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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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.
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
Fugacity and Fugacity coefficient (TB page 208 -209)
*Pressure Explicit form
BITS Pilani, K K Birla Goa Campus
Fugacity and Fugacity coefficient
Volume Explicit form
Like departure functions, 4 ways to estimate fugacity and fugacity coefficient
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
Fugacity from Generalized Equation of State
BITS Pilani, K K Birla Goa Campus
Fugacity from Z factor Correlation
BITS Pilani, K K Birla Goa Campus
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)
BITS Pilani, K K Birla Goa Campus
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)
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
For Benedict-Webb-Rubin
For Lee-Kesler Method recommended by Knapp et al.
Kij ~1
BITS Pilani, K K Birla Goa Campus
For Virial EOS
BITS Pilani, K K Birla Goa Campus
BITS Pilani, K K Birla Goa Campus
Pseudo-critical constant method
Kays Rule
Prausnitz-Gunn Rule
Joffes Relation
BITS Pilani, K K Birla Goa Campus
Rework this problem using the generalized virial coefficient correlation
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
BITS Pilani, K K Birla Goa Campus
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)
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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)
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
Fugacity of a component in a mixture
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
By Virial Coefficient Correlation
BITS Pilani, K K Birla Goa Campus
Problem
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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.
BITS Pilani, K K Birla Goa Campus
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)
BITS Pilani, K K Birla Goa Campus
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)
BITS Pilani, K K Birla Goa Campus
Partial Molar Property
The following can be proven
or
In general,
BITS Pilani, K K Birla Goa Campus
Differentiating G, we get
(Gibbs-Duhem relation) At constant T and P, or
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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]
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
Effect of pressure on chemical potential
BITS Pilani, K K Birla Goa Campus
Effect of temperature on chemical potential
Do it yourself
Starting with G = H TS prove that
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
Temperature dependence on activity coefficient
Pressure dependency
BITS Pilani, K K Birla Goa Campus
Gibbs Duhems equation
At constant T and P,
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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.
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
Properties of solution
Lewis & Randall Rule
For an ideal gas mixture (solution)
(Daltons Law)
(Amagats Law)
BITS Pilani, K K Birla Goa Campus
Entropy change due to mixing
Entropy change due to mixing is given by
BITS Pilani, K K Birla Goa Campus
Phase equilibrium in Ideal solutions
At equilibrium,
But
(Raoults Law)
BITS Pilani, K K Birla Goa Campus
Constraints
Raoults law: 2 unknowns 1 equation
Antoine equation for calculating Psat (t in Celsius and P in torr
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
BITS Pilani, K K Birla Goa Campus
Phase equilibrium problems
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
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
BITS Pilani, K K Birla Goa Campus
Watch your thoughts they become your words Watch your words they become your actions Watch your actions they become your habits Watch your habits they become your character Watch your character it becomes your destiny
BITS Pilani, K K Birla Goa Campus
