TDA 301T-8c - Thermodynamic Properties Real Substances

APPLIED THERMODYNAMICS TDA-301T 2012
Lecture 8: Thermodynamic Properties of Real Substances

By
Prof Alex Sofianos

Bsc Chem Eng, Msc, PhD Ind Chem (Germany), MBL (UNISA)
Course Contents
1. 2. 3. 4. 5. 6. 7. 8. 9. Introduction Conservation of Mass Conservation of Energy Entropy An additional Balance Equation Liquefaction, Power Cycles, Explosions Thermodynamic Properties of Real Substances Equilibrium and Stability One Component Thermodynamics of Multi-Component Systems Estimation of Gibbs Energy and Fugacity of a Component in a Mixture 10. Vapor-Liquid Equilibrium in Mixtures 11. Chemical Equilibrium
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Course Books
1. Chemical, Biochemical & Engineering Thermodynamics 4 Edition, Stanley I. Sandler , John Wiley and Sons (2006) 2. Introduction to Chemical Engineering Thermodynamics (The McGraw-Hill Series in Civil and Environmental Engineering) by J.M. Smith, Hendrik C. Van Ness, and Michael Abbott (2004) 3. Introduction to Chemical Engineering Thermodynamics by J.M. Smith (2001) 4. Engineering and Chemical Thermodynamics by Milo D. Koretsky (2003)
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Assessment TDA 301T

OFFERING TYPE 1. Assignments 2. Class Tests
3. Semester Test Predicate
NUMBER WEIGHT 4 5% 2
1
TOTAL 20 30
50 50
15%
50% 100%
Objectives
At the end of this Chapter, the student must: Be able to evaluate partial derivatives of thermodynamic variables with respect to one variable (e.g. T), while holding a second variable (P) constant! Be able to interrelate partial derivatives arising in thermodynamics Be able to obtain volumetric equation of state parameters from critical properties Be able to solve problems for real fluids using volumetric equations of state (e.g. Van der-Waals or Peng-Robinson)
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Objectives II
At the end of this Chapter, the student must: Be able to construct tables and charts of thermodynamic properties (Sec. 6.4).
Mathematical Preliminaries
Eight thermodynamic state variables thus far discussed: P, T, V, S, U, H, A, G If values of two of them were known: we could calculate the values of the remaining six state variables thermodynamic state of pure, single-phase system is fixed! Mathematically: we choose two variables as independent variables (for the pure, single-phase system, single component system) Remaining six variables are dependent variables
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EXAMPLE: T and V independent variables Any other thermodynamic state variables are dependent variables: U: Internal Energy is a dependent variable! U = U ( T, V) This means that the Internal Energy is a function of temperature and specific volume. The change in internal energy d U , which is a result of differential changes in T and V is therefore:
The subscript on each derivative denotes the variable being held constant: : Shows the differential change in molar internal energy accompanying a diff. change in temperature, whereby the molar volume is constant.
Keep in mind that : (U / T)V and (U / V)T are partial derivatives of the type
)Z
At the same time: X , Y , Z are used to denote the state variables and are used here to represent the state variables P, T, V, S, U, H, A and G Goal of present chapter is to develop methods to allow us to calculate the numerical values of these derivatives Needed for many thermodynamic applications
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We can re-write
As
Above equation says that the Internal Energy is a function of all three independent variables: temperature, total volume and number of moles in the system.
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We can re-write
As
Above equation says that the Internal Energy is a function of all three independent variables: temperature, total volume and number of moles in the system. For a differential change in T , V, or N; the change in internal energy is given as above 12
Note that in equation below
It is necessary to have two subscripts (i.e. two variables are kept constant for each differential change. We remember that any extensive property can be considered to be the product of the related intensive property and its mass (or its mole number). X=XN
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Then the derivative of an extensive property with respect to the intensive property related at a constant mole number is:
Therefore:
We have already seen in Ch. 3 that CV is the constant volume heat capacity CV
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Thermodynamic Partial Derivatives
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Extensive Extensive Derivatives

Further, we can illustrate the derivation of an extensive extensive derivative, i.e property with respect to only an extensive property related at a constant mole number is:
Similarly we get for CP: ??

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More Properties Derivatives

Derivative: (
)Z
may be re-written as:
Order is not important:

First derivative is change in X along a path of constant X; Change in X in response to an imposed change in X
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Triple Product Rule: If X is any dependent variable and Y and Z are two independent variables, using the chain-rule for differentiation, we may write: X = X ( Y, Z ) Then we get:
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Triple Product Rule (continued): The latter can then be simplified if we remember that:
Then we get the Triple Product Rule:
Note the symmetric form of equation in which each variable appears only once in each derivative position
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The Expansion Rule: From equation: which we saw above, we can derive the Expansion Rule by introducing two additional variables, K and L:
Finally if we consider the special case, when L = K we get the Chain Rule
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The Chain Rule: From equation:
With L = Z :
Chain Rule
Hence we can introduce a new variable in evaluating a partial derivative, as with Y in equation above
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Thermodynamic Derivatives
Definitions:
Further Definitions:
Energy Balance
+ G dN
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For Closed Systems we can write *):
Then we have:
And
=T
Alternatively we can write:
*) NOTE: U = U (S, V) ; dU =
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However we may remember that:
Then we have And if we now divide by N we get:
Similarly we can derive:
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Therefore from the First Law we can derive:
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The Maxwell Relations: Expressions for other derivatives:
Then we can get:
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The Maxwell Relations: Similar expressions for other derivatives:
These are the famous Maxwell Relations

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From the First Law we remember: U = Q + W or as derivatives: dU = dQ + dW Since it is obviously true also for reversible changes, we have: dU = dQrev + dWrev We know that dWrev = -P dV reversible work Then we can write: dU = dQrev - P dV From the definition of entropy (Second Law) we
remember: dS =

Fundamental Thermodynamic Relation
And therefore: dQrev = T dS Expression for the reversible heat transfer

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So we can put these together to form an expression for dU which only involves functions of state. For a hydrodynamic system, for instance: dU = T dS - P dV The fundamental thermodynamic relation It involves only functions of state, so it is true for all changes, not just reversible ones This suggests that the natural variable in which to express U are S and V: U = U (S , V) That means that internal energy will be unchanged for processes at constant volume and entropy-29
Fundamental Thermodynamic Relation
not the most common experimental conditions. It is therefore useful to introduce other functions of state, called ``thermodynamic potentials'', which are conserved, or whose change is easily calculated, in common experimental conditions. These are: Enthalpy H = U + P V ; hence, dH = d U +P dV + Vdp and with: dU = T dS - P dV , the fundamental thermodynamic relation, we obtain: dH = d U +p dV + V dP = T dS - P dV + P dV + V dP dH = T dS + V dP
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Fundamental Thermodynamic Relation - ENTHALPY
Helmholtz Free Energy

dH = T dS + V dP At constant pressure (such as chemical reactions in a test tube), dP = 0 dH = T dS + V dP ; dH = T dS and therefore: dH = dQrev so that Heats of reaction are usually measured as enthalpies of reaction (at constant pressure) Helmholtz Free Energy (E) Similarly we get: E =UTS The derivative is: dE = dU TdS S dT We remember that: dU = TdS PdV By substitution: dE = S dT PdV E is constant at constant temperature and volume. 31
Gibbs Free Enthalpy Relation

dH = T dS + V dP Gibbs Free Enthalpy (G) Similarly we get: G =HTS The derivative is: dG = dH TdS S dT We remember that: dH = TdS + PdV By substitution: dG = TdS + PdV S dT PdV Therefore: dG = VdP S dT The Gibbs Free Enthalpy is constant at constant temperature and pressure. These are the conditions under which phase transitions (melting, boiling) take place, and are also relevant to chemical equilibrium
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Maxwells Relations
We remember: dU = T dS P dV fundamental thermodynamic relation On purely mathematical grounds, we may re-write this as: U = U (S, V) ; or
dU = (
)V
dS + (
)S
dV
dU = T dS P dV By comparison with the fundamental relation we see that: Temperature T =

( )V
; Pressure: P = -
( )S
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Maxwells Relations
Temperature T = ( )V ; Pressure: P = - ( )S

These definitions (especially the second) are interesting in their own right. But we can go further, by differentiating both sides of the first equation by V and of the second by S :
( )V
( )S = ( =-
( )V ) S ( ( )S ) V
the order of differentiation in the second derivation is irrelevant, right hand sides are equal, and thus so are the left hand sides, giving:
( )S
=-
( )V
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Maxwells Relations
By starting with , E, H and G, we can get three more relations i. ii. iii. iv.
dU = TdS PdV => T = ( )V and P = - ( )S dE = -SdT PdV => S = ( )V and P = - ( )T dH = TdS + VdP => T = ( )P and V = - ( )S dG = -SdT + VdP => S = ( )V and V = - ( )T
The two equations involving derivatives of S are particularly useful; as they provide a possibility to determine S,
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Heat Capacities
Heat capacities are related to changes of entropy with temperature A heat capacity is the temperature change per unit heat absorbed by a system during a reversible process C dT = dQ rev Specific heat capacity (C)'; the latter is the heat capacity C per kg or per mole The heat capacity is is different for different processes. Useful heat capacities are those at constant volume or constant pressure (for a fluid). Since dQ rev = T dS we have at constant volume CV dT = T dS , so
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Heat Capacities
we have at constant volume CV dT = T dS , so
i.
CV = T ( )V
ii. CP = T
( )P
Heat Capacity at constant volume

Heat Capacity at constant pressure
At constant volume (reversible conditions!) no work is done; therefore: dU = dQ rev + PdV dU = dQ rev i. CV = ( )V expressed in terms of internal Energy

Also (usefully for chemists), at constant pressure dP=0 d H = dQ rev where H is the enthalpy, so
ii. CV =
( )P
expressed in terms of Enthalpy

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Heat Capacities
The specific heat capacity is the heat capacity per unit mass (or per mole). Heat capacities are not independent of temperature (or pressure) in general, but over a narrow temperature range they are often treated as such, especially for a solid. Together with two of Maxwell's relations, we now have expressions for the partial derivatives of the entropy with respect to all easily measurable variables (P, V , T). These can be used to derive expressions for the entropy change in real processes as well! We can show how to do that by using the Van der Waals Equation
P=
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Heat Capacities
We can also derive a relation between , , and other measurable properties of a substance which can be checked experimentally: If a is the isobaric thermal expansion coefficient and kT is the isothermal compressibility With a=
1 ( ) P
and kT = 2
1 ( ) T
We obtain
kT which is always greater than zero.
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CP CV = VT
Heat Capacities
kT This relation is a firm prediction of thermal physics without any approximations whatsoever. It has to be true! For real gases and compressible liquids and solids it can be checked. For relatively incompressible liquids and solids it is hard to carry out processes at constant volume so CV may not be well known and this equation can be used to predict it. For one mole of a van der Waals gas this gives CP CV = R[ 1 2 ()2 -1 ]
CP CV = VT
RTV 3
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Heat Capacities
For one mole of a van der Waals gas this gives
CP CV = R[ 1 -
2 ()2 -1 ]
RTV 3
In the ideal gas case a, b 0 are zero (limit) Above equation then reduces to CP CV = R Question What is the entropy change during the expansion of a van der Waals gas for which CV is a constant? Equation of state for one mole: P= - 2

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Entropy Change Calculation

P=

b represents the volume taken up by the finite size of the molecules, a/V2 is the reduction in pressure due to interactions between the molecules (Van der Waal forces). In this way the two most important corrections neglected in the ideal gas are included. However, the heat capacity at constant volume is still independent of temperature and volume, as in an ideal gas. During an expansion, both the temperature and the volume may change. 42

To calculate the change in entropy, we need
( )V =
from definition of CV = T ( )V
Equation can be modified: Differentiation of V.-d. Waals equation:

( )V = ( )T = ( ) V = Then dS = ( )V dT + ( )T
( )V =
dV , using a Maxwell Relation
If we now substitute: and

( )V =
we obtain:
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Finally dS =

dT +
Choose variables, either (V, T) or , (P, T) and writing dS in terms of infinitesimal changes of these variables then using the definition of the heat capacities, and a Maxwell relation, we obtain something like the second line. Then we can calculate the total entropy change by integrating, first at constant T and then at constant V:
S ( T1, V2) = S ( T1, V1) +
2 1
(1,) ]T
dV
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Finally dS =

dT +
Choose variables, either (V, T) or , (P, T) and writing dS in terms of infinitesimal changes of these variables then using the definition of the heat capacities, and a Maxwell relation, we obtain something like the second line. Then we can calculate the total entropy change by integrating, first at constant T and then at constant V:
S ( T1, V2) = S ( T1, V1) +
2 1
(1,) ]T
dV
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Heat Capacities
Then we can calculate the total entropy change by integrating, first at constant T and then at constant V: S(
(1,) T1, V2) = S ( T1, V1) + [ ]T 2 ) T1, V2) = S ( T1, V1) + ( )T dV 1 2 ) = S ( T1, V1) + ( ) 1 2 (1,) [ ]T 1 2 dT 1 2 1
dV
S(
Similarly:
S ( T1, V2) = S ( T1, V2) + = S ( T1, V2) +
dP
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S ( T2, V2) = S ( T1, V2) +
2 1
(1,) ]T
dP
= S (T1 , V2) +
2 1
dT
= S ( T1, V2) + CV ln
T2 T1
2 1
= S ( T1, V2) + CV
Therefore:
T2 + CV ln T1
2 1
T2 S ( T2, V2) - S ( T1, V2) = CV + CV ln T1 where in the second integration we used the fact that CV is constant.
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T2 S ( T2, V2) - S ( T1, V2) = CV + CV ln T1 We can check our result against those we have already calculated for an ideal gas just by setting b=0 and using the correct CV for a monatomic gas CV = 3/2R
2 1
for an isothermal expansion (T1 = T2) we get: V2 S = R ln V1
for a reversible adiabatic expansion we can use T1 V1 -1 = T2 V2 -1 We remember heat capacities at constant pressure and at constant volume differ by a constant for ideal gases:
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We remember that heat capacities at constant pressure and at constant volume differ by a constant for ideal gases: CP CV = n R reversible adiabatic compression or expansion of an ideal gas the pressure and volume change together in such a way that: P V = constant, where =
Then from the Ideal Gas Law: p V = n R T it follows that: 1 T V -1 = constant and T P
( 1 )
= constant
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Expressions of S, U and H in terms of T and V or T and P (which are the convenient choices (why measurement of S?) S = S (T, V) and
However according to the Maxwell relationship
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Then we obtain:
And by substituting:
We get:
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To obtain complete expressions of dU and dH in measurable entities we start again with equation:
And by substitution of the dS into previous equation:
We get:
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Finally, we can express dH in a similar way as follows:
From equation above and the last one of the previous slide:
dU
We get:
and:
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Table of useful Thermodynamic Functions
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Table of Useful Thermodynamic Functions (Coned)
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Table of Useful Thermodynamic Functions (Coned)
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Ideal Gas And Absolute Temperature Scale

If we consider that P, V and U are only functions of T as in the equations: P V = R T ; and P V = 1 ( T )
and U = 2 ( T ); therefore
we obtain with
C V ( )V ( )V
57

Since:
CV ( ) V
= CV
( )V =
Due to the fact that And :

( )V =
The last equation of previous slide becomes:
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Ideal Gas State Equations

Since: at constant volume can
be written as the derivative
And by integration we get the well known equation for an ideal gas
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From the same equation (below) we can see that CV =
and if we keep P constant we obtain:

= CV
= CV ( )V
( )V
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Ideal Gas State Equations

By comparison of the two equations we can clearly see that CV =

STATEMENTS (Please read!)
Similar partial derivatives with Different State Variables held constant are NOT EQUAL (Illustration 6.2-1)
Similar partial derivatives with Different State Variables held constant are NOT EQUAL (Illustration 6.2-2)
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Changes in Thermodynamic Properties of Real Substances
i. ii. iii. iv.
STATEMENTS
By using partial derivatives develop expressions for The coefficient of thermal expansion, a Isothermal compressibility factor kt The Joule-Thomson Coefficient The difference CP - Cv
Using: a. The Ideal Gas Equation: PV = RT b. The Van der Waals Volumetric Equation of State (P + V2 ) (V b) = R T (Illustration 6.2.3)
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Changes in Thermodynamic Properties of Real Substances

For real substances we need a volumetric equation of state Ideal Gas Equation: Van der Waals P =

Redlich Kwong
Peng Robinson
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Equations of State
For real substances we need a volumetric equation of state Generalized Class
Virial
Benedict Webb Rubin

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Heat Capacity
We start with: And
Using the Commutative Property, which states that in a mixed second derivative, the order of taking derivatives is not important:
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Heat Capacity
We also use: And If we use the same method as with the heat capacity at constant-volume for the constant-pressure heat capacity
We convert above equation into the much more versatile second equation Integration of the above gives:
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Heat Capacity
And By integration for P1= 0 and V1= we obtain:
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Heat Capacity
The same results are expected if one considers the constant-volume heat capacity:
And
By integration for P1= 0 and V1= we obtain for the constant-volume heat capacity:
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Change of State of a Real Gas

ILLUSTRATION 6.5-1 Compare solutions to Problem assuming the gas is ideal, Using a Thermodynamic Properties Chart (Peng Robinson) and Assuming Gas can be described by Van der Waals Equation of State
Nitrogen gas is being withdrawn from a 0.15 m3 cylinder at 10 mol/min. Cylinder initially at 100 bar and 170 K. Cylinder well insulated; no heat transfer between cylinder and gas. i. How many moles of nitrogen will be in the cylinder at any time? ii. What will the temperature and the pressure of the cylinder be after 50 minutes?
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ILLUSTRATION 6.5-1
a. Assume that nitrogen IDEAL GAS b. Use the nitrogen properties chart of Fig. 3.3-3. c. Assume that nitrogen obeys the Van der Waals equation of state. Data: For a.- and b.- use : CP* [J/mol K) = 27.2 + 4.2 X 10 -3 (K) SOLUTION We set up the mass and energy balances for the contents of the cylinder (the System)
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SOLUTION Mass and Energy balances for the contents of the cylinder I.
= =H
or N(t) = N (t=0) + t with = -10 mol/min
II.
We saw during Illustration 4.5.-2 that the entropy balance for the portion of the gas remaining in the cylinder is: Also from

= 0 or S (t=0) = S(t) we get

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V=NV

SOLUTION
Also from
N (t=0) =
V=NV
0.15 3
we get:
= V(=0) V(=0) These equations apply equally to ideal and non-ideal gases Calculation of N(t=0) I. Ideal Gas Equation of State P V = R T or V (t=0) = =
8.31410 5 100 (=0) (=0)
3 170
= 1.4134 x10 -4 m3/mol

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Calculation of N(t=0) I. Ideal Gas Equation of State P V = R T or V (t=0) =
3
(=0) (=0)
=
And
8.31410 5 170 100
= 1.4134 x10 -4 m3/mol
N (t=0) = 1061.3 mol N (t) = (1061.3 10t) mol
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Calculation of N(t=0) ii. Using the Chart of 3.3.-3 (T=170K, P=100 bar) = (T=170K, P=10 MPa) 0.0035 m3/kg V (T=170K, P=10 MPa) = N (T=170K, P=10 MPa) =
28.014 g/mol x 0.0035 m3/kg x
1 1000
= 9.80 x 10 -5 m3/mol
And
N (t=0) =
0.15 3 9.8 105 3/
= 1529.8 mol
N (t) = (1529.8 10t) mol

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Calculation of N(t=0) iii. Using the Van der Waals Equation
We use the constants given in Table 6.4.-1, whereby for nitrogen a value for a = 0.1368 [Pa 106/mol2] and for b = 3.864 [105m3/mol] are listed! Then we have:
P = 100 bar = 107 Pa= Cubic Equation:
8.314170 =0 3.864105
3.864105 =0 2
V(t=0) = 9.435x 10 -5 m3/mol

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And N (t=0) =
0.15 3 9.435 105 3/
= 1589.9 mol
N (t) = (1589.9 10t) mol We can also compute the molar volume of the gas at any later stage from the volume of cylinder (0.15 m3) and N(t) V (t) =
0.15 3 ()
Example: Van der Waals: N (t) = (1589.9 10t) mol = 1589.9 10 x50 = 1089.9 mol
V (t) =
0.15 3 ()
= 1.376 x 10 -4 m3/mol
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Ideal Gas
An ideal gas is an imaginary gas that satisfies the following conditions: Negligible interactions between the molecules, Its molecules occupy no volume (negligible molecular volume), Collisions between molecules are perfectly elastic this is, no energy is lost after colliding. This fluid is imaginary because as we know there are no ideal gases
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Ideal Gas
The ideal gas EOS is inaccurate both qualitatively and quantitatively Qualitatively, ideal gas will not condense no matter what pressure and temperature the system is subjected to. Quantitatively, pressures and volumes used by the ideal gas model are higher than the values that a real gas would have. These were the primary reasons that scientists have made an effort to go beyond the ideal gas EOS: simply because it does not apply for most cases of interest
78
Ideal Gas
The ideal gas EOS is inaccurate both qualitatively and quantitatively Qualitatively, ideal gas will not condense no matter what pressure and temperature the system is subjected to.
1. volume of the gas becomes very large at very low pressures (i.e., as , a concept that agrees with what we know from our experience in the physical world). 2. And second, as (the volume of matter just vanishes if the pressure is high enough: this concept we would not be as willing to accept). These two behaviors are a consequence of the assumptions made in the ideal gas model.
P-v Isotherm for an Ideal Gas
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Ideal Gas
Qualitatively, ideal gas will not condense no matter what pressure and temperature the system is subjected to. Ideal EOS is therefore qualitatively wrong
This figure has an obvious discontinuity (at the vapor+liquid transition). For a real substance, as pressure increases, there must be a point of discontinuity that represents the phase change. Hence, we cannot hope to reproduce the P-V behavior (actual!) using the ideal equation since no discontinuity is to be found. However, the real P-v isotherm can be approximated by ideal behavior at low pressures, as we can see from the plots.80
P-v Isotherm for a Real Gas
Ideal Gas
Quantitatively, ideal gas pressures and volumes used by the ideal gas model are higher than the values that a real gas would have. Ideal EOS is therefore also quantitatively wrong for most conditions of interest at a given volume and temperature, the ideal gas model over-predicts the pressure of the system: P Ideal Gas > P Real Gas real gas does have interaction forces between molecules ideal model assumes that the physical space that the molecules themselves occupy is negligible. In reality molecules are physical particles and they do occupy space
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Real Gas
How can we adjust the ideal model to make it suitable for real gases? The answer: We said that once we have established a base (ideal) model, we look at a real case by estimating how close (or far) it performs with respect to the base (ideal) case, and introducing the corresponding corrections. Such corrections will take into account all the considerations that our original assumptions left out.
We introduce a correction factor Z to account for the

discrepancies between experimental observations and predictions from our ideal model.
82
Real Gas
We introduce a correction factor Z the compressibility
factor , which is defined as: Z = V V ideal V is the real volume occupied by the gas and V ideal is the volume that the ideal model predicts for the same conditions. The ideal volume is given by: V ideal = n R T P Hence, the equation of state for real gases: PV=ZnRT
for Z = 1, this equation collapses to the ideal gas model. In fact, unity is the compressibility factor of any gas that behaves ideally
83
Definition of Equation of State

Assuming an equilibrium state, the three properties needed to completely define the state of a system are pressure (P), volume (V), and temperature (T). Hence, we should be able to formulate an equation relating these 3 variables, of the form f (P,T,V) = 0. Equation of State (EOS) is a semi-empirical functional relationship between pressure, volume and temperature of a pure substance. We can also apply an EOS to a mixture by invoking appropriate mixing rules. The functional form of an EOS can be expressed as: f( P, T, V, ak, k=1, nP ) = 0 , where ak = EOS parameters.
84

Most applicable EOS today are semi-empirical, in the sense that they have some theoretical basis but their parameters (ak) must be adjusted. The number of parameters (np) determines the category/complexity of the EOS. For instance, 1-parameter EOS are those for which np = 1, and 2-parameter EOS are those for which np = 2. The higher np is, the more complex is the EOS. Also, in general terms, the more complex the EOS, the more accurate it is. However, this is not always the case; in some cases a rather simple EOS can do a very good job.
85

A great number of equations of state have been proposed to describe real gas behavior. Only few have persisted through the years, this because of their relative simplicity. In the petroleum industry, the most common modern EOS are the Peng Robinson EOS and Soave-Redlich-Kwong EOS Both of these are cubic EOS and hence derivations of the van der Waals EOS. Other more complex EOS, although they have not yet found widespread application in our field: Lee Kesler EOS Benedict-Webb-Rubin Benedict-Webb-Rubin-Starling
86

We want to use EOS as the basis for generating data: volumetric data, thermophysical data, and to help us perform vapor/liquid equilibrium (VLE) calculations. Not other area of thermodynamics to which so many hours of research have been devoted as that of the topic of EOS. Among the properties derived from an EOS include: Densities (vapor and liquid), Vapor pressures of pure components, Critical pressures and temperatures for the mixture, Vapor-Liquid equilibrium (VLE) information, Thermodynamic properties (H, S, G, A).
87
Equation of State
1873: With van der Waals, a quantitative approach was taken for the first time. He was an experimentalist and proposed the continuity of gases and liquid that won for him a Nobel Prize. He has provided the most important contribution to EOS development. 1927: Ursell proposed a series solution (polynomial functional Virial form) for EOS: P = 1 + b/V + c/V2 + d/V3 + 1940: Benedit, Webb, & Rubbin proposed what can be called the Cadillac of EOS, i.e., the most sophisticated and most accurate for some systems. However, the price to pay is that it is too complicated and not easy to use. 1949: Redlich & Kwong introduced a temperature dependency to the attraction parameter a of the vdW EOS.
88
Equation of State
1955: Pitzer introduced the idea of the acentric factor to quantify the non-sphericity of molecules and was able to relate it to vapor pressure data. 1972: Soave modified the RK EOS by introducing Pitzers acentric factor. 1976: Peng and Robinson proposed their EOS as a result of a study sponsored by the Canadian Gas Commission, in which the main goal was finding the EOS best applicable to natural gas systems. Since then, there has not been any radical improvement to SRK and PR EOS
89
Equation of State
1955: Pitzer introduced the idea of the acentric factor to quantify the non-sphericity of molecules and was able to relate it to vapor pressure data. 1972: Soave modified the RK EOS by introducing Pitzers acentric factor. 1976: Peng and Robinson proposed their EOS as a result of a study sponsored by the Canadian Gas Commission, in which the main goal was finding the EOS best applicable to natural gas systems. Since then, there has not been any radical improvement to SRK and PR EOS
90
van der Waals EOS

van der Waals EOS (vdW EOS) has been around for more than one hundred years, we still recognize its crucial contribution in revolutionizing our thinking about EOS. We talk about vdW EOS mainly because of pedagogical reasons, not because it finds any practical application in todays world. In fact, vdW EOS is not used for any practical design purposes. However, most of the EOS being used widely today for practical design purposes have been derived from vdW EOS. The contributions of vdW EOS can be summarized as follows: It radically improved predictive capability over ideal gas EOS, First to predict continuity of matter between gas and liquid, It formulated the Principle of Corresponding States (PCS), It laid foundations for modern cubic EOS.
91
van der Waals EOS

van der Waals EOS (vdW EOS) accounted for the non-zero molecular volume and non-zero force of attraction of a real substance. Van der Waals realized that there is a point at which the volume occupied by the molecules cannot be neglected. He recognized that molecules must have a finite volume, and that volume must be subtracted from the volume of the container. At the same time, he modified the pressure term to acknowledge the fact that molecules do interact with each other though cohesive forces. These are the two main valuable recognitions that he introduced.
92
van der Waals EOS

van der Waals EOS (vdW EOS) focused his attention on modifying the terms P and V in the original ideal gas law by introducing an appropriate correction. Looking back at the inequality of equation Pideal Preal vdW proposed that the difference of both pressures is the result of the attraction forces cohesive forces neglected in the ideal model and then he postulated the term P attraction, an inverse function of the mean distance between molecules. Pideal = Preal + P
Then he introduced a as a constant of proportionality, Pideal = Preal + a / V2
93
van der Waals EOS

Next van der Waals took care of the inequality with regard to the volume. Any particle occupies a physical space; hence, the space available to the gas is less than the total volume of its container. Let assume we can experimentally determine the physical space that all the molecules in the container occupy, and that we call it b, or the co-volume. vdW then proposed: Vavailable = Vtotal b
94
van der Waals EOS

The inclusion of a parameter b (co-volume) recognizes the role of repulsive forces. Repulsive forces prevent molecules from destroying one another by not letting them get too close. In a condensed state, there is a maximum allowable closeness among molecules. Therefore, it is because of repulsive forces that we cannot compress the volume of a fluid beyond its co-volume value b. If the molecules get too close to each other, repulsion forces take over to prevent their self-destruction. The new EOS becomes then: (from PV = RT) (Preal + a / V2 ) (V b) = RT or
95
van der Waals EOS

where: P = absolute pressure V = molar volume T = absolute temperature R = universal gas constant How do we calculate a and b for each substance? As can be inferred from their definitions, a and b are different for different substances; i.e.,; a CH4 a CH3-CH3 a C3H8 . and b CH4 b CH3-CH3 b C3H8 How do we relate a and b to well-known and easilyobtainable physical properties of substances? Criticality Conditions
96
van der Waals EOS

How do we relate a and b to well-known and easilyobtainable physical properties of substances? Criticality Conditions Indeed, in the previous chapter we recognized that the critical isotherm of a pure substance has a point of inflexion (change of curvature) at the critical point A plot of the isotherms of the Van der Waals equation of state is shown in the next slide
97
van der Waals EOS

The red and blue isotherms similar to those of an ideal gas Black isotherm exhibits an unusual feature; virtually no change in pressure as the volume changes Green isotherm has a region where the pressure decreases with decreasing volume dramatic jump in volume (doted line) signifies a phase transition; from a gaseous to a liquid state
98
van der Waals EOS

- One region where the van der Waals equation works well is for temperatures that are slightly above the critical temperature Tc of a substance - Observe that inert gases like Helium have a low value of a as one would expect since such gases do not interact very strongly, and that large molecules like Freon have large values of b.
99
van der Waals EOS

Further, we see that the black isotherm represents a boundary between those isotherms along which no such phase transition occurs and those that exhibit phase transitions in form of discontinuous changes in the volume. The black isotherm is called the critical isotherm; the point at which the isotherm is flat and has zero curvature is called a critical point.
100
van der Waals EOS

This condition of horizontal inflexion of the critical isotherm at the critical point is mathematically imposed by the expression: 2
=0
and
= 0
These conditions are called the criticality conditions.
It turns out that when one imposes these conditions on vd Waals equation, one is able to derive expressions for the parameters a and b as a function of critical properties
101
van der Waals EOS

Using these two conditions, we can solve for the critical volume Vc and critical temperature Tc and correlate these with the Van der Waals constants: Starting with At the critical point we have;
( )T |at Tc, Vc, Pc = 0 or 2 ( 2 )T |at Tc, Vc, Pc = 0
We get a and b as a function of the critical properties

102
van der Waals EOS

Problem is pure algebra, let's rewrite the simultaneous equations that must be solved for the two unknowns V and T (which solutions we will call VC and TC ): (1) (2)
2 ()
One way is to multiply Equation (1) by:

Then we get: By addition of equations (2) & (3) :
we obtain eq. (4)
(3)
103
van der Waals EOS

Divide Equation (4) by 2an2 and multiply it by V 3 (and bring the negative term to the other side of the equal sign) to get,
(5)
This we now solve with re-arrangement to obtain the critical volume: (6) We substitute Vc in equation (1)
Then we get: (7)
Which can be simplified:
or (8)
104
van der Waals EOS

The critical pressure is obtained by substituting VC and TC into the van der Waals equations of state as solved for p:
Then we get:
(9)
And finally:
(10)
105
van der Waals EOS

From Eq. 6 we can now calculate b:
b=
and a =
9 8
We can further calculate the compressibility Z at the critical point as follows: P V = Z nRT at the critical point we have:
Zc =
We can express a and b in terms of the critical temperature and critical pressure:
and
Zc = = 0.375
3 8
a =
2722 64
b=
106
van der Waals EOS

Or we can express a and b in terms of the critical volume and critical pressure:
a =
3Pc V2c
If we substitute the above values into the vd Waals Equation we get:
b=
And finally:
107
van der Waals EOS

If we define the:
reduced temperature: Tr = reduced pressure: Pr = reduced volume: Vr =
Equation:
becomes:
[Pr +
] [3Vr 1] = 8 Tr
108
van der Waals EOS

Equation:
[Pr +
] [3Vr 1] = 8 Tr
is extremely interesting: It suggests that at given values of the reduced temperatures and reduced pressures all van der Waals fluids will have the same value of reduced volume Further conclusion: the same reduced form equation of state applies, no matter what a and b may be for the particular fluid. If two fluids have the same reduced pressure, reduced volume, and reduced temperature, we say that their states are in corresponding states
109
Parameters for van der Waals EOS

Substance He H2 O2 H2O CCl4 a (L2 atm/mol2) 0.0341 0.244 1.36 5.46 20.4 b (L/mol) 0.0237 0.0266 0.0318 0.0305 0.1383
The parameter b is related to the size of each molecule. The volume that the molecules have to move around in is not just the volume of the container V, but is reduced to ( V - nb ). The parameter a is related to intermolecular attractive force between the molecules, and n/V is the density of molecules. The net effect of the intermolecular attractive force is to reduce the pressure for a given volume and temperature. 110
Example: van der Waals EOS

Use the van der Waals equation to calculate the pressure of a sample of 1.0000 mol of oxygen gas in a 22.415 L vessel at 0.0000C (Note: For an ideal gas, this temperature and volume would lead to conditions of STP, i.e. a pressure of exactly 1.0000 atm)
Solution:
V = 22.4 L T = (0.000 + 273.15) = 273.15K a (O2) = 1.36 L2 atm/mol2 (From Table) b (O2) = 0.0318 L /mol (From Table)
(nRT)/(V-nb) = 1.0014 atm - a (n/V)2 = -0.0027 atm p = (nRT)/(V-nb) - a (n/V)2 = 0.9987 atm If O2 was perfectly ideal, the pressure would be 1.0000 atm.
111
van der Waals EOS
The first term on the right-hand-side of the van der Waals equation, (nRT)/(V-nb), represents the ideal gas pressure corrected for finite molecular volume. In other words the volume is slightly less than 22.415 L due to the mole of O2 in it. the molecules collide a bit more frequently with the walls of the container, because they have less room to fly around in in the middle of the container.
112
van der Waals Solver

http://www.webqc.org/van_der_waals_gas_law.html
The value of 1.0014 atm for this term represents this increase in pressure. The second term in the equation, - a (n/V)2, represents the reduction in pressure due to molecular stickiness. This correction to ideal gas behavior dominates the finite volume correction, leading to a compressibility factor, Z=pV/nRT of less than 1 (0.9987, in fact). Van der Waals equation calculator is a powerful online tool for solving problems using Van der Waals equation equation. Select a quantity to solve for and one of the Van der Waals equation equations to use.
113
van der Waals Solver

http://www.webqc.org/van_der_waals_gas_law.html Solve for Equations
P T n V Input values and select units Temperature (T) Volume (V) Gas constant (R) (std) J/(mol*K) Number of moles (n) Parameters (gas) Measure of the attraction between the particles (a) J*m3/mol2 Volume excluded by a mole of particles (b) m3/mol Solve for Pressure (P)
114
Principle of Corresponding States

Accuracy of Van der Waals equation not very good Critical volume of a fluid is known with less experimental accuracy than either the critical temperature or critical pressure. Compressibility Factor comparison We saw that Zc |Van der Waals = Pc Vc / R Tc = 0.375 In reality critical compressibility for most fluids is in the range of 0.23 0.31 Ideal gas Zc |Ideal gas = 1 !!! Totally out!
115

Critical volume of a fluid is known with less experimental accuracy than either the critical temperature or critical pressure. Critical volume discrepancy can be calculated: Zc |Van der Waals / Zc |real = 3 /8 . Zc |real with Zc |real real fluid critical compressibility Attempt to express compressibility factor as a function of reduced pressure and temperature
116

Critical volume of a fluid is known with less experimental accuracy than either the critical temperature or critical pressure. Critical volume discrepancy can be calculated: Zc |Van der Waals / Zc |real = 3 /8 . Zc |real
with Zc |real real fluid critical compressibility Attempt to express compressibility factor as a function of reduced pressure and temperature
functional relationship between Tr , Pr and Z is determined from experimental data or another EOS, which should be more accurate
117
Critical and other Constants for Selected Fluids
118
Critical and other Constants for selected Fluids (con ed)
119
120
Graph is pretty accurate but there are systematic deviations from the simple corresponding-states relation above. In particular, the compressibility factors for the inorganic fluids are almost always below those for the hydrocarbons. Furthermore, if equation above were universally valid, all fluids would have :he same value of the critical compressibility Zc = Z(Pr = 1, Tr = I); however: from Table , it is clear that Z, for most real fluids ranges from 0.23 to 0.31. 121

A better option would be an equation of the form: Thus to find the value of the compressibility factor for given values Tr and Pr it would be necessary to use a chart of Z = Z(Pr, Tr) prepared from experimental data Alternatively it was suggested that for nonspherical molecules the acentric factor be used as the third correlative parameter, where is defined as:
122
123

Here P vap(Tr = 0.7) is the vapor pressure of the fluid at Tr = 0.7, a temperature near the normal boiling point. In this case the corresponding-states relation would be of the form: However, things become too complex!
124
Generalized Equation of State

van der Waals equation and correspondingstates charts for both the compressibility f actor Z and the thermodynamic departure functions modern application of the corresponding states idea is to use generalized equations of state. Concept already studied with van der Waals Eq.
With the constants a and b obtained from critical properties:
125
PENG ROBINSON Generalized Equation of State
With
126
THANK YOU
127

TDA 301T-8c - Thermodynamic Properties Real Substances

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TDA 301T-8c - Thermodynamic Properties Real Substances

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APPLIED THERMODYNAMICS TDA-301T 2012

Lecture 8: Thermodynamic Properties of Real Substances

Prof Alex Sofianos

Assessment TDA 301T

Thermodynamic Partial Derivatives

Extensive Extensive Derivatives

Similarly we get for CP: ??

More Properties Derivatives

may be re-written as:

Order is not important:

More Properties Derivatives

More Properties Derivatives

Then we get the Triple Product Rule:

More Properties Derivatives

More Properties Derivatives

Alternatively we can write:

Similarly we can derive:

Then we can get:

These are the famous Maxwell Relations

Fundamental Thermodynamic Relation

And therefore: dQrev = T dS Expression for the reversible heat transfer

Fundamental Thermodynamic Relation

Fundamental Thermodynamic Relation - ENTHALPY

Helmholtz Free Energy

Gibbs Free Enthalpy Relation

dU = T dS P dV By comparison with the fundamental relation we see that: Temperature T =

Heat Capacity at constant volume

expressed in terms of Enthalpy

Entropy Change Calculation

Entropy Change Calculation

Equation can be modified: Differentiation of V.-d. Waals equation:

dV , using a Maxwell Relation

If we now substitute: and

Entropy Change Calculation

Entropy Change Calculation

S ( T1, V2) = S ( T1, V2) + = S ( T1, V2) +

Entropy Change Calculation

Entropy Change Calculation

for an isothermal expansion (T1 = T2) we get: V2 S = R ln V1

Entropy Change Calculation

However according to the Maxwell relationship

And by substitution of the dS into previous equation:

Table of useful Thermodynamic Functions

Table of Useful Thermodynamic Functions (Coned)

Table of Useful Thermodynamic Functions (Coned)

Ideal Gas And Absolute Temperature Scale

Ideal Gas And Absolute Temperature Scale

Due to the fact that And :

The last equation of previous slide becomes:

Ideal Gas State Equations

be written as the derivative

Ideal Gas And Absolute Temperature Scale

and if we keep P constant we obtain:

Ideal Gas State Equations

STATEMENTS (Please read!)

Changes in Thermodynamic Properties of Real Substances

i. ii. iii. iv.

Changes in Thermodynamic Properties of Real Substances

Benedict Webb Rubin

And By integration for P1= 0 and V1= we obtain:

Change of State of a Real Gas

Change of State of a Real Gas

Change of State of a Real Gas

or N(t) = N (t=0) + t with = -10 mol/min