2SO3, observed

pressure) vs. T are

mixture
at
1000
K
on derived in (a) Solving a quartic equation can be avoided in this part of the
KP
0.245
1.99
4.96
9.35
0, and xSO3 !of0.440.
0.200 mol of N2, 0.300 mol of H2, and 0.100 mol
ndependent
T problem.) (b)
ideal gases. (b) Find 7.8 (a) For
cind556
and f if we574
con485water, calculate
534
of NH3. T/Kpure liquid
!
#
ossible phases are sider that the chemical species present are H2O, H , OH , and
(a) Using
only
these data,
findformed
#H,
#S
at 534
for
ssume
For the
gas-phase
NF2#G,
" the
3Hand

2NH
, aKclosed
O)
by
hydrogen-bonded
dimers
(Hreaction
value ofideal-gas
the num- 6.29
2association
3reCHEM
211
of A and 18.0 mmol this reaction. (b) Repeat 2for2574
K.of Nto, c4.20and
What
happens
f ifof
weH2, and
action 2H
of degrees
enumber
expression
for system
initially
contains
mol
2O (H
2O)
2. (b)4.50
Problem
Sheet
for Assignment-3
2 ind mol
d to 600 K, and the add hydrogen-bonded
to the
list
species? possible
trimers
(Hmaximum
ded to specify for
the
andofminimum
of the
NHideal-gas
2O)3 PCl
6.14molFor
reaction
3. Give the
Dn isexpression
established. The 1.00
5(g) PCl3(g) " Cl2(g),
te K
K to values
at equilibrium
ofestimate
eachf,of
the
quantities:
j; nisN2;
at following
400
that #H
Appendix
data to
K
P at 1000
7.9useFind
the relation
between
cind
p ifK;
(a)assume
rigid,
permeure
1085
torr and
P, and
n independent
of
T.
conducting
walls separate all the phases of a
the able,
H2; nthermally
NH3.
atsystems,
600 K, find
assuming

asonable choice of system; (b) movable, impermeable, thermally conducting walls
he6.15
standard
enthalpy
of combustion
25C
of
liquid
acetone
(CH
ction A 2B.1. T6.30
(a)
For
the ideal-gas
reaction
A"

reaching
equilibH2B

CO(g)
"3)2CO to
The
CHat4(g)
2O(g)
all
theideal-gas
phases
ofreaction
a system.
t consideration of separate
2
and
CP,m,B(b)#
eCO
and
H2at
O(l)
is -1790

(CH3J/
)2CO(l).
(g)constant
600
K
has kJ/mol.
#H
!Find
217.9
kJ/mol,
$298
!xof
242.5
3H
# and
[x B#S
/(1
)](P/P),
T and
P,
show
thatK
2(g)
f H
f U
and
0.01031
mol
of rium
2at
P 298
B
of
sucrose.
An
(molxK),
! 72.4 kJ/mol.
Estimate(b)
theUse
temperature
nstants
and and
these
isand
the#G
equilibrium
mole fraction.
the resultatof
n the
container;
olid
sucrose
anthe where
B7.2
Section
1
2
1/2
26 xfor
this
reaction.
made.
which
KPor!
T2. at (a)
e from
T1 tosolid
#
" 4z)State
$approximations
z],
where
z!
KP P/P.
to True
show
that
g)
wassucrose,
established
Solid
2 [(z normal
7.10
false?
The
boiling
point
is the
temB(a)
wn.
Find
an Liqex-torr.
sured
as 231.2
nd ribose.
(e)
(c)
A reaction
system
is
initially
composed
of
0.200
mol
ofK,O2
perature
atFor
which
the4(g)
vapor
of2NO
a in
liquid
equals
1 atm.
2. For
the
O
2NO
the
range
298
to 900
O4(g)

6.16
theNthat
N2pressure
2reaction
2(g)
2(g) in the range 298 to
sideal
sucrose
solution
gases.
(Hint: reaches
(b)900
At the
critical point at
of 5000
a pure K
substance,
thebar.
densities
and 1.50
Find of
thetheequilibK,equilibrium
us sucrose solution, rium
liquid mole
and thefraction
vapor areand
equal.
(c) The
possible value P #
moles
of bminimum
O$c>1T>K2
2 and O, given that K
enzene (these two 49.3
K
!
a1T>K
2
e
of f infor
the O
phase
rule is 1. P(d) The normal boiling point of pure
$6 at 4000
2(g) 2O(g) at 5000 K. (d ) Find the equilibrium
! 3 %of10
water is precisely
xture
the vapors
100C.
(e) The enthalpy
of vaporization
a NO
13, b ! $1.304,
and
fractions
in
an10equilibrium
mixture
of
NO2 of
2 4
and
c
!
7307.
(a)
where
a
!
1.09
%
tial pressures PN2 ! mole
liquid becomes zero at the critical point. ( f ) Along a line in Find
gases
at
25C
and
2.00
atm.
Use
Appendix
data.
as
functions
of
T
for
expressions
for
#G,
#H,
#S,
and
#C
orr. Is the mixture in a one-component phase diagram, f " 1. (g)
P At the solid
mponents,
what
is
this
reaction.
(b)
Calculate
#H
at
300
K
and at 0.600
K.

unt of N(g) increase 6.31
liquidgas
pointKof #
a one-component
(h)
CO2SO
At triple
727C,
3.42 for 2SOsystem,
(g) " fO"2(g)

(g).
2
ist
in
equilibrium?
P
2
ibrium at 4000 K in has no normal boiling point. (i) Ice melts above 0.00C if the 3
3.10 of
mmol
of O
and 1.446.2mmol
of6.3
SO3
of SO
6.17 mmol
Complete
the
part (b)
of2,Example
in Sec.
H. Hildebrand and If 2.65
2, work
pressure is 100 torr.
3
empty
vessel6thheld
at 727C,
find
hotograph
is assumed
independent
of T,
thenthe
asplaced
follows.
that
if185-cm
#CPChemistry,
roblem
6.32 in
of Show
Lan
evine
Physical
Edition:
n>molof a sys-3. Pare
What must be true equilibrium
7.11 For each
of the following
conditions,
which
amounts
of all species
andstate
find
the phase
equilibrium
$
1T
2
2
H1T
K
1
1
P
P
2
1
ts in this system? pressure.
(solid, liquid, or gas)
ln of H2O!has the lowest
$ bpotential.
a chemical

(a) 25C and 1 atm; K
(b)
25C
and 0.1
R torr; (c)
T10C Tand
2 500 atm;
P 1T
12
4, write down the
Forand
the10ideal-gas
reaction
B C, a mixture with
(d) 100C
atm; (e) 100C
andA
0.1"atm.
in- 6.32
hen
KP must
roneutrality
condihe
ideal-gas
reaction
1T
2 # T2.000
C
T1mol is at
P 1n
2
A # 1.000 mol, nB # 3.000 mol, and
ction,
!H must n7.12
or the independent
For the H2O phase diagram "
of Fig. 7.1a,Castate
ln the"num-$ 1 b
at 300 K and 1.000 bar.RSuppose
the pressure
is
2
ution of KBr and equilibrium
ber of degrees of freedom (a) along the line
AC; (b) Tin1 the Tliqincreased
to 2.000
bar; find the new equilibrium
s?
(a)between
KP is always
ions
ion isothermally
uidUse
area;this
(c) at
the
triple
point
A.

equation and Appendix data to estimate KP,600 for
less.
(c) Kgive
condition
an amounts.
P is never

2NO
N2OThe
pressure
4(g) vapor
2(g). of water at 25C is 23.76 torr. (a) If
on is the negative of 7.13
as
the following 0.360 gFor
rigid
PCl3container
(g) " Clat2(g),
use data
reaction
PCl
of Hthe
placed in
an5(g)
empty
25C
2O is
e reverse reaction is 6.33
by
T
and
considering
T
as
a
fixed
6.18
(a)
Replacing
T
2K
1 AssumetemP(CO)
# 342.0the in
give
reasonable
with
" 10.0 L, state
what
phase(s)
present
at equilibrium
atChemistry,
25Careand
at
500
K.
idealtheV Appendix
to find
th E
P
on.
( f )a Doubling
4. Problem
7
.14
o
f
L
evine
P
hysical
6
dition:
perature,
we
can
write
the
approximate
equation
(6.39)
in the
les:
(a)
a
gaseous
O
in
each
phase.
(b)
The
same
as
(a),
except
and
the
mass
of
H
ressure
is
439.5
behavior
and
2 neglect the temperature variation in !H. If
coefficients squares
gasform
! $#H/RT
" C, where
the
constant C equals
ln20.0
KP(T)
present
that
the we
that
V
"
L.
State
any approximations
you
make.
rction
CO of"(so
Cl
,
calculate
the
equilibrium
mole fracstart
with
pure
PCl

temperature
2
ln KP(T1) " #H/RT1. 5Derive the following exact equation:
ure gas
of Nin
2, H
2, and
on
World

of all species at 500 K and 1.00 bar.
nitial composition of tions
action equilibrium; 7.14 Ar has normal melting and boiling points of 83.8 and
! $H
S
ln KPis1Tat2 83.8
87.3 K; its triple point
K and
0.7 "
atm,
and
T>RT
T>Rits critical
n that all the N2 and 6.34
At
400
K,
K
#
36
for
N
(g)
"
3H
2NH 3(g).
P
2
2(g) whether
temperature and pressure are 151 K1 and 48 atm.3 State
eolNH
;
(d)
A
gasof3 COF2 are Find
400 or
K gas
forunder
(a) each
" following
NH 3(g);
2 N2(g)
2 H2(g) condiP at liquid,
Ar is aK
solid,
of the
rium
with
the
conalyst for the gas- (b)
(g) atm
and
N2(g)
(g).atm and 80 K; (c) 0.8 atm
2NH
tions:
(a) 30.9
90 "
K; 3H
(b) 20.7
;
(e)
a
iation
of
N
2
. Use data in the and 88 K; (d) 0.8 atm and 84 K; (e) 1.2 atm and 83.5 K; ( f ) 1.2 atm
o partially decom- 6.35
Given the ! G1000 gas-phase values 84.31 kcal/mol for
and 86 K; (g) 0.5 atmf and
84 K.
addition, some of n-pentane,
83.64 kcal/mol for isopentane, and 89.21 kcal/mol
med
to vapor.
7.15neopentane,
Figure 3.7 shows
a reversible
isobaric present
path frominliquid
2C "
2D, it(No
is for
find the
mole fractions
an equilib
water mixture
at #10Cofand
1
atm
to
ice
at
#10C
and
1
atm.
00 mol of A and rium
these gases at 1000 K and 0.50 bar. Use
Fig.
7.1
to
help
devise
a reversible isothermal path between
K
P isnheld
!
theand
relation
H "
Use
! f G data in the NIST-JANAF tables (Sec. 5.9) to
these two
states.
nts.
(b) Ifrelation.
1.000 6.36
neutrality

osel
beata 500
stoichiomeK and

m amounts.

find KP at 6000 K for N(g) N"(g) " e$(g).

7.16 For each pair, state which substance has the greater
at its normal
point: (a)
Ne or Ar;
(b) H2O
$vap Hm Suppose
6.37
thatboiling
for a certain
ideal-gas
reaction,
theorerror in

7.22 The normal boiling point of diethyl ether (ether) is

34.5C, and its !vapHm,nbp is 6.38 kcal/mol. Find the vapor pressure of ether at 25.0C. State any approximations made.
7.23 Use the Clapeyron equation and data from Prob. 2.49 to
find the pressure at which water freezes at (a) $1.00C;
(b) $10.00C.
The
experimental
values
these pressures
5. Problem
7.24 of L(c)
evine
Physical
Chemistry,
6th of
Edition:
are 131 atm and 1090 atm. Explain why the value you found in


(b) is greatly in error.

7.24 The
heat of fusion
of Hg
at 291
its normal
lev38627_ch09.qxd
3/14/08
1:31 PM
Page

melting point,
$38.9C, is 2.82 cal/g. The densities of Hg(s) and Hg(l) at
$38.9C and 1 atm are 14.193 and 13.690 g/cm3, respectively.
Find the melting point of Hg at (a) 100 atm; (b) 500 atm.

(a) Find the average !Hm of sub

range. (b) Find the vapor pressu

7.31 Use Troutons rule to show

boiling point Tnbp due to a sm
roughly !T ! Tnbp !P/(10 12 atm

7.32 (a) At 0.01C, !vap Hm

!fus Hm of ice is 6.01 kJ/mol. Fi
at 0.01C. (b) Compute the slo
lines at the H2O triple point. S
State any approximations made.

7.33 Vapor-pressure data vs.

7.25 (a) Repeat the ethanol example of Sec. 7.3 using
the av289
sented by the Antoine equation

erage of the 25C and 78.3C !vap Hm values instead of the
6. Problem
.13 of LCompare
evine Physical
Chemistry,
6thexperimental
Edition:
78.3C9value.
the result
with the
25C
A$
and1P>torr2
b, each"comp
9.36 Find !mixG, !mixV, !mixS, and !mixH for mixing 100.0 g 9.46 Let phases a ln
vapor pressure. (b) The actual molar volumes of ethanol vapor
equilibrium with each other. Show
of benzene
with and
100.0
gatm,
of toluene
atPM20C
and 1328
Assume
be inwhere
andless
9.13
25C
1and
a 1:07
solution
of Page
72.061
gatm.
of H
lev38627_ch10.qxd
3/14/08
2O are
A, B, and C are constants c
in theAttemperature
pressure
ranges
of this
example
3
ideal solutions, then x a1 " x b1 and
an ideal solution.
2 form
OH
has
a
volume
of
307.09
cm
.
In
this
solug
of
CH
ution-composition 192.252
3
kelvin. The Antoine equation is
than"those predicted by
PV " RT.
" Will inclusion of nonideal3/mol.mFind V
two phases have the same compositio
cm
in
this
solution.
V H2O ! 16.488
tion,
CH
3OH
H
)
and
toluene
(C
H
CH
)
form
nearly
9.37
vapor-pressure
typically
ity ofBenzene
the vapor(Cimprove
or
worsen
the
agreement
of
the
result
6 6
6 5
3
phase.
Hence liquidsrange,
that form
ideal 1s

ideal
solutions.
At
20C
the
vapor
pressure
of
benzene
is
74.7
the temperature range 11C to 16
of (a)The
with
the experimental
25C vapor
pressure?
density
of a methanolwater
solution
that is 12.000 all proportions.
b. 9.1 change if T 9.14
3
torr,
and
that
of
toluene
is
22.3
torr.
(a)
Find
the
equilibrium
par18.3036, B " 3816.44, C " $46
weight percent methanol is 0.97942 g/cm at 15C and 1 atm.
tial
(s)
(buckmin7.26
The
average
enthalpy
ofsolution
sublimation
of C
60
vapor
pressures
above
a 20C
of 100.0
g
of
benzene
For
a
solution
that
is
13.000
weight
percent
methanol,
the
dention to
Section
9.7find vapor pressures of
roblem
9.38
of toluene.
Levine
Physical
Chemistry,
6thwas
Edition:
sterfullerene)
over
the
range
600
to
800
K
determined
by
328
solute HCl in each7. Psity
3
plus
100.0
g
of
(b)
Find
the
mole
fractions
in
the
vapor
is 0.97799 g/cm at this T and P. Since the change in solu- 9.47 compare
withthetheconstant-T-andexperimental v
Consider
"ofthe
allowing
vapor
in equilibrium
withV
solid
at a fixed
mL of a solution tion
phase
thatUse
isthe
inthe
equilibrium
with
theestimate
solution
part
(a).
composition
isDavies
small,
we
can
by
10.37
equation
to estimate
(a)
g
for
0.02
(b)
Use
the
Antoine
equation t
Section
A
nA,2 # n10.9
!
adding
A,1 moles of solvent A
g of a 10.0 weight
temperature to leak into a mass spectrometer and measuring
the
100C. State
any
approximations
25C;pressures
(b) g! for
an aqueous
mol/kgAtCaCl
10.48
Use
(10.83)
and
the &o
1) that
contains
ni moles
100C
theatvapor
of CaCl
hexane
octane are25C
2(aq)
2 inand
"
tion (solution
whose HCl molal- 9.38
#
The
graph
of ln (IT/K) verintegrated V
intensity
I of
the
C60 peaks.
"
1
0V>
0n
2
!
1
V>
n
2
A
A
T,P,n
A
T,P,n
sults,
seeanProb.
8.43.)
B
B mixture
mol/kg,
solution
that
10.9
example
to find
S 298(s
to give
ideally
dilute
solution
1836
and
354has
torr,CaCl
respectively.
A0.02
certain
liquidCuSO
of 4 of ASec.
2 molality
4 molality
$1
sus T was found to have an average slope of $2.18 % 10 K
of A. Experimental vapor-pressu
these
compounds
has a3vapor
pressure
of 666
torr at (c)
100C.
)3 molality
0.005
mol/kg;
g" and
0.01 two
mol/kg,
" and Al(NO
moles7.34
OH)
for
a
methanolwater
solution
at
15C
V
Calculate
(CH
Show
that
$ T1
[C.
K.
Mathews
et
al.,
J.
Phys.
Chem.,
96,
3566
(1992)].
The
10.49
Use
in
2proces
3
is 30.00% CH3OH Find
thatdata
!G when
forthe
thisTAppend
thethe
mole
fractions
in the
liquid mixture and in the vapor solutions show
solution
of1 part
(a).
g# for
"
OHshown
by weight.
Then calculate
1 Assume
atm
thatan
isideal
122%
CH3be
placed
with (7.24).
Hints: In#(7
solids
vapor
pressure
can
to be proportional
to IT &S
1 atm is 8.911 mol/ and
phase.
solution.
298 for (a) H (aq) " OH (a
"

G
"
n
RT
1ln
x i,2 # ln xi
i
"
for
this
(H2O)
and (aq)
use (8.36).
C60(s)CaCl
in this
temperature
(see
Prob.
Find !mol/kg
solution,range.
what 2H
(a)14.36).
Forsolution.
a 0.001
H2O(l) " CO
subHm of25C
2(aq)
and 1 atm. (b) Find V10.38
2(g).
9.39
A solution
of
hexane and heptane
at 30C
with
hexane to
"is required
$ RT 1nA,2 ln xA,2 #
value of
a
in
the
DebyeHckel
equation
(10.64)
ass concentration. 9.15
Use Fig.0.305
9.3 tohas
finda(a)
the molality
atofwhich
! a0;
MgSO
mole
fraction
vapor
pressure
95.0 Vtorr
and
4
10.50 (a) Use Appendix data
of
Table
10.2?
give
agreement
with
the
experimental
g
th
!
the
limit
of(b)anUsewhere x , x , x , and x are the fin
the partial
molar
volume
of MgSO
roblem
10.39
of Levine
Physical
Chemistry,
6Find
Edition:
4(aq) in
vapor-phase
hexane
mole
fraction
of
0.555.
the
vapor
ion in an aqueous8. P(b)
(b) Use
25C
"
"
i,2 for
i,1 Cu(NO
A,2
A,1
the value of a from
part (a)Vand
(10.64)
estimate
3)2(aq).
and to
of
Hany
inga! oftions of the solute and
VState
of Eq.
MgSO
infinitely
2O appressures dilute
of puresolution;
hexane (c)
and heptane
at 430C.
the
solvent
i
ght.
for NaCl(s) NaCl(aq).
(aq).
0.01 mol/kg
mol/kgMgSO
25C CaCl
2
(aq)
solution.
0.05
proximations made.4
Eq. (9.23) to show that for this process
n 450 mL of water
10.51
The
&
in
a
0.0200
mol/kg
HCl
solution
in
10.39
Calculate
g
! law to
At Use
infinite
dilution,
theshow
ionsthat
of for
an electrolyte
are infiG
" n i 1NBS
m i,2 #tables
m i,1 2 give
$ nA,2
9.40 (a)
Raoults
an ideal solution
of
ume of 1.0000 L at 9.16
#
25C
and
1not
atm.
For
atanother.
25C
and
1 atm, the NaSO4 (aq). With the aid of Ap
CH
3OH
3OH
far
apart
dofraction
interact
with
one
Therefore,
B
and
C, at
the
B and
mole
in
theCH
vapor
phase
in equilibrium
ty of 1.2885 g/cm3. nitely
"(2
"
"
1nA,2 #Na
nA,1
q
q
reaction
dielectric
constant
and theis density
g/cm3. ion-pair formation#
V values
V
strong
electrolyte
in solution
the sum is
of 0.787
with
thea solution
is is 32.6
i of
"
Assume
a$
3 .V q
for
the ions.
Some
for
at 25C and where mi,2, mi,1, mA,2, and mA,1 are the f
l aqueous
i values x
*>PC* solutions
10.52 The NBS tables (Sec.
B PB
3
th molality 1.506 1 atm are 16.6 cm3/mol
v
for NaCl, 38.0 cm /mol for KNO3, and potentials of the solute and the so
xB "aqueous
10.40
For
a
25C
solution
of
a
single
strong
elec"
values:
#108.74 kJ/mol for NO
l
nd the KI molarity. 27.8 cm3/mol for NaNO1. $
*V
* # 1KCl
>Pq
2 in water at 25C Comparison of the coefficient of ni in (
(a)xFind
B 1P B
i C for
3
trolyte, the Meissner equation
is
HNO3(ai). Without looking up
1 atm. (b) Find 1 0mi> 0P 2 q
at 25C.
gives
T,nj for KCl in water
density r with sol- and
(b) At 20C the vapor pressure
of benzene (C6H6) is 74.7 torr
one of these numbers must be in
molar concentra- and that of toluene (C H CH ) is 22.3 torr.
I1>2For solutions of benm i,2 # m i,1 " RT 1ln xi,2 # ln xi,1 2
6
5
3
9.17 log
Prove
that the internal energy of a phase satisfies U !
10 g! $ #0.5107z" 0 z# 0
! xi /MA and that zene plus
1>2
10.53
Find the conventional
toluene
(assumed
ideal)
in
equilibrium
with
vapor
at
" cIshort.
%i ni mi .l The proof is1very
"PV $ TS $
v
The
only
way
(9.68)Consider
can hold isthe
if two
25C. (Hint:
20C, plot x B versus x B for benzene. Repeat for toluene. q
"
z
0
z
0
log
3
1
#
b
"
b11
"
0.1I
2
4
9.18 Write the defining
for the partial molar
# equation
10
the ionizationm of"water:
2Of i
ol/kg, where mB is 9.41 At 20C and 1 "atm,
RT ln xHi $
1
the density
of benzene
is
0.8790
i
"
#
Helmholtz
energy
of
substance
i
in
a
solution
and
state
fully
3
H
O
"
OH
.)
3
3
#0.023I
3
cular weight (rela- g/cm and
that
of toluene
is definition
0.8668 cg/cm
Find
b!
0.75
#in0.065q,
!stands
1. "
0.055qe
what every
symbol
your
for.the density of a where f i (T, P) is some function of T
solution of 33.33 g" of benzene
and 33.33 g of toluene at 20C m #
10.54
(10.92)
" Na "SO
mi,1 at Derive
constantEqs.
T and
P. (b) and
Use
where
I !
Im /m.
Hian
Ui $
9.19
Show
that
!For
P2V i. 4(aq), q $ #0.19. Calculate i,2
and
1 atm.
Assume
ideal
solution.
that
the Meissner-predicted g! of Na2SO4(aq) at 0.1 mol/kg andshow10.55
(a) The solubility of O2
%
n
m
,
m
!
m

$
RT
ln
(P
/P)
[Eqs.
(9.23)
9.20
(a)
Use
G
!
an ideal
9.42
Show
that i!mix
i C
i P "
i 0 for
i
isolution. (b) At
m
#OnA,1above
m A,1 "the
n A,2
1m*A $
n
1
mol/kg
and
compare
with
the
values
in
Table
10.2.
A,2
A,2
solutio
pressure of
. (b) The volume and
2
Eq.CP,m
(4.65)
applied
to pure
i to show
" 136
J/(mol
K) forgas
benzene
(C6that
H6) G
andof
25C(6.4)]
and 1and
atm,
#i
O2A,1
in1m
wat
*A
the volumes of its an
*(T,
ni), 0.1 water. Find & f G298 for#n
ideal
gas J/(mol
mixture
Ttoluene
is given
" 156
K)atfor
(Cby
H5G
CH!
Find
ofPai ,the
soC
Table
data:
(a)
10.41
For
the CaCl
i G
iCPuse
P ,m
610.2
3). %
2(aq)
.
state
is
used
for
the
solute
O
olution must equal where
and
nigare
the partial
pressure
number
of25C
moles
Pig100.0
lution
of
of
benzene
and
100.0 gand
toluene
andof
2 (
a spreadsheet
Solver
tooffind
the atMeissner
q. (q
mol/kg
! and