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Handout 4
Handout 4
BC
Distillation Column
A(g)
80oF
A(g)
900oF
Heater
A(g),B(g),C(g)
700oF
B(l), C(l)
some S(l)
Reactor
Condenser
Cooler
N2
To stack
B(v), C(v), N2
some S(v)
S(l)
Stripper
Absorber
S(l)
B & C (dissolved)
A(g),B(g),C(g)
250oF
S(l)
to sewer
N2
This process is expensive, wasteful, & inefficient how would you modify it?
4-1
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
BC
Distillation Column
A(g)
80oF
A(g)
900oF
Heater
A,B,C(g)
700oF
A(g)
550oF
B(l), C(l)
Some S(l)
Reactor
Condenser
Heat
Exchanger
Fresh S(l)
B(v), C(v), N2
some S(v)
S(l)
A(g)
150oF
Absorber
Stripper
S(l), B(soln),
C(soln)
S(l)
A(g),B(g),C(g)
250oF
N2
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.
4-2
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
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 liquidsolid systems. Chapter 6 also considers systems with two liquid phases, but we wont in this
class.
V
T
Tc
V-L equilibrium curve ends at the critical temperature (Tc) and critical pressure (Pc). Below Tc
and Pc , vapor and liquid can coexist as separate phases: at and above them, cant have separate
phases. Look up Tc and Pc in Table B.1.
Diagram shows regions in which species exists as solid, liquid, vapor (below Tc), gas (above Tc
and below Pc), & supercritical fluid (above Tc and Pc).
Look at phase diagrams on p. 241. Note that the solid-liquid equilibrium curve for CO2 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. 242. T & P of the cylinder contents are varied
to follow path ABCDE on phase diagram for water. On p. 241, 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.
A point on the V-L equilibrium curve for water is (50oC, 92.5 torr)
P(torr)
92.5
V
50
T(oC)
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Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
A point on the S-L equilibrium curve for water is (0oC, 760 torr)
0oC = melting point (or freezing point) of water at 1 atm (= normal melting point)
Usually neglect effect of pressure on melting point
The equilibrium curves intersect at 0.01oC 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 (Tb) of water at any P
A: Find p* (37C) [______________ torr] ; B: Find Tb at 32.747 mm Hg [______________oC]
Example: Consider two beakers, one containing n-butane, the other n-octane, at room temperature.
n-C4H10
Tb = 0.6oC
n-C8H18
Tb = 125.5oC
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, pi*(T) for all mixture components (i).
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
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*
where
H v
B
RT
(6.1-3)
log10 p* A
T C
(6.1-4)
Given T(oC), look up A, B, C in Table B.4, calculate log10 p* from Eq. (6.1-4), then
log10 p*
p *(torr) = 10
10
B
T C
__________
____ __________
1.5028
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
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.
H2O(v)
T(oC), P(torr)
P(torr)
Vv (L/mol)
H2O(v)
T(oC), P(torr)
Vv (L/mol)
V
H2O(l)
T(oC), P(torr)
l (g/mL)
I
T(oC)
II
Q: How many of the variables T, P, Vv , 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 Vv = RT/P (or use a real gas
equation of state).
Suppose we double the size of the system but keep system conditions constant:
Extensive variablesthose that would double. (V, m, ni in each phase)
Intensive variablesthose that would remain the same. (T, P, v , l , xi , yi)
# phases
Apply the phase rule to Systems I and II on the previous page to confirm your previous results.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
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.
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 25.3oC. (At equilibrium, no
measurable variable changes with time, although molecules are moving constantly within and
between phases.)
H2O(v) @ 25.3oC, P
Vacuum
Evaporation
H2O
H2O(l)
H2O H2O
H2O(l) @ 25.3oC
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: __________________________________________________________________________
H2O
H2O(l)
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Since we know T and P, then all others set (e.g., w and yw can be calculated from an equation of
state or another constitutive relation; see Raoults Law below).
Q: What is the vapor-phase composition in the container at equilibrium?
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
pi yi P pi* ( T )
(6.31)
where pi is the partial pressure of Species i and pi* 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,
yw
pH* 2O (25.3o C)
yDA
________ torr
0.0302 mol H 2 O(v)/mol
______ torr
P
1 yw 0.970 mol DA/mol
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 yi, the gas temperature T, and the total gas pressure P.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Dry Air
P = 1 atm
Water vapor
T= 25C
Liq. water
Water vapor
and
nitrogen
T= 25C
At equilibrium, what is pH2O (the partial pressure of water)?
Liq. water
n1 (mol/s), V1 (L/s)
100 mol/s
0.350 mol C6 H 6 (v)/mol
0.650 mol N 2 (g)/mol
175o C, 820 torr
Gas
y1[mol C6 H 6 (v)/mol]
(1 y1 )[mol N 2 (g)/mol]
15o C, 760 torr
Condenser
Liquid
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Problem: Calculate the volumetric flow rates of the product streams and the percentage of the entering
benzene that is condensed.
DOF Analysis:
_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.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Case 1: yAP = pA*(T) vapor is saturated: gas mixture holds as much vapor as possible at
T,P. Liquid i may or may not be present. Cooling or compression condensation.
Case 2: yAP < pA*(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: yiP > pA*(T) equilibrium not physically possiblesome vapor must condense.
Eventually at some T (= Tdp , dew point temperature), LHS = RHS saturation. Further
cooling then leads to condensation. Thus we can define the dew point temperature at that
pressure, Tdp, by
yiP = pi*(Tdp)
Raise P at constant T
yi ______________ (up, down, constant), P _____ LHS _________________
pi* _________________ RHS _________________
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).
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
If pi*(T) of liquid < P, liquid evaporates. Molecules of liquid transfer from liquid surface.
If pi*(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?
1.00 mole% H2O(v), 99.0% dry air
@ 25oC, 1000 torr
yw P pw* (Tdp ) yw
0.0100
P
__________ torr
3. Degrees of superheat: D.S. = 13.8oC (=difference between the actual temperature and the dew
point).
hr
yw P
*
pw (25o C)
100% 42.1% yw
0.421(___________ torr)
0.0100
______ torr
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.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
S(l)
N2 (stripping gas)
Stripper
High T and/or low P
4-13
Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
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 SO2 formed during combustion:
2SO2 + O2 2SO3.
SO3, sulfur trioxide, can react to form sulfuric acid (H2SO4), a component of
acid rain (SO3 + H2O H2SO4)
Objective: to transfer most of the SO2 from the gas phase to a liquid phase before it can get into
the atmosphere.
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 20oC 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 6.41 on p. 255. (Uses tabulated data for partial pressures for SO2-H2O system.)
Raoults law and Henrys law: Simple equilibrium relations for multicomponent gas-liquid systems.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
pi yi P xi pi* (T )
where pi* = vapor pressure of Component i. Raoults Law is an approximation that applies to vapor
and liquid phases in equilibrium. Note: If xi = 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 xi 1 (the solvent in a very dilute solution)
Apply with care to dissimilar liquids, never to immiscible liquids (e.g., hydrocarbons & water).
Example: A liquid mixture contains 40.0 mole% C6H6(l) (benzene) and 60.0 mole% C7H8(l)
(toluene) at 90oC. Find vapor phase pressure and composition.
Solution: B = C6H6, T = C7H8
yB (mol B(v)/mol)
(1yB) (mol T(v)/mol)
90oC, P(torr)
0.400 mol B(l)/mol
0.600 mol T(l)/mol
90oC
Gibbs Phase Rule: DF = 2 + nspecies nphases = 2 + 2 2 = 2. Since two intensive variables have been
specified for the system (xB = 0.400, T = 90oC), all other intensive variables (in this case, P and yB)
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:
pB* = 10^(6.89272 1203.531/(90+219.888))
pT* = ________________________________________________
yBP = _______________________________________
___________________________________________
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Solutions:
Observe: (a) Pressure is weighted average of component vapor pressures at 90oC. (b) Vapor is
enriched in more volatile component: xB = 0.400 mol B(l)/mol, yB = 0.626 mol B(v)/mol.
pi yi P xi Hi (T )
where Hi (atm/mole fraction) = Henrys law constant for Component i. Note that Hi(T) denotes a
function of T, not times T. It is specific to a pair of species (e.g. SO2 in H2O). Most accurate when
applied to a nondissociating, nonionizing, nonreactive component of a liquid mixture for which xi 0
(e.g., the solute in a very dilute solution, or absorbed gas with a low solubility). Look up Hi (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: _________ (___________________________________________________________________)
H (units of atm)
O2
4.259 x 104
H2
7.099 x 104
N2
9.770 x 104
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) xi 1 (Raoults law); (2) xi 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.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Example: A system at equilibrium at 20oC and pressure P(atm) contains water and CO2 in liquid and
gas phases. The gas phase is 10.0 mole% CO2, and CO2 is only slightly soluble in water. We wish to
determine P and the composition of the liquid phase.
0.100 mol CO2(g)/mol
0.900 mol H2O(v)/mol
20oC, P(atm)
xC [mol CO2(dissolved)/mol]
(1xC) [mol H2O(l)/mol]
20oC
(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
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
(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 HCO2 ?
(c) A pot is partially filled with tap water at 20oC 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
100oC?
Is any vaporization occurring between the emission of the small bubbles and boiling?
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Explain.
Bubble and Dew Point Calculations for Ideal Solutions (Section 6.4c)
Tn bp (benzene) = 80.1oC
Tn bp (toluene) = 110.6oC
Heat
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 80.1oC. That would be wrong.
In fact, the first bubble would form at 95oC and would contain 62.1 mole% benzene and 37.9%
toluene.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Tn bp (benzene) = 80.1oC
Tn bp (toluene) = 110.6oC
Heat liquid mixture at constant pressure. Find T at which first vapor bubble forms (bubble point
temperature) and composition of the bubble.
Since liquid and vapor (bubble) are in equilibrium, and benzene and toluene are similar in structure,
Raoults law applies to each species:
Benzene: (pB =) yB(760) = 0.40pB*(Tbp)
Toluene: (pT =) (1yB)(760) = 0.60pT*(Tbp)
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 Tbp):
xB = 0.400 ; P = 760
pB* = 10^(6.89272 1203.531/(Tbp + 219.888))
pT* = 10^(6.95805 1346.773/(Tbp + 219.693))
yB*760 = xB*pB*
(1yB)*760 = (1xB)*pT*
Solution:
Tbp
95.146
pB*
1181.4
pT *
479.064
Note that Tbp is between normal boiling points of benzene (80.1oC) and toluene (110.6oC), & the
vapor enriched in more volatile species.
Can easily repeat the calculation for new values of xB and P, or do a sweep of xB from 0 to 1.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Cool at constant pressure, find T at which first liquid droplet forms (dew point temperature),
composition of the droplet.
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.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Vapor
Tbp
T
x
2. Repeat for full range of x from 0 to 1, generate two curves.
Fixed P
Vapor
T vs. x
T vs. y
Both phases
Tbp
Liquid
Mole fraction of A
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? ___________________________
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Exercises: Use the Txy diagram for benzene and toluene to solve the following problems:
1. An equimolar liquid mixture of B & T is slowly heated from 20oC to 105oC 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 20oC to 105oC?
______________________________________________________________________________
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
_______________________________________________
_____________________________________________
(d) At what temperature does the last bubble condense? ___________________________________
(e) What is the vapor composition of the last bubble? ______________________________________
3.
An equimolar B-T vapor mixture is cooled from 120oC to 95oC at 1 atm. Use the Txy diagram to
determine the fraction condensed and compositions of the liquid and vapor streams.
nv (mol)
yB [mol B(v)/mol]
Basis: 100 mol
0.50 mol B(v)/mol
0.50 mol T(v)/mol
120oC, 1 atm
and xB = _____________________________
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
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?
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 6.4-3 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 Excel with Solver, both of which do all
the trial-and-error calculations for you.
Example 6.4-5 on p. 263. Be able to explain how you would do the calculation if you didnt have the
Txy diagram.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
x (mol A/mol)
(1x) [mol S(l)/mol]
(6.5-1)
The effective vapor pressure of the solvent is lowered by the presence of the solute. The extent of the
lowering is
ps* xps* (6.5-3)
regardless of what the solute and solvent are.
Fig. 6.5-2
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.
Tb Tbs Tbo
RTbo2
x
H
(6.5-4)
Tm Tmo Tms
2
RTmo
x
H
(6.5-5)
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)