SOLUTION
THERMODYNAMICS:
APPLICATIONS
TABLE OF CONTENTS
01 02 03
NATURE OF MIXING HEAT EFFECTS
EXCESS PROCESSES OF MIXING
PROPERTIES PROCESSES
01
NATURE OF
EXCESS
PROPERTIES
EXCESS
PROPERTIES
They are defined as the difference
between the property of real
solution and ideal solution which is
important in Thermodynamics and
phase equilibria.
EXCESS
PROPERTIES
ME =Excess Property
M = Molar Property of Real Solution
Mid = Molar Property of Ideal Solution
COMMONLY USED
EXCESS PROPERTIES
Excess Enthalpy
(HE)
determined by
Excess Gibbs mixing experiments Excess Entropy
Free Energy (G ) E
(S E)
comes from experiment
through reduction of
vapor/liquid equilibrium
data
*Functions of Temperature, Pressure and Composition.
Six Binary
Liquid
Mixtures at
50°C
OBSERVATIONS
ΔG is ΔH is either
always positive or
negative negative
TΔS is always
positive The maxima/minima
As x1 → 1 and x1 → often appear at the
0, ΔG, ΔH, TΔS → 0 center (50% mol)
COMMON FEATURES
When an excess property
All excess properties Although 𝐺𝐸 vs. 𝑥1 is
𝑀𝐸 has a single sign (as
approximately parabolic in
become zero as either does 𝐺𝐸 in all six cases),
shape, both 𝐻𝐸 and 𝑇𝑆𝐸
species approaches the extreme value of 𝑀𝐸
exhibit individualistic
purity. (maximum or minimum)
composition
often occurs near the
dependencies.
equimolar composition.
EXAMPLE 1
For an ethanol/chloroform
mixture, if ΔG = -750 J/mol
and ΔH = 750 J/mol. Estimate
the entropy change of
mixing.
ΔG = -750 J/mol; ΔH = 750 J/mol
TΔS = 1500 J/mol
ΔH −ΔG
ΔS =
𝑻
𝟕𝟓𝟎 −(−𝟕𝟓𝟎)
ΔS =
𝟓𝟎+𝟐𝟕𝟑.𝟏𝟓
𝑱
ΔS = 𝟒. 𝟔𝟒𝟏𝟖 ;
𝑲
02
MIXING
PROPERTIES
PROPERTY CHANGES OF MIXING
The thermodynamic properties of mixtures are required for the
analysis of these mixing and unmixing processes.
where M can represent any intensive thermodynamic property of the
mixture, for example, U, 𝐶𝑝, S, G, or 𝑍.
SIMPLIFIED PROPERTY
CHANGES OF MIXING FORMULAS
BINARY SYSTEM WITH PARTIAL
EXCESS PROPERTIES
B. At what
EXAMPLE 2 composition(s)
A binary mixture at 70 °C has do(es) these values
the following departures: exist?
ΔG(x1), J/mol = 400x12 – 400x1
HE(x1), J/mol = 5000x1 – 5000x12
C. Determine the
departure function for
A. What are the maximum the enthalpy of mixing.
values of the Gibbs Free Energy
and enthalpy of mixing?
A binary mixture at 70 °C has the following departures:
ΔG(x1), J/mol = 400x12 – 400x1
HE(x1), J/mol = 5000x1 – 5000x12
A. What are the maximum values of the Gibbs Free Energy and
enthalpy of mixing?
ΔG(x1), J/mol = 400x12 – 400x1
@ x1 = 0.5 (Maximum value)
ΔG = 400 (0.5)2 – 400 (0.5)
ΔG = -100 J/mol
A binary mixture at 70 °C has the following departures:
ΔG(x1), J/mol = 400x12 – 400x1
HE(x1), J/mol = 5000x1 – 5000x12
A. What are the maximum values of the Gibbs Free Energy and
enthalpy of mixing?
HE(x1), J/mol = 5000x1 – 5000x12
@ x1 = 0.5 (Maximum value)
ΔH = 5000(0.5) – 5000(0.5)2
ΔH = 1250 J/mol
B. At what composition(s) do(es) these
values exist?
X1 = 0.5
C. Determine the departure function for the
enthalpy of mixing.
ΔH −ΔG 5000x1 – 5000x12 −(400x12 – 400x1)
ΔS = ΔS =
𝑻 𝟑𝟒𝟑.𝟏𝟓
−𝟓𝟒𝟎𝟎𝒙𝟏𝟐 +𝟓𝟒𝟎𝟎 𝒙𝟏
ΔS =
𝑻
EXAMPLE 3
Determine
The heat of mixing for liquid
expressions
species 1 and 2 at fixed T and P,
measured calorimetrically is
represented in some
appropriate
units by the equation as functions of 𝑥1.
The heat of mixing for liquid species 1 and 2 at fixed T and P, measured
calorimetrically is represented in some appropriate
units by the equation
Determine expressions as functions of 𝑥1.
ΔH = x1 (1 – x1) (40x1 + 20(1-x1))
ΔH = (x1 – x12) (40x1 + 20-20x1)
ΔH = 40x12 + 20x1 – 20x12 – 40x13 – 20x12 + 20x13
ΔH = 20x1 - 20x13 𝑑
𝐻𝐸 = 20 – 60x12
𝑑𝑥1
The heat of mixing for liquid species 1 and 2 at fixed T and P, measured
calorimetrically is represented in some appropriate
units by the equation
Determine expressions as functions of 𝑥1.
𝑑
ΔH = 20x1 - 20x13 𝑑𝑥1
𝐻 𝐸 = 20 – 60x12
= 20x1 - 20x13 + (1 – x1) (20 – 60x12 )
= 20x1 - 20x13 + 20 – 60x12 – 20x1 + 60x13
= 40x13 – 60x12 + 20
The heat of mixing for liquid species 1 and 2 at fixed T and P, measured
calorimetrically is represented in some appropriate
units by the equation
Determine expressions as functions of 𝑥1.
𝑑
ΔH = 20x1 - 20x13 𝑑𝑥1
𝐻 𝐸 = 20 – 60x12
= 20x1 - 20x13 – x1 (20 – 60x12 )
= 20x1 - 20x13– 20x1 + 60x13
= 40x13
03
HEAT EFFECTS
ON MIXING
PROCESSES
The heat of mixing, as defined by
the previous equation is:
This gives the enthalpy change
when pure species are mixed at
constant 𝑇 and 𝑃 to form one
mole (or a unit mass) of solution.
1. ENTHALPY/CONCENTRATION
DIAGRAMS
An enthalpy/concentration (𝐻–𝑥)
diagram plots enthalpy as a
function of composition (mole
fraction or mass fraction of one
species) for a series of isotherms,
all at a fixed pressure (usually 1
standard atmosphere).
EXAMPLE 4
Find the quantity of heat that must
be removed to restore the initial
temperature (25°C) when pure
water is mixed continuously with a
90% aqueous solution of sulfuric
acid to dilute it to 50%. The figure
below shows the excess enthalpies
of H2SO4(1)/H2O(2) at 25°C.
a. Label the points of pure
species.
b. Specify the initial points.
c. Connect the points.
d. Intersect with the final
state.
Note: The energy balance
for this process, assuming
negligible kinetic- and
potential-energy changes, is
the difference between the
final and initial enthalpies:
Q =ΔH = −303.2688 − (−99.2991)
Q =−203.9667 kJ/kg
2. HEAT OF SOLUTION
When solids or gases are
dissolved in liquids, the heat
effect is called a heat of solution
and is based on the dissolution of
1 mol of solute.
EXAMPLE 5
Calculate the heat of formation of LiCl
in 12 mol of H2O at 25°C. The heat of
formation of LiCl(s) is
-408,610 J while the dissolution of 1
mole of this compound in 12 moles of
H2O is -33,614 J.
Calculate the heat of formation of LiCl in 12 mol of H2O at 25°C.
The heat of formation of LiCl(s) is -408,610 J while the dissolution of
1 mole of this compound in 12 moles of H2O is -33,614 J.
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