The Advanced Placement

Examination in Chemistry
Part II - Free Response Questions & Answers
1970 to 2005
Solids, Liquids & Solutions
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Advanced Placement Examination in Chemistry.
Ques tions copyright 1970!00" #y the College
Entrance Examination $oard% Princeton% &' 0(")1.
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1970
What is meant by the lattice energy of an ionic
compound? What quantities need to be determined and
how are they used to calculate the lattice energy of an
ionic compound.
Answer:
attice energy ! quantity of energy released in the
formation of one mole of an ionic solid from its
separated gaseous ions.
"he energy quantities needed to be determined:
sublimation of solid metal
ioni#ation of gaseous atomic metal $ioni#ation
energy%
dissociation of gaseous non!metal
ion formation by gaseous atomic non!metal
$electron affinity%
"hey are used with &ess's aw to determine the
combination of gaseous ions. "his is the (orn!&aber
)ycle.
1971
*ol+e the following problem
Ag(r(s) Ag
,
(aq) , (r
!
(aq) -sp . /./10
!1/
Ag
,
(aq) , 0 1&/(aq) Ag$1&/%0
,
(aq) - . 1.710
,7
$a% &ow many grams of sil+er bromide2 Ag(r2 can be
dissol+ed in 30 milliliters of water?
$b% &ow many grams of sil+er bromide can be
dissol+ed in 30 milliliters of 10 molar ammonia
solution?
Answer:
$a% 4Ag
,
54(r
!
5 . -sp . /./10
!1/
. X
0
X . 3.710
!7
6 . 4Ag
,
5 . mol7 Ag(r that dissol+e
0 . 050 L
5 . 7 1 0
7
mol A gBr
1 L

187 . 8 g A gBr
1 mol A gBr
=
. 3.810
!9
g Ag(r
$b% Ag(r(s) Ag
,
(aq) , (r
!
(aq) -sp . /./10
!1/
Ag
,
(aq) , 0 1&/(aq) Ag$1&/%0
,
(aq) - . 1.710
,7
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
Ag(r , 0 1&/ Ag$1&/%0
,
, (r
!
- . -sp- . 3.910
!9
4Ag$1&/%0
,
5 . 4(r
!
5 . X 6: 41&/5 . $10 ! 0;% 6
K =
[ Ag ( NH
3
)
+
][ Br

]
[ NH
3
]
2
=
X _ X
( 10 2 X )
2
= 5 . 6 1 0
6
X . 0.810
!0
6 . 4(r
!
5 . mol7 dissol+ed Ag(r
$0.810
!0
mol7%$1<7.< g7mol%$0.030 % . 0.00 g
Ag(r
1971
6olarity and molality are two ways of e=pressing
concentration.
$a% )learly distinguish between them
$b% >ndicate an e=perimental situation where
e=pressing concentrations as molarity is
particularly appropriate.
$c% >ndicate an e=perimental situation where
e=pressing concentration as molality is particularly
appropriate.
Answer:
$a% molarity $6% ! molar concentration: composition
or concentration of a solution e=pressed as number
of moles of solute per liter of solution.
molality $m% ! solution concentration e=pressed as
number of moles of solute per ?ilogram of sol+ent.
many possibilities2 e=amples:
$b% Acid ! base titrations
$c% 6olecular weight determination by free#ing point
depression change.
1970 @
$a% &ow many moles of (a$>A/%0 is contained in 1.0
liter of a saturated solution of this salt at 03. -sp
of (a$>A/%0 . 9.310
!10
$b% When 0.100 liter of 0.090 molar (a$1A/%0 and
0.130 liter of 0.10 molar ->A/ are mi=ed at 03)2
how many milligrams of barium ion remains in
each milliliter of the solution? Assume that the
+olumes are additi+e and that all acti+ity
coefficients are unity.
Answer:
$a% (a$>A/%0 (a
0,
, 0 >A/
!
-sp . 4(a
0,
54>A/
!
5
0
. 9.310
!10
4(a
0,
5 . ;: 4>A/
!
5 . 0;: $;%$0;%
0
. 9.310
!10
; . 3.310
!8
6 . mol7 of dissol+ed (a$>A/%0
$b% initial mol (a
0,
. $0.090 mol7%$0.100% . 0.0090
mol
initial mol >A/
!
. $0.130%$0.100 mol7% . 0.01<0
mol
after reaction2 essentially all (a
0,
reacts while >A/
!
. B0.01<0 ! $0%$0.0090%C mol . 0.0090 mol70.030
. 0.0086 4>A/
!
5
[ Ba
2 +
] =
K
sp
[ IO
3

]
2
=
6 . 5 1 0
10
( 0 . 024 )
2
= 1 . 1 1 0
6
M
1 . 1 1 0
6
mol
100 0 mL

137340 mg B a
2+
1 mol
=
. 1.310
!8
mg 7 m (a
0,
197/ @
"he molar solubility of sil+er bromide is diminished by
the addition of a small amount of solid potassium
bromide to a saturated solution. &owe+er2 the molar
solubility of sil+er bromide is increased by the addition
of solid potassium nitrate2 a salt whose ions are not
common to those of sil+er bromide.
D=plain these e=perimental obser+ations in terms of the
principles in+ol+ed.
Answer:
Ag(r(s) Ag
,
(aq) , (r
!
(aq): As -(r dissol+es2 the
concentration of (r
!
ions increase and force the
equilibrium to shift to the left $e)hatelier's principle%
where the concentrations of the ions in solution
decrease and less can dissol+e.
"he di+erse $EuncommonF% ion effect G Ethe salt
effectF. As the total ionic concentration of a solution
increases2 interionic attractions become more
important. Acti+ities become smaller than the
stoichiometric or measured concentrations. Hor the ions
in+ol+ed in the solution process this means that a higher
concentration must appear in solution before
equilibrium is established. ! the solubility must increase.
1978 @
"wo bea?ers2 one containing 100 milliliters of a 0.10
molal solution of sucrose $a non+olatile nonelectrolyte% the
other containing 100 milliliters of pure water2 are
placed side by side in a closed system2 such as under a
bell Iar. D=plain in terms of the principles in+ol+ed what
changes2 if any2 occur to bring the system to
equilibrium.
Answer:
$1% Jolume of sugar solution increases: $0% +olume of
pure water decreases: $/% water bea?er finally empty.
Kaoult's aw2 +apor pressure and +olatility
@escription of process $rates of +apori#ation and
condensation%
1973 @
Alcohol dissol+es in water to gi+e a solution that boils
at a lower temperature than pure water. *alt dissol+es
in water to gi+e a solution that boils at a higher
temperature than pure water. D=plain these facts from
the standpoint of +apor pressure.
Answer:
An alcohol!water solution has a higher than normal
$pure water% +apor pressure because alcohol is a
+olatile solute and contributes substantially to the +apor
of the solution. "he higher the +apor pressure2 the
lower the boiling point. A salt!water solution has a
lower than normal +apor because salt is a non!+olatile
solute and solute!sol+ent interaction decrease the +apor
of the solution2 the lower the +apor pressure2 the higher
the boiling point.
1979 (
$a% )alculate the molality of a 00.0 percent by weight
aqueous solution of 1&8)l. $6olecular weight:
1&8)l . 3/.3%
$b% >f this 1&8)l solution is assumed to be ideal and is
completely dissociated into ions2 calculate the
pressure of this solution at 09.0).
$c% Actually a solution of 1&8)l of this concentration
is not ideal. )alculate the apparent degree of
dissociation of the 1&8)l if the free#ing point of
this solution is !13./)? $6olal free#ing point
constant . 1.<9)%
Answer:
$a%
20 . 0
80 . 0
1000 = 250 g NH
4
Cl in 1000g H
2
O
250 g
1 k g H
2
O

1 mol N H
4
Cl
53.5 g
= 4 . 67
mol
1 kg
= 4 . 67 molal
$b% L1 . $L%$X1%
mol ions . $0%$8.97 mol% . 9./8 mol
1 ?g water . 33.9 mol water
X
1
=
55 . 6
55 . 6 + 9 . 34
= 0 . 856
L1. $09.< mm &g%$0.<39% . 03.3 mm &g
$c% Assume no dissociation.
" . ?fm . $1.<9%$8.97% . <.99)
i . 13./ 7 <.99 . 1.79
$1.79 ! 1.00%$100% . 79M dissociated
1977 @
"he solubility of Nn$A&%0 is not the same in the
following solutions as it is in pure water. >n each case
state whether the solubility is greater or less than that in
water and briefly account for the change in solubility.
$a% 1!molar &)l $c% 1!molar 1aA&
$b% 1!molar Nn$1A/%0 $d% 1!molar 1&/
Answer:
$a% greater: Nn$A&%0(s) , 0 &
,
Nn
0,
, 0 &0A
$b% lower: increased 4Nn
0,
5 decreases 4A&
!
5 and
decreases the amount of Nn$A&%0 in solution. -
sp
.4Nn
0,
54A&
!
5
0
$c% greater: Nn$A&%0(s) , 0 A&
!
Nn$A&%8
0!
$)an also
site common ion effect%
$d% greater: Nn$A&%0(s) , 8 1&/ Nn$1&/%8
0,
, A&
!
1977 @
"he state of aggregation of solids can be described as
belonging to the following four types:
$1% ionic $/% co+alent networ?
$0% metallic $8% molecular
Hor each of these types of solids2 indicate the ?inds of
particles that occupy the lattice points and identify
forces among these particles. &ow could each type of
solid be identified in the laboratory?
Answer:
Larticles (inding
Horces
D=perimental
>dentification
ionic , O ! ions electrostatic
attraction
conducti+ity of
fused salt
metallic , ions electrostatic
attraction
between
ions and
electrons
conducti+ity of
the solid
co+alent
networ?
atoms co+alent
bonds
high melting
pt.2 e=treme
hardness2 etc.
molecular molecules +an der
Waals
low melting
pt.2 non!
conducti+ity of
fused salt2 etc.
197< @
"he free#ing point and electrical conducti+ities of three
aqueous solutions are gi+en below.
*olution Hree#ing Dlectrical
$0.010 molal% Loint )onducti+ity
sucrose !0.01<9) almost #ero
formic acid !0.001/) low
sodium formate !0.0/91) high
D=plain the relationship between the free#ing point and
electrical conducti+ity for each of the solutions abo+e.
Account for the differences in the free#ing points
among the three solutions.
Answer:
sucrose
a non electrolyte
0.010 mol7?g lowers free#ing point 0.01<9)
formic acid
a wea? electrolyte: low conductance as a result of
low ion concentration
mtotal P 0.010 molal due to partial ioni#ation and
"f somewhat greater than 0.01<9)
sodium formate
a salt and strong electrolyte
appro=imately 100M dissociation into ions2 mtotal
approaching 0.00 molal
1979 A
A saturated solution of lead iodate in pure water has a
lead ion concentration of 8.010
!3
mole per liter at
00).
$a% )alculate the +alue for the solubility!product
constant of Lb$>A/%0 at 03).
$b% )alculate the molar solubility of Lb$>A/%0 in a 0.10
molar Lb$1A/%0 solution at 03).
$c% "o /// milliliters of a 0.100!molar Lb$1A/%0
solution2 997 milliliters of 0.8/3!molar ->A/ is
added. )alculate the concentrations of Lb
0,
and
>A/
!
in the solution at equilibrium at 03).
Answer:
$a% Lb$>A/%0(s) Lb
0,
, 0 >A/
!
-sp . 4Lb
0,
54>A/
!
5
0
. $8.010
!3
%$<.010
!3
%
0
. 0.910
!1/
$b% 4Lb
0,
5 . $0.10 , ;% 6 0.10 6
4>A/
!
5
0
. $0X% 6
-sp . 4Lb
0,
54>A/
!
5
0
. 0.910
!1/
. $0.10%$0X%
0
X . <.110
!7
6 . mol Lb$>A/%0 dissol+ed per
solution.
$c% initial mol Lb
0,
. 0.0800 mol
initial mol >A/
!
. 0.090 mol
ppt must occur: after ppt2 mole >A/
!
in solution .
$0.090 ! 0.0<0% mol . 0.010 mol
4>A/
!
5 . 0.010 6 since the +olume is 1.00
-sp . 4Lb
0,
54>A/
!
5
0
. 0.910
!1/
. 4Lb
0,
5$0.010%
0
4Lb
0,
5 . 3.<10
!10
6
19<0 (
$a% A solution containing /.0/ grams of an un?nown
compound dissol+ed in 100.0 grams of water
free#es at !0.97). "he solution does not conduct
electricity. )alculate the molecular weight of the
compound. $"he molal free#ing point depression
constant for water is 1.<9) ?g mole
!1
%
$b% Dlemental analysis of this un?nown compound
yields the following percentages by weight
&.9.78M: )./<.70M: A.31.39M. @etermine the
molecular formula for the compound.
$c% )omplete combustion of a 1.03 gram sample of
the compound with the stoichiometric amount of
o=ygen gas produces a mi=ture of &0A(g) and
)A0(g). What is the pressure of this gas mi=ture
when it is contained in a /.00 liter flas? at 107)?
Answer:
$a% "f . ?fm: 0.97) . $1.<9)m
!1
%$m%
m . 0.30 mol solute7?g sol+ent
>n this solution2 /.0/ g solute in 100.0 g water or
/0./ g solute in 1 ?g of water
mol . wt . =
32.3 g
1 kg s olvent

1 kg s olvent
0.52 mol
= 6 2
g
mol
$b%
62g
1 mol c mpd

0.0974 g H
1g cmpd

1 mol H
1 g H
=
6.0 mol H
1 mol c mpd
62g
1 mol c mpd

0.3870 g C
1g cmpd

1 mol C
12 g C
=
2.0 mol C
1 mol c mpd
62g
1 mol c mpd

0.5156 g O
1g cmpd

1 mol O
16 g O
=
2.0 mol O
1 mol c mpd
. )0&9A0
$c% 0 )0&9A0 , 3 A0 9 &0A(g) , 8 )A0(g)
1 . 0 5 g C
2
H
6
O
2

1 mol C
2
H
6
O
2
62 g C
2
H
6
O
2

10 mol g as
2 mol C
2
H
6
O
2
=
. 0.0<87 mol gas
L . $nK"% 7 J
P =
( 0 . 0847 mol ) 0 . 08205
L _ atm
mol _ K
( )
( 400 . K )
3 . 00L
= 0 . 926 at m.
19<0 @
Account for the differences in solubility described in
each of the following e=perimental obser+ations:
$a% (a)A/2 (a*A/2 and (a*A8 are only slightly soluble
in water2 but the first two dissol+e in &)l solution
whereas (a*A8 does not.
$b% )u* cannot be dissol+ed by warm dilute &)l but it
does dissol+e in warm dilute &1A/.
$c% Ag)l2 &g0)l0 and Lb)l0 are only slightly soluble in
water2 but Ag)l does dissol+e in ammonia solution
whereas the other two do not.
$d% He$A&%/ and Al$A&%/ are only slightly soluble in
water2 but Al$A&%/ dissol+es in concentrated
1aA& whereas He$A&%/ does not.
Answer:
$a% (a)A/(s) (a
0,
, )A/
0!
(a*A/(s) (a
0,
, *A/
0!
(a*A8(s) (a
0,
, *A8
0!
@issol+ing ta?es place if equilibrium is shifted to
the right.
)A/
0!
, &
,
&)A/
!
, &
,
&0A , )A0(g)
*A/
0!
, &
,
&*A/
!
, &
,
&0A , *A0(g)
>n these two cases2 equilibrium is shifted to the
right by the production of a remo+ed product $a
gas%.
*A8
0!
, &
,
do not react since *A8
0!
is a wea?
(ronsted base.
$b% Warm dilute &1A/ o=idi#es *
0!
to * $or higher%.
"his reaction shifts the equilibrium between )u*(s)
and its ions toward the ions.
$c% Ag)l(s) , 0 1&/ 4Ag$1&/%05
,
, )l
!
sil+er ions comple= with ammonia to form the
soluble 4Ag$1&/%05
,
2 neither &g0
0,
nor Lb
0,
form
such comple=es.
$d% Al$A&%/(s) , A&
!
Al$A&%8
!
$or similar%
Al$A&%/ is amphoteric. "he product is a
hydro=oaluminate ion2 He$A&%/ is not amphoteric.
19<8 )
Qi+e a scientific e=planation for the following
obser+ations. Rse equations or diagrams if they are
rele+ant.
$a% >t ta?es longer to coo? an egg until it is hard!
boiled in @en+er $altitude 1 mile abo+e sea le+el%
than it does in 1ew Sor? )ity $near sea le+el%.
$b% (urn coal containing a significant amount of sulfur
leads to Tacid rain.U
$c% Lerspiring is a mechanism for cooling the body.
$d% "he addition of antifree#e to water in a radiator
decreases the li?elihood that the liquid in the
radiator will either free#e or boil.
Answer:
$a% Water boils at a lower temperature in @en+er than
in 1S) because the atmospheric pressure is less at
high altitudes. At a lower temperature2 the coo?ing
process is slower2 so the time to prepare a hard!
boiled egg is longer.
$b% * , A0 *A0 $as coal is burned%
*A0 , &0A &0*A/ $in the atmosphere%
&0*A/ is sulfurous acid.
$c% Japori#ation or e+aporation of sweat from the
s?in is an endothermic process and ta?es heat from
the body and so cool the s?in.
$d% )olligati+e properties2 which depend on the
number of particles present2 are in+ol+ed.
*olute $the antifree#e% causes the lowering of the
+apor pressure of the sol+ent. When the +apor
pressure of the sol+ent is lowered2 the free#ing
point is lowered and the boiling point is raised.
19<3 (
"he formula and the molecular weight of an un?nown
hydrocarbon compound are to be determined by
elemental analysis and the free#ing!point depression
method.
$a% "he hydrocarbon is found to contain 9/.89 percent
carbon and 9.38 percent hydrogen. )alculate the
empirical formula of the un?nown hydrocarbon.
$b% A solution is prepared by dissol+ing 0.3/ grams of
p!dichloroben#ene $molecular weight 187.0% in
03.<9 grams of naphthalene $molecular weight
10<.0%. )alculate the molality of the p!
dichloroben#ene solution.
$c% "he free#ing point of pure naphthalene is
determined to be <0.0). "he solution prepared in
$b% is found to ha+e an initial free#ing point of
73.7). )alculate the molal free#ing!point
depression constant of naphthalene.
$d% A solution of 0.80 grams of the un?nown
hydrocarbon dissol+ed in 09.7 grams of
naphthalene is found to free#e initially at 79.0).
)alculate the apparent molecular weight of the
un?nown hydrocarbon on the basis of the free#ing!
point depression e=periment abo+e.
$e% What is the molecular formula of the un?nown
hydrocarbon?
Answer:
$a% Assume 100. g sample of the hydrocarbon
9 3.46 g C
1 mol C
12 . 01 g C
= 7 . 782 mol C
6 .54 g H
1 mol H
1 . 008 g H
= 6 . 49 mol H
7.782 mol C
6.49 mol H
=
1 . 20
1 . 00
; C
1 . 20
H
1 . 00
= C
6
H
5
$b%
m =
mol s olute
1 . 0 kg solvent
=
2 .53 g
1 mol
147.0 g
0 . 0 2586 kg
= 0 . 666 mol a l
$c% "f . $<0.0 ! 73.7%) . 8.3)
?f . "f 7m . 8.3) 7 0.999 molal . 9.<)7molal
$d% "f . $<0.0 ! 79.0%) . 8.0)
1
4 . 0 _ C

6 . 8 _ C _ k g solvent
1 mol s olute

2 .43 g solute
0 .0267 kg solvent
=
.138 g7mol
$e% )9&3 . 77
V empirical units7mol . 138777 . 0
molecular formula . $)9&3%0 . )10&10
19<9 @
Qi+e a scientific e=planation for each of the following
obser+ations. Rse equations or diagrams if they seem
rele+ant.
$a% Qraphite is used to ma?e electrodes2 while
diamond2 another allotrope of carbon2 is a +ery
poor conductor of electricity.
$b% Lutting roc? salt on an icy dri+eway melts the ice
e+en when the air temperature is !10).
$c% 4question and answer in the QA*D* section5
$d% )arbon dio=ide2 rather than a stream of water2
should be used to e=tinguish an oil fire.
Answer:
$a% @istinction or correctly implied distinction
between the structures of graphite and diamond.
Hreedom of mo+ement of electrons in graphite
resulting from the structure.
$b% "he roc? salt forms a concentrated solution with
+ery little water from the ice. "he solution now has
a free#ing point lower than the temperature of the
ice2 therefore2 the ice melts.
$c% 4question and answer in the QA*D* section5
$d% )arbon dio=ide is more dense than air and so
pushes the air away from the fire.
Water is more dense than the oil and so ends up
below the oil2 lea+ing the oil still in contact with
the air: or the hot burning oil quic?ly +apori#es the
water creating steam that spatters the oil into the
air.
19<7 @
>n 1<<8 the *wedish chemist *+ante Arrhenius
proposed that salts dissociate into two or more
separate2 independent2 ionic fragments when they
dissol+e in water.
$a% Qi+e one piece of e=perimental e+idence that more
than 1 mole of particles is formed when 1 mole of
a salt dissol+es in water.
$b% Qi+e one piece of e=perimental e+idence that the
particles formed when a salt dissol+es in water are
charged.
$c% D=plain why the heat of neutrali#ation is always
the same when 1 mole of any monoprotic strong
acid reacts with enough strong base to form a
neutral solution.
$d% D=plain why hydrogen chloride2 &)l2 dissociated
when it dissol+es in water but not when it dissol+es
in ben#ene.
Answer:
$a% "he free#ing point depression $or any colligati+e
effect% that occurs when a mole of a salt is
dissol+ed is greater than when a mole of a non!
dissociated substance is dissol+ed. $"he greater the
number of solute particles the greater the
colligati+e effect.%
$b% "he solution of a salt conducts electricity.
$c% D+ery neutrali#ation between a strong acid and a
strong base in+ol+es the same reaction:
&
,
(aq) , A&
!
(aq) &0A
since both the strong acid and the strong base are
completely dissociated. *pectator ions ha+e no
appreciable effect.
$d% (ecause of the polar nature of water2 it is capable
of sol+ating the ions that result from the
dissociation2 whereas the nonpolar ben#ene
interacts +ery wea?ly with these ions. AK
(ecause of the greater dielectric constant of water2
it is better able to separate the ions.
19<< @
"he normal boiling and free#ing points of argon are
<7./ - and <8.0 -2 respecti+ely. "he triple point is at
<0.7 - and 0.9< atmosphere.
$a% Rse the data abo+e to draw a phase diagram for
argon. abel the a=es and label the regions in
which the solid2 liquid and gas phases are stable.
An the phase diagram2 show the position of the
normal boiling point.
$b% @escribe any changes that can be obser+ed in a
sample of solid argon when the temperature is
increased from 80 - to 190 - at a constant
pressure of 0.30 atmosphere.
$c% @escribe any changes that can be obser+ed in a
sample of liquid argon when the pressure is
reduced from 10 atmospheres to 1 atmosphere at a
constant temperature of 100 -2 which is well
below the critical temperature.
$d% @oes the liquid phase of argon ha+e a density
greater than2 equal to2 or less than the density of
the solid phase? D=plain your answer2 using
information gi+en in the introduction to this
question.
Answer:
$a%


0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
81 82 83 84 85 86 87 88 89
Pressure (atm.)
Temperature (K)
normal
B.P.
Solid
Liuid
!as
$b% "he argon sublimes.
$c% "he argon +apori#es.
$d% "he liquid phase is less dense than the solid phase.
*ince the free#ing point of argon is higher than the
triple point temperature2 the solid!liquid
equilibrium line slopes to the right with increasing
pressure. "hus2 if a sample of liquid argon is
compressed $pressure increased% at constant
temperature2 the liquid becomes a solid. (ecause
increasing pressure fa+ors the denser phase2 solid
argon must be the denser phase.
19<9 @
)onsider three unlabeled bottles2 each contain small
pieces of one of the following metals.
! 6agnesium
! *odium
! *il+er
"he following reagents are used for identifying the
metals.
! Lure water
! A solution of 1.0 molar &)l
! A solution of concentrated &1A/
$a% Which metal can be easily identified because it is
much softer than the other two? @escribe a
chemical test that distinguishes this metal from the
other two2 using only one of the reagents abo+e.
Write a balanced chemical equation for the
reaction that occurs.
$b% Ane of the other two metals reacts readily with the
&)l solution. >dentify the metal and write the
balanced chemical equation for the reaction that
occurs when this metal is added to the &)l
solution. Rse the table of standard reduction
potentials $attached% to account for the fact that
this metal reacts with &)l while the other does
not.
$c% "he one remaining metal reacts with the
concentrated &1A/ solution. Write a balanced
chemical equation for the reaction that occurs.
$d% "he solution obtained in $c% is diluted and a few
drops of 1 6 &)l is added. @escribe what would
be obser+ed. Write a balanced chemical equation
for the reaction that occurs.
Answer:
$a% *odium is softest of the three.
1a added to water gas and base
1a , &0A &0 , 1aA&
$b% 6g reacts with &)l. 6g , 0 &
,
6g
0,
, &0
Keduction potentials2 D: 6g . !0./7+: Ag . ,
0.<0+. 6g2 not Ag2 reacts with &)l
$c% Ag , 8 &
,
, 1A/
!
/ Ag
,
, 1A , 0 &0A OR
Ag , 0 &
,
, 1A/
!
Ag
,
, 1A0 , &0A
$d% A white precipitate forms: Ag
,
, )l
!
Ag)l(s)
1990 A
"he solubility of iron$>>% hydro=ide2 He$A&%02 is
1.8/10
!/
gram per litre at 03).
$a% Write a balanced equation for the solubility
equilibrium.
$b% Write the e=pression for the solubility product
constant2 -sp2 and calculate its +alue.
$c% )alculate the p& of a saturated solution of
He$A&%0 at 03).
$d% A 30.0 millilitre sample of /.0010
!/
molar He*A8
solution is added to 30.0 millilitres of 8.0010
!9
molar 1aA& solution. @oes a precipitate of
He$A&%0 form? D=plain and show calculations to
support your answer.
Answer:
$a% He$A&%0 He
0,
, 0 A&
!
$b%
1.8/10
/
g

1 mol
<9.9 g
=1.3910
3
mol

He$A&%
0
. 1.3910
!3
6 . 4He
0,
5
. /.1<10
!3
6 . 4A&
!
5
-sp . 4He
0,
54A&
!
5
0
. $1.3910
!3
%$/.1<10
!3
%
0
. 1.9110
!18
$c%
[ H
+
] =
1 . 0 1 0
14
[ OH

]
=
1 . 0 1 0
14
3 . 18 1 0
5
= 3 . 14 1 0
10
M
p& . !log4&
,
5 . 9.30
AK
pA& . !log4A&
!
5 . !log$/.1<10
!<
% . 8.30
p& . 18 ! pA& . 9.30
$d% 30.0 m of /.0010
!/
6 He
0,
diluted of 100.0 m .
1.3010
!/
6 He
0,
30.0 m of 8.0010
!9
6 A&
!
diluted of 100.0 m .
0.0010
!9
6 A&
!
Q . 4He
0,
54A&
!
5
0
. $1.3010
!/
%$0.0010
!9
%
0
. 9.0010
!13
Lrecipitate will 1A" form since Q W -sp
199/ A
Dlemental analysis of an un?nown pure substance
indicated that the percent composition by mass is as
follows.
Dlement Lercent by 6ass
)arbon 89.00M
&ydrogen 0.78/M
)hlorine 8<.0/M
A solution that is prepared by dissol+ing /.130 grams
of the substance in 03.00 grams of ben#ene2 )9&92 has a
free#ing point of 1.10). $"he normal free#ing point of
ben#ene is 3.30) and the molal free#ing!point
depression constant2 -f2 for ben#ene is 3.10)7molal.%
$a% @etermine the empirical formula of the un?nown
substance.
$b% Rsing the data gathered from the free#ing!point
depression method2 calculate the molar mass of the
un?nown substance.
$c% )alculate the mole fraction of ben#ene in the
solution described abo+e.
$d% "he +apor pressure of pure ben#ene at /3) is
130. millimeters of &g. )alculate the +apor
pressure of ben#ene o+er the solution described
abo+e at /3).
Answer:
$a% moles 7 100 g ) & )l
89.00710.01 0.78/71.00< 8<.0/7/3.83
. 8.0<1 . 0.700 . 1./90
mol ratio / 0 1
empirical formula: )/&0)l
$b% "f . $-f%$m%
8./<=3.10

molal
( )
/.130
g
molmass
0.00300?g
=187
g
mol
$c% mol fraction . mol ben#ene 7 total mol
=
25. 00
78. 11
3 . 150
147
+
25. 00
78. 11
= 0 . 938
$d% +apor pressure . mol fraction Lo
. $0.9/<%$130 mm% . 181 mm &g
1998 @ $Kequired%
@iscuss the following phenomena in terms of the
chemical and physical properties of the substances
in+ol+ed and general principles of chemical and
physical change.
$a% As the system shown abo+e approaches
equilibrium2 what change occurs to the +olume of
water in bea?er A? What happens to the
concentration of the sugar solution in bea?er (?
D=plain why these changes occur.
$b% A bell Iar connected to a +acuum pump is shown
abo+e. As the air pressure under the bell Iar
decreases2 what beha+ior of water in the bea?er
will be obser+ed? D=plain why this occurs.
$c% 4see Kedo= section5
$d% A water solution of >0 is sha?en with an equal
+olume of a nonpolar sol+ent such as ""D $tri!
chlorotrifluoroethane%. @escribe the appearance of
this system after sha?ing. $A diagram may be
helpful.% Account for this obser+ation.
Answer:
$a% +olume of water decreases while the concentration
of sugar solution decreases.
Lure water has a higher +apor pressure than does
the 10M sugar solution and when equilibrium is
reached the water will e+aporate and the solution
will increase in +olume.
$b% "he water will boil when the pressure in the bell Iar
reaches the +apor pressure of the water. (oiling
occurs when the +apor pressure of the liquid is in
equilibrium with the pressure abo+e the liquid.
$d% $i% Water and ""D will form separate layers
because the polar water is not miscible with the
non!polar ""D.
iodine
in T T E
wat er
$ii% "he ""D will be the bottom layer because its
density is greater than the water.
$iii% "he non!polar iodine will dissol+e better in the
non!polar ""D and form a pin?ish!purple tint.
1998 @
Hor each of the following2 use appropriate chemical
principles to e=plain the obser+ation.
$a% *odium chloride may be spread on an icy sidewal?
in order to melt the ice: equimolar amounts of
calcium chloride are e+en more effecti+e.
$b% At room temperature2 1&/ is a gas and &0A is a
liquid2 e+en though 1&/ has a molar mass of 17
grams and &0A has a molar mass of 1< grams.
$c% ) $graphite% is used as a lubricant2 whereas )
$diamond% is used as an abrasi+e.
$d% Louring +inegar onto the white residue inside a
?ettle used for boiling water results in a
fi##ing7bubbling phenomenon.
Answer:
$a% 1a)l(s) 1a
,
(aq) , )l
!
(aq)
)a)l0(s) )a
,
(aq) , 0 )l
!
(aq)
"he free#ing point of an aqueous solution is lower
than the free#ing point of water. A higher molality
of a solution lowers the free#ing point more and an
equimolar amount of the two solids gi+es a larger
molal solution from the calcium chloride as
illustrated by the abo+e equations.
$b% Water is more polar than ammonia creating
stronger attractions $>6H% between molecules and
ma?ing it a liquid.
$c% @iamond2 the hardest naturally occurring
substance2 has each carbon atom surrounded by a
tetrahedral arrangement of other carbon atoms
$see drawing%. "he networ? solid structure is
stabili#ed by co+alent bonds2 formed by the
o+erlap of sp
3
hybridi#ed carbon atomic orbitals. A
diamond has uniform +ery strong bonds in all
directions in the crystal.
Qraphite has a different ?ind of bonding based on
layers of carbon atoms arranged in fused si=!
member rings $see drawing%. Dach carbon atom in
a layer is surrounded by three other carbons in a
trigonal planar arrangement with 100 bond
angles. "he slipperiness is caused by noting that
graphite has +ery strong bonds within layers but
little bonding between the layers which allows the
layers to slide past one another quite readily.
$d% )alcium and magnesium carbonates are left behind
from the e+aporation of hard water. "hese
carbonates decompose and release carbon dio=ide
gas when reacted with the acetic acid in the
+inegar.
)a)A/(s) , 6g)A/(s) , )&/)AA&(aq) )a
0,
(aq) ,
6g
0,
(aq) , &0A(l) , )A0(g) , )&/)AA
!
(aq)
1993 @
"he phase diagram for a pure substance is shown
abo+e. Rse this diagram and your ?nowledge about
changes of phase to answer the following questions.
$a% What does point V represent? What characteristics
are specific to the system only at point V?.
$b% What does each point on the cur+e between V and
W represent?
$c% @escribe the changes that the system undergoes as
the temperature slowly increases from X to Y to Z
at 1.0 atmosphere.
$d% >n a solid!liquid mi=ture of this substance2 will the
solid float or sin?? D=plain.
Answer:
$a% "riple point. All three states of the substance
coe=ist $equilibrium%: the solid and the liquid ha+e
identical +apor pressures.
$b% )ur+e VW represents the equilibrium between the
liquid and its +apor. Along this line the liquid will
be boiling. "he points represent the +apor pressure
of the liquid as a function of temperature.
$c% At point X the substance is a solid2 as its
temperature increases $at constant pressure%2 at point
Y the solid is in equilibrium with its +apor and will
sublime. Hrom point Y to Z it e=ist only as a +apor.
$d% *in?. A positi+e slope of the solid!liquid line
indicates that the solid is denser than its liquid and2
therefore2 will sin?.

1993 @ (repeated in the thermo section)
ead iodide is a dense2 golden yellow2 slightly soluble
solid. At 03)2 lead iodide dissol+es in water forming a
system represented by the following equation.
Lb>0(s) Lb
0,
, 0 >
!
H . ,89.3 ?iloIoules
$a% &ow does the entropy of the system Lb>0(s) ,
&0A(l) change as Lb>0(s) dissol+es in water at 03)?
D=plain
$b% >f the temperature of the system were lowered
from 03) to 13)2 what would be the effect on
the +alue of Ksp? D=plain.
$c% >f additional solid Lb>0 were added to the system at
equilibrium2 what would be the effect on the
concentration of >
!
in the solution? D=plain.
$d% At equilibrium2 G . 0. What is the initial effect
on the +alue of G of adding a small amount of
Lb$1A/%0 to the system at equilibrium? D=plain.
Answer:
$a% Dntropy increases. At the same temperature2
liquids and solids ha+e a much lower entropy than
do aqueous ions. >ons in solutions ha+e much
greater Edegrees of freedom and randomnessF.
$b% Ksp +alue decreases. Ksp . 4Lb
0,
54>
!
5
0
. As the
temperature is decreased2 the rate of the forward
$endothermic% reaction decreases resulting in a net
decrease in ion concentration which produces a
smaller Ksp +alue.
$c% 1o effect. "he addition of more solid Lb>0 does not
change the concentration of the Lb>0 which is a
constant $at constant temperature%2 therefore2
neither the rate of the forward nor re+erse reaction
is affected and the concentration of iodide ions
remains the same.
$d% G increases. >ncreasing the concentration of Lb
0,
ions causes a spontaneous increase in the re+erse
reaction rate $a Eshift leftF according to
e)hatelier's Lrinciple%. A re+erse reaction is
spontaneous when the GP0.
1999 (
)oncentrated sulfuric acid $1<.8!molar &0*A8% has a
density of 1.<8 grams per milliliter. After dilution with
water to 3.00!molar2 the solution has a density of 1./<
grams per milliliter and can be used as an electrolyte in
lead storage batteries for automobiles.
$a% )alculate the +olume of concentrated acid required
to prepare 1.00 liter of 3.00!molar &0*A8.
$b% @etermine the mass percent of &0*A8
in the
original concentrated solution.
$c% )alculate the +olume of 3.00!molar &0*A8
that can
be completely neutrali#ed with 10.3 grams of
sodium bicarbonate2 1a&)A
/
.
$d% What is the molality of the 3.00!molar &0*A8?
Answer:
$a% M1J1 . M0J0 : $3.00 M%$1.00 % . $1<.8 M%$J0%
J0 . 0.0</
$b% 1<.8 mol71 9<.1 g &0*A871 mol . 1<03 g
&0*A8
1 1.<8 g71 m 1000 m71 . 1<80 g
solution
mass M . 1<03 g71<80 g 100 . 9<.1M
$c% 0 1a&)A/ , &0*A8 0 &0A , 1a0*A8 , 0 )A0
10.3 g 1a&)A/ 1 mol 1a&)A/7<8.0 g 1a&)A/
1 mol &0*A870 mol 1a&)A/ 1 73.00 mol
&0*A8 . 0.0100
$d% molality . mol solute71 ?g sol+ent
3.00 mol71 9<.1 g &0*A871 mol . 310 g &0*A8
1 1./< g71 m 1000 m71 . 1/<0 g
solution
1/<0 g solution ! 310 g &0*A8 . <70 g sol+ent
3.00 mol &0*A870.<70 ?g sol+ent . 3.9< m
199< A $Kequired%
*ol+e the following problem related to the solubility
equilibria of some metal hydro=ides in aqueous
solution.
$a% "he solubility of )u$A&%0(s) is 1.7010
!9
gram per
100. milliliters of solution at 03).
$i% Write the balanced chemical equation for the
dissociation of )u$A&%0(s) in aqueous
solution.
$ii% )alculate the solubility $in moles per liter% of
)u$A&%0 at 03).
$iii% )alculate the +alue of the solubility!product
constant2 Ksp2 for )u$A&%0 at 03).
$b% "he +alue of the solubility!product constant2 Ksp,
for Nn$A&%0 is 7.710
!17
at 03).
$i% )alculate the solubility $in moles per liter% of
Nn$A&%0 at 03) in a solution with a p& of
9./3.
$ii% At 03)2 30.0 milliliters of 0.100!molar
Nn$1A/%0 is mi=ed with 30.0 milliliters of
0./00!molar 1aA&. )alculate the molar
concentration of Nn
0,
(aq) in the resulting
solution once equilibrium has been
established. Assume that +olumes are
additi+e.
Answer
$a%i )u$A&%0 )u
0,
, 0 A&
!
ii
1 . 72 10
6
g
0 . 10 0 L

1 mol
97.5 g
= 1 . 76 10
7
mol
L
iii Ksp . 4)u
0,
54A&
!
5
0
. 41.7910
!7
54/.3/10
!<
5
0
. 0.0010
!00
$b%i Nn$A&%0 Nn
0,
, 0 A&
!
Ksp . 4Nn
0,
54A&
!
5
0
p& 9./3 . pA& 8.93: 4A&
!
5 . 10
!pA&
4A&
!
5 . 10
!8.93
. 0.0810
!3
M
4Nn
0,
5 . solubility of Nn$A&%0 in
mol
7
[Zn
2 +
] =
K
sp
[OH

]
2
=
7 . 7 10
1 7
( 2 . 24 10
5
)
2
= 1 . 5 10
7
M
ii 4Nn
0,
5init . 0.100M
50 mL
100 mL
. 0.0300 M
4A&
!
5init . 0./00M
50 mL
100 mL
. 0.130 M
X . conc. loss to get to equilibrium
Ksp . 7.710
!17
. $0.0300 ! X%$0.130 ! 0X%
0
4Nn
0,
5 . 0.0300 ! X . /.110
!18
M
199< (
An un?nown compound contains only the three
elements )2 &2 and A. A pure sample of the compound
is analy#ed and found to be 93.90 percent ) and 9.88
percent & by mass.
$a% @etermine the empirical formula of the compound.
$b% A solution of 1.370 grams of the compound in
19.0< grams of camphor is obser+ed to free#e at a
temperature 13.0 )elsius degrees below the
normal free#ing point of pure camphor. @etermine
the molar mass and apparent molecular formula of
the compound. $"he molal free#ing!point
depression constant2 K2 for camphor is 80.0
?gX-Xmol
!1
.%
$c% When 1.370 grams of the compound is +apori#ed
at /00) and 1.00 atmosphere2 the gas occupies a
+olume of 377 milliliters. What is the molar mass
of the compound based on this result?
$d% (riefly describe what occurs in solution that
accounts for the difference between the results
obtained in parts $b% and $c%.
Answer
$a%
65.60
12.011
= 5.462
9.44
1.0079
= 9.37
24.96
16.00
= 1.56
5.462
1.56
= 3 . 50
9.37
1.56
= 6 . 00
1.56
1.56
= 1 . 00
$)/.3&9A1%0 . )7&10A0
$b% "HL . !m .!
mol solute
kg solvent
. !
g solvent
molar mass
kg solvent
molar mass .
(g solute)( k

)
(kg solvent)( T
"P
)
=
(1.570 g)(40.0
kg _ K
mol
)
(0.01608 kg)(15.2_C)
. 037
g
7mol
)7&10A0 . 10<
g
7mol :
037
710< . 0
2 $)7&10A0%0 . )18&08A8
$c% LJ .
grams
molar mass
K"
molar mass .
grams R T
P V
(1.570 g) 0.08205
L atm
mol K



_

573K
1.00 atm 0.577 L
. 10<
g
7mol
$d% since the apparent molar mass from free#ing point
change is twice that determined by the +apor2 the
molecules of the compound must associate in
camphor to form dimers2 OR the compound must
dissociate in the gas phase.
199< @
Answer each of the following using appropriate
chemical principles.
$a% Why does it ta?e longer to coo? an egg in boiling
water at high altitude than it does at sea le+el?
Answer
$a% At a high altitude the pressure is lower and the
boiling point of water is lower. *ince the
temperature of the boiling water is less2 it ta?es
longer to coo? the egg.
2000 D Required
The molar mass of an unknown solid, which is
nonvolatile and a nonelectrolyte, is to be determined
by the freezing-point depression method. The pure
solvent used in the experiment freezes at 10C and has
a known molal freezing-point depression constant, K

.
Assume that the following materials are also available.
test tubes stirrer pipet
stopwatch graph paper
thermometer balance beaker
ice hot-water bath
(a) Using the two sets of axes provided below, sketch
cooling curves for (i) the pure solvent and for (ii)
the solution as each is cooled from 20C to 0.0C
Pure Solvent
"ime 0
0
3
10
13
00
Solution
"ime 0
0
3
10
13
00
(b) Information from these graphs may be used to de-
termine the molar mass of the unknown solid.
(i) Describe the measurements that must be
made to determine the molar mass of the
unknown solid by this method.
(ii) Show the setup(s) for the calculation(s) that
must be performed to determine the molar
mass of the unknown solid from the experi-
mental data.
(iii) Explain how the difference(s) between the
two graphs in part (a) can be used to obtain
information needed to calculate the molar
mass of the unknown solid.
(c) Suppose that during the experiment a significant
but unknown amount of solvent evaporates from
the test tube. What effect would this have on (he
calculated value of the molar mass of the solid
(i.e., too large, too small, or no effect)? Justify
your answer.
(d) Show the setup for the calculation of the percent-
age error in a students result if the student obtains
a value of 126 g mol
-1
for the molar mass of the
solid when the actual value is 120. g mol
-1
.
Answer:
(a) (i) pure solvent
"ime 0
0
3
10
13
00
(ii) solution
"ime 0
0
3
10
13
00
(b) (i) mass of pure solvent; freezing point of pure
solvent; mass of unknown solid solute added to
pure solvent; freezing point of resulting solution
(ii) determine the change in freezing point, T
T = K

m, where m = and moles solute =

therefore, molar mass =
(iii) the change in temperature is the difference in
the flat portions of the graph.
"ime 0
0
3
10
13
00
T
(c) Too small. If solvent evaporates then its mass de-
creases and the recorded denominator in the
equation in (b)(i) is larger than the expt. value
and the resulting answer decreases.
(d) % error = 100%
2001 A Required
Answer the following questions relating to the
solubility of the chlorides of silver and lead.
(a) At 10C, 8.9 10
-5
g of AgCl(s) will dissolve in
100. mL of water.
(i) Write the equation for the dissociation of
AgCl(s) in water.
(ii) Calculate the solubility, in mol L
1
, of AgCl(s)
in water at 10C.
(iii) Calculate the value of the solubility-product
constant, Ksp for AgCl(s) at 10C.
(b) At 03)2 the +alue of K
sp
for Lb)l
0
(s) is 1.9 10
!3
and the +alue of K
sp
for Ag)l(s) is 1.< 10
!10
.
$i% >f 90.0 m of 0.0800 M 1a)l(aq) is added to
90.0 m of 0.0/00 M Lb$1A
/
%
0
(aq)2 will a
precipitate form? Assume that volumes are
additive. Show calculations to support your
answer.
(ii) Calculate the equilibrium value of [Pb
2+
(aq)]
in 1.00 L of saturated PbCl
2
solution to which
0.250 mole of NaCl(s) has been added.
Assume that no volume change occurs.
(iii) If 0.100 M NaCl(aq) is added slowly to a
beaker containing both 0.120 M AgNO
3
(aq)
and 0.150 M Pb(NO
3
)
2
(aq) at 25C, which will
precipitate first, AgCl(s) or PbCl
2
(s)? Show
calculations to support your answer.
Answer:
(a) (i) AgCl Ag
+
+ Cl

(ii) = 6.2 10
-6
M
(iii) K
sp
= [Ag
+
][Cl

] = (6.2 10
-6
)
2
= 3.9 10
-11
(b) (i) No
= 0.0200 M [Cl

]
= 0.0150 M [Pb
+
]
trial Ksp
= [Pb
2+
][Cl

]
2
= (0.0150)(0.0200)
2
=
6.010
-6
; trial K
sp
< K
sp
, no ppt.
(ii) K
sp
= [Pb
2+
][Cl

]
2
, [Pb
2+
] = K
sp
/[Cl

]
2
[Pb
2+
] = = 2.610
-4
M
(iii) AgCl
[Cl

] = . . 1.310
!9
M
PbCl
0
[Cl

] =
K
sp
[Pb
2
+
]
=
1.6

10

5
0.150
= 0.0103 M
Ag)l will form a ppt when the 4)l
G
5 e=ceeds
1.310
!9
M. "he formation of Lb)l
0
(s) requires a
4)l
G
5 that is o+er 9 million times more
concentrated.
2001 D Required
Answer the questions below that relate to the five
aqueous solutions at 25C shown above.
(a) Which solution has the highest boiling point?
Explain.
(b) Which solution has the highest pH? Explain.
(c) Identify a pair of the solutions that would produce
a precipitate when mixed together. Write the
formula of the precipitate.
(d) Which solution could be used to oxidize the Cl

(aq) ion? Identify the product of the oxidation.

(e) Which solution would be the least effective
conductor of electricity? Explain.
Answer:
(a) solution 1, Pb(NO
3
)
2
. This compound will
dissociate into three ions with the highest total
particle molality. The greater the molality, the
higher the boiling point. Solutions 2, 3, and 5 will
produce two ions while solution 4 is molecular.
(b) solution 5, KC
2
H
3
O
2
. The salt of a weak acid (in
this case, acetic acid) produces a basic solution,
and, a higher pH.
(c) solution 1, Pb(NO
3
)
2
, and solution 2, NaCl. PbCl
2
(d) solution 3, KMnO
4
, ClO
3

(e) solution 4, C
2
H
5
OH. Ethyl alcohol is covalently
bonded and does not form ions in water.
Therefore, the solution is not a better conductor of
electricity than water, which is also covalently
bonded.
2003 D Required
For each of the following, use appropriate chemical
principles to explain the observations. Include
chemical equations as appropriate.
(a) In areas affected by acid rain, statues and
structures made of limestone (calcium carbonate)
often show signs of considerable deterioration.
(b) When table salt (NaCl) and sugar (C
12
H
22
O
11
) are
dissolved in water, it is observed that
(i) both solution have higher boiling points than
pure water, and
(ii) the boiling point of 0.10 M NaCl(aq) is higher
than that of 0.10 M C
12
H
22
O
11
(aq).
(c) Methane gas does not behave as an ideal gas at
low temperatures and high pressures.
(d) Water droplets form on the outside of a beaker
containing an ice bath.
#$s%er&
(a) limestone reacts with acid to produce a soluble
substance, a gas, and water which wash away
CaCO
3
(s) + H
+
(aq) Ca
2+
(aq) + CO
2
(g) + H
2
O(l)
(b) (i) a solution made from a non-volatile solute has
a higher boiling point than the pure solvent
because the solution has a lower vapor pressure
than the water (Raoults Law) . the temperature of
the solution has be higher to produce enough
vapor pressure to equal the atmospheric pressure
(i.e., boiling)
(ii) the amount of boiling point elevation depends
on the number of non-volatile particles in solution.
since the salt dissociates into 2 particles for every
NaCl that dissolves, it will increase the boiling
point more that an equal concentration of sugar (a
molecular cpd) that does not dissociate or ionize.
(c) at low temperatures and high pressures, the
methane molecules are slow and closer together.
under these conditions, van der Waal forces
become measurable and significant and creates a
deviation from ideal behavior. at high pressure the
volume of a real molecule is also significant.
(d) a water vapor molecules collide with the cool
beaker, the molecules lose kinetic energy, slow
down, attract others, and condense into a liquid
2004 A Required
Answer the questions relating to the solubilitys of two
silver compounds, Ag
2
CrO
4
and Ag
3
PO
4
Silver chromate dissociates in water according to the
following equation:
Ag
2
CrO
4
(s) 2 Ag
+
(aq) + CrO
4
2
(aq)
K
sp
= 2.610
12
at 25 C
(a) Write the equilibrium constant expression for the
dissolving of Ag
2
CrO
4
.
(b) Calculate the concentration in mol L
1
, of Ag
+
in a
saturated solution of Ag
2
CrO
4
at 25 C.
(c) Calculate the maximum mass in grams of
Ag
2
CrO
4
that can dissolve in 100. mL of water at
25 C.
(d) A 0.100 mol sample of solid AgNO
3
is added to
1.00 L saturated solution of Ag
2
CrO
4
. Assuming
no volume change, does [CrO
4
2
] increase, de-
crease, or remain the same? Justify your answer.
In a saturated solution of Ag
3
PO
4
at 25 C, the concen -
tration of Ag
+
is 5.310
5
M. The equilibrium constant
expression for the dissolving of Ag
3
PO
4
is shown be-
low:
K
sp
= [Ag
+
]
3
[PO
4
3
]
(e) Write the balanced equation for the dissolving of
Ag
3
PO
4
in water.
(f) Calculate the value of K
sp
for Ag
3
PO
4
in water.
(g) A 1.00 L sample of saturated Ag
3
PO
4
solution is
allowed to evaporate at 25 C to a final volume of
500. mL. What is [Ag
+
] in the solution? Justify
your answer.
#$s%er&
(a) K
sp
= [Ag
+
]
2
[Cr
2
O
7
2
]
(b) [Cr
2
O
7
2
] = X; [Ag
+
]

= 2X
(2X)
2
(X) = K
sp
= 2.610
12
X = 8.710
5
mol L
1
2X = [Ag
+
] = 1.710
4
mol L
1
(c) amt. Ag
2
CrO
4
= X = 8.710
5
mol L
1
(8.710
5
mol L
1
)(331.74 g mol
1
) =
= 0.0287 g L
1
in 100 mL, 100 mL = 0.0029 g
(d) decrease, since the silver nitrate dissolves and pro-
duces an increase in [Ag
+
], this causes a LeChate-
lier shift to the left and results in a decrease in the
products, including chromate ions
(e) Ag
3
PO
4
(s) ) 3 Ag
+
(aq) + PO
4
3
(aq)
(f) [PO
4
3
] =
K
sp
= [Ag
+
]
3
[PO
4
3
] = (5.310
5
)
3
(

)
= 2.610
18
(g) [Ag
+
] = 5.310
5
M. In a saturated solution the
molar concentration is independent of the total
volume. As the volume evaporates and becomes
half, half of the Ag
+
will precipitate out.
2005 '
Answer the following questions about a pure com-
pound that contains only carbon, hydrogen, and
oxygen.
(a) A 0.7549 g sample of the compound burns in
O
2
(g) to produce 1.9061 g of CO
2
(g) and 0.3370 g
of H
2
O(g).
(i) Calculate the individual masses of C, H, and
O in the 0.7549 g sample.
(ii) Determine the empirical formula for the com-
pound.
(b) A 0.5246 g sample of the compound was dis-
solved in 10.0012 g of lauric acid, and it was de-
termined that the freezing point of the lauric acid
was lowered by 1.68 C. The value of K
f
of lauric
acid is 3.90 C m
1
. Assume that the compound
does not dissociate in lauric acid.
(i) Calculate the molality of the compound dis-
solved in the lauric acid.
(ii) Calculate the molar mass of the compound
from the information provided.
(c) Without doing any calculations, explain how
to determine the molecular formula of the
compound based on the answers to parts (a)
(ii) and (b)(ii).
(d) Further tests indicate that a 0.10 M aqueous solu-
tion of the compound has a pH of 2.6 . Identify the
organic functional group that accounts for this pH.
#$s%er&
(a) (i) 1.9061 g = 0.5198 g of C
0.3370 g H
2
O = 0.03744 g of H
0.7549 g sample
0.5198 g C
0.0374 g H
0.1977 g of Oxygen
(ii) 0.5198 g C = 43.32 mmol C
0.0374 g H = 37.4 mmol H
0.1977 g O = 12.36 mmol O
dividing each by 12.36 gives
3.5 C : 3 H : 1 Oxygen, OR 7 C : 6 H : 2 O, thus
an empirical formula of C
7
H
6
O
2
(b) (i) molality = = = 0.431 m
(ii) molar mass = =
= = 122 g/mol
(c) from (a)(ii), the molar mass of C
7
H
6
O
2
= 122.0
g/mol
since the two molar mass are the same, the
empirical formula = molecular formula
(d) low pH indicates an organic acid containing the
carboxyl functional group, COOH.
[likely benzoic acid]