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Program
rl
AP@ Chemistry
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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.
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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
tBl
tOH-l[H*] =
1.0
x lg-la
Electron charge, e
@ 25"C
1023
mol-l
Equilibrium Constants
pH =
pOH = pKr,
K,
+logl$J
t, = K,(RT\^"
(water)
Kn (gas pressure)
tBl
where Arr
m s-l
=KnxKu
108
Kh
la
= 3.0 x
- _lgAl
^n =
1.1
mass
joule
Speed of light, c
pH
K. (molar concentrations)
11"
= standard enthalpy
THERMOCHEMISTRY/KINETICS
= -n?F E"
En = acti"'ation energy
ASo =
A.Go
= >AGf products
->LCi
reactants
AG"=411"-fAS'
pressure
,t = rate constant
A = frequency factor
q = lnc\T
AH
Cr=#
ln[A],-ln[A]n =-11
f
li
^l
LAlr
_
r^l
Gas constant, R
_ ut
LAlo
-4-
Half-reaction
E'(V)
2F-
2.87
co2*
1.82
Au(.r)
1.50
F2Q) + 2eCo3* + e-
Au3* + 3e-
-,
-
Cl2(8)+ 2e-
-)
2CI_
r.36
O2(g)+ 4H+ + 4e
2H,O(/)
t.23
Br2(l)+ 2e-
-J
2Br-
1.07
2Hg2* + 2e-
--)
Hg22*
0.92
Hg(/)
0.85
Ag'+e
-+
Ag(.t)
0.80
Hgr2* + 2e-
-t
Fe3* + e-
-l- c-)+
0.71
I2$)+ 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
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
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
r,
ffi"
rz-\Mt
molarity. M = moles
molality = moles
LTI =iKrxmolalitY
LT,,=iKrxmolality
= iMRT
A=abc
OXIDATION-REDUCTION; ELECTROCHEMISTRY
Gas constant, R
^ tcl'lDld
Q=*,where
lAl" IB]'
aA+bB+cC+dD
I
Ecell =
logK =
E:,,
PT
-:*lno
ttYf
= E?,,
K,
o osq?
'-
for
K1, tor
nE"
0.0592
HrO = 1.86 K
k-e
mol-]
-5-
AP@
II
Time-55
minutes
l,
II
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
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
.6-
AP@
(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)
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.
843 mL
157.70 g
158.08 g
(a) Calculate the mass, in grams, of the dry air that was in the
l.l8 g L-l
(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
After the experiment was completed, the instructor informed the student that the unknown gas was carbon
dioxide (44.0 g mol-l).
(f)
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.
(g) Describe the steps of a laboratory method that the student could
.7.
AP@
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.
(i)
(ii)
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
totally consumed.
Inttiating most reactions involving chlorine gas involves breaking the Cl-Cl bond, which has a bond energy
of 242 kJ mol-r.
(c)
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
+ Cl
+Cl +CH,CI,+H
H + Cl -+ HCI
CH,CI
All
species are
fast equilibriunt
slox,
.fasr
fasr
fast
a catalyst. or is
(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.
-8-
AP@
Part B
Time-40 minutes
NO CALCULATORS MAY BE USED FOR PART B.
Answer Question 4 below. The Section
4'
II
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.
Mg
(ii) Which
t ,*t'->
Mh"*
zr@
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?
-9-
AP@
(ii)
(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.
0-
AP@
II
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
,I
,)
Co(s)
c(')
+ Co2(s)
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'
if
the temperature
Ereater than
I,
less than
l,
or equal to
(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.
answer.
"On the basis of the data in the table, it can be predicted that reaction
reaction X will occur."
than
.11.
AP@
6. Answer
(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.
bond angle rs close to 90o. On the basis of this information, which atomic
forces.
(i)
Conrpare the strength of the London (dispersion) forces in liquid HrS to the strength of the London
(ii)
Conrpare the strength of the dipole-dipole forces in liquid HrS to the strength of the dipole-dipole
STOP
END OF EXAM
-12-