (Figure 1) is that the adsorption is in multi-molecular layers on the surface rather than a mono-molecular one. Farrar  and Amer [9, 8] used the water vapor adsorption isotherm method by applying BET theory based on the assumption that the isotherm is made up of monolayer physical adsorption combined with capillary condensation as follows:
At values of
7. Prediction of adsorbed layers (Wm & Wme) and adsorption capacity (Wa)
In order to estimate
The following linear form of the BET equation can be applied using the gravimetric of a single layer of adsorbed molecules over the entire surface of the soil particles:
At high relative water vapor pressures, it can be assumed that the amount is equal unit, and then Equation (8) becomes:
where the suffixes (e) and (i) refer to the external and internal surfaces, respectively. The values of
Equation (9) can be represented in the linear equation y = mx + c, where y =
8. Soil specific surface area
The specific surface of the adsorbent (soil) can be calculated by determining the number of molecules (volumetrically or gravimetrically) and multiplying this by the cross-sectional area of the molecules. Assuming that a single water molecule occupies some constant area on the sorbent surface (usually taken as 10.8˚A2), the total specific surface area (
However, the internal specific surface area (
In general, high clay content in soil means increasing the specific surface areas, hygroscopic water, soil moisture content and retention, and water adsorption capacity (Wa) (Figure 3).
Hygroscopic water exists as a very thin film at the solid-liquid interfaces of the soil particles. At the maximum hygroscopic water (
9. Absorption water in relation to P/Po and pF scale
Equation (7) can be developed to predict the vapor pressure (
where, A = 1/WmC, and B = C-1/WmC
Then at Wa:
Relative vapor pressure [P/Po]wa at
By applying the intercept (1/Wm) and the slope (C-1/Wm), we can obtain W% at P/Po values.
On the other hand, soil water potential (ψ) values corresponded to the total range (0.0
where pF = soil moisture potential, expressed as the common logarithm of the suction (ψ) in cm of water; H is the relative humidity (H=
10. Application of Wa for prediction of soil wetting
The increase in soil water suction is associated with a decreasing thickness of the hydration envelopes covering the soil particle surfaces and vice versa. The following equation was advanced by Nerpin & Chudnovski  to describe soil wetness (h) within limited suction ranges:
Taking moisture adsorption capacity (
or in log form;
By plotting log
Substituting the coefficients parameters log
The moisture potential (ψi) can be expressed in log h (= pF), and called soil matric suction or pressure head (h), which is expressed as potential per weight (m) in SI units. In this case, the pF term is useful to apply as pF = log h, when h is expressed in cm (Figure 4).
Agam N., Berliner P: Diurnal water content changes in the bare soil of a coastal desert. 2004. J. Hydrometeor., 5, 922–933.
Amer A.M: Moisture dynamics and available water capacity in root zone as influenced by swelling pressure and water table in tropical soils. 2014: Final Report, submitted to SENESCYT, Prometeo Project, Ecuador.
Amer A.M: Prediction of hydraulic conductivity and sorptivity in soils at steady state infiltration. 2011. Archives of Agronomy and Soil Science. Published Online July 2011. http://www.tandfonline.com/loi/gags20 http://dx.doi.org/10.1080/03650340.2011.572877.
Amer A.M: Moisture adsorption capacity and surface area as deduced from vapor pressure isotherms in relation to hygroscopic water of soils. 2009. Biologia, 64: 516–521.
Amer A.M., Logsdon S.D., Davis D: Prediction of hydraulic conductivity in unsaturated soils. 2009. Soil Sci., 174, 9: 508–515.
Amer, A.M: Soil Hydro-physics & Agricultural Irrigation and Drainage."2nd Part, Water Requirements and Irrigation & Drainage". 2004. El-Dar Al-Arabia Publishing Foundation, Cairo, Egypt, I.S.B.N 977-258-195-7. (in Arabic).
Amer A.M: Soil hydro-physics. 1st Part, 2003. Al-Dar Alarabia Publishing Foundation, Cairo, Egypt, ISBN 9 77-258-179-5. (in Arabic).
Amer A.M: Surface area measurements as related to water vapour adsorption in arid soils of Egypt. 1993. pp. 619–627. In: Proceedings of the. IV Int. Conf. Desert development, Mexico City, Mexico.
Amer A.M: An approach towards estimation of the external specific surface from soil moisture characteristics curve. 1986. Int. R. T. Conf. Micro-Irrigation, Budapest, Hungary.
Brunauer S., Emmett P.H., Teller E: Adsorption of gases in multi-molecular layers. 1938. J. Am. Chem. Soc., 60: 309.
El-Fiky Y.S: Studies on hydro-physical and physicochemical properties of new reclaimed soils in Egypt. 2002. Ph.D. Thesis, Soil Sci. Dept., Faculty of Agric. Menoufia Univ., Egypt.
Farrar D.M: The use of vapor pressure and moisture content measurements to deduce the internal and external surface area of soil particles. 1963. J. Soil Sci., 14: 303–321.
Globus A.M: On specific soil surface area computing by one point on the water vapor sorption isotherm. 1996. Eurasian Soil Sci., 28: 154–155.
Goebel M., Bachmann J., Woche S. K., Fischer W. R., Horton R: Water potential and aggregate size effects on contact angle and surface energy. 2004. Soil Sci. Soc. Am. J., 68: 383–393.
Hillel D: "Particle sizes and specific surface" in Environmental soil physics. 1998. Academic press, NY.
Jacobs A. F. G., Heusinkveld B. G., Berkowicz S. M: Dew deposition and drying in a desert system: A simple s imulation model. 1999. J. Arid Environ., 42, 211–222.
Kosmas C., Marathianou M., Gerontidis S., Detsis V., M., Tsara M., Poesen J: Parameters affecting water vapour adsorption by the soil under semi-arid climatic conditions. 2001 Agric. Water Manage., 48, 61–78.
Nerpin V., Chudnovski A.F: Energy and mass-transfer in plant-soil-air system. 1975. Hydro-Meteo Izdat., Leningrad. (in Russian).
Orchiston, H. D: Adsorption of water vapour: 1. Soils at 25°C. 1954 .Soil Sci. ,76, 453–465.
Verhoef A., Diaz-Espejo A., Knight J. R., Villagarcia L., Fernandez J. E: Adsorption of water vapor by bare soil in an olive grove in Southern Spain. 2006. Journal of Hydrometeorology, 7, 1011–1026.