Advanced Placement Chemistry: 1996 Free Response Answers

Question 1 is question 4 in previous years, question 2 is question 1 in previous years and questions 3&4 are
questions 2&3 in previous years.
students are now allowed 10 minutes to answer question 1, after which they must seal that portion of the
test.
[delta is used to indicate the capital !ree" letter.
[square root applies to the num#ers enclosed in parenthesis immediately followin$
%ll simplifyin$ assumptions are &ustified within '(.
)ne point deduction for a si$nificant fi$ure or math error, applied only once per pro#lem.
*o credit earned for numerical answer without &ustification.
1+ ,eaction question
-a+ .a.)3 ///0 .a) 1 .)2
-#+ *i 1 .u
21
///0 *i
21
1 .u
hydrated ions accepta#le with correct char$e
1 point for *i-)2+2 as product
-c+ 23)4
2
4 1 2
1
///0 223044
incorrect char$e on 223044 when only one product occurs, 1 point only
1 product point for transfer if 2
1
from an ionic reactant to product when a phosphate
species is incorrectly #ut consistently written.
-d+ .l2 1 5r/ ///0 .l4 1 5r2
no credit for monatomic .l as reactant or 5r as product
-e+ *23 1 2.223)2 ///0 .223)24 1 *24
1
1 product point for *24.223)2
1 point for *23 1 2
1
///0 *24
-f+ -*24+2.)3 1 5a
21
1 )24 ///0 *23 1 5a.)3 1 22)
1 product point for either *23 or 5a.)3
2 product points for all three species correct
-$+ *2)3 1 22) ///0 2*)2
1 product point for 2
1
1 *)24
-h+ 6n)44 1 .2)4
2
4 ///0 6n)2 1 .)2
no penalty for )24 or 22) in equation
no point earned for 6n
21
as product
2+
a+ two points total 7 one point for correct su#stitutions7 one point for computation
[2
1
8 [).l4 8 square root -0.14 9 3.2 9 104
:
+ 8 ;.< 9 104
'
6
since =a
8 - [2
1
[).l4 + > [2).l
8 [2
1

2
> c2).l
-#+ two points total? one point each
).l4 1 22) @8880 2).l 1 )24 -or *a).l 1 22) ///0 *a
1
1 2).l 1 )24+
=# 8 =w > =a 8 1 9 104
14
A 3.2 9 104
:
8 3.1 9 104
<
-c+ two points total7 one for concentrations and one for p2 calc.
.oncentrations #efore reaction?
[2).l 8 [-0.0400+ -0.14+ > 0.0'0 8 0.11 6
[)24 8 [-0.0100+ -0.';+ > 0.0'0 8 0.11 6
Bhus reaction is essentially complete and e9actly equals a solution of *a).l and [).l4 8 0.11 6 -or reaction is at
equivalence point+.
Bhen
[)24 8 [2).l
=# 8 [)24
2
> 0.11 8 3.1 9 104
<
[)24 8 square root [-0.11+ -3.1 9 104
<
+ 8 1.: 9 104
4
p)2 8 3.<3
p2 8 14 / 3.<3 8 10.2<
-d+ two points7 one for half/neutraliCed7 one for mmol calcs.
p2 8 <.4D therefore [2
1
8 3.2 9 104
:
p2 8 p=a , or [2
1
8 =a.
Eo [).l4 > [2).l 8 1 , or solution must #e half neutraliCed.
initial mmol 2).l 8 '0.0 9 0.20 8 10.0 mmol
mmol *a)2 required 8 10.0 A 2 8 '.0 mmol
-e+ one point
From equation, 1 mol 2
1
produced for each 1 mole of 2).l produced, thus [2
1
8 [2).l 8 0.0;' therefore p2 8
1.1D
3+
-a+ two points7 one for line of answer
/ 232.< G>= 8 EH -.22;+ / -2;1.4 1 200.D+ G.>=
EH -.22;+ 8 22D.; G>=
units i$nored7 1 point earned for D:.D G>=7 1 point lost if stoichiometry is not implied in
process
-#+ three points total7 one point each portion7 any value for B -e.$., 2<3 = or 2D: =+ is allowa#le?
[delta2H 8 -/ :4.< "G+ / -22;.< "G+ 8 /311.4"G
8 / 311.4"G / -2D: =+ -/ 0.232<"G>=+
8 / 311.4 "G 1 ;D.3 "G
8 / 242.1 "G
*e$ative [delta!H therefore reaction is spontaneous, or =eq 0 1 therefore reaction is spontaneous, or products are
favored at equili#rium.
-c+ two points
ln = 8 242.1 A [-:.31 9 104
3
+ -2D:+ 8 D<.<
= 8 3 9 10
42
-1,2,or 3 si$nificant fi$ures accepta#le+
-d+ two points7 first point earned for correct su#stitution and correct num#er of #onds, second point earned for
settin$ equal to [delta2r9n and correct calculation of answer7 no points earned for Ie9trapolationI techniques to find
car#on/car#on triple #ond ener$y7 JK is the ener$y of the car#on/car#on triple #ond.
/ 311.4 "G 8 [-2+ -43;+ 1 JK 1 -2+ -414+ / [-34<+ 1 -;+ -414+
JK 8 :20 "G
4+
-a+ one point
L161 8 L262
-1.00M+ -'.20 mol>M+ 8 -9+ -1:.4 mol>M+
9 8 '.2 mol > -1:.4 mol>M+ 8 0.2:3 M -or 2:3 mM+
-#+ two points
mass 1 liter of concentrated 22E)4 8 1 M 9 -1.:4 $>mM+ 9 -1,000 ml>M+ 8 1,:40 $ 22E)4
1:.4 mol 22E)4 9 D:.1 $>mol 8 1,:0' $ 22E)4
mass percent 22E)4 8 -1,:0' $ > 1,:40 $+ 9 100 8 D:.1(
-c+ three points
Etoichiometric ratio of *a2.)3 to 22E)4 8 2?1
10.' $ *a2.)3 9 -1 mol *a2.)3 > :4.0 $ *a2.)3+ 8 0.12' mol *a2.)3
Eince 1 mol 22E)4 reacts with 2 mol *a2.)3, 0.12' mol *a2.)3 reacts with 0.0;2' mol 22E)4
0.0;2' mol 22E)4 8 L 9 6 8 -L+ -'.20 6+
L 8 0.0;2' mol > -'.20 mol>M+ 8 0.0120 M -or 12.0 mM+
-d+ three points
molality 8 moles solute > 1,000 $ solvent 8 moles solute > 1 "$ solvent
mass of 1 M of '.20 6 22E)4 8 1 M 9 -1,000 mM > 1 M+ 9 -1.3: $ 1 mM+ 8 1,3:0 $
mass of 22E)4 in 1 M 8 -'.20 mol>M+ -D:.1 $.mol+ 8 '10 $
mass of 22) in 1 M 8 1,3:0 / '10 8 :<0 $
molality 8 -'.20 mol 22E)4 > :<0 $+ 9 -1,000 $ > 1 "$+ 8 '.D: m
*ote? no credit earned for '.20 mol > 1.3: "$ 8 '.<< m
'+ -a+ two points
.)2
#ecause all contain same num#er of molecules -moles+, and .)2 molecules are the heaviest
*ote? total of 1 point earned if .)2 not chosen #ut same num#er of molecules -moles+ is specified
-#+ two points
%ll are equal
#ecause same temperature, therefore same avera$e "inetic ener$y
*ote? &ust restatement of Isame conditions, etc.I does not earn second point
-c+ two points
.)2
either one?
it has the most electrons, hence is the most polariCa#le
it has the stron$est intermolecular -Mondon+ forces
*ote? also allowa#le are Ipolar #ondsI, Iinelastic collisionsI7 claimin$ lar$er siCe or lar$er molecular volume does
not earn second point
-d+ two points
2e
%ny one?
$reatest movement throu$h the #alloom wall
smallest siCe
$reatest molecular speed
most rapid effusion -!rahamNs law+
;+ for e9planation point in D -a+, -c+, and -d+, credit is earned at step indicted in boldface type.
-a+ two points
.alculated 6m-2%+ too low
6-*a)2+ 80 L-*a)2+ 80 n(Na!" 80 n-2%+ 80 6m-2%+
-6 8 n A L+ and -6m 8 mA n+
-#+ two points
.alculated 6m-2%+ not affected
%ny one of the followin$ reasons. Oater?
does not chan$e n-2%+
chan$es only 6-2%+ // sense of dilution
is not a reactant
-c+ two points
.alculated 6m-2%+ too hi$h
e#$ivalence point 80 n-*a)2+ 80 n-2%+ 80 6m-2%+
(e%pected p! hi&her"
*ote? Ino effect if *a)2 standardiCed with same indicatorI earns 2 points7 no credit earned if p28< or neutral
-d+ two points
.alculated 6m-2%+ too low
L-*a)2+ 80 n(Na!" 80 n-2%+ 80 6m-2%+
*ote? point earned for L-*a)2+ only if?
-i+ no e9planation point is earned in -a+
-ii+ e9planation in -a+ also includes L-*a)2+
<+
-a+ two points
Bhe si$n of the cell potential will #e positive
#ecause -any one is sufficient+?
= is $reater than 1
the reaction is spontaneous -occurs+
JH for Er
21
is more positive
Etandard reduction potential for Er more ne$ative
JH 8 1 0.'2 L
*ote? only 1 point earned for &ust JH positive #ecause =eq positive.
-#+ one point
Bhe o9idiCin$ a$ent is 6$
21
-c+ two point
Bhe cell potential would increase
Eince all ions are at 1 6, Q for the system is 1 and JH 8 -,B>nF+ ln =
so as B increases, so should JH
*ote? no credit lost if student reco$niCes =eq dependence on B. For temperature chan$e in this pro#lem, decrease in
ln = term is small relative to the term ,B>nF
),
*o chan$e, #ecause in the *ernst equation Jcell 8 JH / -,B>nF+ ln Q
ln Q 8 0, and Jcell 8 JH
*ote? this second approach earns 1 point only
-d+ two points
Jcell will increase
Pn the equation Jcell 8 JH / -0.0'D2 > n+ lo$ Q
Q 8 0.1 therefore lo$ Q is ne$ative therefore term after JH is positive therefore Jcell increases
),
with the concentration of 6$
21
lar$er than that of Er
21
, Me .hatelierNs principle predicts the reaction will have a
lar$er drivin$ force to the ri$ht and a more positive Jcell
-e+ one point
%t equili#rium, Jcell 8 0
*ote? I#alancedI, IneutralI, or Ino net reactionI not accepted
:+
-a+ one point
2 *) 1 2 22 ///0 *2 1 2 22)
-#+ two points
*2)2 and *2) are intermediates
#ecause they appear in the mechanism #ut not in the overall products -or reactants+
-c+ three points7 one for each half of conclusion -1+ answer, third for conclusion -2+ answer
Etudent indicates conclusion -1+ is correct,
#ecause the sum of the e9ponents in rate law is 2 1 1 8 3
Etudent indicates conclusion -2+ is incorrect,
#ecause no step involves two *) molecules and a 22 molecule
-d+ two points7 B $oes up therefore " $oes up?
#ecause increasin$ num#er of collisions #etween reactants
are occurin$ with sufficient ener$y to form an activated comple9
),
B $oes up therefore rate $oes up
#ecause no chan$e in concentration of reactants, therefore " must increase
),
from %rrhenius equation -not required in %3 .hemistry curriculum, #ut noted in some student responses+?
as B $oes up, " $oes up
),
$raph as #elow with proper e9planation
D+
-a+ two points
2ydro$en #ondin$ -or dipole/dipole attraction+ in 2F is $reater than it is in 2.l
*ote? only one point earned if simply stated that 2F has $reater intermolecular forces than 2.l
-#+ two points
%sF3 has a tri$onal pyramid shape and #ond dipoles do *)B cancel -or asymmetric molecule+
%sF' has a tri$onal #ipyramid shape and #ond dipoles cancel -or symmetric shape+
*otes? e9planation must refer to shape in order to earn point7 one point earned if only correct Mewis structures are
$iven.
-c+ two points
*)24 has resonance structures
2*)2 has no resonance structures
),
one */) sin$le #ond, one *8) dou#le #ond
*ote? one point earned if only correct Mewis structures, includin$ resonance for *)24 $iven.
-d+ two points
Eulfur uses d or#itals -or e9panded octet+, o9y$en has no d or#itals in its valence shell
),
Eulfur is a lar$er atom, can accomodate more #onds.