CHE 205 Chemical Process Principles

Section 4: EPCP, Chapter 6

4-1
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)
Balances on Multiphase Systems

A B, B C Afeedstock, Bdesired product, Cbyproduct (waste)








A(g) A(g) A(g),B(g),C(g) B(l), C(l)
80
o
F 900
o
F 700
o
F some S(l)
Heater Reactor
Condenser













A(g),B(g),C(g) N
2

250
o
F

This process is expensive, wasteful, & inefficient how would you modify it?
A(g), 150
o
F
to stack
Cooler
Distillation Column
Absorber
Stripper
S(l)
B & C (dissolved)
S(l)
to sewer
S(l)
N
2

To stack
C(l), some S(l)
to disposal
B(v)
to purification and packaging
B(v), C(v), N
2

some S(v)
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-2
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)
A B, B C Afeedstock, Bdesired product, Cbyproduct (waste)




Distillation Column


A(g) A(g) A,B,C(g) A(g) B(l), C(l)
80
o
F 900
o
F 700
o
F 550
o
F Some S(l)
Heater Reactor
Condenser

Heat
Exchanger



S(l)
A(g)
150
o
F


Absorber Stripper


S(l), B(soln),
C(soln)
A(g),B(g),C(g) N
2


250
o
F

Q: What types of information do we need to know to design this system?
A:


- The function of most chemical process units is to separate mixtures into their components, as in the process just shown. Read text, pp. 237238;
try Test Yourself on p. 238.
Fresh S(l)
S(l)
C(l), some S(l)
to disposal
B(v), C(v), N
2

some S(v)
B(v)
to purification and packaging
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-3
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)
- Most separation processes work by getting different components into different phases and
separating the phases. To design them, we need to know how species distribute themselves
between phases at equilibrium. In this section well consider liquid-vapor systems and liquid-
solid systems. Chapter 6 also considers systems with two liquid phases, but we wont in this
class.

Phase Diagrams (Section 6.1a)
- Form pairsdesignate one pair member as A, other as B.
- Look at phase diagrams on p. 242. Note that the solid-liquid equilibrium curve for CO
2
slopes to the
right, unlike the one for water. (The slopes are highly exaggeratedthe curves are actually almost
vertical.)
- Consider the cylinder filled with water at the top of p. 241. T & P of the cylinder contents are varied
to follow path ABCDE on phase diagram for water. On p. 242, the state of the cylinder is shown for
each point on that path.
A: Explain the top row to your partner and state how you would calculate the water volume at each
point assuming that you know the mass of water in the cylinder.
B: Now you do the same for the bottom row.

- Major features of phase diagram (pure species):
Three equilibrium curves: solid-vapor, solid-liquid, vapor-liquid





V-L equilibrium curve ends at the critical temperature (T
c
) and critical pressure (P
c
). Below T
c

and P
c
, vapor and liquid can coexist as separate phases: at and above them, cant have separate
phases. Look up T
c
and P
c
in Table B.1.
Diagram shows regions in which species exists as solid, liquid, vapor (below T
c
), gas (above T
c

and below P
c
), & supercritical fluid (above T
c
and P
c
).
A point on the V-L equilibrium curve for water is (50
o
C, 92.5 torr)







50
o
C =boiling point of water at P =92.5 torr
92.5 torr =vapor pressure of water at T =50
o
C
V
P(torr)
T(
o
C)
L
50
92.5
S
L
V
P
T
T
c
P
c

CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-4
Normal boiling point =T
b
at 1 atm (100
o
C for water)
Look up normal boiling points of different species in Table B-1
Example:
T
nbp
(toluene) =___________
o
C
T
b

(toluene, P =__________) = __________
o
C; p*(toluene, ________
o
C) =_______
A point on the S-L equilibrium curve for water is (0
o
C, 760 torr)
0
o
C =melting point (or freezing point) of water at 1 atm (=normal melting point)
Usually neglect effect of pressure on melting point
A point on the S-V equilibrium curve for water is (5
o
C, 3 torr)
5
o
C =sublimation point of water (ice) at 3 torr
3 torr =vapor pressure of ice at 5
o
C
The equilibrium curves intersect at 0.01
o
C and 4.58 torr triple point of water (only point where
all three phases can coexist)
Note: The statements we have made about the states of water at given conditions apply only to pure
water. At normal ambient temperatures and pressures, for example, pure water must be liquid, but
water vapor can exist at those conditions in an air-water vapor mixture. (In fact, youre breathing it
now.)
- Table B-3 provides vapor pressure (p
*
) of water at any T, boiling point (T
b
) of water at any P
A: Find p
*
(37C) [____________ torr] ; B: Find T
b
at 32.747 mm Hg [____________
o
C]
- Work through Test Yourself on p. 243.

Estimating Vapor Pressures (Section 6.1b)
- Volatility: Tendency to go from liquid (or solid) to vapor
High vapor pressure high volatility
Low boiling point high volatility
Example: Consider two beakers, one containing n-butane, the other n-octane, at room temperature.







What would happen if the lids were removed?
The butane would __________________________________________________________
The octane would __________________________________________________________
- Many separation processes rely on the high volatility of some species in a mixture and nonvolatility
(evaporation, drying) or much lower volatility (flash vaporization, distillation, condensation) of other
species in the mixture. To design separation processes based on relative volatility, we need to know
or estimate vapor pressures, p
i
*(T) for all mixture components (i).
n-C
4
H
10
T
b
=0.6
o
C
n-C
8
H
18
T
b
=125.5
o
C
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-5
- 4 Ways To Estimate Vapor Pressure (p
*
) from a given T:
1. Measure it. Reliable but time-consuming and costly.
2. Look it up Table B.3 of F&R for water, Perrys Chemical Engineers Handbook, Handbook of
Chemistry & Physics, etc.
3. Use a graphical correlation. The Cox chart, Fig. 6.1-4, p. 247, has nearly linear correlations of
vapor pressure with temperature (see pp. 245246 to know how it is constructed and why the
plots are nearly linear):
Given T, find vapor pressure p
*
. Example: (p*)
propane
(55
o
F) =_________ psi
Given p
*
, find boiling point T. Example: (T
b
)
acetone
(2 psi) =_______
o
F
4. Fit a function to the data. Use it to estimate p* for any T in range of experimental data.
(a) Clausius-Clapeyron equation (Eq. 6.1-3, p. 244).
ln *

p
H
RT
B
v
= +
A
(6.1-3)
where A

H
v
(kJ /mol) =heat of vaporization of the species
R [kJ /(mol-K)] = 8.314x10
3
(gas constant)
T(K) =absolute temperature
Given p* vs. T data, plot ln p* vs. 1/T (rectangular) or p* vs. 1/T (semilog). Find A

H
v

and B using methods of Ch. 2, then use Eq. (6.1-3) to estimate p* for any given T or vice
versa. (See Ex. 6.1-1, p. 244).
Note, this expression was derived assuming that the heat of vaporization is constant and
independent of temperature. In reality, it varies slightly with T. The approximation is OK
over a small temperature range.
(b) Antoine equation (Eq. 6.1-4, p. 246 & Table B.4). More accurate than Clausius-Clapeyron
but harder to estimate parameters (3 instead of 2).
10
log *
B
p A
T C
=
+
(6.1-4)
Given T(
o
C), look up A, B, C in Table B.4, calculate log
10
p* from Eq. (6.1-4), then
10

log *
*(torr) =10 10
B
A
p
T C
p

+
=
Example: For water at T =30
o
C

10
________________
log * ______________ 1.5028
__________ ______________
p = =
+

1.5028
* 10 torr =31.827 torr p =

(From Table B.3, p* =31.824 torr, so Antoine equation is extremely accurate.)

CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-6
Extensive and Intensive Variables and the Gibbs Phase Rule (Section 6.2)
Consider the following two closed systems at equilibrium. Think about where each one is on the phase
diagram.




Q: How many of the variables T, P,

v
V , and (for System II)
l
would you have to specify to be able to
determine the others for each of these two systems? (Suggestion: Refer to the phase diagram.)
A: For System I, you need to specify both T and P (i.e., 2 variables) to know where you are in the vapor
region of the phase diagram. Once you know T and P, you can calculate

v
V =RT/P (or use a real gas
equation of state).
For System II, you need to specify _____________________________________________________
Once you know _________, you can calculate ___________________________________________
Next consider the following closed system with components A, B, C. We can identify a number of
variables describing the physical state of the system in both the liquid and vapor phases:

Vapor: T, P, V
vapor
, m
v
(kg),
v
(kg/L)
n
Av
(mol A), n
Bv
, n
Cv
y
A
[mol A(v)/mol], y
B
, y
C



Liquid: T, P, V
liq
, m
l
(kg),
l
(kg/L)
n
Al
(mol A), n
Bl
, n
Cv
x
A
[mol A(l)/mol], x
B
, x
C


- Say closed system is at equilibriumnothing changes with time.
- Suppose we double the size of the system but keep system conditions constant:
Extensive variablesthose that would double. (V, m, n
i
in each phase)
Intensive variablesthose that would remain the same. (T, P,
v
,
l
, x
i
, y
i
)
- Degrees of freedom of an equilibrium system: DF =Number of intensive variables that must be
specified to determine all the others.
- Gibbs Phase Rule: DF =2 +c H r

#chemical species #phases #independent reactions among the chemical species
Apply the phase rule to Systems I and II on the previous page to confirm your previous results.
H
2
O(v)
T(
o
C), P(torr)

v
V (L/mol)
I
H
2
O(v)
T(
o
C), P(torr)

v
V (L/mol)
H
2
O(l)
T(
o
C), P(torr)

l
(g/mL) II
V
P(torr)
T(
o
C)
L
S
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-7
- Go through Example 6.2-1 on p. 248 and Test Yourself on p. 249.
- Dont confuse the degrees of freedom for an arbitrary process system (which you have been
calculating since Chapter 4) with the degrees of freedom calculated using the Gibbs Phase Rule. The
first one tells you how many process variables (extensive and intensive) must be specified to calculate
the rest. The Gibbs Phase Rule tells you the number of intensive variables that must be specified for
a system at equilibrium in order to calculate all the other intensive variables.
Vapor-liquid equilibrium (VLE) for a single species
- Evacuate a container, charge with pure liquid water, seal. Water evaporates (molecules of liquid
enter vapor phase). As water vapor builds up, reverse flow (condensation) begins. Eventually rate of
condensation equals rate of evaporation, & system reaches equilibrium at 25.3
o
C. (At equilibrium, no
measurable variable changes with time, although molecules are moving constantly within and
between phases.)

Vacuum H
2
O(v) @ 25.3
o
C, P


Evaporation

H
2
O(l) t H
2
O(l) @ 25.3
o
C


Q: What is P in the gas phase in the container at equilibrium? (Hint: liquid and vapor are coexisting
at the same temperature. Think about the phase diagram.)
A: P = _____________________________.
Q: This is also the pressure at the upper surface of the liquid. What happens to P as you move into
the liquid (say, to a depth h below the surface)?
A: __________________________________________________________________________

Vapor-liquid equilibrium for a multicomponent gas with a single condensable species
(Section 6.3). Apply to evaporation, condensation, drying, air conditioning, humidification.
Add liquid water to an open container, seal. Come to equilibrium at 25.3
o
C and 800 torr. Neglect
dissolution of air in liquid water (it happens, but only to a very slight extent.)

Dry air (DA) H
2
O(v), air @ 25.3
o
C, 800 torr

y
w
[mol H
2
O(v)/mol]
Evaporation (1y
w
)

[mol DA/mol]

H
2
O(l) H
2
O(l) @ 25.3
o
C





P
atm
H
2
O H
2
O
H
2
O
H
2
O
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-8

Q: What is the condition of the water vapor at equilibrium?
A: Saturatedgas phase holds as much water vapor as it can at that temperature & pressure.
Note: If a liquid and its vapor coexist at equilibrium, the vapor must be saturated. (If the gas
phase could hold more of the vapor, more liquid would evaporate until the gas phase becomes
saturation.) Corollary: You can only condense a saturated vapor.
Q: What is the vapor-phase composition in the container at equilibrium?
A: Calculate using Raoults Law.

- Raoults law for a single condensable species. Suppose Species i is a component of a gas at
temperature T and pressure P. If i is (a) the only condensable species in the gas (i.e. the only species
that would condense if the temperature were lowered by a moderate amount at the system pressure),
and (b) saturated, then to a good approximation
p y P p T
i i i
= =
*
( ) (6.31) Raoults Law, single condensable species
where p
i
is the partial pressure of Species i and p
i
* is the vapor pressure at the system temperature.
Raoults Law is an additional equation relating unknown variables that we can count in the DOF
analysis. It applies only to saturated vapors. For the system on the preceding page,

2
* o
H O
2
(25.3 C)
_____________ torr
0.0302 mol H O(v)/mol
___________ torr
1 0.970 mol DA/mol
w
DA w
p
y
P
y y
= = =
= =

- In a chemical process with a single condensable species, if you are told that either (a) the vapor of
that species is saturated, or (b) the vapor of that species is coexisting with the liquid at equilibrium
(which means it must be saturated), then you can apply Raoults law [Eq. (6.3-1)] and a relationship
for the vapor pressure as a function of temperature (such as the Antoine equation) to relate the mole
fraction y
i
, the gas temperature T, and the total gas pressure P.

Example: Material balances on an equilibrium condensation process













6 6
2
o
100 mol/s
0.350 mol C H (v)/mol
0.650 mol N (g)/mol
175 C, 820 torr

2 6 6 2
o
[mol C H (l)/s], (L/s)
15 C, 760 torr
n V

1 1
1 6 6
1 2
o
(mol/s), (L/s)
[mol C H (v)/mol]
(1 )[mol N (g)/mol]
15 C, 760 torr
n V
y
y

Gas
Liquid
Condenser
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-9


Q: The benzene vapor in the product gas stream must be saturated. Explain why.
A: _________________________________________________________________________________

Q: In terms of labeled variables, what is the percentage condensation of benzene?
A: % C
6
H
6
condensed =


Problem: Calculate the volumetric flow rates of the product streams and the percentage of the entering
benzene that is condensed.

- DOF Analysis: ___ unknowns (
1
,____________________) n
___ balances (_________________________)
_1_ _______________________
_1_ _______________________
_1_ _______________________
= 0 DF

- System equations. Write all of the equations you need to determine all of the requested quantities
from the given information.











- Solution:
1 2 6 6
________ L/s, ________ L/s, % C H condensed =______________ V V = =


CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-10
Saturated and superheated vapors





- Suppose A is the only condensable species in the gas mixture. Then
Case 1: y
A
P = p
A
*(T) vapor is saturated: gas holds as much vapor as possible at T,P.
Liquid i may or may not be present. Cooling or compression condensation.
Case 2: y
A
P < p
A
*(T) vapor is superheated: gas contains less vapor than it can hold at
saturation. Cooling or compression no condensation until <becomes =, at which point
vapor is saturated
Case 3: y
i
P > p
A
*(T) equilibrium not possiblesome vapor must condense.
- Cool a superheated vapor at constant pressure: What happens?
Initially, y
i
P < p
i
*(T).
Lower T at constant P y
i
& P stay constant (why?) Left-hand-side (LHS) constant,
p
i
* decreases (why?) RHS decreases
Eventually at some T (=T
dp
, dew point temperature), LHS =RHS saturation. Further
cooling then leads to condensation. Thus
y
i
P = p
i
*(T
dp
)
Degrees of superheat: DS =T T
dp
- Compress a superheated vapor at constant temperature: What happens?
Initially, y
i
P < p
i
*(T).
Raise P at constant T
y
i
______________ (up, down, constant), P _____ LHS _________________
p
i
*
_________________ RHS _________________
Eventually at some P (=saturation pressure), LHS =RHS saturation. Further
compression then leads to condensation. Thus
y
i
P
satn
= p
i
*(T)
- If a vapor at T is saturated, it is at its dew point. (Note: For a single species, dew point and boiling
point are the same temperature (point on the VLE phase diagram. For a mixture, the dew point and
the boiling point (bubble point) are different. Stay tuned, Section 6.5).
- Work through Example 6.32.
A(v), non-condensable gases
at T(
o
C), P(atm)
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-11
- Two mechanisms for transferring a liquid to a gas phase (top of p. 253)
If p
i
*(T) of liquid < P, liquid evaporates. Molecules of liquid transfer from liquid surface.
If p
i
*(T) of liquid > P, liquid boils. Bubbles of vapor form in liquid (usually at vessel wall),
erupt from liquid.
- How many ways can we find to give you a mole fraction of a condensable vapor?





1. Mole fraction: y
w
=0.0100 mol H
2
O/mol
2. Dew point: T
dp
=11.2
o
C (=T at which condensation would begin if the gas were cooled at
constant pressure).

* o
*
(11.2 C) __________ torr
( ) 0.0100
__________ torr
w
w w dp w
p
y P p T y
P
= = = =
3. Degrees of superheat: D.S. =13.8
o
C (=difference between the actual temperature and the dew
point).
o o o o
. . 13.8 C 25 C 13.8 C 11.2 C (Proceed as above)
dp dp
D S T T T = = = =
D.S. =0 means ______________________________________
4. Relative saturation, or relative humidity for air-water system: h
r
=42.1% (=ratio of the partial
pressure of the vapor to its saturation partial pressure at the same temperature)given by Eq.
(6.3-4):
* o
0.421(__________ torr)
100% 42.1% 0.0100
____________ torr (25 C)
w
r w
w
y P
h y
p
= = = =
For a saturated vapor, s
r
(or h
r
for air-water) =___________%
5. Molal saturation (molal humidity): Eq. (6.3-5)
6. Absolute saturation (absolute humidity): Eq. (6.3-6)
7. Percentage saturation (percentage humidity): Eq. (6.3-7)
8. Or, you could be told that the vapor is saturated or that it is in equilibrium with a pure liquid of
the same species, in which case
*
Vapor is saturated ( )/
w w
y p T P =
- In a material balance problem, if you are given any of the quantities in Items 28, label the mole
fraction on the flow chart and count Raoults law or the defining equation of the given quantity as
a relation in the degree-of-freedom analysis.
- Do Test Yourselves on pp. 253 & 254 and Example 6.3-3.
1.00 mole% H
2
O(v), 99.0% dry air
@ 25
o
C, 1000 torr
Table _______ or Antoine equation
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-12
Multicomponent Gas-Liquid Systems (Sect. 6.4)
Earlier in Chapter 6 we discussed systems with one condensable species. Now lets extend that to
systems with several species that can condense. We want to know how components are distributed in the
liquid and the vapor phases, so we can design and analyze several common separation processes.
Vaporization/Condensation: Partially vaporize a liquid mixture of volatile species or partially
condense a vapor mixture. The vapor product will be richer in the more volatile species, the liquid
product richer in the less volatile species.







Distillation: Do a series of vaporizations and condensations to improve the separation of components
you can get in a single stage operation. Schematics of multistage distillation are shown on p. 296 of
the text and in the Visual Encyclopedia of Chemical Engineering Equipment (Chemical separations
Distillation columns Plate distillation columns)
Absorption or (environmental) scrubbing: Bubble (sparge) a non-condensable gas through a liquid
solvent or spray a liquid solvent mist into a stream of gas, generally at low T and high P, getting some
or essentially all of the gas into solution. (Examples: SO
2
in stack gas dissolves in solvent in a
scrubbing tower; HCl dissolves in water to make hydrochloric acid; CO
2
dissolves in liquid to make
soda). The higher the solubility of the gas at equilibrium, the more concentrated the product solution
can be. Schematics of absorbers are shown on p. 296 of the text and in the Visual Encyclopedia of
Chemical Engineering Equipment (Chemical separations Absorbers Spray columns, bubble
columns, wet scrubbers)
Desorption or stripping: Bring a dissolved species out of solution into the gas phase at low T and/or
high P (desorption), possibly by bubbling an insoluble gas through the solution (stripping). Note that
absorption and stripping operations may be linked to transfer a species from one gas mixture to
another one.









Absorber (or Scrubber) Stripper
Low T and/or high P Low T and/or high P
A(g), B(g), C(g)
A(g)
S(l), B(soln), C(soln)
B(g), C(g), N
2
(g)
S(l)
N
2
(stripping gas)
100 mol/s
0.500 mol C
5
H
12
(l)/mol
0.500 mol C
6
H
14
(l)/mol
71.4 mol/s
0.600 mol C
5
H
12
(v)/mol
0.400 mol C
6
H
14
(v)/mol
28.6 mol/s
0.250 mol C
5
H
12
(l)/mol
0.750 mol C
6
H
14
(l)/mol
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-13
ExampleSO
2
scrubbing: A =stack gases, B =SO
2
, no C, S =alkaline solvent or slurry
- Why is this an important system? The stack gas comes from a coal-fired furnace or boiler. Trace
amounts of sulfur in the fuel result in SO
2
formed during combustion:
2SO
2
+O
2
2SO
3
.
SO
3
reacts with water vapor in the atmosphere to form H
2
SO
4
, sulfuric acid (acid rain):
SO
3
+H
2
O H
2
SO
4

- Objective: to transfer most of the SO
2
from the gas phase to a liquid phase before it can get into
the atmosphere.
- What information do we need to know to design this system?
o How soluble is SO
2
in water?
o How much SO
2
is coming in?
o What are the regulatory requirements for how much SO
2
can leave in the emissions?
o How much solvent will I lose in the gas stream? This is a concern especially if the
solvent is expensive if its water, we may not care.
Other Examples: Here are some familiar phenomena. See if you know whats going on.
1. A cold can of soda is opened and bubbles slowly form and emerge. What are they, and why is that
happening?
2. A warm can of soda is opened and bubbles rapidly form and emerge. Why is this process different
from the previous process?
3. A pot is partially filled with tap water at 20
o
C and heated on a stove. You first see a lot of very small
bubbles coming out of the water (the water is only lukewarm at the time), then the flow of small
bubbles stops. Eventually the water boilslarge bubbles form below the water surface (mostly at the
bottom surface of the pot) and burst out. What do you think is going on?
In Chapter 6, well find out these answers and answers to other questions about familiar phenomena.

Vapor-liquid equilibrium data: Read through Section 6.4a and make sure you understand Example 6.4-
1 on p. 255. (Uses tabulated data for partial pressures for SO
2
-H
2
O system.)
Raoults law and Henrys law: Simple equilibrium relations for multicomponent gas-liquid systems.
Consider a 2-component condensable gas-liquid system at equilibrium.
n
v
(mol vapor)
y
A
[mol A(v)/mol]
y
B
[mol B(v)/mol] (=1y
A
)
T(
o
C), P(torr)
n
l
(mol liquid)
x
A
[mol A(l)/mol]
x
B
[mol B(l)/mol] (=1x
A
)
T(
o
C), P(torr)

CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-14

- Raoults law (Eq. 6.41)
p y P x p T
i i i i
= =
*
( )
where p
i
* =vapor pressure of Component i. Raoults Law is an approximation that applies to vapor
and liquid phases in equilibrium. Note: If x
i
=1, (6.4-1) reduces to (6.3-1) for a single condensable
species. Raoults law most accurate when applied to
mixtures of structurally similar liquids (straight-chain alcohols, aromatic hydrocarbons,...)
pentane, hexane, heptane
methanol, ethanol, propanol
benzene, toluene, xylene
a component of a liquid mixture for which x
i
~ 1 (the solvent in a very dilute solution)
Apply with care to dissimilar liquids, never to immiscible liquids (e.g., hydrocarbons & water).

Exercise:

What is p
N2
(the partial pressure of nitrogen)?





T=25C
At equilibrium, what is the pressure of the vapor in the container?




T=25C
At equilibrium, what is p
H2O
(the partial pressure of water)?


Dry Air
P =1 atm
Water vapor
Liq. water
Water vapor
and
nitrogen
Liq. water
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-15

Example: A liquid mixture contains 40.0 mole% C
6
H
6
(l) (benzene) and 60.0 mole% C
7
H
8
(l)
(toluene) at 90
o
C. Find vapor phase pressure and composition.
Solution: B =C
6
H
6
, T =C
7
H
8

y
B
(mol B(v)/mol)
(1y
B
) (mol T(v)/mol)
90
o
C, P(torr)

0.400 mol B(l)/mol
0.600 mol T(l)/mol
90
o
C

Gibbs Phase Rule: DF =2 +n
species
n
phases
=2 +2 2 =2. Since two intensive variables have been
specified for the system (x
B
=0.400, T =90
o
C), all other intensive variables (in this case, P and y
B
)
are fixed.
Both components are aromatic hydrocarbons apply Raoults law for each one (2 eqs. in 2
unknowns), using the Antoine equation (Table B.4) for the vapor pressures. The E-Z Solve program
is as follows (we will use pBv and pTv to stand for the vapor pressures of benzene and toluene,
respectively):
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-16
pBv =10^(6.89272 1203.531/(90+219.888)) Antoine equation for benzene
pTv =___________________________________________________ Antoine equation for toluene
yB*P =_______________________________________ Raoults law for benzene
_____________________________________________ Raoults law for toluene

Solutions: pBv =p
B
*
(90
o
C) =1021 torr
pTv =p
T
*
(90
o
C) =407 torr
P =652 mm Hg
yB =0.626
Q: Which is more volatilebenzene or toluene? A: ___________________________
Observe: (a) Pressure is weighted average of component vapor pressures at 90
o
C. (b) Vapor is
enriched in more volatile component: x
B
=0.400 mol B(l)/mol, y
B
=0.626 mol B(v)/mol.
- Henrys law (Eq. 6.42): p y P x H T
i i i i
= = ( )
where H
i
(atm/mole fraction) =Henrys law constant for Component i. Note that H
i
(T) denotes a
function of T, not times T. It is specific to a pair of species (e.g. SO
2
in H
2
O). Most accurate when
applied to a nondissociating, nonionizing, nonreactive component of a liquid mixture for which x
i
~ 0
(e.g., the solute in a very dilute solution, or absorbed gas with a low solubility). Look up H
i
(T) in
Perrys Chemical Engineers Handbook & other standard references.
Q: The ___________ (higher, lower) the value of H, the greater the solubility of a gas in a liquid.
A: _________ (___________________________________________________________________)
- Ideal solution: VLE relationships for all components can be described by either Raoults or Henrys
Law over the entire composition range. If a solution is not ideal, need to use more complex phase
equilibrium relations (a topic treated in CHE 316).
When you use Raoults law or Henrys law for a solution component and are asked to justify doing
so, you can say any of four things: (1) x
i
~ 1 (Raoults law); (2) x
i
~ 0 (Henrys law, nondissociating
nonionizing nonreactive species); (3) mixture of structurally similar compounds (Raoults law); and
if all else fails, (4) we assume ideal solution behavior.
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-17
Example: A system at equilibrium at 20
o
C and pressure P(atm) contains water and CO
2
in liquid and
gas phases. The gas phase is 10.0 mole% CO
2
, and CO
2
is only slightly soluble in water. We wish to
determine P and the composition of the liquid phase.

0.100 mol CO
2
(g)/mol
0.900 mol H
2
O(v)/mol
20
o
C, P(atm)

x
C
[mol CO
2
(dissolved)/mol]
(1x
C
) [mol H
2
O(l)/mol]
20
o
C

(a) Use Gibbs Phase Rule to demonstrate that all unknown intensive variables can be determined (at
least in principle) from the given information.




(b) Which VLE correlations (laws) would you use to express the vapor-liquid equilibrium relationship
for
CO
2
: ___________s law, because _____________________________________________________
H
2
O: ___________s law, because _____________________________________________________
(c) The Henrys law constant for carbon dioxide in water at 20
o
C is 1.38x10
4
atm/mole fraction.
Calculate P and x
C
.





CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-18
Exercise. Use Henrys Law p y P x H T
i i i i
= = ( ) to explain some familiar phenomena:
(a) A cold can of soda (CO
2
dissolved in water and nonvolatile additives) is opened and bubbles
slowly form and emerge. Explain why, using Henrys law in your explanation.




(b) A warm can of soda is opened and bubbles rapidly form and emerge. Explain why this process is
different from the previous process, again using Henrys law. What is the effect of T on H
CO2
?




(c) A pot is partially filled with tap water at 20
o
C and heated on a stove. You first see a lot of very
small bubbles coming out of the water (the water is only lukewarm at the time), then the flow of
small bubbles stops. Eventually the water boilslarge bubbles form below the water surface
(mostly at the bottom surface of the pot) and burst out.
What are the small bubbles? (Hint: Theyre not water.) Why are they forming?








What are the large bubbles? Why is the temperature at which they form slightly greater than
100
o
C?




Is any vaporization occurring between the emission of the small bubbles and boiling? Explain.



CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-19

Bubble and Dew Point Calculations for Ideal Solutions (Section 6.4c)

T
n bp
(benzene) =80.1
o
C
T
n bp
(toluene) =110.6
o
C


0.40 mol C
6
H
6
(l)/mol
0.60 mol C
7
H
8
(l)/mol
20
o
C, 760 torr

- Heat liquid mixture at constant pressure. At some temperature, the first bubble of vapor forms.
Speculate on the temperature at which it happens (the bubble point temperature) and the composition
of the vapor in the bubble.
A logical guess would be that a bubble of pure benzene would form at 80.1
o
C. That would be wrong.
In fact, the first bubble would form at 95
o
C and would contain 62.1 mole% benzene and 37.9%
toluene.

Now lets find out how to do those calculations.
Heat
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-20

T
n bp
(benzene) =80.1
o
C
T
n bp
(toluene) =110.6
o
C


0.400 mol C
6
H
6
(l)/mol
0.600 mol C
7
H
8
(l)/mol
20
o
C, 760 torr

- Heat liquid mixture at constant pressure. Find T at which first vapor bubble forms (bubble point
temperature) and composition of the bubble.



~ 0.400 mol C
6
H
6
(l)/mol
~ 0.600 mol C
7
H
8
(l)/mol
T
bp
(
o
C), 760 torr

y
B
(mol C
6
H
6
(v)/mol)
(1y
B
) (mol C
7
H
8
(v)/mol)
T
bp
(
o
C), 760 torr
Since liquid and vapor (bubble) are in equilibrium, and benzene and toluene are similar in structure,
Raoults law applies to each species:
Benzene: (p
B
=) y
B
(760) =0.40p
B
*(T
bp
)
Toluene: (p
T
=) (1y
B
)(760) =0.60p
T
*(T
bp
)
Substitute Antoine eqn. for vapor pressures, use Solver with 2 eqns. in 2 unknowns (or add equations
to get Eq. (6.44) on p. 259 for T
bp
):

xB =0.400 ; P =760 specify xB (mol B(l)/mol) and P (mm Hg)
pBv =10^(6.89272 1203.531/(Tbp +219.888)) vapor pressure of benzene
pTv =10^(6.95805 1346.773/(Tbp +219.693)) vapor pressure of toluene
yB*760 =xB*pBv Raoults law for benzene
(1yB)*760 =(1xB)*pTv Raoults law for toluene

Solution: Tbp pBv pTv yB
95.146 1181.4 479.064 0.621792
- Note that T
bp
is between normal boiling points of benzene (80.1
o
C) and toluene (110.6
o
C), & the
vapor enriched in more volatile species.
- Can easily repeat the calculation for new values of x
B
and P, or do a sweep of x
B
from 0 to 1.
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-21
- Dew point calculations proceed similarly





0.40 mol C
6
H
6
(v)/mol
0.60 mol C
7
H
8
(v)/mol
150
o
C, 760 torr
Cool at constant pressure, find T at which first liquid droplet forms (dew point temperature),
composition of the droplet.



~0.40 mol C
6
H
6
(v)/mol
~0.60 mol C
7
H
8
(v)/mol
T
dp
(
o
C), 760 torr

x
B
(mol C
6
H
6
(l)/mol)
x
T
(mol C
7
H
8
(l)/mol) [=1x
B
]
T
dp
(
o
C), 760 torr

- Exercise: Derive the equations for the dew point temperature and initial droplet composition
(mole fraction of benzene). Also derive Eq. (6.47) for the dew point temperature.






Notes:
- Henrys Law applies only for components that are dilute AND nondissociating, nonionizing,
nonreactive. For example, HCl in water would quickly ionize completely so Henrys Law cannot be
used.
- In this course, when you have a piece of equipment and vapor and liquid streams exit as products, you
can assume that the streams are in equilibrium and that the vapor is saturated (i.e. can apply Raoults
or Henrys Law), unless told otherwise.
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-22
Txy/Pxy diagrams (Fig. 6.41, p. 262)
1. For binary mixtures (A & B) at a specified pressure, assume x (liquid-phase mole fraction of lighter
component A), calculate T
bp
and y (mole fraction of A in vapor phase in equilibrium with liquid) as
above. Plot T vs. x and y as shown:







2. Repeat for full range of x from 0 to 1, generate two curves.










- Start with liquid mixture, x =z. Heat slowly at constant pressure. First bubble forms when T reaches
the T-x curve. Go horizontally right to T-y curve, read mole fraction of A in vapor.
- Keep heatingmove into two-phase region. More liquid evaporates. At a specified T, go left to T-x
curve to read liquid-phase composition, right to T-y curve to read vapor-phase composition.
- Heat more. Eventually reach T at which only a drop of liquid remains. Mole fraction in vapor is then
z; read mole fraction in liquid drop by going left to T-x curve.
- Questions:
1. What is the physical significance of T where the two curves meet at x =0? _________________

2. What about T at the intersection at x =1? ___________________________

z
T

Liquid
Vapor
x
y
T

T
bp
Liquid Vapor
Both phases
0 1
Mole fraction of A
Fixed P
T vs. y
T vs. x
T
bp
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-23

Exercises: Use the Txy diagram for benzene and toluene to solve the following problems:
An equimolar liquid mixture of B & T is slowly heated from 20
o
C to 105
o
C at 1 atm.
(a) At what temperature does the first bubble form? ______________________________________
(b) What is the vapor composition of the first bubble? ____________________________________
(c) What happens to the liquid and vapor phase amounts and compositions (x and y) as heating
proceeds?
______________________________________________________________________________
(d) At what temperature does the last droplet vaporize? ____________________________________
(e) What was the liquid composition of the last droplet? ___________________________________
(f) From the graph, what is the normal boiling point of benzene? ___________________________
(g) What is the normal boiling point of toluene? __________________________________________
(h) What happens if we start out with pure liquid benzene and heat from 20
o
C to 105
o
C?
______________________________________________________________________________
2. A 60% benzene40% toluene vapor mixture is slowly cooled from 120
o
C to 50
o
C at 1 atm.
(a) What is the dew point temperature? _________________________________________________
(b) What is the composition of the first liquid droplet? _____________________________________
(c) What happens to the liquid and vapor phase amounts and compositions as cooling proceeds?
________________________________________________________________________________
(d) At what temperature does the last bubble condense? ___________________________________
(e) What is the vapor composition of the last bubble? ______________________________________
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-24
3. An equimolar B-T vapor mixture is cooled from 120
o
C to 95
o
C at 1 atm. Use the Txy diagram to
determine the fraction condensed and compositions of the liquid and vapor streams.






Finish labeling the flowchart.

DOF Analysis





From the Txy diagram, y
B
=__________________ and x
B
=_____________________________
Briefly state how you would calculate the fraction (moles condensed/mole fed)?



Exercise
- Suppose a test problem begins, A liquid mixture contains 30.0 mole% A and 70.0 mole% B.
(Specific species are given in place of A and B.) What questions might follow?




- What else might be asked if the species are benzene and toluene and the pressure is constant at 1 atm?






Basis: 100 mol
0.50 mol B(v)/mol
0.50 mol T(v)/mol
120
o
C, 1 atm
n
v
(mol)
y
B
[mol B(v)/mol]
CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-25
Boiling vs. Evaporation. Read the two paragraphs on p. 263 ending with Eq. (6.4-9). Be able to (a)
describe and distinguish between the mechanisms of boiling and evaporation (vaporization), (b) estimate
the boiling point of a liquid mixture of known composition at a specified pressure assuming Raoults law
is valid, (c) explain why the actual boiling point of the mixture would be slightly greater than the
calculated value (see footnote on p. 263).

Practice

- Example 6.4-2 on p. 258.
- Example 6.4-3 on p. 260. Understand the trial-and-error procedures shown in the solution, and also
recognize that you dont need to use any of them if you have E-Z Solve or Excel with Goalseek, both
of which do all the trial-and-error calculations for you.
- Example 6.4-4 on p. 262.
- Example 6.4-5 on p. 263. Be able to explain how you would do the calculation if you didnt have the
Txy diagram.
- Test Yourself on p. 264.
- Problem 6-60 in workbook.

CHE 205 Chemical Process Principles
Section 4: EPCP, Chapter 6

4-26
Colligative Solution Properties (Section 6.5c)

Dissolve a nonvolatile (negligible vapor pressure), nonreactive, nondissociative solid, A, in a solvent, S.






Apply Raoults law to the solvent.


* *
( ) (1 ) ( ) ( )
s s s
p T x p T p T = < (6.5-1)
The effective vapor pressure of the solvent is lowered by the presence of the solute. The extent of the
lowering is
* *
s s
p xp A = (6.5-3)
regardless of what the solute and solvent are.







Figure 6.5-2 shows that the vapor pressure lowering also has the effect of raising the boiling point and
lowering the freezing point of the solvent at a fixed pressure. For dilute solutions (x 0), the boiling
point elevation and freezing point depression are given by the approximate relations of Eqs. 6.5-4 and
6.5-5.

2
2
(6.5-4)

(6.5-5)

bo
b bs bo
v
mo
m mo ms
m
RT
T T T x
H
RT
T T T x
H
A = =
A
A = =
A

Work through Test Yourself, Example 6.5-4 on p. 270.

x (mol A/mol)
(1x) [mol S(l)/mol]
p
s
(torr) [no solute in vapor phase]
Fig. 6.5-2