Solution Thermodynamics

BITS Pilani
K K Birla Goa Campus

Prof. Srinivas Krishnaswamy Department of Chemical Engineering

BITS Pilani
K K Birla Goa Campus

Chemical Engineering Thermodynamics (CHE C311) 2011 - 2012

Looking Back!!!!!
Thermodynamic Potentials (U, H, A, G) Fundamental Relations (4) Partial Derivatives and associated relations Maxwell relations Departure functions or Residual properties General expressions for du, dh, ds Volume Expansivity and Isothermal Compressibility General expressions for heat capacities The Clausius Clapeyron equation Estimating departure functions
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What next??
Revisiting Gibbs free energy Gibbs free energy as a generating function Chemical potential Fugacity of pure species Estimating Fugacity of pure species Estimating Fugacity of component in a mixture Mixing rules Concept of partial molar property Estimating partial molar properties Excess properties Activity coefficient models

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Gibbs Free Energy as a Generating function

An alternative form of a fundamental property relation as defined in dimensionless terms:
G d RT V RT H RT T V H dP dT 2 RT RT G RT P

G RT P

The Gibbs energy when given as a function of T and P therefore serves as a generating function for the other thermodynamic properties, and implicitly represents complete information.
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Fugacity and Fugacity coefficient

Residual Gibbs energy:

GR

G Gig

G, Gig = the actual and ideal gas values of the Gibbs energy at the same temperature and pressure Residual volume:

V V

V V

ig

RT P

RT Z 1 P
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Fugacity and Fugacity coefficient (TB page 208 -209)

The fundamental property relation for residual properties applies to fluids of constant composition
GR d RT VR RT HR RT VR dP RT G R / RT P HR dT ( 6.42 ) 2 RT

( 6.43 )
T

G R / RT T

( 6.44 )
P

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Fugacity and Fugacity coefficient (TB page 208 -209)

*Pressure Explicit form

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Fugacity and Fugacity coefficient

Volume Explicit form

Like departure functions, 4 ways to estimate fugacity and fugacity coefficient

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BITS Pilani, K K Birla Goa Campus

Fugacity and Fugacity coefficient

Free Energy as Generating function

Beattie- Bridgman Equation

where Ao, Bo, C, a, b,c are constants

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Fugacity from Generalized Equation of State

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Fugacity from Z factor Correlation

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Fugacity coefficient through virial coefficient relation

ln = ln (f/P) = (Bo + B1)Pr/Tr B1 = 0.139 (0.172 / Tr4.2)
Problem: Estimate the fugacity and fugacity coefficient for ethylene using the Virial coefficient correlation (0.9963 bar)

where Bo = 0.083 (0.422 / Tr1.6)

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Fugacity problems
1. Estimate the fugacity of carbon monoxide at 50 bar and 200 bar if the following data is given:
P (in bar) 25 50 100 200 400

0.9890 0.9792 0.9741 1.0196 1.2482

2. Determine the fugacity and fugacity coefficient of noctane at 427.85 K and 0.215 Mpa using the Lee Kesler data (0.2368 MPa)

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Properties of real gas mixtures

Till date we have dealt with pure species (focus on gases) But in most real situations, more than one species are present resulting in a mixture Methods discussed earlier need to be modified by including an additional composition variable to predict properties of real gas mixtures Constants which appear in EOS which characterize pure species behaviour can be averaged to get mixture constants Equations which express mixture constants in terms of pure species constants are called MIXING RULES
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Mixing rules
A mixing rule expresses a mixture constant am in terms of composition expressed in mole fraction yi and the pure component constant ai, i.e. am = yiyjaij aii = ai, ajj = aj, (based on interaction of like pairs of molecules) and aij is based on interaction of unlike pairs of molecules Equations which provide the interaction constant in terms of pure component constants are called combining rules aij = (aii + ajj) / 2 = (ai + aj) / 2 ----- sqrt(aij ajj) = sqrt(aiaj) am = yiai am = [ yisqrt(ai)]2
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Mixing Rules
For Cubic Equation of State (RK, SRK, PR)
In the absence of data, Kij can be set equal to zero

For Beattie-Bridgman EOS

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 For Benedict-Webb-Rubin

For Lee-Kesler Method recommended by Knapp et al.

Kij ~1

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 For Virial EOS

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 Pseudo-critical constant method

Kays Rule

Prausnitz-Gunn Rule

Joffes Relation

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Rework this problem using the generalized virial coefficient correlation

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Prediction of Departure functions for real gas mixtures

Make use of Kays rule/ Modified Prausnitz Gunn/ Joffes relation to evaluate Tcm, m In terms of Virial EOS

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Practice problems
1. The Vander Waals constants for n-butane and n-octane are (1) n-butane a = 1.3874 Pa(m3/mol)2; b = 0.1163e- 3 m3/mol (2) n-octane a = 3.7890 Pa(m3/mol)2; b = 0.237e- 3 m3/mol Estimate the Vander Waals constants for an equimolar mixture of n-butane and n-octane (am = 2.4405 Pa (m3/mol)2; bm = 0.1796e-3 m3/mol 2. Estimate the enthalpy and entropy departures of an equimolar mixture of n-butane and n-octane at 600K and 16 bar using the Vander Waals EOS ( 1.203 kJ/mol and 1.145 J/mol.K)
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Fugacity and Fugacity Coefficient for real gas mixture

Determine the fugacity and fugacity coefficient of an equimolar mixture of n- butane and n-octane at 600K and 16 bar using virial coefficient correlation

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Estimation of fugacity coefficient (Problems)

1. Determine the fugacity and fugacity coefficient for an equimolar mixture of n-butane and n-octane at 600 K and 16 bar using the van der Waals EOS (0.9018, 14.43 bar)
2. Rework the above problem using the pseudo-critical constants method. Make use of Kays rule for pseudocritical constant and the Lee-Kesler data for the 3 parameter law of corresponding states (0.914, 14.62 bar) 3. Rework Problem 1 using the virial coefficient correlation (1.104, 17.66 bar)
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Fugacity of a component in a mixture

For a pure substance, the fugacity at constant T is defined by dg = vdP = RTdlnf g go = RTln(f/P)
Similarly in mixtures the partial molar fugacity of a component i is defined as dgi = dP = RTdlnfi (put a bar and toodle ^ on fi) = RTln = RTln

The partial fugacity is not a partial molar property

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Fugacity of a component in a mixture

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Problem
Estimate the partial fugacities of the equimolar mixture of nbutane (1) and n-octane (2) at 600 K and 16 bar. Make use of the RK equation of state Tc and Pc values for n butane are 425.2 K and 37.97 bar Tc and Pc values for n butane are 569.4 K and 24.97 bar 1. Estimate the pure component constants based on RK EOS 2. Use the mixing rules to find constants for mixture. If Kij is not known, set it equal to zero 3. Estimate Z (In this problem take it equal to 0.8688) 4. The calculate the partial fugacities
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By Virial Coefficient Correlation

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Problem

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Fugacity of liquid and solid

If a liquid or solid is in equilibrium with its own vapor, then,

fv is evaluated and equated to fl at T and Psat and then translated to fl at required T and P > Psat

Poynting Pressure Correction

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Problem
The saturation pressure of n-octane at 427.85 K is 0.215 MPa. Estimate the fugacity of liquid n-octane at 427.85 K and 1.0 MPa.

(0.2475 MPa)
This approximation is not valid for substance like acetic acid which forms dimers in the vapour phase.

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RECAP
(Finding real gas volume) / Departure Functions / Fugacity Equation of State Compressibility factor correlations for EOS Generalized factor correlations Virial coefficients (Finding real gas volume) / Departure Functions / Fugacity Equation of State Compressibility factor correlations for EOS Generalized factor correlations Virial coefficients

PURE SUBSTANCE
GAS / VAPOUR

MIXTURES (MIXING RULES)

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Partial Molar Property

The partial molar property is defined as,
where M is an extensive property and represents the change in the property M of a mixture per mol of component i when temperature, pressure and mole numbers of all other constituents are held constant
We use smaller case letters

Solution properties, M Partial properties, Pure-species properties,

= i (Chemical Potential)

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Partial Molar Property

The following can be proven
or

In general,

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 Differentiating G, we get

(Gibbs-Duhem relation) At constant T and P, or

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BITS Pilani, K K Birla Goa Campus

Method of Intercepts to evaluate partial molar properties

From graph, V1 = AB = AC BC

V2 = DF = DE + DF

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Problems on partial molar property

1. In order to prepare 2 m3 of alcohol water solution, alcohol of mole fraction X1 = 0.40 is required to be mixed with water at 25 oC. Determine the volumes of alcohol and water needed to prepare the mixture
Partial molar volume of alcohol: 38.3 10 6 m3/mol Partial molar volume of water: 17.2 10 6 m3/mol Molar volume of alcohol = 39.21 10 6 m3/mol Molar volume of water = 18 10 6 m3/mol [1.223 m3, 0.8424 m3]

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Problems on partial molar property

In a binary liquid system, the enthalpy of species 1 and 2 at constant temperature and pressure is represented by the following equation
H = 400 x1 + 600 x2 + x1x2 (40x1 + 20 x2) where H is in J / mol Determine expressions for partial molar enthalpies for species 1 and 2 as function of x1 and the numerical values of the pure species enthalpies H1 and H2 H1 (partial) = 420 60 x12 + 40 x13

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Problems on partial molar property

1. The partial molar volume of water (1) in methanol (2) at 25 oC and 1 atm is approximated by 18.1 + ax22 where a = 3.2 cm3/mol. Determine an expression for the partial molar volume of methanol at the same condition given that V2 = 40.7 cm3/mol at 25 oC and 1 atm. Determine the partial molar volume of methanol at infinite dilution.
2. The molar volume of a binary solution at 25 oC is given a
X1 V 106 (m3/mol) 0 20 0.2 21.5 0.4 24 0.6 27.4 0.8 32 1.0 40

Calculate partial molar volumes of components 1 and 2 at X1 = 0.5 and 0,75

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Chemical Potential
Useful intensive thermodynamic property
Partial derivative of H, A and G of the ith component in a multicomponent system

Rate of increase in Gibbs free energy per mole of component i added

dGP,T = GP,T =
idni ini

The Chemical potential is thus seen to be the contribution of that component to the Gibbs free energy of the solution
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Role of in equilibrium
Consider 2 phases a and b in equilibrium
GP,T =
ini

At the same temperature and pressure chemical potential or partial molar free energy of a component in every phase must be the same under equilibrium conditions

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Effect of pressure on chemical potential

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Effect of temperature on chemical potential

Do it yourself

Starting with G = H TS prove that

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Let us recap!!!
GR d RT VR RT H RT
R

VR dP RT G R / RT P
R

HR dT ( 6.42 ) 2 RT

Use lower case for g

( 6.43 )
T

VR RT HR RT T

ln f P

G / RT T

ln f T

( 6.44 )
P

Mixture Fugacity
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Let us recap!!!
dgi gi RTd ln f i gi
0

f i RT ln o fi

H o Hi RT H o Hi RT

T T

ln f i T ln f i T

Fugacity of component in a mixture

Vi V RT

ln f i P

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Activity and Activity coefficient

Measure of the effective of a component Results from interaction of molecules in non-ideal gas or solution and is dimensionless Depends on temperature, pressure and composition
The numerator has a toodle on top

The fugacity of component i as a pure substance at the temperature and pressure is also the standard state fugacity of component i

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Activity and Activity coefficient

The activity coefficient is the mixture is defined as the ratio of activity ai of a component to its mole fraction xi in the liquid mixture

The numerator for f has a toodle on top and not a bar

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Temperature dependence on activity coefficient

Pressure dependency

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Gibbs Duhems equation

At constant T and P,

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Problems
1. The activity coefficient of component 1 in a binary solution is represented by

Where a, b and c are independent of concentration. Obtain an expression for 2 in terms of x1 2. For a binary system if the activity coefficient of component is ln 1 = ax22, then derive the expression for component 2

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Problems
1. Estimate the entropy change due to mixing when 2.8 l of oxygen and 19.6 L of hydrogen at 1 atm and 25 oC are mixed to prepare a gaseous mixture

0.754 cal/mol.K 2. At 25 oC, 0.7 moles of helium are mixed with 0.3 moles of argon. Calculate the free energy and enthalpy change of mixing. Assume ideal gas behavior (- 1511.79 J and 0) 3. A 20 L vessel is divided into 2 compartments with the help of a removable partition. The first compartment contains 12 L of hydrogen and the second compartment contains 10 L of nitrogen. Now the partition is withdrawn and gases allowed to mix isothermally at 1 atm and 298 K. Estimate G, H and S of mixing.
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Excess Properties
Excess Property = Actual Property of mixture at given T and P Property it would have as an ideal solution at same temperature and mixture ME = M Mideal

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Properties of solution
Lewis & Randall Rule

For an ideal gas mixture (solution)

(Daltons Law)

(Amagats Law)
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Entropy change due to mixing

Entropy change due to mixing is given by

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Phase equilibrium in Ideal solutions

At equilibrium,

But

(Raoults Law)
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Constraints
Raoults law: 2 unknowns 1 equation

Antoine equation for calculating Psat (t in Celsius and P in torr

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BITS Pilani, K K Birla Goa Campus

BITS Pilani, K K Birla Goa Campus

BITS Pilani, K K Birla Goa Campus

BITS Pilani, K K Birla Goa Campus

BITS Pilani, K K Birla Goa Campus

BITS Pilani, K K Birla Goa Campus

Phase equilibrium problems

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BITS Pilani, K K Birla Goa Campus

Flash calculations
Rearranging Raoults law expression,
Ki is the equilibrium ratio or K factor of component i

material balance around the flash drum

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BITS Pilani, K K Birla Goa Campus

Objective assessment
Revisiting Gibbs free energy Gibbs free energy as a generating function Chemical potential Fugacity of pure species Estimating Fugacity of pure species Estimating Fugacity of component in a mixture Mixing rules Concept of partial molar property Estimating partial molar properties Excess properties Activity coefficient models

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