n0

(,-J- CollegeBoard

- Advanced
Placement
Program

rl

AP@ Chemistry

Free-Response Ouestions

The College Board

The College Board is a not-for-profit membership association rvhose mission is to connect students to college success and
opportunit)'. Founded in 1900, the association is composed of more than 5,600 schools, colleges, universities and other
educational organizations. Each year, the College Board sen'es seven million students and their parcnts,23,000 high schools and
3,800 colleges through major programs and services in college readiness, college admissions, guidance, assessment, tlnancial aid,
enrollment, and teaching and learning. Among its best-known programs are the SAT@, the PSAT/NMSQT@ and the Adi'anced
Placement Program@ (AP@). The College Board is committed to the principles of excellence and equiry, and that commitment is
embodied in all of its programs, services, activities and concerns.

The College Board. All rights reserved. College Board, Advanced Placement Progranr, AP, AP Cc-ntral, SAT, and the
acorn logo are registered trademarks of the College Board. PSAT/NIISQT is a registered trademark of the College Board and
National ivlerit Scholarship Corporation.

Permission to use copyrighted College Board materials may be requested online at:
rn*r'.collegebo ard.com/inquiry/cbpermit.html.

Visit the College Board on the Web: www.collegeboard.com.

AP Central is the official online home for the AP Program: apcentral.collegeboard.com.

INFORMATION N ftM TABLE BELOW AND N TFIE TABLES ON PAGES 3-5 MAY BE USEFTJ'I- N ANSWERING
THE QUESIONS IN THIS SECTION OF Tt{E EXAMINAION.
Nh'(Y

z=

; J;;l i
1-,,Xr-i

cctrS

(3

r-o

O
*/

;;E.t

'-d

=s
d

-A-

i- arE
+ Ao y_w,3l
:cn: n,
r-_

- z3

v^/A-

z
z
f-{

a.l

va

-'1-;

,t
-f-l

r'Ng

fT{

5r)a'

!T

..27,:*EE

A
v
,YI

Irr
.r

rl

\o-1)g
....r

r\
v

:i

|lir

A
-v
A

z7

-9;

-frl

-,\t\
(.r-a

ii 3l

!3
S0.q

cito

6a

Zp1

-aa)
(,

F-

rirzS

SF; P=CDX

OOQ

3il^i

O
.^ >: rl
.)<Act

-cFi:

.;7t
-F?
"Fn

r-5lQ f
c\
:i

c.3A
'old;

s>3* t-- '\

!a fi

"(n2 o\0ra

:;L:<

c! cl

sE$

*s;

cAl\o

co

Aa

5,23

o{

ALq
;^.rO

$*i-

.l

.t

CEq !4,!
-.-Fi?

i-:F

'c .l

iaH't

r3
ir :i

-E

Lg \o
'- v v cc
-frF
ex R,'qi
,c

c tr,4

c'r)

c\
.r'i a
c=.o

-a

oa-

-,-93
$F3

oo3

&

-ii!i

-z:

t-

cO

t-l
+N;

-E

x CFrr,

ci

004
n<3 =F(!

E;

HC

r,:i

F58 cFr

<.

e8

NCI)v

-c\

,-I
-F\o

ca

t.-Lci
a f- rrl c\

F.

r-

)-(
tv.
FI
A

i3x

-=.]-:

V I V-. .rfY;.r1
) ..l+
A,

-l

|-{

-J

F>R

-Eg
0O "q
r\
sf<5

r-

.-r--

b0a

f-l

"i<e

,r'a= cot k

r5

N\V

rr]
.r,faS

r,c/)-

-(en

f{

ij

&

a-

<frrO

FI
ttl

U3
il <h
ol

ta

OU
F!
a)o
(h6

trO

k;-oi

-l
t-;
ol

T.

colY:

aE(3
d.F

'l

t\
q-]

\/

-:

-,c(g

-2-

(,q
Z\
ai ;r-N
*, \J
rl

=4

.-^

-N

ti.

GO ON TO THE NEXT PAGE.

ADVANCED PLACEMENT CHEMISTRY EQUATIONS AND CONSTANTS

ATOMIC STRUCTURE

E=ltv

E = energy

i' = frequency
2 = wavelength
p = momentum

c=)-t

P=ntu

ntu

-2.118 x

l;-

10-18

u = velocity
n = principal quantum number
,??

EQUILIBRIUM

[H-l[A-]

_ toH-ltHB+l

Ku

Avogadro's number = 6.022 x

tBl

tOH-l[H*] =

1.0

x lg-la

Electron charge, e
@ 25"C

1023

mol-l

= -1.602 x l0-19 coulomb

-log[H+], pOH = -loglOH-l

=pH+pOH
fA-|
pAn t toctHAi

Equilibrium Constants

K" (weak acid)

K, (weak base)

pH =

pOH = pKr,

K,

+logl$J

t, = K,(RT\^"

(water)

Kn (gas pressure)

tBl

PK,, = -logKn, pKt, = -logK,,

where Arr

m s-l

I electron volt per atom = 96.5 kJmol-l

=KnxKu

108

Boltzmann's constant, k = 1.38 x 10-23 J K-l

Kh

la

= 3.0 x

Planck's constant, h = 6.63x 10-34 J s

- _lgAl
^n =

1.1

mass

joule
Speed of light, c

pH

K. (molar concentrations)

moles product gas

S" = standard entropy

moles reactant gas

11"

= standard enthalpy

THERMOCHEMISTRY/KINETICS

G' = standard free energy

lS' products -)S" reactants

LH = t lH,' nroducrs -F nA; reacranrs

= -RT lnK = -2.303Rf logK

E" = standard reduction potential

7 = temperature
lr = moles
,7' = mass
Q = heat
c = specific heat capacity
Cp = molar heat capacity at consl.ant

= -n?F E"

En = acti"'ation energy

ASo =

A.Go

= >AGf products

->LCi

reactants

AG"=411"-fAS'

pressure

,t = rate constant
A = frequency factor

AG = AC" + RT lnQ = AGo + 2.303 RT logQ

q = lnc\T
AH
Cr=#

Faraday's constant,'5 = 96,500 coulombs per mole

of electrons

ln[A],-ln[A]n =-11
f

li

^l
LAlr

_
r^l

Gas constant, R

_ ut

LAlo

= 8.31J mol-l K-L

= 0.0821 L atm mol-lK-l
= 62.4 L ton mol-l K-l
= 8.31 volt coulonrb rnol-l K-l

lnft = _{cl_l+ lnA

fi \.r/

-4-

GO ON TO THE NEXT PAGE.

STANDARD REDUCTION POTENTIALS IN AQUEOUS SOLUTION AT 25"C

Half-reaction

E'(V)

2F-

2.87

co2*

1.82

Au(.r)

1.50

F2Q) + 2eCo3* + e-

Au3* + 3e-

-,
-

Cl2(8)+ 2e-

-)

2CI_

r.36

O2(g)+ 4H+ + 4e

2H,O(/)

t.23

Br2(l)+ 2e-

-J

2Br-

1.07

2Hg2* + 2e-

--)

Hg22*

0.92

Hg(/)

0.85

Ag'+e

-+

Ag(.t)

0.80

Hgr2* + 2e-

-t

Fe3* + e-

-l- c-)+

0.71

I2$)+ 2e-

2r-

0.53

Cu+ + e-

-)
-)

Cu(.s)

0.52

Cn2* + 2e-

--)

Cu(s)

0.34

cu2t + e-

--)

Cu*

0.15

sn4* + 2e-

--)

sn2*

0.15

S(s)+ 2H* + 2e-

HzS(s)

0.14

2H+ + 2e-

-)

u2ts)

0.00

Pb2* + 2e-

--)

Pb(.i)

sn2* + 2e-

-+

Sn(s)

Ni2+ + 2e-

-+

Ni(.s)

-0.25

co2* + 2e-

Co(.r)

cd2* + 2e-

Cd(.i)

cr3* + e-

_?

cr2*

- 0.28
- 0.40
- 0.41

Fe2* + 2e-

-+

Fe(.r)

-0.41

Crls;

Hg2* +

2r-

cr3n + 3e-

He(/)

zn2* + 2e-

-)

Zn(s)

2H2O(l)+ 2e-

-+

H2(s) + 2OH-

Mn2* + 2e-

Mn(s)

Al3+ + 3e-

-.)

Al(.i)

Be2* + 2e-

-t

Be(.i)

Mg2* + 2e-

Mg(s)

0.79

0.13

0.14

0.11
0.16
0.83

- l.l8
- 1.66
- 1.70

Cs+

+e-

-+

Cs(s)

-2.37
-2.71
-2.87
-2.89
-2.90
-2.92
-2.92
-2.92

L1+

+e-

-J

Li(s)

Na* + e-

--)

Na(.i)

caz* + 2e-

Ca(.i)

sr2* + 2e-

-,

Sr(s)

Ba2* + 2e-

-+

Ba(s)

Rb'+e-

-)
-)

Rb(s)

K(.t)

K* +e-

-3-

3.05

GO ON TO THE NEXT PAGE.

GASES, LIQUIDS, AND SOLUTIONS

p = pleSsure

PV = nRT

/)\
Ip*[4]<v-ntt=nRT
\ V')
PA

Protot

Pt,,t,,t

PA

"M

K='C

P,V,

x Xo,where Xo

PB

V = volume
I = temperature
n = number of moles
D = density
/7? = mass
u = velocity

moles A

total moles

+ Pc +...

+ 273

= root-mean-square speerJ
KE = kinetic energy
r = rtte of eflusion
M = molar mass
7r = osmotlc pressure
i = van't Hoff factor
Kt = molal freezing-point depression constant
K,r = molal boiling-point ele.yation constant
.-1 = absolhuncc
(r = molar absorptivity
6 = parh lengrh
c = concentration
O = reuetion quotient
.I = cunent (arr-rperes)
q = charge (coulombs)
/ = time (seconds)
E" = standard reduction pote:rtial
K = equilibrium constant

u,,,.,

P,V,
T2

D=!
v

BFT trtr

--nil!
tt=t_=,_

\m

\M

per molecule = !^r=

KE '2

KE per nrolg = iRi"

I

r,

ffi"
rz-\Mt
molarity. M = moles
molality = moles

solute per liter solution

solute per kilogram solvent

LTI =iKrxmolalitY

LT,,=iKrxmolality

= iMRT

A=abc

OXIDATION-REDUCTION; ELECTROCHEMISTRY
Gas constant, R

^ tcl'lDld
Q=*,where
lAl" IB]'

= 0.0821 [- atm mo]-lK-1

I
= 62.1 L tun'mol K-l

aA+bB+cC+dD

= 8.31 volt. coulomb mol-lK-l

Boltzmann's constant, k = 1.38 x l0-23 J K-i

I
Ecell =

logK =

E:,,

PT

-:*lno
ttYf

= 8.31 J mol-l K-l

= E?,,

K,

o osq?

'-

for

K1, tor

nE"
0.0592

HrO = 1.86 K

k-e

mol-]

HrO = 0.512 K kg mol-r

I arm = 760 mm Hg
= 760 torr

STP = 0.00"C and 1.0 atm

Faraday's constant, '8 = 96,500 coulombs per mole
of electrons

-5-

GO ON TO THE NEXT PAGE.

AP@

CHEMISTRY FREE.RESPONSE OUESTIONS

CHEMISTRY
Section

II

(Total tinre-95 minutes)

Part A

Time-55

minutes

YOU IVIAY USE YOUR CALCULATOR FOR PART A.

CLEARLY SHOW THE METHOD USED AND THE STEPS INVOLVED IN ARRIVING AT YOUR ANSWERS.
It is to lour advantage to do thrs, since you may obtain partial credit if you do and you will receive little or no credit if
you do not. Attention should be paid to significant figures.
Be sure to rvrite all your answers to the questions on the lined pages following each question in the booklet with the
pink cover. Do N(fT write your answers on the green insert.
Answer Questions I , 2, and 3. The Section

l,

II

score weighting for each question is 20 percent.

Ansrverthefcllowingquestionsthatrelatetothechemistrl'ofhalogenoxoacids.

(a) Use the information in the table below to answer part (a)(i).
K, at 298 K

Acid

(i)
(ii)
(iii)

1.9

HOBr

2.4

x 10-e

l0-8

Which of the two acids is stronger, HOCI or HOBr

Justify your answer in terms of Kn

Dra'w a complete Lewis electron-dot diagram for the acid that you identified in part (aXi).

Hypoiodous acid has the formula HOI. Predict whether HOI is a stronger acid or a weaker acid than
the acid that you identified in part (aXi). Justify your prediction in terms of chemical bonding.

(b) Write

(c) A

HOCI

the equation for the reaction that occurs between hypochlorous acid and water.

M NaOCI solution is prepared by dissolving solid NaOCI in distilled water at 298 K. The hydrolysis
reaction t)Cl-(aq) + H.O(1) | HOCI(aq) + OH-(aq) occurs.
1.2

(i)
(ii)
(iii)

Write the equilibrium-constant expression for the hydrolysis reaction that occurs between OCI-(aq)
and HrO(/).
Calculate the value of the equilibrium constant at 298 K for the hydrolysis reaction.
Cak:ulate the value

of IOH-] in the

1.2

M NaOCI solution

at 298 K

The College Board. All rights reserved.

Visit the College Board on the \Veb: www.collegeboard.com.

.6-

GO ON TO THE NEXT PAGE.

AP@

CHEMISTRY FREE-RESPONSE OUESTIONS

(d) A buffer solution is prepared by dissolving some solid NaOCI in a solution of HOCI at298 K, The oH of
the buffer solution is determined to be 6.48.

(i)
(ii)

Calculate the value

of [HrO+] in the buffer solurion.

Indicate which of HOCI(aq) or OCI-(a4) is presenr at rhe hrgher concenrrarion in rhe buffer solution.
Support your answer with a calculation.

2. A

student was assigned the task of determining the molar mass of an unknown gas. The student measured the
mass of a sealed 843 mL rigid flask that contained dry air. The student then flushed the f'lask vrith the unknown

gas,resealedit,andmeasuredthemassagain.Boththeairandtheunknowngaswere at23.0"1:and750.torr.

The data fbr the experiment are shown in the table below.

Volume of sealed flask

843 mL

Mass of sealed flask and dry air

157.70 g

Mass of sealed flask and unknown gas

158.08 g

(a) Calculate the mass, in grams, of the dry air that was in the

sealed flask. (The density of drv air is

l.l8 g L-l

at 23.0'C and 750. ton.)

(b) Calculate the mass, in grams, of the sealed flask itself (i.e., if it had no air in it).

(c)

Calculate the mass, in grams, of the unknown gas that was added to the sealed flask.

(d) Using the information above, calculate the value of the molar

mass of the unknown sas.

After the experiment was completed, the instructor informed the student that the unknown gas was carbon
dioxide (44.0 g mol-l).

(e) Calculate the percent error in the value of

(f)

the molar mass calculated in part (d).

For each of the fbllowing two possible occurrences, indicate whether it by itself could hav,: been responsible
for the error in the student's experimental result. You need not include any calculations with yorr ani*...
For each of the possible occurrences, justify your answer.
Occurrence

1:

The flask was incompletely flushed with CO2(S). resulting in some dry air remainin_e
in the flask.

Occurrence2: Thetemperatureof theairwas23.0oC,butthetemperatureof the COr(g) waslowerthan

the reported 23.0"C.

(g) Describe the steps of a laboratory method that the student could

use to verify that the volurne of the rigid

flask is 843 mL at23.0"C. You need not include any calculations with your answer,

The College Board. Ail rights reserved.

Visit the College Board on the \\reb: ivwv.collegeboard.com.

.7.

GO ON TO THE NEXT PAGE.

AP@

CHEMISTRY FREE.RESPONSE OUESTIONS

CH.(s) + 2 Cl2(s)

3.

-+

CH,CI2( B) + z HCI(s)

Methane gas reacts with chlorine gas to form dichloromethane and hydrogen chloride, as represented by the
equation above.

(a) A 25.0 g :iample of methane gas is placed in a reaction

(i)
(ii)

vessel containing 2.58 mol

of Cl2(S).

Identify the limiting reactant when the methane and chlorine gases are combined. Justify your answer
with a calculation.
Calculate the total number of moles

of CHrCl,(g) in the container after the limiting

reactant has been

totally consumed.
Inttiating most reactions involving chlorine gas involves breaking the Cl-Cl bond, which has a bond energy
of 242 kJ mol-r.

(b) Calculate the amount of energy,

(c)

in joules. needed to break a single

Cl-Cl

bond.

Calculate the longest wavelength of light, in meters. that can supply the energy per photon necessary to
break the Cl-Cl bond.

The followinEl mechanism has been proposed for the reaction of methane gas with chlonne gas.
in the gas phase.

1
Step 2
Step 3
Step4
Step 5

Cl, e 2 Cl
CH* + Cl -+ CH, + HCI

Step

CH., + Cl, -+ CH.,CI

+ Cl

+Cl +CH,CI,+H
H + Cl -+ HCI

CH,CI

(d) In the mechanism, is CH.CI

All

species are

fast equilibriunt
slox,
.fasr

fasr
fast

a catalyst. or is

it an intermediate? Justify your answer.

(e) Identify the order of the reaction with respect to each of the following according to the mechanism. In each
case, justLfy your answer.

(i)

CH-'(s)

1ti) Clr(s)

STOP
lf you finish before time is called, you may check your work on this part only.
Do not turn to the other part of the test until you are told to do so.

The College Board. Ali rights reserved.

Visit the College Board on the Web: www.collegeboard.com.

-8-

AP@

CHEMISTRY FREE-RESPONSE OUESTIONS

CHEMISTRY

Part B
Time-40 minutes
NO CALCULATORS MAY BE USED FOR PART B.
Answer Question 4 below. The Section

4'

II

score weighting for this question is 10 percent.

For each of the following three reactions, write a balanced equation in part (i) and answer the question in
part (ii)' In part (i), coefficients should be in terms of lowest whole numbers. Assume that solytions are aqueous
unless otherwise indicated. Represent substances in solutions as ions if the substances are extensively ionized.
Omit formulas for any ions or molecules that are unchanged by the reaction. You may use the
space at the
".pt1,
bottom of the next page for scratch work, but only equations that are written in the answer bor:es
provrded will
be sraded.

EXAMPLE:
A strip of magnesium metal is added to a solution of silver(i) nitrate.

(i) Balanced equation:

Mg
(ii) Which

t ,*t'->

Mh"*

zr@

substance is ox idized in the reaction?

lAn Lt r*',,t

(a) A sample of solid iron(III) oxide is reduced completely with solid carbon
Balanced equation:

(ii)

What is the oxidation number of carbon before the reaction. and what is the oxidation number of
carbon after the reaction is complete?

The College Board. All rights reserved.

Visit the College Board on the \Veb: rwwv,collegeboard.com.

-9-

GO ON TO THIE NEXT PAGE.

AP@

CHEMISTRY FREE.RESPONSE OUESTIONS

(b) Equal volumes of equimolar solutions of ammonia

and hydrochloric acid are combined.

(i) Balanced equation:

(ii)

Indicate whether the resultin-e solution is acidic, basic, or neutral. Explain.

(c) Solid mer:ury(Il) oxide decomposes as it is heated in an open test tube in a fume hood.
(i) Balanced equation:

(ii)

After the reaction is complete, is the mass of the material in the test tube greater than, less than, or
equa:l to the mass of the original sample? Explain.

YOU MAY USE THE SPACE BELOW FOR SCRATCH WORK, BUT ONLY EQUATIONS
THA'I ARE WRITTEN IN THE ANSWER BOXES PROVIDED WILL BE GRADED.

The College Board. All rights reserved.

Visit the College Board on the Web: www,collegeboard.com.
-1

0-

GO ON TO THE NEXT PAGE.

AP@

CHEMISTRY FREE-RESPONSE OUESTIONS

Answer Question 5 and Question 6. The Section

II

score weighting for these questions is

l5 percent

each.

Your responses to these questions will be graded on the basis of the accuracy and relevance of the information cited.
Explanations should be clear and well organized. Examples and equations may be included in your responses where
appropriate. Specific answers are preferable to broad, diffuse responses.

Reaction

Equation

LHi,,s

ASfnt

AGint

C(s) + HzO(s)

CO(s) + H2(s)

+131kJ mol-r

+134 J

co2(s) +H2(s)

Co(s) + H,o(s)

+41 kJ mol-r

+42 J mol-l K-l

,I

,)

Co(s)

c(')

+ Co2(s)

Answer the following questions using the information related to reactions X ,

mol-l K-l

Y,

+9i kJ mol-r
+ 29 kJ

mol-l

'l

and

Z in the table

above.

(a) For reaction X, write the expression for the equilibrium constant, K,,.
(b) For reaction X, will the equilibrium constant,

K'

increase. decrease, or remain the same

if

the temperature

rises above 298 K ? Justify your answer.

(c) Forreaction Y at298 K, is the value of K,

Ereater than

I,

less than

l,

or equal to

l? Justiiy your answer.

(d) For reaction Y at 298 K, which is larger: the total bond energy of the reactants or the total bond energy of
the products'/ Explain.

(e) Is the following starement true or false? Justify your

answer.

"On the basis of the data in the table, it can be predicted that reaction
reaction X will occur."

Y rvill occur more rlpidly

than

(f) Considerreaction Z at298K.

(i) Is A5" for the reaction positive, negative, or zero'/ Justify your answer.
(ii) Determine the value of A11o for the reaction.
(iii) A sealed glass reaction vessel contains only CO(g) and a small amount of C(s). If a :eaction occurs
and the temperature is held constant at298 K, rvill the pressure in the reaction vessel increase,
decrease, or remain the same over time? Explain.

The College Board. All rights reserved.

Visit the College Board on the \Veb: www.collegeboard.com.

.11.

GO ON TO THiE NEXT PAGE.

AP@

6. Answer

CHEMISTRY FREE.RESPONSE OUESTIONS

the following questions related to sulfur and one of its compounds.

(a) Consider lhe two chemical species S and S2-.

(i) Write the electron configuration (e.g.. 1s2 2s2 . . .) of each species.
(ii) Explain why the raclius of the Sl- ron is larger than the radius of the S atom.
(iii) Which of the two species rvould be attracted into a magnetic field? Explain.
(b) The 52- icn is isoelectronic with the Ar atom. From which species, 52- or Ar, is it easier to remove

an

electron? Explain.

(c) In the Hrli molecule, the H-S-H

bond angle rs close to 90o. On the basis of this information, which atomic

orbitals o1'the S atom are involved in bonding with the H atoms?

(d) Two typeri of intermolecular forces present in liquid HrS

are London (dispersion) forces and dipole-dipole

forces.

(i)

Conrpare the strength of the London (dispersion) forces in liquid HrS to the strength of the London

(dispersion) forces in liquid H.,O. Explain.

(ii)

Conrpare the strength of the dipole-dipole forces in liquid HrS to the strength of the dipole-dipole

forc':s in liquid H1O. Explain.

STOP
END OF EXAM

, The College Board. All rights reserved.

Visit the College Board on the Web: www.collegeboard.com.

-12-