Chapter 5&6 PDF

CBE202 Part One: Mass Balance
Chapters 5&6: Material balance for single

and multi-phase systems
Introduction to Chemical and Biomolecular Engineering

Tae-Hyun Bae
Department of Chemical and Biomolecular Engineering
Office: 4108@W1-3
thbae@kaist.ac.kr
CBE202: Introduction to Chemical and Biomolecular Engineering

Procedures for MB calculations
• Mass balance for reactive process

ü Based on molecular species balances
ü Based on atomic species balances
ü Based on extent of reactions
Independent atomic species balance

- Sometimes the no. of independent atomic species balance is lower than
the no. of atoms present in the reactions
• The basis in mole or mole/time is always used for the sake

of convenience
CBE202: Introduction to Chemical and Biomolecular Engineering 2

Reduced balance equations (reactive)
• Continuous steady-state process

Input + generation = accumulation + output + consumption
Total mass: input = output

Total mole: input ¹ output
Reactant: input = output + consumption
Product: input + generation = output
Inert: input = output
• Mass balance on atomic species

input = output

Chapters 5 & 6: Material
balance for single and multi-
phase systems
• Ideal and non-ideal gas systems
• Multiphase systems

How to obtain physical properties?
Physical properties (e.g., density or specific gravity) of a process material are
often required to be determined before carrying out a complete mass balance
on a process. Three ways to obtain values of physical properties:
Three ways to obtain values of physical properties:
(1) Look it up.

Perry’s Chemical Engineers’ Handbook, CRC handbook of chemistry and
physics etc.
(2) Estimate it.

Empirical correlations
Reid, Prausnitz and Poiling, “The properties of gas and liquid mixtures.”
(3) Measure it.

By experiment

Ideal gas law
The ideal gas law can be derived from the kinetic theory of gases by
assuming that
• gas molecules have a negligible volume,
• exert no forces on one another, and
• collide elastically with the walls of their container.
The equation usually appears in the form:
(1)
Eq. (1) is an approximation and works well for gases with

temperatures above about 0 oC and pressure below about 1 atm.

Ideal gas law
The Gas Constant, R
8.314 m3×Pa/mol×K
8.314 kJ/kmol×K
0.08314 liter×bar/mol×K
0.08314 m3×bar/kmol×K
0.08206 liter×atm/mol×K
kcal/kmol×K
1.987
liter×mm Hg/mol×K
62.36
ft3×atm/lb-mole×oR
0.7302
ft3×psia/lb-mole×oR
10.73
Btu/lb-mole×oR
1.987

Ideal gas law
At standard temperature (Ts) and pressure (Ps),
To get V for an ideal gas at any T and P, the following equation can
be used:
(2)

Exercise
A stream of air enters a 7.50-cm ID pipe at a velocity of

60.0 m/s at 27 oC and 1.80 bar (gauge). At a point downstream, the air
flows through a 5.00 cm ID pipe at 60 oC and 1.53 bar (gauge). What is
the velocity of the gas at this point?
Answer: 165.8 m/s

Ideal gas mixture
A gas mixture with components A, B, ... are contained in a volumeV at a

temperature T and total pressure P.
Definition of partial pressure (pA) and pure component volume (vA) of A in the
mixture:
pA : the pressure that would be exerted by nA moles of A alone in the same total
volume V at the same temperature T
vA : the volume that would be occupied by nA moles of A alone at the total

pressure P and temperature T of the mixture
T, P, V T, pA, V
T, P, vA

Ideal gas mixture
Ideal gas law also applies to gas mixtures:

Based on partial pressure: (3)
Based on pure component volume:

(4)
Divide eqs. (3) and (4) by eq.(1), PV = nRT, yields:
(5)
(6)
Since yA + yB + … = 1,
pA + pB + … = (yA + yB + …)P = P
vA + vB + … = (yA + yB + …)V = V

Ideal gas mixture
Density of pure gas,
Density of gas mixture,
Where,

Exercise
The mass composition of a gas mixture is given as follows:
H 2, 0.07
N 2, 0.49
CO2, 0.44
100 mol of this gas mixture is contained in a vessel of 3.5 m3 at 37 oC.
Calculate the partial pressure (atm) and pure component volume (m3) of
each individual gas.
Answer:

Nonideal gases
At a sufficiently low temperature and/or a sufficiently high pressure,

ideal gas equation of state provides poor description of the gas behavior.
Therefore, more complex but more accurate equations need to be used.
Critical temperature and pressure

How well or poorly the ideal gas law fits PVT data for a species often
depends on,
where Tr : reduced temperature

Pr : reduced pressure
Tc : critical temperature
Pc : critical pressure

Nonideal gases
What is critical temperature and pressure?
The highest temperature at which a species can coexist in two phases (liquid
and vapor) is the critical temperature of that species, Tc, and the
corresponding pressure is the critical pressure, Pc.
Tc and Pc of some common compounds
Tc (K) Pc (atm)
H2 33.3 12.8
He 5.26 2.26
N2 126.2 33.5
CH4 190.7 45.8
C2H5OH 516.3 63.0
H 2O 647.4 218.3 (Table B.1 of textbook)
A substance at Tc and Pc is at its critical state, and at temperatures above Tc and pressures above
Pc are referred to as supercritical fluids which are neither vapor nor liquid.
Vapor : a gaseous species below its critical temperature
Gas: a species above its critical temperature

Nonideal gases
1. Virial equations
Where B, C and D: 2nd, 3rd and 4th Virial coefficients (functions of T)
Often truncated equation after the 2nd term is used:
w = acentric factor (related to geometry and polarity of a molecule)

Nonideal gases
2. van der Waals equation
Deviations from ideal behavior:
- account for attractive forces between molecules
b - account for the volume occupied by molecules themselves

Nonideal gases
3. Soave-Redlich-Kwong (SRK) equations

Exercise
The measured volumetric flow rate of ethane at 10.0 atm absolute and 35
oC is 1.00 ´ 103 L/h. Determine the specific volume (L/mol) and the mass
flow rate of ethane (kg/h) using the virial equation of state truncated after
the second term.
Answer:

The compressibility factor
Alternatively, compressibility factor (z) can be used to relate PTV.
The compressibility factor of a gaseous species is defined:
The extent to which z differs from 1 is a measure of the extent to which the gas
is behaving nonideally.
Compressibility factor equation of state:
The value of z for various gases can be obtained from generalized

compressibility charts.

Figure 1 Generalized compressibility chart, low pressures. (From D.M. Himmelblau, Basic Principles and Calculations in
Chemical Engineering, 3rd Edition, copyright ã 1974, P.175. Reprinted by permission of Prentice Hall, Inc., Englewood Cliffs, NJ.)

Figure 2 Generalized compressibility chart, medium pressures. (From D.M. Himmelblau, Basic Principles and Calculations in
Chemical Engineering, 3rd Edition, copyright ã 1974, P. 176. Reprinted by permission of Prentice Hall, Inc., Englewood

Figure 3 Generalized compressibility chart, high pressures. (From D.M. Himmelblau, Basic Principles and Calculations in
Chemical Engineering, 3rd Edition, copyright ã 1974, P. 177. Reprinted by permission of Prentice Hall, Inc.,

The procedure for using the generalized compressibility chart for PVT
calculations :
1. Tc, Pc (e.g. Table B.1)
2. For H2 or He, using Newton’s corrections to determine adjusted

critical constants based on:
Tc = Tc + 8 K Pc = Pc + 8 atm
a a
3. Calculate Tr, Pr and Vrideal
4. Use the compressibility charts to determine z, then solve for the

unknown variable.

Example
One hundred moles of nitrogen are contained in a 5 liter
vessel at -20.6 oC. Estimate the pressure in the cylinder.
Solution:
Tc = 126.2 K
Pc = 33.5 atm

Þ
Multiphase Systems Single-component phase equilibrium (pure substance)
Phase diagram
A phase diagram of a pure substance is a plot of pressure vs temperature that shows the
conditions at which the substance exists as a solid, a liquid and a gas. The phase
diagram of water is shown below:
S-L equilibrium curve
C E V-L equilibrium curve

D
B
S-V equilibrium curve

Several familiar terms may be defined with reference to the phase diagram:
(T, P) P T
Boiling point
temperature of the
substance at pressure P
V-L equilibrium curve Vapor pressure of the
substance at normal boiling point
temperature T (P = 1 atm)
S-V equilibrium curve Sublimation point
S-L equilibrium curve Melting or freezing point
S-L-V point Triple point
Right limit of V-L equilibrium curve Critical point

Estimation of vapor pressure

The vapor pressure of a species is a measure of its volatility.
A relationship between p*, the vapor pressure of a pure substance, and T, the
absolute temperature, is the Clapeyron equation:
(1)
Where,

Unless the pressure is extremely high, the specific volume of liquid is negligible
relative to that of the vapor, i.e.
(2)
Apply the ideal gas equation of state to the vapor,
(3)
Substitute eqs. (2) and (3) into (1), we obtain:
Þ Clausius-Clapeyron equation:
(4)
where B is a constant that varies from one substance to another.

Example : Vapor pressure estimation using
the Calusius-Clapeyron Equation
The vapor pressure of benzene is measured at two temperatures,

with the following results:
T1 = 7.6 oC,
T2 = 15.4 oC,
Calculate the latent heat of vaporization and the parameter B in the

Clausius-Clapeyron equation and then estimate p* at 42.2 oC using this
equation.

the Calusis-Clapeyron Equation
Solution
p* (mm Hg) T (oC) T (K)

40 7.6 280.8
60 15.4 288.6
The slope of the line through the two data points on a plot of ln p* versus
1/T for Clausius-Clapeyron equation is:

the Clausius-Clapeyron Equation (Cont’d)
The intercept B is obtained from eq. (4) as
The Clausius-Clapeyron equation is therefore,
Check: T2 = 15.4 oC = 288.6 K,

the Clausius-Clapeyron Equation (Cont’d)
Finally, at T = 42.2 oC = 315.4 K,
The heat of vaporization of benzene, , may be estimated from the

slope of the Clausius-Clapeyron plot ( ) as,

Single-component phase equilibrium
Antoine Equation
- a relatively simple empirical equation that correlates vapor
pressure-temperature data
where
Example: The vapor pressure of acetaldehyde at 25 oC is determined as follows:

Single-component phase equilibrium: Cox chart
Vapor pressure, (psi)
Temperature (oF)
(From A. S. Foust et al., Principles of Unit Operations, Wiley, New York, 1960, P. 550.)

The Gibbs phase rule
Types of process variables

According to IUPAC, an intensive
quantity is one whose magnitude is
independent of the size of the
Process variables system whereas an extensive
quantity is one whose magnitude is
additive for subsystems.
Extensive variables Intensive variables

• Mass • Temperature
• Volume • Pressure
• etc. • Density
• Specific volume
• Mass fraction
• Mole fraction
• etc.

The number of intensive variables that can be specified independently for

a system at equilibrium is called the degrees of freedom of the system.
Let
Õ = number of phases in a system at equilibrium
c = number of chemical species
DF = degrees of freedom
The relationship among DF, c and Õ is given by the Gibbs phase rule.
If no reactions occur among the system components, the phase rule is
DF = 2 + c - Õ
For a system with r independent reactions which have proceeded to equilibrium,
DF = 2 + c - Õ-r

Degrees of freedom
Mass balance calculations

The number of process variables that must be specified for a
process before the remaining variables can be calculated.
Gibbs phase rule
The number of intensive variables that must be specified for a

system at equilibrium before the remaining intensive variables
can be calculated.

Example
Determine the degrees of freedom for each of the following systems at
equilibrium. Specify a feasible set of independent variables for each system.
Independent
System Õ c DF
variables
1. pure liquid water 1 1 2 T, P
2. mixture of water and wet air 2 2 2 T, P
3. Brine 1 2 3 T, P, C
4. a vapor-liquid mixture of ethanol 2 2 2 T, P
and butanol
5. a mixture of water, ice and water 3 1 0 -
vapor
DF = 2 + c - Õ

Example
Determine the degrees of freedom for each of the following systems at
equilibrium. Specify a feasible set of independent variables for each system.
1) NaCl crystal suspended in an aqueous NaCl solution.

2+2-2=2
2) A gaseous mixture containing H2, Br2 and HBr, given that the single
reaction H2 + Br2 Û 2 HBr, has proceeded to equilibrium.
2+3-1-1=3
3) Humid air in equilibrium with condensed water (consider dry air as a
single species).
2+2-2=2
4) A vapor-liquid mixture of four hydrocarbons
2+4-2=2

Multiphase Systems Gas-liquid systems: one condensable component
Consider water-air mixture system:
Apply the Gibbs phase rule to the equilibrium system, (c).
DF = 2 + c - Õ = 2

Since DF = 2 + c - Õ = 2 for such a system,
Intensive variables
Temperature
Pressure only two out of all intensive variables
Density can be specified, and the rest shall be
Specific volume uniquely determined based on the
Mass fraction known values of the first two
Mole fraction variables.
etc.
Suppose T and P are specified, how to calculate the mole

fraction of water in the gas phase, ?

Raoult’s Law (for system with single condensable species)
where yi = mole fraction of component i in an saturated gas atT

P = total pressure of the gas
pi*= the pure-component vapor pressure

Several important points and terms concerning the gas-liquid systems

are summarized here:
1. A gas in equilibrium with a liquid must be saturated with the

volatile components of that liquid.
2. The partial pressure of a vapor at equilibrium in a gas mixture containing a

single condensable component cannot exceed the vapor pressure of the
pure component at the system temperature. If pi = pi*, the vapor is saturated.
If pi > pi*, the condensation of the vapor will occur.
3. A vapor present in a gas in less than its saturation amount is

referred to as a superheated vapor. For such a vapor,
pi = yiP < pi*(T)

(Cont’d)
4. If a gas containing a single superheated vapor is cooled at constant

pressure, the temperature at which the vapor becomes saturated is
referred to as the dew point of the gas. From Raoult’s law,
pi = yiP = pi*(Tdp)
The difference between the temperature and the dew point of a gas is
called the degrees of superheat of the gas.
5. If evaporation takes place at a temperature such that p*< P, the process

involves transfer of molecules from the surface of the liquid to the gas
above the surface, while if p*= P, vapor bubbles form throughout the entire
liquid: that is, the liquid boils. The temperature at which p*= P is the boiling
point of the liquid at the given pressure.

Example: Material balances around a condenser
A stream of air at 100 oC and 5260 mm Hg contains 10.0% water by volume.
1. Calculate the dew point and degrees of superheat of the air.
Solution
From Table B.3, Tdp = 90 oC
Therefore, the air has 100 – 90 = 10 oC of superheat.

Example: Material balances around a condenser (Cont’d)
2. Calculate the percentage of the vapor that condenses and the final
composition of the gas phase if the air is cooled to 80 oC at constant
pressure.
Solution
Since the air becomes saturated at 90 oC, further cooling must lead to
condensation. Since the products are liquid water in equilibrium with a gas
phase, the water vapor in the gas must remain saturated.
Basis: 100 mol feed gas

100 mol n2 mol
Condenser
H2O(v), 10.0% H2O(v), y,
BDA, 90.0% BDA, 1-y ,
T=100oC, T=80oC,
P=5260 mmHg P=5260 mmHg
Saturated with H2O
H2O(liq.), n1 mol
Note: BDA (bone-dry air) means the water-free component of an air-water vapor mixture.

Degree-of-freedom analysis:
ndf = no. of unknowns – no. of independent equations
3 (n1, n2 and y) 2 (mass balance)
= 3 – 2 = 1 >0
Can the problem be solved?

Additional equation comes from the observation that the gas at the condenser
outlet is saturated with water. Apply Raoult’s law:
Balance on BDA, Total mol balance,
100 = n1 + n2
n1 = 3.5 mol H2O condensed
Percentage condensation,

3. Calculate the percentage condensation and the final gas-phase

composition if, instead of being cooled, the air is compressed isothermally to
8500 mm Hg.
100 mol n2 mol
Solution Condenser
Basis: 100 mol feed gas H2O(v), 10.0% H2O(v), y, BDA,
BDA, 90.0% 1-y T=100oC,
T=100oC, P=8500 mmHg
P=5260 mmHg
Saturated with H2O
H2O(liq.), n1 mol
Raoult’s law:
Balance on BDA, Total mol balance,
100 = n1 + n2
n1 = 3.5 mol H2O condensed
Percentage condensation,

Several additional quantities are commonly used to describe the state and
composition of a gas containing a single condensable vapor.
Saturation – refers to any gas-vapor combination

Humidity – refers specifically to an air-water system
1. Relative saturation (Relative humidity):
2. Molal saturation (Molal humidity):
3. Absolute saturation (Absolute humidity):
4. Percentage saturation (Percentage humidity):

Exercise
Humid air at 75 oC, 1.1 bar, and 30% relative humidity is fed into a
process unit at a rate of 1000 m3/h. Determine,
1. The molar flow rates of water, dry air, and oxygen entering the process unit.
2. The molal humidity, absolute humidity, and percentage humidity of the air.
3. The dew point.
Solution 1.
P = 1.1 bar = 825 mm Hg

Exercise (Cont’d)
The molar flow rate of wet air is given by the ideal gas equation of state as:
Consequently,

Exercise (Cont’d)
2.
3.

Multiphase Systems Multicomponent gas-liquid systems
If there are more than one condensable components in a system, there are
relationships governing the distribution of a substance between gas and liquid
phases.
Two simple approximate relationships:
1. Raoult’s Law
pA = yAP = xA pA*(T)
Raoult’s law is generally valid when:
1) xA, the mole fraction of A in the liquid phase, is close to 1,or
2) the mixture consists of similar substances, such as benzene & toluene, etc.
2. Henry’s Law
pA = yAP = xA HA(T)
Where HA(T) is Henry’s law constant.

Henry’s law is generally valid when xA is close to zero.

Multiphase Systems Multicomponent gas-liquid systems
Consider the following two systems at equilibrium:
Gas: T, P Vapor: T, P
Gas Vapor
O2 and H2O Benzene &
toluene
Gas-liquid: Liquid Liquid

Vapor-liquid:
Benzene &
- Henry’s law: O2 and H2O - Raoult’s law :
toluene
- Raoult’s law:
A gas-liquid system in which the vapor-liquid equilibrium relationship for every volatile species
is either Raoult’s law or Henry’s law is said to exhibit ideal solution behavior.

Example: Raoult’s law and Henry’s law
1. A gas containing 1.0 mol% ethane is in contact with water at 20

oC and 20 atm. Estimate the mole fraction of dissolved ethane.
Solution
Hydrocarbons normally are relatively insoluble in water, so that the solution

of ethane is probably extremely dilute. Let us therefore apply Henry’s law.
Page 2-126 of Perry’s Chemical Engineers’ Handbook gives:
Based on Henry’s law,

Example: Raoult’s law and Henry’s law (Cont’d)
2. An equimolar liquid mixture of benzene (B) and toluene (T) is in

equilibrium with its vapor at 30 oC. What is the system pressure and
the composition of the vapor?
Solution
Since benzene and toluene are structurally similar compounds, we may apply
Raoult’s law. Table B.4 of the text gives:
Based on Raoult’s law,

Vapor-liquid equilibrium calculations for ideal solutions
Bubble point calculations
First vapor bubble is formed
T Tbp, P P T, Pbp
L L
heat
Assume: 1) the liquid behaves as an ideal solution and Raoult’s law applies to all
the components,
2) the gas phase can be considered ideal.
1. Calculation of bubble-point temperature, Tbp:
pi = xi pi*(Tbp) i = A, B, C, ...
P = xA pA*(Tbp) + xB pB*(Tbp) + xC pC*(Tbp) +... (1)
Tbp can be obtained from Eq . (1) by trial and error.

Bubble point calculations
First vapor bubble is formed
T Tbp, P P T, Pbp
L L
heat
Composition of the vapor phase (first bubble),

yi = p i / P (2)
2. Calculation of bubble-point pressure, Pbp:

Pbp = xA pA*(T) + xB pB*(T) + xC pC*(T) + ... (3)

Dew point calculations
First drop of liquid is formed

V V
T Tdp, P P T, Pdp
heat
3. Calculation of dew-point temperature, Tdp:
i = A, B, C, ... (4)
(5)
Tbp can be obtained from Eq. (5) by trial and error. Composition of the liquid phase
(first dew) can be found from eq. (4).

Dew point calculations
First drop of liquid is formed

V V
T Tdp, P P T, Pdp
heat
4. Calculation of dew-point pressure, Pdp:
(6)

Example 1:Bubble- and dew-point calculations
Calculate the temperature and composition of a vapor in equilibrium with a liquid
that is 40 mol% benzene-60 mol% toluene at 1 atm. Is the calculated
temperature a bubble-point or dew-point temperature?
Solution Let A = benzene and B =toluene This is bubble-point
calculation. Use eq. (1),
760 mm Hg = 0.4 pA*(Tbp) + 0.6 pB*(Tbp)
Rewrite the above equation in the form:

f(Tbp) = 0.4 pA*(Tbp) + 0.6 pB*(Tbp) - 760 = 0
Evaluate p* based on Antoine equation using constants in Table B.4,

Example 1:Bubble- and dew-point calculations (Cont’d)
Solution algorithm: T (oC) pA* (mm Hg) pB* (mm Hg) f(Tbp) Tnew (oC)
1) Assume a temperature. 80 758.34 291.09 -282.01 100
100 1351.35 556.12 114.21 90

2) Evaluate pA*(Tbp) and pB*(Tbp) for
90 1021.80 406.57 -107.34 95
that temperature from the Antoine
95 1177.69 476.69 -2.91 95.2
equation.
95.2 1184.29 479.68 1.52 95.1
3) Calculate f(Tbp).
95.1 1180.98 478.18 -0.70 95.15
4) If ½f(Tbp)½is not close to 0,
95.15 1182.63 478.93 0.41 95.13
assume another T and repeat
95.13 1181.97 478.63 -0.03
steps 2 to 4 until ½f(Tbp)½is
(It is easy to do such trial-and-error searches using
sufficiently close to 0. spreadsheet programs.)
The solution is taken to be Tbp = 95.13 oC. At this temperature,

pA = xA pA*(Tbp) = 0.4 ´ 1182 = 472.8 mm Hg
pB = xB pB*(Tbp) = 0.6 ´ 478.6 = 287.2 mm Hg
Þ P = 472.8 + 287.4 = 760 mm Hg
Composition of the gas phase, yA = 472.8/760 = 0.622 mol benzene/mol
yB = 287.2/760 = 0.378 moltoluene/mol
Example 2: Bubble- and dew-point calculations
Calculate the temperature and composition of a liquid in equilibrium with a gas
mixture containing 10 mol% benzene, 10 mol% toluene and the balance nitrogen
(which may be considered noncondensable) at 1 atm. Is the calculated
temperature a bubble-point or dew-point temperature?
Solution Let A = benzene and B =toluene

This is dew-point calculation. Use eq. (5),
Rewrite the above equation in the form:
Evaluate p* based on Antoine equation using constants in Table B.4,

Example 2: Bubble- and dew-point calculations (Cont’d)
A trial and error procedure similar to that in Example (1) gives rise to,
Tdp = 52.4 oC
at which, pA* = 297.2 mm Hg

pB* = 101.9 mm Hg
Then from eq. (4),

Graphical representations of V-L equilibrium
Vapor-liquid equilibrium calculations for binary (two-component) systems can be
simplified considerably using a Txy diagram and Pxy diagram.

Multiphase Systems solid-liquid
Colligative solution properties
(solute & solvent) Solution Pure solvent

Vapor pressure D Vapor pressure
Boiling point D Boiling point
Freezing point D Freezing point
Osmotic pressure Osmotic pressure
D
D only depends on the concentration of solute in the solution, not on what the
solute and solvent are. Such properties are referred to as colligative solution
properties.

Consider a solution in which the solute mole fraction is x and the vapor pressure of
the pure solvent at the solution temperature is ps*.
Assume the solute is nonvolatile, nonreactive, and nondissociative.
ps
A solution containing a
nonvolatile solute
x
Based on Raoult’s law,
ps (T) = (1-x) ps*(T) (1)
Since the solute is nonvolatile, the solvent is the only component of the liquid solution
that is also in the vapor. The pressure exerted by this vapor is referred to as the
effective solvent vapor pressure:
(ps*)e = ps = (1-x) ps* (2)
The vapor pressure lowering,
D ps*= ps* - (ps*)e = x ps* (3)

According to the above equation, if a solution contains 20 mol% solute,
psolvent = (1-20%) p*solvent = 0.8 p*solvent

regardless of the temperature, the pressure, and what the solute and solvent are.
P
Po
Pure solvent
Solution
Tms Tm0 Tb0 Tbs T

Phase- equilibrium curves for pure solvent and solution
The higher the solute concentration, the greater is the separation between the pure
solvent and the solution curves.

DTb and DTm can be derived based on Raoult’s law and the Clausius-Clapeyron
equation for dilute solutions (x ® 0),
DTb = Tbs – Tb0 = (4)
DTm = Tm0 - Tms = (5)
where

Exercise: Colligative property calculation
A solution of 5.000 g of a solute in 100.0 g of water is heated slowly at a

constant pressure of 1.00 atm and is observed to boil at 100.421 oC.
Estimate the molecular weight of the solute, the effective solvent vapor
pressure at 25 oC, and the solution freezing point at 1 atm.
Properties of water:
Answer:

Multiphase Systems liquid-liquid
Equilibrium between two liquid phases
+ Asingle
phase
H2O Acetone mixture
The distribution coefficient

Water and acetone are miscible liquids (partition ratio) of acetone in
MIBK and water
MIBK is added
Acetone depleted water phase

Liquid
extraction H2O
A single Phase boundary
phase
mixture MIBK
Acetone enriched MIBK phase (xa, mass fraction of acetone)
Water and MIBK are partially miscible liquids

MIBK: methyl isobutyl ketone

Multiphase Systems liquid-liquid
Phase diagrams for ternary systems
The behavior of partially miscible ternary (three-component) systems may be represented

on a triangular phase diagram.

Exercise: extraction of acetone from water using MIBK
One thousand kilograms of a 30.0 wt% solution of acetone in water a second
stream of pure methyl isobutyl ketone (MIBK) is fed to a mixer. The mixture is
then fed to a settler where two phases form and are withdrawn separately at 25
oC. How much MIBK must be fed to the process to reduce the acetone
concentration in the water-rich phase to 5 wt%, assuming that the fluids remain
in the settler long enough for equilibrium to be achieved?
m1
MIBK-rich phase
1000 kg
mixer settler
W: 70 wt%
m2
A: 30 wt% Water-rich phase
A: 5 wt%
MIBK m0

Triangular phase diagrams for water-acetone-MIBK at 25 oC (composition in wt%)

Solution Basis: 1000 kg of water and acetone mixture fed to the mixer
Sine the two product streams are in equilibrium, their compositions must lie on the
phase envelope and must be connected by a tie line. According to the phase diagram,
Water-rich phase MIBI-rich phase

Acetone 5% 10%
Water 93% 3%
MIBK 2% 87%
Total mass balance: 1000 + m0 = m1 +m2 m0 = 2334 kg MIBK

Acetone balance: 700 = m1 x 10% + m2 x 5% m1 = 2667 kg
Water balance: 300 = m1 x 3% + m2 x 93% m2 = 667 kg

(Cont’d) (Slide 9)
apply ideal gas equation to the air
Apply ideal gas equation for air at entrance point (1) and the downstream point (2),
(1)
(2)
Divide (1) by (2) we obtain,

First convert the mass composition into the molar composition
Apply ideal gas equation for the gas mixture to calculate the total pressure.
Since the gas mixture is an ideal gas mixture,

The Viral equation of state truncated after the 2nd term is
Substitute the value of P, R, T and B into the truncated Viral equation,

Solve the above equation, we obtain
Since the physical problem should have a unique solution, only one of them is the
correct answer.
To determine the answer, use one the following two methods:

1) Estimate the specific volume using ideal gas equation of state.
2) Determine the compressibility factor, z, based on the calculated values
Check the compressibility chart based on Pr and Tr values, z »0.94.

Based on the above calculations, the correct specific volume is
Molar flow rate,
Mass flow rate,

Assign M = molecular weight of the solute (g/mol).

M can be calculated from the following equation:
The effective solvent vapor pressure is

(ps*)e = ps = (1-x) ps*=(1-0.0148)x 23.756 = 23.404 mm Hg

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CBE202 Part One: Mass Balance

Chapters 5&6: Material balance for single

Introduction to Chemical and Biomolecular Engineering

CBE202: Introduction to Chemical and Biomolecular Engineering

• Mass balance for reactive process

Independent atomic species balance

• The basis in mole or mole/time is always used for the sake

CBE202: Introduction to Chemical and Biomolecular Engineering 2

• Continuous steady-state process

Total mass: input = output

• Mass balance on atomic species

CBE202: Introduction to Chemical and Biomolecular Engineering 3

CBE202: Introduction to Chemical and Biomolecular Engineering 4

Three ways to obtain values of physical properties:

(1) Look it up.

(2) Estimate it.

(3) Measure it.

CBE202: Introduction to Chemical and Biomolecular Engineering 5

The equation usually appears in the form:

Eq. (1) is an approximation and works well for gases with

CBE202: Introduction to Chemical and Biomolecular Engineering 6

The Gas Constant, R

CBE202: Introduction to Chemical and Biomolecular Engineering 7

At standard temperature (Ts) and pressure (Ps),

CBE202: Introduction to Chemical and Biomolecular Engineering 8

A stream of air enters a 7.50-cm ID pipe at a velocity of

Answer: 165.8 m/s

CBE202: Introduction to Chemical and Biomolecular Engineering 9

A gas mixture with components A, B, ... are contained in a volumeV at a

vA : the volume that would be occupied by nA moles of A alone at the total

CBE202: Introduction to Chemical and Biomolecular Engineering 10

Ideal gas law also applies to gas mixtures:

Based on pure component volume:

Divide eqs. (3) and (4) by eq.(1), PV = nRT, yields:

CBE202: Introduction to Chemical and Biomolecular Engineering 11

Density of pure gas,

Density of gas mixture,

CBE202: Introduction to Chemical and Biomolecular Engineering 12

100 mol of this gas mixture is contained in a vessel of 3.5 m3 at 37 oC.

CBE202: Introduction to Chemical and Biomolecular Engineering 13

At a sufficiently low temperature and/or a sufficiently high pressure,

Critical temperature and pressure

where Tr : reduced temperature

CBE202: Introduction to Chemical and Biomolecular Engineering 14

CBE202: Introduction to Chemical and Biomolecular Engineering 15

Where B, C and D: 2nd, 3rd and 4th Virial coefficients (functions of T)

Often truncated equation after the 2nd term is used:

w = acentric factor (related to geometry and polarity of a molecule)

CBE202: Introduction to Chemical and Biomolecular Engineering 16

Deviations from ideal behavior:

- account for attractive forces between molecules

b - account for the volume occupied by molecules themselves

CBE202: Introduction to Chemical and Biomolecular Engineering 17

CBE202: Introduction to Chemical and Biomolecular Engineering 18

CBE202: Introduction to Chemical and Biomolecular Engineering 19

Compressibility factor equation of state:

The value of z for various gases can be obtained from generalized

CBE202: Introduction to Chemical and Biomolecular Engineering 20

CBE202: Introduction to Chemical and Biomolecular Engineering 21

CBE202: Introduction to Chemical and Biomolecular Engineering 22

CBE202: Introduction to Chemical and Biomolecular Engineering 23

1. Tc, Pc (e.g. Table B.1)

2. For H2 or He, using Newton’s corrections to determine adjusted