Osmotic pressure ideal solution

Virial Isotherm Equation. No isotherm equation based on idealized physical models provides a generally valid description of experimental isotherms in gas-zeolite systems (19). Instead (6, 20, 21, 22) one may make the assumption that in any gas-sorbent mixture the sorbed fluid exerts a surface pressure (adsorption thermodynamics), a mean hydrostatic stress intensity, Ps (volume filling of micropores), or that there is an osmotic pressure, w (solution thermodynamics) and that these pressures are related to the appropriate concentrations, C, by equations of polynomial (virial) form, illustrated by Equation 3 for osmotic pressure ... 

Osmotic pressure is often expressed by Equation 2.10, known as the Van t Hoff relation, but this is justified only in the limit of dilute ideal solutions. As we have already indicated, an ideal solution has ideal solutes dissolved in an ideal solvent. The first equality in Equation 2.9 assumes that yw is unity, so the subsequently derived expression (Eq. 2.10) strictly applies only when water acts as an ideal solvent (yw = 1.00). To emphasize that we are neglecting any factors that cause yw to deviate from 1 and thereby affect the measured osmotic pressure (such as the interaction between water and colloids that we will discuss later), riy instead of n has been used in Equation 2.10, and we will follow this convention throughout the book. The increase in osmotic pressure with solute concentration described by Equation 2.10 is... 

Figure 3.5. Idealized plot of osmotic pressure against solute concentration.

Osmotic pressure of solutions. Experimental data show that the osmotic pressure n of a solution is proportional to the concentration of the solute and temperature T. Van t Hoff originally showed that the relationship is similar to that for pressure of an ideal gas. For example, for dilute water solutions,... 

Osmotic pressure is one of four closely related properties of solutions that are collectively known as colligative properties. In all four, a difference in the behavior of the solution and the pure solvent is related to the thermodynamic activity of the solvent in the solution. In ideal solutions the activity equals the mole fraction, and the mole fractions of the solvent (subscript 1) and the solute (subscript 2) add up to unity in two-component systems. Therefore the colligative properties can easily be related to the mole fraction of the solute in an ideal solution. The following review of the other three colligative properties indicates the similarity which underlies the analysis of all the colligative properties ... 

For example, the measurements of solution osmotic pressure made with membranes by Traube and Pfeffer were used by van t Hoff in 1887 to develop his limit law, which explains the behavior of ideal dilute solutions. This work led direcdy to the van t Hoff equation. At about the same time, the concept of a perfectly selective semipermeable membrane was used by MaxweU and others in developing the kinetic theory of gases. 

The partitioning principle is different at high concentrations c > c . Strong repulsions between solvated polymer chains increase the osmotic pressure of the solution to a level much higher when compared to an ideal solution of the same concentration (5). The high osmotic pressure of the solution exterior to the pore drives polymer chains into the pore channels at a higher proportion (4,9). Thus K increases as c increases. For a solution of monodisperse polymer, K approaches unity at sufficiently high concentrations, but never exceeds unity. 

We may therefore sum up the results in the statement that the laws of osmotic pressure of a dilute solution are formally identical with the laws of gas pressure of an ideal gas (van t Hoff s Gaseous Theory of Solution). 

Now it is a consequence of the experiments of Pfeffer, which proved that the osmotic pressure was equal to the pressure which would be exerted by the same number of molecules of an ideal gas occupying the volume of the solution, that ... 

Chapters 7 to 9 apply the thermodynamic relationships to mixtures, to phase equilibria, and to chemical equilibrium. In Chapter 7, both nonelectrolyte and electrolyte solutions are described, including the properties of ideal mixtures. The Debye-Hiickel theory is developed and applied to the electrolyte solutions. Thermal properties and osmotic pressure are also described. In Chapter 8, the principles of phase equilibria of pure substances and of mixtures are presented. The phase rule, Clapeyron equation, and phase diagrams are used extensively in the description of representative systems. Chapter 9 uses thermodynamics to describe chemical equilibrium. The equilibrium constant and its relationship to pressure, temperature, and activity is developed, as are the basic equations that apply to electrochemical cells. Examples are given that demonstrate the use of thermodynamics in predicting equilibrium conditions and cell voltages. 

Id. Treatment of Data.—Typical osmotic data are shown in Figs. 38 and 39. Here the ratio ( n/c) of the osmotic pressure to the concentration is plotted against the concentration. If the solutions behaved ideally, van t Hoff s law Eq. (11) would apply and m/c should be independent of c. Owing to the large effective size of the polymer molecules in solution (Fig. 34) and the interactions between them which consequently set in at low concentrations, /c increases with c with a... 

Osmotic pressure of the solvent. In dilute ideal solutions the osmotic pressure n of the solution obeys the equation... 

A theory close to modem concepts was developed by a Swede, Svante Arrhenins. The hrst version of the theory was outlined in his doctoral dissertation of 1883, the hnal version in a classical paper published at the end of 1887. This theory took up van t Hoff s suggeshons, published some years earlier, that ideal gas laws could be used for the osmotic pressure in soluhons. It had been fonnd that anomalously high values of osmotic pressure which cannot be ascribed to nonideality sometimes occur even in highly dilute solutions. To explain the anomaly, van t Hoff had introduced an empirical correchon factor i larger than nnity, called the isotonic coefficient or van t Hoff factor,... 

The activity coefficient of the solvent remains close to unity up to quite high electrolyte concentrations e.g. the activity coefficient for water in an aqueous solution of 2 m KC1 at 25°C equals y0x = 1.004, while the value for potassium chloride in this solution is y tX = 0.614, indicating a quite large deviation from the ideal behaviour. Thus, the activity coefficient of the solvent is not a suitable characteristic of the real behaviour of solutions of electrolytes. If the deviation from ideal behaviour is to be expressed in terms of quantities connected with the solvent, then the osmotic coefficient is employed. The osmotic pressure of the system is denoted as jz and the hypothetical osmotic pressure of a solution with the same composition that would behave ideally as jt. The equations for the osmotic pressures jt and jt are obtained from the equilibrium condition of the pure solvent and of the solution. Under equilibrium conditions the chemical potential of the pure solvent, which is equal to the standard chemical potential at the pressure p, is equal to the chemical potential of the solvent in the solution under the osmotic pressure jt,... 

The osmotic pressure of an electrolyte solution jt can be considered as the ideal osmotic pressure jt decreased by the pressure jrel resulting from electric cohesion between ions. The work connected with a change in the concentration of the solution is n dV = jt dV — jrel dV. The electric part of this work is then JteldV = dWcl, and thus jzc] = (dWei/dV)T,n. The osmotic coefficient 0 is given by the ratio jt/jt, from which it follows that... 

Here Jv is the volumetric flow rate of fluid per unit surface area (the volume flux), and Js is the mass flux for a dissolved solute of interest. The driving forces for mass transfer are expressed in terms of the pressure gradient (AP) and the osmotic pressure gradient (All). The osmotic pressure (n) is related to the concentration of dissolved solutes (c) for dilute ideal solutions, this relationship is given by... 

The nion term is simply an expression for the osmotic pressure generated across a semipermeable membrane effectively, the gel serves as a membrane which restricts the polyelectrolytes to one phase, while small ions can readily redistribute between phases. Assuming that the ions form an ideal solution, the expression for nion becomes simply... 

The dissolution of a solute into a solvent perturbs the colligative properties of the solvent, affecting the freezing point, boiling point, vapor pressure, and osmotic pressure. The dissolution of solutes into a volatile solvent system will affect the vapor pressure of that solvent, and an ideal solution is one for which the degree of vapor pressure change is proportional to the concentration of solute. It was established by Raoult in 1888 that the effect on vapor pressure would be proportional to the mole fraction of solute, and independent of temperature. This behavior is illustrated in Fig. 10A, where individual vapor pressure curves are... 

We have assumed that the solution is so dilute that its volume closely approximates the volume of the solvent constituting it. Note that this volume corresponds to the STP molar volume of an ideal gas. The osmotic pressure equation also resembles the ideal gas equation. 

Fig Reduced Osmotic pressure p/C as a function of the concentration of the solution C (1) polymer solution, (2) ideal solution. 

Equation 3.27 forms the basis for determination of Molecular weight from light scattering data. Like Osmotic pressure measurements, it is essential to consider the non-ideality of solutions and the concentration dependence. Following Debye, eq. 3.27 gets modified to... 

In this equation, u is the osmotic pressure in atmospheres, n is the number of moles of solute, R is the ideal gas constant (0.0821 Latm/K mol), T is the Kelvin temperature, V is the volume of the solution and i is the van t Hoff factor. If one knows the moles of solute and the volume in liters, n/V may be replaced by the molarity, M. It is possible to calculate the molar mass of a solute from osmotic pressure measurements. This is especially useful in the determination of the molar mass of large molecules such as proteins. 

V, is the molar volume of polymer or solvent, as appropriate, and the concentration is in mass per unit volume. It can be seen from Equation (2.42) that the interaction term changes with the square of the polymer concentration but more importantly for our discussion is the implications of the value of x- When x = 0.5 we are left with the van t Hoff expression which describes the osmotic pressure of an ideal polymer solution. A sol vent/temperature condition that yields this result is known as the 0-condition. For example, the 0-temperature for poly(styrene) in cyclohexane is 311.5 K. At this temperature, the poly(styrene) molecule is at its closest to a random coil configuration because its conformation is unperturbed by specific solvent effects. If x is greater than 0.5 we have a poor solvent for our polymer and the coil will collapse. At x values less than 0.5 we have the polymer in a good solvent and the conformation will be expanded in order to pack as many solvent molecules around each chain segment as possible. A 0-condition is often used when determining the molecular weight of a polymer by measurement of the concentration dependence of viscosity, for example, but solution polymers are invariably used in better than 0-conditions. 

Consider the equilibrium in a vertical cylinder of suspension of density pi in a suspension medium of density of unit cross-section and height. o o. If at a height x there are n particles per unit volume and at a height xJr x,n->cM particles per unit volume the difference in osmotic pressures due to the particles on the assumption that the suspension conforms to the laws of an ideal solution will be... 

For ideal solutions the osmotic pressure is simply given by CkT. Hence, the osmotic pressure difference between the mid-plane region and the... 

This is because the pure solvent tends to dilute the solution the solute, however, cannot pass through the membrane to dilute itself. Ideally, the osmotic pressure is given by... 

The osmotic pressure can be measured accurately for colloidal solutes, and one molecular parameter of interest that is readily determined by osmometry is the number average molecular weight of the solute. Molecular weights determined by osmometry are absolute values no calibration with known standards or any assumed theoretical models is required. Even the assumption of solution ideality is not a problem, since results are extrapolated to zero solute concentration before calculations are made. 

Equation (20) provides the relationship we have sought between osmotic pressure and concentration. If the solution is ideal, we may replace activity by mole fraction. Then Equation (20) becomes... 

---