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SOLUTION THERMODYNAMICS

LESSON 12:

PARTIAL MOLAR PROPERTIES

Objectives:

∂(nM )

**THERMODYNAMICS OF BIOLOGICAL SYSTEMS
**

· To define partial molar properties M ≡ (1.1)

∂ni

i

**· To understand the concepts of chemical potential and
**

fugacity this equation defines partial molar property of species i in

· Study ideal and non-ideal solutions solution, where the generic symbol i may stand for the partial

· Analyse and apply various composition models molar internal energy , the partial molar enthalpy, the partial

molar entropy ,the partial molar Gibbs energy ,etc.It is a

We have learnt that the applications of chemical-engineering

response function, representing the change of total property nM

thermodynamics are often to systems wherein composition is a

due to addition at constant T and P of a differential amount of

primary variable. In the chemical, petroleum, and pharmaceutical

species i to a finite amount of solution.Comparison of

industries multicomponent gases or liquids commonly

Equations written for the Gibbs energy show that the chemical

undergo composition changes as the result of mixing and

potential and the partial molar Gibbs energy are identical; i.e.,

separation processes, the transfer of species from one phase to

another, or chemical reaction. Because the properties of such µ i ≡ Gi (1.2)

systems depend strongly on composition as well as on Equations Relating Molar and Partial Molar

temperature and pressure, our purpose in this chapter is to Properties

develop the theoretical foundation for applications of thermo-

The definition of a partial molar property, Eq. (1.1), provides

dynamics to gas mixtures and liquid solutions.

the means for calculation of partial properties from solution-

The theory is introduced through derivation of a fundamental property data. Implicit in this definition is another, equally

property relation for homogeneous solutions of variable important, equation that allows the reverse, i.e., calculation of

composition. Convenience here suggests the definition of a solution properties from knowledge of the partial properties.

fundamental new property called the chemical potential, upon The derivation of this equation starts with the observation that

which the principles of phase and chemical-reaction equilibrium the thermodynamic properties of a homogeneous phase are

depend. This leads to the introduction of a new class of functions of temperature, pressure, and the numbers of moles

thermodynamic properties known as partial properties. The of the individual species which comprise the phase. Thus for

mathematical definition of these quantities allows them to be thermodynamic property M:

interpreted a properties of the individual species as they exist in

solution. For example, in a liquid solution of ethanol and water nM = Μ (T , P, n1 n 2. .......ni .....)

the two species have partial molar properties whose values are

somewhat different from the molar properties of pure ethanol The total differential of nM is:

and pure water at the same temperature and pressure.

∂(nM ) ∂(nM) ∂(nM )

Property relations for mixtures of ideal gases are important as d (nM) =

∂ dP + ∂T dT + ∑i ∂ni P,T ,n dni

P T .n P,n

references in the treatment of real-gas mixtures, and they form

j

the basis for introduction of yet another important property, where subscript n indicates that all mole numbers are held

the fugacity. Related to the chemical potential, it is vital in the constant, and subscript nj that all mole numbers except nj are

formulation of both phase-and chemical-reaction-equilibrium held constant. Because the first two partial derivatives on the

relations. right are evaluated at constant n and because the partial deriva-

Finally, a new class of solution properties is introduced. Known tive of the last term is given by Eq. (1.1) this equation has the

as excess properties, they are based on an idealization of simpler form:

solution behavior called the ideal solution behavior called the ∂M ∂M

ideal solution. Its role is like that of the ideal gas in that it d (nM) = n ∂P dP +n ∂T dT+ ∑iM i dni (1.3)

T .x P. x

serves as a reference for real-solution behavior. Of particular

interest is the excess Gibbs energy, a property which underlines Where subscript x denotes differentiation at constant composi-

the activity coefficient, introduced from a practical point of view tion.

in the preceding chapter. Since ni = xin

Partial Properties Dni = xi dn + n dxi

The definition of chemical potential as the mole number When dni is replaced by this expression, and d(nM) is replaced

derivative of nG suggests that other derivatives of this kind by the identity.

should prove useful in solution thermodynamics. d (nM) º n dM + M dn

Thus

**© Copy Right: Rai University
**

2.202 43

4) and (1. (1. accommodate either. For the important special case of changes at constant T and P.4) identified by only a subscript. playing a role opposite to that of Eq. x i one understands that the defining equation for Mi.4) by n yields the alternative expression: Solution properties M nM = ∑n i i M i (1. Since Eq. (1. as in form on either basis.P) (1. is The terms containing n are collected and separated from those an apportioning formula which arbitrarily assigns to each species containing dn to yield: i a share of the mixture property. x ∂T P . ∂M ∂M dT − ∑ M i dxi n and owing to molecular interactions cannot have private dM − dP − properties of their own.6). in properties rather than of partial molar properties. be zero is for each term in brackets to be zero.4) is a general expression for M. one is free to choose a system of any size. with a subscript to identify the species. x i an overbar. Known as summabil. x ∂T P .5) Partial properties Mi Equations (1. Nevertheless.x P. the three kinds of properties used in solution thermodynamics are distinguished by the following symbolism: Multiplication of Eq. Thus for + M − ∑ x i M i dn = 0 practical purposes they may be assigned as property values to i the individual species. The symbol M may express solution properties on a unit-mass In application.5) are new and vital. There. (1. properties. by m.202 . (1. properties of the individual species as and they exist in the pure state at the T and P of the solution are M= ∑x Mi i i (1. expressed here as: ∂M ∂M dP + dT − ∑ x i d M i = 0 x1 d M 1 + x 2 d M 2 = 0 (C) ∂P T . The constituents of a solution are in fact intimately intermixed. tion by direct application of Eq. For binary systems. In summary. and to choose any variation in its size. T. ∂P T . (B) and This equation must be satisfied for all changes in P. it follows that eliminating in favor of in Eq. differentiation however. (1. (1. one merely replaces n.4). moles. becomes: dM= ∑ x d M + ∑ M dx i i i i i i M = x1 M 1 + x 2 M 2 (A) Another general equation for d M.1).1). the number of represented by dn. (1. (1. partial molar properties. Partial properties are denoted by ∂P T . an alternative procedure may be more convenient. we generally speak simply of partial fore. they allow calculation of mixture properties from Partial Properties in Binary Solution partial properties. the symbol is therefore. In addition. x i as defined by Eq. Equations for partial properties can always be derived from an which provides for the calculation of partial properties from equation for the solution property as a function of composi- mixture properties. x ∂T P . This is a proper interpretation provided T . Eq.3) becomes: Equation (1. x i Since.6S) dM i = M1 − M 2 (D) dx1 © Copy Right: Rai University 44 2. Eq. the summability relation. yields a general expression for d M: Written for a binary solution. In order to general. ∂M ∂M The molar (or unit-mass) properties of solutions are repre- dM= dP + dT + ∑ M i dx i sented by the plain symbol M. Equation (1. and speaks of partial specific The only way that the left side of this equation can then. Property relations are the same represented by n. as basis as well as on a mole basis. representing mass. Pure-species properties M ity relations.1). (C) gives: caused by changes of state in a homogeneous phase. Thus n and dn are independent and arbitrary. yields the Gibbs/Duhem dM = x1 d M 1 + M 1 dx1 + x 2 d M 2 + M 2 dx 2 (B) equation: 2 Gibbs/Duhem equation is Eq.4) implies that a molar solution property is given THERMODYNAMICS OF BIOLOGICAL SYSTEMS as a sum of its parts and that is the molar property of species i ∂M ndM + Mdn ∂P = n ∂T ∂M dP +ndT + ∑M i ( xi dn + ndxi ) as it exists in solution.1). and the symbol is . it dM= M 1 dx1 − M 2 dx1 simplifies to: or ∑ x dM i i = 0 (constant T. have all the characteristics of properties of the individual species as they exist in solution. and the combining the result with Eq.

P and nj yields: ∂V ∂S By Eq.PdV + S m IdnI .202 45 . We demonstrate this by example. more complex. © Copy Right: Rai University 2.ll learn how practical properties are related to one dx = dx2 another. the last in solution. and on this basis treat ∂P T . similarly one can write the Gibbs- dx1 Duhem equation for dU=TdS . we may view the definition ∂G i of as a formula which also defines how a solution property is = Vi apportioned among its constituent species. Every equation that provides a liner relation among thermody- namic properties of a constant-composition solution has as its counterpart an equation connecting the corresponding partial properties of each species in the solution.Elimination first of and then of from Eqs.1. (1.x of the solution. x partial properties as though they represent values of properties of the individual species in solution. n ∂G ∂G d Gi = i dP + i dT plus the two additional equations: ∂P ∂T T .x ∂ Gi ∂G1 ∂ (nS ) = ∂ (nV ) In a constant-composition solution. Nevertheless. M 2 = M − x1 (1. Gibb-Duhem equation can be used to calculate the chemical potential of the Thus for binary systems.1) this becomes: = − (a.T . From Van Ness and Abbott: “The partial property is inter- ∂G i = −Si preted as the value of the property of species as is exists in ∂T solution. n j T . is a function of P and T.1) ∂T P . equation a. n ∂P T . n ∂ni P . (A) and (D) yields: but dU=TdS . Compute defines enthalpy: given the binary correlation H=U+PV We can write the change in Gibbs Free Energy in term number of mole as dG = S(nIdmI + m idnI).1 yields the For n moles nH = nU + P(nV) Maxwell relation. and cannot actually have identifiable separate properties of its own. dm2 =RT(dx2/x2) after integrated and find m2 where we have constant C but it is in term of T and P therefore we can d (nG ) = (nV )dP − (nS )dT + ∑ G i dni (1. so dx + dx2 = 0 or Now we.pdV + S m IdnI at equilibrium. ∂T = − ∂n ∂P P. Differentiations with respect to ni at constant T. We can therefore write simply by analogy many two equations are most simply expressed: equations that relate partial properties. and one can always and pressure on the partial Gibbs energy (or chemical potential reason logically to correct conclusions from this point of view” potential). and are given in detail by Van Ness and Abbott.PdV + S m IdnI. Relation among Partial Properties therefore dm2 =-RT(dx/x2) and x1 + x2 = 1.9) write m2 = m20 + RT(lnx2) i Finally we can define a Raoult’s law as P2 = x2 P20 Application of the criterion of exactness.n j and therefore : These examples illustrate the parallelism that exists between where subscript n indicates constancy of all nj and therefore of equations for a constant-composition solution and the composition. dH=TdS . In view of Eq. Since by Eq we derive the following equation Therefore. is one of fundamental equa- THERMODYNAMICS OF BIOLOGICAL SYSTEMS tions. However. Partial properties lend These equations allow calculation of the effect of temperature themselves completely to this interpretation. Consider the equation that Example of computing partial molar properties. the partial properties are readily solute from that of the solvent in a binary ideal system.7) S m IdnI = -Sdt + Vdp.VdP + S m IdnI and dM dF=-SdT .(1. each species in a solution is an intimate part P.8) dx1 S m IdnI = -Sdt + Vdp=0 (T. The corre- without subscripts refer to the solvent and the one with sponding equations for multi component systems are much subscripts 2 refer to the solute. dm2 =-(n/n2)dm2 = -(x/x2)dm we also have m = m 0 + RTlnx .).T . x P. P constant). calculated directly from an expression for the solution property S m IdnI = -Sdt + Vdp= nd m + n2dm2 =0 where as symbol as a function of composition at constant T and P. and subscript nj indicates that all mole numbers corresponding equations for the partial properties of the species except the i th are held constant.n i P . Subtracting two equations yield: dM M1 = M + x (1.

the volume of a solution containing 1000 g of water and n moles of methanol is given by: Calculate the partial molar volume for methanol when the molality of the solution is 0 and also when the molality is 1. The volume of aqueous NaOH solutions containing 1000. 2. Using the first equation we get: Using the second equation we substitute to get: This is exactly the same as obtained with the first equation. Also. J = n1 + n2 where n1 and n2 refer to the amount of substance of component 1 and 2 respectively. but are related by experimentally.31m + 1.] Notes Both of these expressions are used in texts and both give the same answer. any extensive thermodynamic property J may be written in terms of the partial molar quantities © Copy Right: Rai University 46 2. V/cm3 = 1001. H2O = 18.54m2 where m is the molality. Questions 1. Calculate the partial molar volumes of H2O in these two solutions.53 .m.0 a.m.0 mol kg-1.4. The molar volume of pure methanol is 40 cc/mole. Derive an expression for the partial molar volume of NaOH and calculate the partial molar volume of NaOH in an infinitely dilute solution and at a molality of 1.0 a.THERMODYNAMICS OF BIOLOGICAL SYSTEMS Recall that and as.u. If we consider this then we get 4.0 g of H2O is given by.202 . Define what is meant by the term partial molar property and The above definition of does not take into consideration that describe how a partial molar property can be determined th are not all independent. For a general two-component system.u. [MW of NaOH = 40. 3. Which you use is a matter of convenience.

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