CHEMICAL ENGINNERING

THERMODYNAMICS

Unit 4
THERMODYNAMIC BEHAVIOR
OF MIXTURES
CHEMICAL ENGINEERING THERMODYNAMICS
 4. Thermodynamic behavior of mixtures:
4.1 Partial Molar Properties
4.2 Mixing Properties
4.3 Ideal Gas Mixtures
4.4 Fugacities and Fugacity Coefficients
4.5 Ideal Mixtures
4.6 Excess Properties. Activities and Activity
Coefficients
 CHEMICAL ENGINEERING THERMODYNAMICS
4.1 Partial molar properties
Let consider a mixture of N moles where Ni moles are the moles in the mixture
corresponding to species i, therefore ΣNi = N, where i = 1, 2, 3, …,n
Molar composition xi = Ni/N, and = 1
For any fluid mixture property B (U, H, S, A, G), where B = B(T, P, N 1, N2, …Nn)
dB = (∂B/∂P)T,Ni dT + (∂B/∂T)P,Ni dP + j≠i
(∂B/∂Ni)T, = j≠i
(∂B/∂Ni)T, = = T,P,Nj≠i
Bi is the partial molar property of B with respect to the compound i of the
mixture and depends on T, P and the mixture composition.
In general (T, P, N1, N2, …Nn) ≠ Bi(T, P) which is the same property for the
pure i compound at the same T and P
IF B = G, (∂G/∂Ni)T,P = = µi, or chemical potential of the species i
Therefore:
dG = - S dP + V dP + if divided by N, per mole of mixture:
dG = - S dP + V dP +
 CHEMICAL ENGINEERING THERMODYNAMICS
4.1 Partial molar properties
It is posible to demonstrate that the same equations valid for normal properties
are also valid for partial molar properties. For example:
d = - dP + dP + xj)T,P,xj,i≠j,n
This derivation is at constant molar fractions (i ≠ j, n) with the exception of the
one with respect the derivation is made (j) and also another one such as the n
one, because n Ni are independent but only n-1 xj are independent (
And for 1 mole
(∂B/∂Ni)T,P,Nj = [∂(B/N)/∂Ni]T,P,Nj = /N – (B/N2) (∂N/∂Ni)T,P,Nj = ( – B)/N
Therefore = B + N (∂B/∂Ni)T,P,Nj
dB = (∂B/∂P)T,Ni dT + (∂B/∂T)P,Ni dP +
At constant T, P (dT = dP = 0) and Nj≠i, and dividing by dNi

=B-
 CHEMICAL ENGINEERING THERMODYNAMICS
4.1 Partial molar properties
For a binary mixture of compounds A and C
= B - and = B -
CHEMICAL ENGINEERING THERMODYNAMICS
4.1 Partial molar properties
Gibbs-Duhem equation
d(NG) = d()) = ) + )
but also d(NG) = - SdP + VdP +)
Combining both equations:
) + ) = - SdP + VdP +)
) = - SdP + VdP
At constant T and P,
)=0
What must be fulfilled by any equations used to estimate = µi
Therefore of the N equations for these estimations only n-1 are
independent.
A similar derivation can be developed for any other partial molar
property
 CHEMICAL ENGINEERING THERMODYNAMICS
4.2 Mixing Properties
The change of properties by mixing is the difference of a
thermodynamic property (V, U, H, S, A, G) between its actual value and
the result of the linear combination of this property values for the
different species forming the mixture at a reference state. The most
common reference state uses to be each compound pure and at the
same T and P of the mixture but other reference states (real or
hypothetical) can be used
ΔBmix = B(T, P, N1, N2, …, Nn) - or
ΔBmix = B(T, P, x1, x2, …, xn-1) -
ΔBmix = f(T, P, x1, x2, …, xn-1) and of the reference state selected
The corresponding partial molar property can also be derived:
= - Bj Therefore ΔBmix = Nj or ΔBmix = xj
= ΔBmix -
And applying the G-D eq. = 0 at T an P constant
 CHEMICAL ENGINEERING THERMODYNAMICS
4.2 Mixing Properties

Enthalpies of liquid
mixtures H2SO4 – H2O
 CHEMICAL ENGINEERING THERMODYNAMICS
4.3 Ideal gas mixtures
The PVTN behavior of mixtures is estimated using the same volumetric
equations of state using as parameters combinations of the
corresponding parameters of the pure compounds.

The simplest mixing rules are:

bm = am = []2

For a better fitting with the real behavior the calculation of a m can be
made using more complex equations with additional parameters such as
am = where aij = (1-δij) , i ≠ j, aii = ai, ajj = aj and δii = δjj = 0
Where δij are called binary interaction parameters and are specific for
any binary mixture of the compounds i and j of the mixture. They are
estimated from phase equilibrium experimental data
 CHEMICAL ENGINEERING THERMODYNAMICS
4.3 Ideal gas mixtures
The PVTN behavior of mixtures is estimated using the same volumetric
equations of state using as parameters combinations of the
corresponding parameters of the pure compounds.

The simplest mixing rules are:

bm = am = []2

For a better fitting with the real behavior the calculation of a m can be
made using more complex equations with additional parameters such as
am = where aij = (1-δij) , i ≠ j, aii = ai, ajj = aj and δii = δjj = 0
Where δij are called binary interaction parameters and are specific for
any binary mixture of the compounds i and j of the mixture. They are
estimated from phase equilibrium experimental data
 CHEMICAL ENGINEERING THERMODYNAMICS
4.3 Ideal gas mixtures
An ideal gas mixture is defined as the fulfilling the following conditions:
 The behavior of an ideal gas (V = NRT/P or V = RT/P and U or H

changing only with T and no with P)

 ΔV
mix = ΔHmix = 0

These equalities imply that = Vi and = Hi , partial molar properties

equal to pure compounds properties at the same T and P.
VIGM = , HIGM =
VIGM = , HIGM =
But mixing always implies a change in entropy:
IGM
= Si – R ln Pi/P = Si – R ln yi,

SIGM = y – R
GIGM = y – RT

Most gas mixtures at not very high pressures behave as IGM

CHEMICAL ENGINEERING THERMODYNAMICS
4.4 Fugacities and Fugacity Coefficients
The fugacity of a compound in a mixture is defined as (constant T):
dGi(T, P, {yi}) = RT Ln
Where is the fugacity of compound i in the given mixture and it is also
a function of T, P and {yi}
If we integrate the previous differential expression from a state at the
same T, P and composition but with ideal gas behavior to the real
state of the mixture:

Gi(T, P, {yi}) - GiIGM(T, P, {yi}) = RT Ln - RT Ln Pi = RT Ln [/(yiP)]

= [/(yiP)]
Where is the fugacity coefficient of compound i in the given mixture
and it is also a function of T, P and {yi}
When P→0 all fluids behave as ideal gases → Pi = yiP and → 1
From RT Ln Φi = → RT Ln =
Pure i i in a mixture
 CHEMICAL ENGINEERING THERMODYNAMICS
4.4 Fugacities and Fugacity Coefficients
Fugacity variation with P:

Fugacity variation with T:

{∂[G/(RT)]/∂T}P = (∂G/∂T)P/(RT) – G/(RT2) = - S(RT) - H/(RT2) + TS/(RT2)
{∂[G/(RT)]/∂T}P = – H/(RT2)
Therefore, as Gi – Gi0 = RT Ln fi/P and - = RT Ln (/P)
Where the 0 superindex means i at the reference state (usually pure I at the same T and P than the mixture)

{∂[(Gi – Gi0)/(RT)]/∂T}P = [∂Ln(fi/P)/∂T]P = - (Hi – Hi0)/(RT2)

{∂[( – )/(RT)]/∂T}P = {∂Ln[/(yiP)]/∂T}P = - ( – )/(RT2)
For an IGM H does not depend on P and ΔHmix = 0
H0 = where are the CP of each i compound as an ideal gas
CHEMICAL ENGINEERING THERMODYNAMICS
4.5 Ideal mixtures
An ideal mixture is defined as an IGM but eliminating the conditions of
ideal gas behavior (this is not a good reference for liquids). So they
must fullfil only: ΔVmix = ΔHmix = 0
VIM = (≠ NRT/P), HIM =
VIM = (≠ RT/P), HIM =
But most liquid mixtures do not behave as ideal mixtures
IM
= Si – R ln = Si – R ln xi,
SIM = x – R
GIM = x – RT
ΔSmixIM = – R
ΔGmixIM = RT
In an ideal mixture IM
= y i f i0

Gas mixtures use to behave as IM but only liquid mixtures of

similar and non-polar compounds behave as IM.
CHEMICAL ENGINEERING THERMODYNAMICS
4.6 Excess Properties. Activities and Activity
Coefficients
(T,P,{xi}) - (T,P,{xi}) = µi - µi0 = RT Ln ai = RT Ln (/fi0)
Where ai is called the activity of the species i in the mixture and the 0
superindex means the i species in a reference state.
Depending of the type of mixtures different reference (or standard
states are used. The most common is the compound pure at the
same T and P as the mixture, but in some cases this is not a
convenient reference state. For example when the pure compound a
the T and P of the mixture appears at a different phase (a solid salt or
a gaseous compound when pure and liquid when dissolved in a liquid
solvent). In those cases other reference or standard states are used:
 For gases dissolved in liquids the compound at infinite dilution in

the solution (xi → 0)

 For solids dissolved in liquids its 1 molal solution behaving as and
ideal mixture (hypothetical state).
CHEMICAL ENGINEERING THERMODYNAMICS
4.6 Excess Properties. Activities and Activity
Coefficients

If the pure compound at the same T and P of the mixture is used as

standard state fi0 = fi(T,P)

For and ideal mixture = x f Therefore aIM = x

For non ideal mixtures ai/xi = /(x f) = γi activity coefficient

CHEMICAL ENGINEERING THERMODYNAMICS
4.6 Excess Properties. Activities and Activity
Coefficients
Excess properties: BEX = B – BIM or BEX = B – BIM
BEX = ) and EX
= j - jID
BEX = EX and ΔjEX = Δj - ΔjID

The excess properties do not depend on the standard state if the

same standard state is used for both B and BID
The most important excess property is GEX = HEX – T SEX, where
HEX = ΔHmix
The solutions with SEX = 0 are called regular solutions and their GEX
can be calculated using only heats of mixing
An important equation is:
RTLn() = RTLn(γixi) = i = iEX + iIM = iEX + RT Ln xi
Therefore iEX = RT ln(γi)and Ln(γi) is equal to the partial molar
excess Gibbs free energy divided by (RT)
CHEMICAL ENGINEERING THERMODYNAMICS
4.6 Excess Properties. Activities and Activity
Coefficients
)P,x = (1/R) [∂(/T)/∂T)/]P,x = - iEX/(RT2) = - i/(RT2) as iIM = 0

P)T,x = [(1/(RT)] [∂/∂P)/]T,x = - iEX/(RT2) = - i/(RT2) as iIM = 0

An important equation (Gibbs-Duhem) can also be derived:

/(RT) = = - [ΔHmix/(RT2)] dT + [ΔVmix/(RT)] dP
At constant T and P

= 0 or /∂Nk)T,P, Nj≠k = 0
This equation is used to control the consistency of the models to
estimate activity coefficients and of data used to estimate their values
CHEMICAL ENGINEERING THERMODYNAMICS
4.6 Excess Properties. Activities and Activity
Coefficients
CHEMICAL ENGINEERING THERMODYNAMICS
4.6 Excess Properties. Activities and Activity
Coefficients
CHEMICAL ENGINEERING THERMODYNAMICS
4.6 Excess Properties. Activities and Activity
Coefficients
There are many GEX models that can be used to calculate activity
coefficients. They content from 1 to various parameters that must be
estimated from experimental data (Van Laar, Margules, Hildebrand-
Scatchard, Flory-Huggins, Wohl, Wilson, NTRL UNIQUAC, ..)

When no experimental data are available the UNIQUAC model can

be used through the UNIFAC group contribution procedure to
estimate the UNIQUAC parameters