Lecture

Multiphase systems
Equilibrium Equilibrium
Ch i l ilib i th t t i hi h th t ti f th t t Chemical equilibrium, the state in which the concentrations of the reactants
and products have no net change over time
Diffusion equilibrium, when the concentrations of the diffusing substance in
the two compartments are equal the two compartments are equal
Donnan equilibrium, the distribution of ion species between two ionic solutions
separated by a semipermeable membrane or boundary
Dynamic equilibrium, the state in which two reversible processes occur at the Dynamic equilibrium, the state in which two reversible processes occur at the
same rate
Equilibrium constant, a quantity characterizing a chemical equilibrium in a
chemical reaction
Solubility equilibrium, any chemical equilibrium between solid and dissolved
states of a compound at saturation
Thermodynamic equilibrium, the state of a thermodynamic system which is in
thermal, mechanical, and chemical equilibrium
Vapor-liquid equilibrium, where the rates of condensation and vapourization of
a material are equal
Phasediagram: Singlecomponent Phase diagram: Single component
All transition temperatures (Tm, Tb, Ts, etc.) are functions of pressure
T d t t t li id b d i T i i P To condense water: convert vapor to liquid by decreasing T, or increasing P
To evaporate water: convert liquid to vapor by increasing T, or decreasing P
To freeze water: convert liquid to solid by decreasing T, or increasing P
Gibbsphaserule Gibbs phase rule
S h l d l t i i th t A B d C Suppose you have a closed vessel containing three components, A, B, and C
distributed between gas and liquid phases, and you wish to describe this system
to someone else in sufficient detail for that person to duplicate it exactly. What
must you specify? must you specify?
T, P, mA, mB, mC, xA (or yA), xB (or yB),
These variables are not all independent once some of them are specified, others
are fixed by nature, and in some cases, may be calculated from physical y , , y p y
properties of the system components.
Define degrees of freedom (F ) the number of intensive variables that can be
specified independently for a system at equilibrium:
F = 2 + C P
Equation known as Gibbs phase rule. q p
C is the number of components, which for non-reactive systems (in separations),
equals to the number of chemical species;
P is the number of phases that can exist in the system p y
Examples: Gibbsphaserule Examples: Gibbs phase rule
Example 1 Example 1
Determine the degrees of freedom for pure nitrogen gas at equilibrium.
Here, c = 1 (only one species); P = 1 (gaseous phase)
S F 2 So, F = 2.
We can arbitrarily set 2 intensive properties. Beyond that, all the intensive
properties are fixed. So, if we define T and P for the system, and are fixed for p p , y ,
this specific set of conditions.

Example 2: Example 2:
Determine the degrees of freedom for each of the following system at equilibrium.
Specify a feasible set of independent variables for each system.
(a). pure liquid water
(b). a mixture of liquid, solid, and vapor water
(c) a vapor-liquid mixture of acetone and methyl-ethyl-ketone (c). a vapor liquid mixture of acetone and methyl ethyl ketone
The common form of ice, liquid water and
water vapor exist together in equilibrium at
the triple point of water. Since under such
conditions C = 1 and P = 3, F =0, ie system
will be invariant. The triple point of water is
0.0098 oC and 4.58 mm Hg.
VLE in binary systems VLE in binary systems
M th t b t f d f h t th More than one component can be transferred from one phase to another
Each phase may (or may not) contain some of each component
Occurs in separation processes such as distillation, adsorption, stripping, and
scrubbing scrubbing
VLE inbinarysystem VLE in binary system
Estimationof Vapor pressure Estimation of Vapor pressure
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A
=
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T T R
H
p
p
v
v
v
1 1
ln
1 1
Examplesof vapor pressure Examples of vapor pressure
1 The vapor pressure of 1 propanol is 10 0 torr at 14 7 C Calculate the vapor 1. The vapor pressure of 1-propanol is 10.0 torr at 14.7 C. Calculate the vapor
pressure at 52.8 C. Given: Heat of vaporization of 1-propanol = 47.2 kJ/mol
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A
=
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H p
v
v
1 1
ln
ln[10 torr/P
T2,vap
] = (47.2 kJ/mol/0.008314 kJ/Kmol)[1/325.95 K - 1/287.85 K]
ln[10 torr/P ] = 5677( 4 06 x 10 )
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T T R p
v
ln
1 1
ln[10 torr/P
T2,vap
] = 5677(-4.06 x 10
-4
)
ln[10 torr/P
T2,vap
] = -2.305
take the antilog of both sides 10 torr/P
T2,vap
= 0.997
P
T2
/10 torr = 10 02 P
T2,vap
/10 torr = 10.02
P
T2,vap
= 100.2 torr
2. a) Use the Clausius-Clapeyron equation and calculate the vapor pressure
(mm Hg) of trichloroethylene at 15 C, given that the vapor pressure is 100. mm
Hg at a temperature of 31 C. The enthalpy of vaporization of trichloroethylene is
34.7 kJ/mol.
(b) Calculate the enthalpy of vaporization for a compound if its vapor pressure is
71 mm Hg at 14 C and 352 mm Hg at 38 C.
E l Example
Example
Estimationof Vapor pressure Estimation of Vapor pressure
Components Range of A B C Components Range of
Temperature (T),
K
A B C
Acetone 241-350 21.5439 2940.46 -35.93
Ammonia 179-261 21.8407 2132.50 -32.98
Benzene 280-377 20.7934 2788.51 -52.36
Ethanol 270-369 21.8045 3803.98 -41.68
Methanol 257-364 234801 362655 -3429 Methanol 257-364 23.4801 3626.55 -34.29
Toluene 280-410 20.9063 3096.52 -53.67
Water 284-441 23.1962 3816.44 -46.13

Raoults Law Raoult s Law
Id l l ti i t h ti b l l t d b d Ideal solution: mixture whose properties can be calculated based on
the knowledge of the corresponding properties of the pure components
and the composition of the solution
Assumptions:
molecules are similar in size
molecules have similar intermolecular interactions
Where
P is the total pressure
p
i
is the partial pressure of species i
P
i
*(T) is the vapor pressure of species i at T
Raoults Law applied when the mole fraction in the liquid phase Raoult s Law applied when the mole fraction in the liquid phase
approaches unity, or for solutions very similar in chemical nature;
relates the partial pressure with the mole fraction in the liquid phase
Exampleof RaoultsLaw Example of Raoult s Law
Wh t i th h i h 164 f l i (C H O ) i dd d What is the change in vapor pressure when 164 g of glycerin (C
3
H
8
O
3
) is added
to 338 mL of H
2
O at 39.8 C.
The vapor pressure of pure H
2
O at 39.8 C is 54.74 torr
The densit of H O at 39 8 C is 0 992 g/mL The density of H
2
O at 39.8 C is 0.992 g/mL.
Solution:
164 f l i 1 8 l 164 g of glycerin =1.78 mol
338 mL of H
2
O = 18.63 mol

water
= n
water
/(n
water
+ n
glycerin
) = 1.78/(1.78+18.63) = 0.91
P P
0
P
water
=
water
P
0
water
P
water
= 0.91 x 54.74 torr
P
water
= 49.8 torr
Change in pressure is P
final
- P
O
Change = 49.8 torr - 54.74 torr
change = -4 94 torr change = -4.94 torr
Relativevolatility Relative volatility
Relative volatility is a measure of the differences in volatility between two Relative volatility is a measure of the differences in volatility between two
components, and hence their boiling points. Ratio of pure component vapor
pressures
x y /
/
x o
B B
A A
AB
x y
x y
/
/
= o
B B
A A
AB
x p
x p
/
/
= o
x
x
y
ave
ave
) 1 ( 1
=
o
o
y
A
= mole fraction of component A in the vapour,
x
A
= mole fraction of component A in the liquid.
More volatile component Less boiling component Relativevolatility More volatile component
(normal boilingpoint
o
C)
Less boiling component
(normal boilingpoint,
o
C)
Relativevolatility
Benzene(80.1) Toluene(110.6) 2.34
Toluene(110.6) p-Xylene(138.3) 2.31
Benzene(80.6) p-Xylene(138.3) 4.82
m-Xylene(139.1) p-Xylene(138.3) 1.02
Pentane(36.0) Hexane(68.7) 2.59
Hexane(68.7) Heptane(98.5) 2.45
VLE-curve: Benzene-Toluene mixture
at 1 atmosphere
0.9
1
06
0.7
0.8
i
n

v
a
p
o
u
r
,

y
Equilibrium curve
0.4
0.5
0.6
o
n

o
f

b
e
n
z
e
n
e

x
y
ave
) 1 ( 1
=
o
0.2
0.3
M
o
l
e

f
r
a
c
t
i
o
45
o
diagonal line
x
ave
) 1 ( 1 o
0
0.1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of benzene in liquid , x
Henrys Law Henry s Law
where H
i
(T) is Henrys Law constant at T. It generally increases with
increase in temperature. More soluble, less H. At high pressures or p , g p
for gases of high solubility the law looses its validity. For amonia in
water at 20oc, H = 2.7 atm/mol fraction.
Henrys Law applies for dilute solutions of any compound i (i.e., xi
0); relates partial pressure in the gaseous phase with the mole
fraction in the liquid phase e g air dissolved in water fraction in the liquid phase. e.g., air dissolved in water
Example: How many grams of carbon dioxide gas is dissolved in a 1 L
Example of application of Henrys Law
Example: How many grams of carbon dioxide gas is dissolved in a 1 L
bottle of carbonated water if the manufacturer uses a pressure of 2.4 atm
in the bottling process at 25 C?
Given: H of CO in water = 1 65 x 10^3 atm/(mol fraction) at 25 C Given: H of CO
2
in water = 1.65 x 10 3 atm/(mol fraction) at 25 C
Solution:
Mole fraction of CO2 dissolved in water = x= p/H = 2.4/ (1.65*10^3)=
0 001452 0.001452
Moles of CO2/moles of water =x /(1-x) = 0.00145
1 lit of water = 1000/18 = 55.55 moles
Therefore mole of CO2 dissolved = 0 00145*55 55 = 0 081 moles Therefore mole of CO2 dissolved = 0.00145 55.55 = 0.081 moles
= 0.081*44 = 3.553 gms
Vapor liquidEquilibriumRatio Vapor-liquid Equilibrium Ratio
Saturation Saturation
Saturation Saturation
Relative Saturation and Relative Humidity Relative Saturation and Relative Humidity
Molal SaturationandMolal Humidity Molal Saturation and Molal Humidity
Note: Note:
[n
i
/n
i-freegas
]
actual
= [p
i
/(P-p
i
]
actual
and
[n/n ] = [p/(P-p)] [n
i
/n
i-free gas
]
sat
= [p
i
/(P-p
i
)]
sat
TheDry Bulb Wet Bulb temperatures The Dry Bulb, Wet Bulb temperatures
D B lb T T Dry Bulb Temperature - T
db
The Dry Bulb temperature, usually referred to as air temperature
It is called "Dry Bulb" because the air temperature is indicated by a y p y
thermometer not affected by the moisture of the air.
Dry-bulb temperature - T
db
, can be measured using a normal thermometer
freely exposed to the air but shielded from radiation and moisture. freely exposed to the air but shielded from radiation and moisture.
Wet Bulb Temperature - T
wb
The Wet Bulb temperature is the temperature of adiabatic saturation. This
is the temperature indicated by a moistened thermometer bulb exposed to is the temperature indicated by a moistened thermometer bulb exposed to
the air flow.
The rate of evaporation from the wet bandage on the bulb, depends on the
h idit f th i Th ti i d d h th i t i humidity of the air. The evaporation is reduced when the air contains more
water vapor.
The wet bulb temperature is always lower than the dry bulb temperature
b t ill b id ti l ith 100% l ti h idit (th i i t th t ti but will be identical with 100% relative humidity (the air is at the saturation
line).
Dew Point Temperature - T
dp
The Dew Point is the temperature at which water vapor starts to condense The Dew Point is the temperature at which water vapor starts to condense
out of the air (the temperature at which air becomes completely saturated).
Above this temperature the moisture will stay in the air.
if the dew-point temperature is close to the dry air temperature - the if the dew point temperature is close to the dry air temperature the
relative humidity is high
if the dew point is well below the dry air temperature - the relative humidity
is low is low
Someproblems Some problems
Basis:
100 mole
product gas product gas