The Advanced Place-

ment Examination in
Chemistry
Part II - Free Response Questions &
Answers
1970 to 2005

Acid - Base
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1970 the equilibrium will be pushed nearly totally to
(a) What is the pH of a 2.0 molar solution of acetic the left resulting in a decrease of the hydrogen ion
acid. Ka acetic acid = 1.8x10-5 by 0.143M. Therefore, the [H+]eq = 0.357M -
0.143M = 0.214M.
(b) A buffer solution is prepared by adding 0.10 liter
of 2.0 molar acetic acid solution to 0.1 liter of a
1.0 molar sodium hydroxide solution. Compute 1970
the hydrogen ion concentration of the buffer solu- H3PO2,H3PO3, and H3PO4 are monoprotic, diprotic and
tion. triprotic acids, respectively, and they are about equal
strong acids.
(c) Suppose that 0.10 liter of 0.50 molar hydrochloric HClO2, HClO3, and HClO4 are all monoprotic acids,
acid is added to 0.040 liter of the buffer prepared but HClO2 is a weaker acid than HClO3 which is
in (b). Compute the hydrogen ion concentration weaker than HClO4. Account for:
of the resulting solution.
(a) The fact that the molecules of the three phospho-
Answer: rus acids can provide different numbers of pro-
(a) CH3COOH(aq) <=> H+(aq) + CH3COO-(aq) tons.
+ −
−5 [H ][CH3COO ] (b) The fact that the three chlorine acids differ in
Ka = 1.8 ∞10 =
[ CH3COOH] strengths.
[H+] = [CH3COO-] = X Answer:
[CH3COOH] = 2.0 - X, X << 2.0, (2.0- X) = 2.0 (a) the structure for the three acids are as follows:
H H O
X2
H P O O P O H H O P O H
1.8x10-5 = 2.0
O O O
X = 6.0x10-3 = [H+]; pH = -log [H+] = 2.22
H H H
(b) 0.1 L x 2.0 mol/L = 0.20 mol CH3COOH
The hydrogen atom(s) bonded directly to the phos-
0.1 L x 1.0 mol/L = 0.10 mol NaOH phorus atom is/are not acidic in aqueous solution;
the 0.10 mol of hydroxide neutralizes 0.10 mol only those hydrogen atoms bonded to the oxygen
CH3COOH with 0.10 mol remaining with a con- atoms can be released as protons.
centration of 0.10 mol/0.20 L = 0.5 M. This also (b) The acid strength is successively greater as the
produces 0.10 mol of acetate ion in 0.20 L, there- number of oxygen atoms increases because the
fore, [CH3COO-] = 0.50 M. very electronegative oxygen atoms are able to
[ H + ][0.50]
draw electrons away from the chlorine atom and
1.8 ∞10−5 =
[ 0.50] the O-H bond. This effect is more important as
[H+] = 1.8x10-5 = pH of 4.74 the number of attached oxygen atoms increases.
This means that a proton is most readily produced
(c) [CH3COOH]o = [CH3COO-]o by the molecule with the largest number of at-
0.040 L tached oxygen atoms.
= 0.50 M x 0.14 L = 0.143 M
0.10 L 1970
A comparison of the theories Arrhenius, Bronsted and
[H+]o = 0.50 M x 0.14 L = 0.357 M
Lewis shows a progressive generalization of the acid
base concept. Outline the essential ideas in each of mol HCl that reacted w/KOH = 0.050 mol
these theories and select three reactions, one that can 0.050 mol KOH = 2.81 g = 56.1% of sample
be interpreted by all three theories, one that can be in- the remaining KCl amounts to 16.3%
terpreted by two of them, and one that can be inter-
preted by only one of the theories. Provide these six
interpretations. 1972
Answer: Given a solution of ammonium chloride. What addi-
Arrhenius tional reagent or reagents are needed to prepare a buf-
acid = produce H+ ions in aqueous solution fer from the ammonium chloride solution?
base = produce OH- ions in aqueous solution Explain how this buffer solution resists a change in pH
Bronsted-Lowry when:
acid = proton (H+) donor; base = proton acceptor (a) Moderate amounts of strong acid are added.
Lewis (b) Moderate amounts of strong base are added.
acid = e- pair acceptor; base = e- pair donor (c) A portion of the buffer solution is diluted with an
Examples: equal volume of water.
Interpreted by all three Answer:
HCl + H2O -->H+(aq) + Cl-(aq) Since ammonium chloride is a salt of a weak base, the
NaOH + H2O --> Na+(aq) + OH-(aq) weak base is needed, ammonia, NH3.
Interpreted by two (a) When moderate amounts of a strong acid, H+, are
NH3 + HCl <=> NH4+ + Cl- added, the ammonia reacts with it. The concentra-
Interpreted by only one tion of the hydrogen ion remains essentially the
BF3 + NH3 --> F3B:NH3 same and therefore only a very small change in
pH.
1972 (repeated in gases topic)
NH3 + H+ <=> NH4+
A 5.00 gram sample of a dry mixture of potassium hy-
droxide, potassium carbonate, and potassium chloride (b) When moderate amounts of a strong base, OH-,
is reacted with 0.100 liter of 2.00 molar HCl solution are added, the ammonium ion reacts with it. The
(a) A 249 milliliter sample of dry CO 2 gas, measured concentration of the hydrogen ion remains essen-
at 22ºC and 740 torr, is obtained from this reac- tially the same and therefore only a very small
tion. What is the percentage of potassium carbon- change in pH.
ate in the mixture? NH4+ + OH- <=> NH3 + H2O
(b) The excess HCl is found by titration to be chemi- (c) By diluting with water the relative concentration
cally equivalent to 86.6 milliliters of 1.50 molar ratio of [NH4+]/[NH3] does not change, therefore
NaOH. Calculate the percentages of potassium there should be no change in pH.
hydroxide and of potassium chloride in the origi-
nal mixture. 1973
Answer: A sample of 40.0 milliliters of a 0.100 molar HC 2H3O2
(a) K2CO3 + 2 HCl -->CO2 + 2 KCl + H2O solution is titrated with a 0.150 molar NaOH solution.
PV ( 740torr )(249mL) Ka for acetic acid = 1.8x10-5
mol CO2 = = =
RT 62400
mL_torr
( 295K) (a) What volume of NaOH is used in the titration in
( mol_K ) order to reach the equivalence point?
= 0.0100 mol CO2 (b) What is the molar concentration of C2H3O2- at the
0.10 mol CO2  1 mol K2CO3 / 1mol CO2  138.2 g equivalence point?
K2CO3 /1 mol K2CO3 = (c) What is the pH of the solution at the equivalence
=1.38 g K2CO3 point?
1.38 g K2CO3/5.00 g mixture  100% = 27.6% K2CO3 Answer:
(b) orig. mol HCl = 0.100 L  2.00M = 0.200 mol (a) MaVa=MbVb
reacted with K2CO3 = 0.020 mol
(0.100M)(40.0 mL) = (0.150M)(Vb)
excess HCl = 0.0866L  1.50M = 0.130 mol
 Vb = 26.7 mL 4.00gNaOH 1 mol
∞ = 0.20M
(b) acetate ion is a weak base with 0.50L 40.0g
(a)
K
Kb=Kw/Ka = 1.010-14/1.810-5 = 5.610-10 [ H+ ] = w = 5 ∞10−14 ; pH = −log[H+ ] = 13. 3
− 4. 00mmol 0. 20
[ CH3COO ]o = = 0. 0600M
( 40. 0mL + 26. 7 mL ) 0.100 mol
[ OH −] = −X
[CH3COO-]eq = 0.600M -X (b) 1.00L
[OH-] = [CH3COOH] = X [NH4+] = 0.50M - X; [NH3] = 0.50M + X
X2 (0. 50 −X )(0.100 −X )
5.6 ∞10
−10
=
−5
; X = 9.66 ∞10 M 1. 8 ∞10−5 = ; X = 0.100 M
( 0. 0600 −X ) (0. 50 + X )

0.0600M-9.6610-5M = 0.0599M [CH3COO-]eq using the Henderson-Hasselbalch equation

⊇[ NH + ]_ ⊇0.40_
+ Kw 1. 0 ∞10−14 −10 pH = pKa+ logℑ 4 
= 4.74 + logℑ = 4.57
[H ] = = −5 = 1. 04 ∞10 M ⊄0.60↓
[ OH
−
] 9 . 66 ∞10 ⊄[ NH 3]↓
(c)
pH = -log [H+] = -log(1.0410-10) = 9.98
1975
Reactions requiring either an extremely strong acid or
1974 A
an extremely strong base are carried out in solvents
A solution is prepared from 0.0250 mole of HCl, 0.10
other than water. Explain why this is necessary for
mole propionic acid, C2H5COOH, and enough water to
both cases.
make 0.365 liter of solution. Determine the concentra-
Answer:
tions of H3O+, C2H5COOH, C2H5COO-, and OH- in this
solution. Ka for propionic acid = 1.3x10-5 Water is amphoteric and can behave either as an acid
Answer: in the presence of a strong base or as a base in the
presence of strong acid.
C2H5COOH + H2O <=> C2H5COO- + H3O+
Water also undergoes autoionization.
[C2H5COO-] = X
[C2H5COOH] = (0.10mol/0.365L) - X 1976
[H3O+] = (0.0250mol/0.365L) + X H2S + H2O <=> H3O+ + HS- K1 = 1.0x10-7
(X )(0.0685 + X ) HS- + H2O <=> H3O+ + S2- K2 = 1.3x10-13
Ka = = 1.3 ∞10−5; X = 5.2 ∞10−5 H2S + 2 H2O <=> 2 H3O + S
+ 2-
K = 1.3x10-20
0.274 −X
Ag2S(s) <=> 2 Ag+ + S2- Ksp= 5.5x10-51
[C2H5COO-] = 5.210-5M; [C2H5COOH] = 0.274M
(a) Calculate the concentration of H3O+ of a solution
[H3O+] = 0.0685M; which is 0.10 molar in H2S.
Kw
[ OH −] = = 1. 46 ∞10 −13 M (b) Calculate the concentration of the sulfide ion, S2-,
0. 0685 in a solution that is 0.10 molar in H2S and 0.40
molar in H3O+.
1975 A (c) Calculate the maximum concentration of silver
(a) A 4.00 gram sample of NaOH(s) is dissolved in ion, Ag+, that can exist in a solution that is
enough water to make 0.50 liter of solution. Cal- 1.510-17 molar in sulfide ion, S2-.
culate the pH of the solution.
Answer:
(b) Suppose that 4.00 grams of NaOH (s) is dissolved (a) H2S + H2O <=> H3O+ + HS-
in 1.00 liter of a solution that is 0.50 molar in
[ H3O+ ][HS−] −7
NH3 and 0.50 molar in NH4+. Assuming that there = 1. 0 ∞10
is no change in volume and no loss of NH3 to the [H2 S]
atmosphere, calculate the concentration of hy- let X = [H3O+] = [HS-]
droxide ion, after a chemical reaction has oc- X2
curred. [Ionization constant at 25ºC for the reac- = 1. 0 ∞10−7
0.10 −X
tion NH3 + H2O -->NH4+ + OH-; K = 1.8x10-5]
X ïï 0.10; X = 1.0x10-4 M = [H3O+]
Answer:
(b) H2S + 2 H2O <=> 2 H3O+ + S2- the addition of 27.4 milliliters of the 0.135 molar
[ H3O+ ]2 [S2 −] NaOH.
= 1. 3 ∞10 −20 (a) Calculate the number of moles of acid in the orig-
[ H2S]
inal sample.
[ 0. 40]2[S2 −]
= 1. 3 ∞10 −20 (b) Calculate the molecular weight of the acid HA.
[ 0.10] ; [S2-] = 8.110-21M (c) Calculate the number of moles of unreacted HA
(c) Ag2S(s) <=> 2 Ag+ + S2-; [Ag+]2[S2-] = 5.510-51 remaining in solution when the pH was 5.65.
5.5 ∞10 −51 (d) Calculate the [H3O+] at pH = 5.65
[ Ag+ ] = −17 = 1. 9 ∞10
−17
M
1.5 ∞10 (e) Calculate the value of the ionization constant, Ka,
of the acid HA.
1977 Answer:
The value of the ionization constant, Ka, for (a) at equivalence point, moles HA = moles NaOH
hypochlorous acid, HOCl, is 3.110-8.
= MbVb = (0.0274 L)(0.135 M) = 3.70 x10-3 mol
(a) Calculate the hydronium ion concentration of a HA
0.050 molar solution of HOCl.
mass HA 0.682g
(b) Calculate the concentration of hydronium ion in a molec.wt . = = −3 = 184 g/mol
(b) mol HA 3.70 ∞10 mol
solution prepared by mixing equal volumes of
0.050 molar HOCl and 0.020 molar sodium (c) HA + OH- --> A- + H2O
hypochlorite, NaOCl. initial: 0.00370 mol
(c) A solution is prepared by the disproportionation added: (0.0106L)(0.135M) = 0.00143 mole
reaction below. Cl2 + H2O --> HCl + HOCl
remaining: (0.00370 - 0.00143) = 0.00227 mol
Calculate the pH of the solution if enough chlo-
rine is added to water to make the concentration (d) pH = -log[H3O+]; [H3O+] = 10-pH = 10-5.65
of HOCl equal to 0.0040 molar. = 2.2x10-6M
Answer: [H3O + ][ A−] (2. 2 ∞10 −6 )(0. 00143 / v)
K a = =
(a) HOCl + H2O <=> H3O+ + OCl- [ HA] (0. 00227 / v)
+ − 2
(e)
[H O ][OCl ] X
3. 2 ∞10−8 = 3 = = 1.4x10-6
[ HOCl] ( 0. 050 −X )
X = [H3O+] = 4.0x10-5M 1978 D
(b) HOCl + H2O <=> H3O+ + OCl- Predict whether solutions of each of the following
[ H3O+ ][0. 010 + X ] salts are acidic, basic, or neutral. Explain your predic-
= 3. 2 ∞10 −8 tion in each case
[0. 0250 −X ] ; X << 0.010 (a) Al(NO3)3 (b) K2CO3 (c) NaBr
X = [H3O+] = 8.0x10-8M Answer:
(c) Cl2 + H2O --> HCl + HOCl (a) acidic; Al3+ + H2O <=> AlOH2+ + H+;
[HOCl] = [HCl] = 0.0040M hydrolysis of Al3+;
HCl as principal source of H3O +
Al(OH2)n3+ as Bronsted acid, etc.
pH = -log[H3O ] = 2.40
+
(b) basic; CO32- + H2O <=> HCO3- + OH- ; or
hydrolysis of CO32- as conjugate to a weak acid,
1978 A etc.
A 0.682 gram sample of an unknown weak monopro-
(c) neutral; Na+ from strong base; Br- from strong
tic organic acid, HA was dissolved in sufficient water
acid
to make 50 milliliters of solution and was titrated with
a 0.135 molar NaOH solution. After the addition of
1979 B
10.6 milliliters of base, a pH of 5.65 was recorded.
A solution of hydrochloric acid has a density of 1.15
The equivalence point (end point) was reached after
grams per milliliter and is 30.0% by weight HCl.
(a) What is the molarity of this solution of HCl? H2O OH-
(b) What volume of this solution should be taken in 2nd reaction H2O OH-
order to prepare 5.0 liters of 0.20 molar hy- C2H5OH C2H5O-
drochloric acid by dilution with water? (c) ethoxide is a stronger base than ammonia.
(c) In order to obtain a precise concentration, the A stronger base is always capable of displacing a
0.20 molar hydrochloric acid is standardized weaker base. Since both reactions are quantita-
against pure HgO (molecular weight = 216.59) by tive, in terms of base strength, OH- > NH3 in 1st
titrating the OH- produced according to the fol- reaction; C2H5O- > OH- in 2nd rxn.
lowing quantitative reaction.
HgO(s) + 4 I- + H2O --> HgI42- + 2 OH- 1980 A
Methylamine CH3NH2, is a weak base that ionizes in
In a typical experiment 0.7147 grams of HgO re- solution as shown by the following equation.
quired 31.67 milliliters of the hydrochloric acid CH3NH2 + H2O <=> CH3NH3+ + OH-
solution for titration. Based on these data what is
(a) At 25ºC the percentage ionization in a 0.160 mo-
the molarity of the HCl solution expressed to four
lar solution of CH3NH2 is 4.7%. Calculate [OH-],
significant figures.
[CH3NH3+], [CH3NH2], [H3O+], and the pH of a
Answer: 0.160 molar solution of CH3NH2 at 25ºC
1.15g 1000mL 30.0gHCl 1 mol
∞ ∞ ∞ = 9.5M (b) Calculate the value for Kb, the ionization constant
(a) 1 mL 1L 100g 35.5g
for CH3NH2, at 25ºC.
(b) MfVf = MiVi (c) If 0.050 mole of crystalline lanthanum nitrate is
(0.20M)(5.0L) = (9.5M)(V) added to 1.00 liter of a solution containing 0.20
V = 0.11 L mole of CH3NH2 and 0.20 mole of its salt CH3N-
0. 7147g H3Cl at 25ºC, and the solution is stirred until equi-
= 0. 003300 mol HgO librium is attained, will any La(OH) 3 precipitate?
(c) 216. 59g mol Show the calculations that prove your answer.
mol OH- prod. = 2 (mol HgO) = 0.006600 mol (The solubility constant for La(OH) 3, Ksp = 1x10-19
mol HCl req. = mol OH- prod. = 0.006600 mol at 25ºC)
0. 006600mol Answer:
M HCl = = 0. 2084M (a) CH3NH2; 0.160M x 4.7% = 7.5x10-3 M ionizing
0. 03167L
(0.160M - 0.0075M) = 0.0152M @ equilibrium
1979 D [CH3NH3+] = [OH-] = 7.5x10-3 M
NH4 + OH <=>NH3 + H2O
+ -
Kw
+ −12
H2O + C2H5O- <=> C2H5OH + OH- [ H3O ] = −3 = 1.3 ∞10 M
7. 5 ∞10
The equations for two acid-base reactions are given
above. Each of these reactions proceeds essentially to pH = -log [H3O+] = 11.89
completion to the right when carried out in aqueous [CH3 NH +3 ][OH −] ( 7.5∞10−3 )2
solution. K b = =
[CH 3 NH 2 ] 0.152
(a) Give the Bronsted-Lowry definition of an acid (b)
and a base. =3.7x10-4
(b) List each acid and its conjugate base for each of ( 0.20 + X )( X )
K b = 3. 7 ∞10−4 = ♠X
the reactions above. (c) (. 020 −X )
(c) Which is the stronger base, ammonia or the = [OH-]
ethoxide ion. C2H5O-? Explain your answer.
Q = [La3+][OH-]3 = (0.050)(3.7x10-4)3
Answer:
(a) acid = proton donor; base = proton acceptor = 2.5x10-12
(b) Acid Conjugate base Q > Ksp, therefore, La(OH)3 precipitates
1 reaction
st
NH4 +
NH3
1981 D (b) The pH remains unchanged because the ratio of
Al(NO3)3 K2CO3 NaHSO4 NH4Cl the formate and formic acid concentration stays
(a) Predict whether a 0.10 molar solution of each of the same.
the salts above is acidic, neutral or basic. (c) initial concentrations
(b) For each of the solutions that is not neutral, write 5. 00mL
1. 00M HCl ∞ = 0. 0476M
a balanced chemical equation for a reaction oc- 105mL
curring with water that supports your prediction. 100mL
0. 40M HCOOH ∞ = 0. 38M
Answer: 105mL
(a) Al(NO3)3 - acidic K2CO3 - basic 100mL
0. 60M HCOO- ∞ = 0. 57M
NaHSO4 - acidic NH4Cl - acidic 105mL
(b) Al3+ + H2O --> Al(OH)2+ + H+ concentrations after H+ reacts with HCOO-
0.38M + 0.05M = 0.43M HCOOH
Al(H2O)63+ + H2O --> [Al(H2O)5OH]2+ + H3O+
0.57M - 0.05M = 0.52M HCOO-
Al + 3 H2O --> Al(OH)3 + 3 H
3+ +
0. 43M
[ H3O+ ] = 1.8 ∞10 −4 ∞ = 1.5 ∞−4 M
CO32- + H2O --> HCO3- + OH- 0. 52M
HSO4 + H2O --> SO4 + H3O
- 2- +
(d) 0.800L  2.00M HCOOH = 1.60 mol
NH4 + H2O --> NH3 + H3O
+ +
0.200L  4.80M NaOH = 0.96 mol OH-
at equil., (1.60 - 0.96) = 0.64 mol HCOOH and
1982 A 0.96 mol HCOO-
A buffer solution contains 0.40 mole of formic acid, + −4 0. 64M −4
[ H3O ] = 1.8 ∞10 ∞ = 1.2 ∞ M
HCOOH, and 0.60 mole of sodium formate, 0. 96M
HCOONa, in 1.00 litre of solution. The ionization
constant, Ka, of formic acid is 1.8x10-4. 1982 D
(a) Calculate the pH of this solution. A solution of barium hydroxide is titrated with 0.1-M
(b) If 100. millilitres of this buffer solution is diluted sulfuric acid and the electrical conductivity of the so-
to a volume of 1.00 litre with pure water, the pH lution is measured as the titration proceeds. The data
does not change. Discuss why the pH remains obtained are plotted on the graph below.
constant on dilution.
(c) A 5.00 millilitre sample of 1.00 molar HCl is
added to 100. millilitres of the original buffer so-
lution. Calculate the [H3O+] of the resulting solu-
tion.
(d) A 800.-milliliter sample of 2.00-molar formicConductivity, λ
acid is mixed with 200. milliliters of 4.80-molar
NaOH. Calculate the [H3O+] of the resulting solu-
tion.
Answer:
(a) using the Henderson-Hasselbalch equation
⊇[A−] _ 10 20 30 40 50 60 70 80
pH = pKa+ logℑ 
⊄[HA]↓ Millilitres of 0.1-M H2SO4
(a) For the reaction that occurs during the titration
−4 ⊇0.60 _ described above, write a balanced net ionic equa-
= −log(1.8 ∞10 ) + logℑ 
⊄0.40 ↓ tion.
= 3.92 {other approaches possible} (b) Explain why the conductivity decreases, passes
through a minimum, and then increases as the
 volume of H2SO4 added to the barium hydroxide 9.9916x10-3 mol
is increased. H2C2O4 + 2 NaOH --> Na2C2O4 + 2 H2O
(c) Calculate the number of moles of barium hydrox- 9. 9916 ∞10 −3 mol ∞ 2molNaOH = 1. 9983 ∞10−2 mol
ide originally present in the solution that is 1molH2C2O4
titrated. 1. 9983 ∞10 −2 mol
M NaOH = = 0. 4846M
(d) Explain why the conductivity does not fall to zero 0. 04124 L
at the equivalence point of this titration. (b) mol HX = mol NaOH
Answer:
0.03821 L x 0.4846 M = 0.01852 mol HX
(a) Ba2+ + 2 OH- + 2 H+ + SO42- --> BaSO4(s) + 2 H2O
0. 01852 mol
(b) The initial conductivity is high because of the ∞250. 00mL = 0.09260 mol HX
(c) 50. 00mL
presence of Ba and OH ions. The conductivity
2+ -

decreases because Ba2+ forms insoluble BaSO4 15.126 g g

MW = = 163. 3 mol
with the addition of SO42-. The conductivity also 0. 09260 mol
decreases because OH combines with the addition (d) The calculated molecular weight is smaller than
-

of H+ ions by forming H2O. true value, because:

Beyond the equivalence point conductivity in- measured g H2C2O4 is larger than true value,
creases as H+ and SO42- ions are added. calculated mol H2C2O4 is larger than true value,
(c) # mol Ba(OH)2 = # mol H2SO4 calculated mol NaOH is larger than true value,
=0.1M  0.04L = 0.004 mol calculated M NaOH is larger than true value
(d) BaSO4(s) dissociates slightly to form Ba and 2+ calculated mol HX is larger than true value, there-
SO4 , while the water ionizes slightly to form H
2- + fore,
and OH . g HX (true value )
MW =
-

mol HX (calculated , and too large

)
1983 B
The molecular weight of a monoprotic acid HX was to 1983 C
be determined. A sample of 15.126 grams of HX was (a) Specify the properties of a buffer solution. De-
dissolved in distilled water and the volume brought to scribe the components and the composition of ef-
exactly 250.00 millilitres in a volumetric flask. Sev- fective buffer solutions.
eral 50.00 millilitre portions of this solution were (b) An employer is interviewing four applicants for a
titrated against NaOH solution, requiring an average job as a laboratory technician and asks each how
of 38.21 millilitres of NaOH. to prepare a buffer solution with a pH close to 9.
The NaOH solution was standardized against oxalic Archie A. says he would mix acetic acid and
acid dihydrate, H2C2O4.2H2O (molecular weight: sodium acetate solutions.
126.066 gram mol ). The volume of NaOH solution
-1
Beula B. says she would mix NH4Cl and HCl
required to neutralize 1.2596 grams of oxalic acid di- solutions.
hydrate was 41.24 millilitres. Carla C. says she would mix NH4Cl and NH3
(a) Calculate the molarity of the NaOH solution. solutions.
Dexter D. says he would mix NH3 and NaOH so-
(b) Calculate the number of moles of HX in a 50.00 lutions.
millilitre portion used for titration.
Which of these applicants has given an appropri-
(c) Calculate the molecular weight of HX. ate procedure? Explain your answer, referring to
(d) Discuss the effect of the calculated molecular your discussion in part (a). Explain what is wrong
weight of HX if the sample of oxalic acid dihy- with the erroneous procedures.
drate contained a nonacidic impurity. (No calculations are necessary, but the following
Answer: acidity constants may be helpful: acetic acid, K a=
1.2596 g 1.8x10-5; NH4+, Ka = 5.6x10-10)
g
Answer:
(a) mol H2C2O4.2H2O = 126.066 mol =
(a) A buffer solution resists changes in pH upon the (d) pH 2.88 = 1.32x10-3M [H+] = [C6H5COO-]
addition of an acid or base. [ H+ ][C6 H5CO− −3 2
2 ] = (1.32 ∞10 )
[ C6H5CO 2 H] =
Preparation of a buffer: (1) mix a weak acid + a Ka 6. 33 ∞10−5
salt of a weak acid; or (2) mix a weak base + salt
= 2.75x10-2M [C6H5COOH]
of a weak base; or (3) mix a weak acid with about
half as many moles of strong base; or (4) mix a total dissolved = (2.75x10-2M + 1.32x10-3M as ions)
weak base with about half as many moles of = 2.88x10-2M
strong acid; or (5) mix a weak acid and a weak
base. 1984 C
(b) Carla has the correct procedure, she has mixed a Discuss the roles of indicators in the titration of acids
weak base, NH3, with the salt of a weak base, and bases. Explain the basis of their operation and the
NH4Cl. factors to be considered in selecting an appropriate in-
dicator for a particular titration.
Archie has a buffer solution but a pH of around 5.
Answer:
Beula doesn’t have a buffer solution, her solution
An indicator signals the end point of a titration by
consists of a strong acid and a salt of a weak base.
changing color.
Dexter does not have a buffer solution, since his An indicator is a weak acid or weak base where
solution consists of a weak base plus a strong the acid form and basic form of the indicators are of
base. different colors.
An indicator changes color when the pH of the so-
1984 A
lution equals the pKa of the indicator. In selecting an
Sodium benzoate, C6H5COONa, is the salt of a the
indicator, the pH at which the indicator changes color
weak acid, benzoic acid, C6H5COOH. A 0.10 molar
should be equal to (or bracket) the pH of the solution
solution of sodium benzoate has a pH of 8.60 at room
at the equivalence point.
temperature.
For example, when a strong acid is titrated with a
(a) Calculate the [OH-] in the sodium benzoate solu- strong base, the pH at the equivalence point is 7, so we
tion described above. would choose an indicator that changes color at a pH
(b) Calculate the value for the equilibrium constant = 7. {Many other examples possible.}
for the reaction:
C6H5COO- + H2O <=> C6H5COOH + OH- 1986 A
(c) Calculate the value of Ka, the acid dissociation In water, hydrazoic acid, HN3, is a weak acid that has
constant for benzoic acid. an equilibrium constant, Ka, equal to 2.8x10-5 at 25ºC.
A 0.300 litre sample of a 0.050 molar solution of the
(d) A saturated solution of benzoic acid is prepared
acid is prepared.
by adding excess solid benzoic acid to pure water
at room temperature. Since this saturated solution (a) Write the expression for the equilibrium constant,
has a pH of 2.88, calculate the molar solubility of Ka, for hydrazoic acid.
benzoic acid at room temperature. (b) Calculate the pH of this solution at 25ºC.
Answer: (c) To 0.150 litre of this solution, 0.80 gram of
(a) pH =8.6, pOH =5.4 sodium azide, NaN3, is added. The salt dissolved
[OH-] =10-pOH = 3.98x10-6M completely. Calculate the pH of the resulting so-
(b) [C6H5COOH] = [OH-] lution at 25ºC if the volume of the solution re-
mains unchanged.
[C H COH][OH −] (3. 98 ∞10 −6 ) 2
Kb = 6 5 − = −6 (d) To the remaining 0.150 litre of the original solu-
[C6H 5CO2 ] (0.1 −3. 98 ∞10 )
tion, 0.075 litre of 0.100 molar NaOH solution is
= 1.58x10-10 added. Calculate the [OH-] for the resulting solu-
K 1. 0 ∞10 −14 tion at 25ºC.
Ka = w = = 6.33 ∞10 −5
Kb 1. 58 ∞10 −10 ) Answer:
(c)
(a) HN3 <=> H+ + N3-
 [H + ][N3−]
Ka = 1987 A
[ HN3 ]
NH3 + H2O <=> NH4+ + OH- Ammonia is a weak base
(b) [H+] = [N3-] = X that dissociates in water as shown above. At 25ºC, the
X2 base dissociation constant, Kb, for NH3 is 1.8x10-5.
2. 8 ∞10−5 = ; X = 1. 2 ∞10 −3 M
0. 050 (a) Determine the hydroxide ion concentration and
pH = -log[H ] = 2.93
+
the percentage dissociation of a 0.150 molar solu-
− 0.80g 1mol tion of ammonia at 25ºC.
[N 3 ] = ∞ = 0.082M
(c) 0. 150 L 65g (b) Determine the pH of a solution prepared by
[ H+ ]( 0. 082) adding 0.0500 mole of solid ammonium chloride
2. 8 ∞10 −5
= ; [H + ] = 1. 7 ∞10−5 M to 100. millilitres of a 0.150 molar solution of
0. 050
pH = 4.77 ammonia.
(d) (0.075L)(0.100M) = 0.0075 mol NaOH (c) If 0.0800 mole of solid magnesium chloride,
(0.150L)(0.050M) = 0.0075 mol HN3 MgCl2, is dissolved in the solution prepared in
part (b) and the resulting solution is well-stirred,
OH- + HN3 --> H2O + N3- ; neut. complete
K will a precipitate of Mg(OH)2 form? Show calcu-
Kb = w lations to support your answer. (Assume the vol-
N - + H O <=> HN + OH- ; Ka
3 2 3 ume of the solution is unchanged. The solubility
1. 0 ∞10 −14
[HN 3 ][ OH −] X2 product constant for Mg(OH)2 is 1.5x10-11.
= − =
2. 8 ∞10−5 [ N3 ] ⊇0. 0075 _ Answer:
⊄ 0. 225 ↓ (a) [NH4+] = [OH-] = X; [NH3] = (0.150 - X)
X = [OH-] = 3.5x10-6M [NH +4 ][OH −] X2
Kb =
[ NH 3]
1986 D ; 1.8x10-5 = 0.150 – X
H2SO3 HSO3- HClO4 HClO3 H3BO3 X= [OH-] = 1.6x10-3 M
Oxyacids, such as those above, contain an atom 1.6 ∞103
bonded to one or more oxygen atoms; one or more of % diss. = 0.150 x 100% = 1.1%
these oxygen atoms may also be bonded to hydrogen. (b) [NH4+] = 0.0500 mol/0.100L = 0.500M
(a) Discuss the factors that are often used to predict [NH3] = 0.150M
correctly the strengths of the oxyacids listed (0. 500)( X )
1. 8 ∞10−5 = ; X = [OH −] = 5. 4 ∞10−6 M
above. 0.150
(b) Arrange the examples above in the order of in- pOH = 5.27; pH = (14 - 5.27) = 8.73
creasing acid strength. (c) Mg(OH)2 <=> Mg2+ + 2 OH-
Answer:
[Mg2+] = (0.0800mol/0.100L) = 0.800M
(a) 1) As effective nuclear charge on central atom in-
creases, acid strength increases. OR [OH-] = 5.4x10-6M
As number of lone oxygen atoms (oxygen atoms Q = [Mg2+][OH-]2 = (0.800)(5.4x10-6)2
not bonded to hydrogen) increases, acid strength = 2.3x10-11
increases. OR Q > Ksp so Mg(OH)2 precipitates
As electronegativity of central atom increases,
acid strength increases. 1987 B
2) Loss of H by a neutral acid molecule reduces The percentage by weight of nitric acid, HNO3, in a
+

acid strength. OR sample of concentrated nitric acid is to be determined.

Ka of H2SO3 > Ka of HSO3- (a) Initially a NaOH solution was standardized by
(b) H3BO3 < HSO3- < H2SO3 < HClO3 < HClO4 titration with a sample of potassium hydrogen ph-
thalate, KHC8H4O4, a monoprotic acid often used
H3BO3 or HSO3- weakest (must be together) as a primary standard. A sample of pure
 KHC8H4O4 weighing 1.518 grams was dissolved in
water and titrated with the NaOH solution. To 1988 D
reach the equivalence point, 26.90 millilitres of 12
base was required. Calculate the molarity of the X
NaOH solution. (Molecular weight: KHC8H4O4 = 10
204.2) X
(b) A 10.00 millilitre sample of the concentrated ni- 8
X
tric acid was diluted with water to a total volume pH 6 X
of 500.00 millilitres. Then 25.00 millilitres of the X
X X
diluted acid solution was titrated with the stan- 4X
dardized NaOH solution prepared in part (a). The
equivalence point was reached after 28.35 millil- 2
itres of the base had been added. Calculate the mo-
larity of the concentrated nitric acid. 0
0 5 10 15 20 25 30
(c) The density of the concentrated nitric acid used in millilitres of NaOH
this experiment was determined to be 1.42 grams
A 30.00 millilitre sample of a weak monoprotic acid
per millilitre. Determine the percentage by weight
was titrated with a standardized solution of NaOH. A
of HNO3 in the original sample of concentrated
pH meter was used to measure the pH after each incre-
nitric acid.
ment of NaOH was added, and the curve above was
Answer: constructed.
1mol
1. 518g ∞ = 7. 434 ∞10 −3 mol acid (a) Explain how this curve could be used to deter-
(a) 204. 2g
mine the molarity of the acid.
= mol NaOH required to neut. (b) Explain how this curve could be used to deter-
7. 434 ∞10 −3 mol mine the dissociation constant Ka of the weak
= 0. 2764M NaOH monoprotic acid.
0. 02690L
28. 35mLNaOH 0. 2764mol 1molHNO3 (c) If you were to repeat the titration using a indica-
∞ ∞ = tor in the acid to signal the endpoint, which of the
(b) 25. 00mLHNO 3 1L 1molNaOH
following indicators should you select? Give the
= 0.3134M HNO3 reason for your choice.
MfVf=MiVi;(0.3134M)(500mL) = (M)(10.00mL) Methyl red Ka = 1x10-5
Cresol red Ka = 1x10-8
M = 15.67M HNO3
Alizarin yellow Ka = 1x10-11
g L HNO3
% HNO3 in conc. sol’n = ∞100% (d) Sketch the titration curve that would result if the
(c) g L sol ’n
weak monoprotic acid were replaced by a strong
grams HNO3 in 1 L conc. solÆn = monoprotic acid, such as HCl of the same molar-
15.67molHNO3 63.02g ity. Identify differences between this titration
∞ = 987.5 g L curve and the curve shown above.
1L 1 mol
grams sol’n in 1 L conc. Sol’n Answer:
(a) The sharp vertical rise in pH on the pH-volume
1.42g sol’n 1000 mL
∞ = 1420 g L curve appears at the equivalence point (about 23
1 mL 1L mL). Because the acid is monoprotic, the number
( 0.01523 L)(0.2211 molL) of moles of acid equals the number of moles of
[HA] = = 0.04810M
0.07000 L NaOH. That number is the product of the exact
[OH −][HA] Kw 1. ∞10−14 volume and the molarity of the NaOH. The mo-
K= − = = −5 = 1.3 ∞10−10 larity of the acid is the number of moles of the
[A ] Ka 7.7 ∞10
acid divided by 0.30L, the volume of the acid.
− 7.789 ∞10−3 mol (b) At the half-equivalence point (where the volume
[A ] = = 0.0914M
0.08523 L of the base added is exactly half its volume at the
 equivalence point), the concentration [HX] of the Answer:
weak acid equals the concentration [X-] of its an- (a) (0.2211M)(0.03523L) = 7.789x10-3 mol
ion. Thus, in the equilibrium expression [H+][X-]/ 1.3717g/7.789x10-3 mol = 176.1g/mol
[HX] = Ka, [H+] = Ka. Therefore, pH at the half-
equivalence point equals pKa. (b) at pH 4.23, [H+] = 8.0x10-8M
( 0.02000L)(0.2211mol_L−1 )
(c) Cresol red is the best indicator because its pKa [A−] = = 0.06317M
(about 8) appears midway in the steep equiva- 0.07000L
lence region. This insures that at the equivalence ( 0.01523L)(0.2211mol_L−1 )
point the maximum color change for the minimal [HA] = = 0.04810M
0.07000L
change in the volume of NaOH added is ob- [H + ][A−] (5. 9 ∞10 −5 )(0. 06317)
served. K= = = 7. 7 ∞10 −5
[ HA] (0. 04810)
(d)
(c) A- + H2O <=> HA + OH-
12 [OH −][HA] Kw 1. ∞10 −14 −10
Longer equivalence X K= − = = −5 = 1.3 ∞10
10 [A ] K a 7. 7 ∞10
region for strong acid X
(d) at equiv. pt.
8 7. 789 ∞10 −3 mol
X
[ A−] = = 0. 0914M
pH 6 X 0. 08523L
X X X [OH-]2 = (1.3x10-10)(9.14x10-2) = 1.2x10-11
4Same
X
volume of NaOH
added for equivalence point [OH-] = 3.4x10-6M
2 pOH =-log(3.4x10-6) =5.47; pH = (14-5.47)= 8.53
Acid portion at lower
0 pH for strong acid 1990 D
0 5 10 15 20 25 30 Give a brief explanation for each of the following.
millilitres of NaOH
(a) For the diprotic acid H2S, the first dissociation
1989 A constant is larger than the second dissociation
In an experiment to determine the molecular weight constant by about 105 (K1 ~ 105 K2).
and the ionization constant for ascorbic acid (vitamin (b) In water, NaOH is a base but HOCl is an acid.
C), a student dissolved 1.3717 grams of the acid in
(c) HCl and HI are equally strong acids in water but,
water to make 50.00 millilitres of solution. The entire
in pure acetic acid, HI is a stronger acid than HCl.
solution was titrated with a 0.2211 molar NaOH solu-
tion. The pH was monitored throughout the titration. (d) When each is dissolved in water, HCl is a much
The equivalence point was reached when 35.23 millil- stronger acid than HF.
itres of the base has been added. Under the conditions Answer:
of this experiment, ascorbic acid acts as a monoprotic (a) After the first H+ is lost from H2S, the remaining
acid that can be represented as HA. species, HS-, has a negative charge. This increases
(a) From the information above, calculate the molec- the attraction of the S atom for the bonding elec-
ular weight of ascorbic acid. trons in HS-. Therefore, the bond is stronger, H+ is
harder to remove, and K2 is lower.
(b) When 20.00 millilitres of NaOH had been added
during the titration, the pH of the solution was (b) Polar H2O can separate ionic NaOH into Na+(aq)
4.23. Calculate the acid ionization constant for and OH-(aq), giving a basic solution. In HOCl,
ascorbic acid. chlorine has a high attraction for electrons due to
its greater charge density. This draws electrons in
(c) Calculate the equilibrium constant for the reaction the H-O bond towards it and weakens the bond.
of the ascorbate ion, A-, with water. H+ can be removed, making an acidic solution.
(d) Calculate the pH of the solution at the equiva- (c) Water is a more basic solvent (greater attraction
lence point of the titration. for H+) and removes H+ from HCl and HI equally.
 Acetic acid has little attraction for H +, but the H+ [base]
pH = pK a + log
separates from the larger I- more easily than from [acid]
the smaller Cl-. -
[C 3H 5O2]
(d) The bond between H and Cl is weaker than the 5. 20 = 4. 89 + log
[HC 3H 5O2]
bond between H and F. Therefore, HCl is a
stronger acid. -
[C 3H 5O2]
log = 0. 31 = 2. 1
[HC 3H 5O2]
1991 A
The acid ionization constant, Ka, for propanoic acid, (d) [C2H5COO-] = 0.50 M; [C2H5COOH] = 0.35 M
C2H5COOH, is 1.3x10-5. [OH-] = 0.0040 mol/0.100 L = 0.040 M
(a) Calculate the hydrogen ion concentration, [H+], in this neutralizes 0.04 M of the acid, giving [C 2H5-
a 0.20-molar solution of propanoic acid. COOH] = 0.31 M and the propanoate ion in-
(b) Calculate the percentage of propanoic acid mole- creases by a similar amount to 0.54 M.
cules that are ionized in the solution in (a). +
[H ](0. 54) -5 + -6
= 1. 3 x 10 , [ H ] = 7. 5 x 10 M
(c) What is the ratio of the concentration of 0. 31
propanoate ion, C2H5COO-, to that of propanoic pH = - log [H+] = 5.13
acid in a buffer solution with a pH of 5.20?
OR
(d) In a 100.-milliliter sample of a different buffer
solution, the propanoic acid concentration is 0.35- (d) using [ ]’s or moles of propanoic acid and
molar and the sodium propanoate concentration is propanoate ion...
0.50-molar. To this buffer solution, 0.0040 mole 0. 54
pH = pK a + log
of solid NaOH is added. Calculate the pH of the 0. 31
resulting solution. = 4.89 + 0.24 = 5.13
Answer:
[H + ][C2 H5 COO] 1992 D
[C2 H5 COOH] The equations and constants for the dissociation of
(a) = Ka three different acids are given below.
[H+] = [C2H5COO-] = X HCO3- <=> H+ + CO32- Ka = 4.2 x 10-7
[C2H5COOH] = 0.20 M - X H2PO4- <=> H+ + HPO42- Ka = 6.2 x 10-8
assume X is small, , 0.20 - X ~ 0.20 HSO4- <=> H+ + SO42- Ka = 1.3 x 10-2
X2 (a) From the systems above, identify the conjugate
= 1.3∞10−5 ; X = 1.6 ∞10−3 M = [ H+ ]
0.20 pair that is best for preparing a buffer with a pH
(b) from (a), X = amount of acid that ionized, there- of 7.2. Explain your choice.
fore, (b) Explain briefly how you would prepare the buffer
1.6 ∞103
solution described in (a) with the conjugate pair
you have chosen.
0.20 x 100% = 0.81% ionized
(c) If the concentrations of both the acid and the con-
(c) @ pH 5.20, [H+] = antilog (-5.20) = 6.31x10-6 M jugate base you have chosen were doubled, how
−6
(6.3∞10 )[C2H5COO ] −
−5
would the pH be affected? Explain how the ca-
= Ka = 1.3∞10 pacity of the buffer is affected by this change in
[ C2H5COOH]
concentrations of acid and base.
[C2 H5 COO] 2.1
= (d) Explain briefly how you could prepare the buffer
[C2 H5 COOH] 1
solution in (a) if you had available the solid salt
OR of the only one member of the conjugate pair and
(c) Henderson-Hasselbalch solution of a strong acid and a strong base.
Answer:
(a) Best conjugate pair: H2PO4-, HPO42-. When 7.2 = −4 [ X][X ] X2
pH = pKa for this pair when [H2PO4 ] = [HPO4 ].
- 2- K b = 5 . 25 ∞1 0 = ≅
[0.225 −X ] 0.225
(b) Dissolve equal moles (or amounts) of H2PO4 , and
-
X = [OH-] = 1.09x10-2 M
HPO42- (or appropiate compounds) in water.
solved using quadratic: X = [OH-] = 1.06x10-2 M
(c) pH not changed. Capacity of buffer would in-
crease because there are more moles of conjugate (b) [CH3NH3 ] = 0.0100 mol / 0.1200 L = 0.0833 M
+

acid and conjugate base to react with added base or CH3NH2 = 0.120 L x 0.225 mol/L = 0.0270 mol
or acid. [0.0833 + X ][X ] 0.0833X
(d) Add strong base to salt of conjugate acid OR add Kb = 5.25∞10−4 = ≅
[ 0.225 −X ] 0.225
strong acid to salt of conjugate base.
X = [OH-] = 1.42x10-3 M; pOH = 2.85; pH = 11.15
Add 1 mole conjugate acid to 1/2 mole strong
base OR 1 mole conjugate base to 1/2 mole OR
strong acid. [base]
pH = pKa + log
OR [ acid]
Use pH meter to monitor addition of strong base 1∞10−14 −11
Ka = −4 = 1.91∞10 ; pKa = 10.72
to conjugate acid OR strong acid to conjugate 5.25∞10
base. (0.225)
pH = 10.72 + log = 11.15
(0.0833)
1993 A
OR
CH3NH2 + H2O <=> CH3NH3+ + OH-
Methylamine, CH3NH2, is a weak base that reacts ac- [ acid]
pOH = pKb + log ; pKb = 3.28
cording to the equation above. The value of the ioniza- [base]
tion constant, Kb, is 5.25x10-4. Methylamine forms (0.0833)
pOH = 3.28 + log = 2.85; pH = 11.15
salts such as methylammonium nitrate, (CH 3NH3+) (0.225)
(NO3-).
(c) HCl must be added.
(a) Calculate the hydroxide ion concentration, [OH-],
[0.0833 + X ][0.0010]
of a 0.225-molar aqueous solution of methy- Kb = 5.25∞10−4 =
lamine. [ 0.225 −X ]
(b) Calculate the pH of a solution made by adding X = 0.0228 M
0.0100 mole of solid methylammonium nitrate to 0.0228 mol/L x 0.120 L = 2.74x10-3 mol HCl
120.0 milliliters of a 0.225-molar solution of
OR
methylamine. Assume no volume change occurs.
[base] [ base]
(c) How many moles of either NaOH or HCl (state 11.00 = 10.72 + log ; log = 0.28
[ acid] [ acid]
clearly which you choose) should be added to the
solution in (b) to produce a solution that has a pH [base] ( 0.225 −X )
= 1.905 = ; X = 0.0227M
of 11.00? Assume that no volume change occurs. [ acid] ( 0.0833 + x )
(d) A volume of 100. milliliters of distilled water is 0.0227 M x 0.120 L = 2.73x10-3 mol HCl
added to the solution in (c). How is the pH of the
[CH 3 NH +3 ]
solution affected? Explain.
[CH 3 NH 2 ]
Answer: (d) The ratio does not change in this buf-
[CH3NH +3 ][OH −] fer solution with dilution, therefore, no effect on
Kb = pH.
(a) [ CH3NH 2 ]

CH3NH2 + H2O <=> CH3NH3+ + OH- 1993 D (Required)

[ ]i 0.225 0 0 The following observations are made about reaction of
[ ] -X +X +X sulfuric acid, H2SO4. Discuss the chemical processes
[ ]eq 0.225-X X X involved in each case. Use principles from acid-base
theory, oxidation-reduction, and bonding and/or inter- (c) Sketch a graph using the axes provided, showing
molecular forces to support your answers. the shape of the titration curve that results when
(a) When zinc metal is added to a solution of dilute 100. milliliters of the HCl solution is added
H2SO4, bubbles of gas are formed and the zinc slowly from a buret to the Na 3PO4 solution. Ac-
disappears. count for the shape of the curve.
(b) As concentrated H2SO4 is added to water, the tem-
perature of the resulting mixture rises.
(c) When a solution of Ba(OH)2 is added to a dilute
H2SO4 solution, the electrical conductivity de-
pH
creases and a white precipitate forms.
(d) When 10 milliliters of 0.10-molar H2SO4 is added
to 40 milliliters of 0.10-molar NaOH, the pH 0
changes only by about 0.5 unit. After 10 more mL HCl
milliliters of 0.10-molar H2SO4 is added, the pH
(d) Write the equation for the reaction that occurs if a
changes about 6 units.
few additional milliliters of the HCl solution are
Answer:
added to the solution resulting from the titration
(a) Zn is oxidized to Zn2+ by H+ which in turn is re- in (c).
duced by Zn to H2. Identify H2(g) or Zn dissolving
Answer:
as Zn2+.
(a) PO43- + H+ --> HPO42-; HPO42- + H+ --> H2PO4-
Zn(s) + 2 H+(aq) --> Zn2+(aq) + H2(g)
(b) HPO42-
Explicit: Redox or e- transfer or correctly identify
. .–
oxidizing agent or reducing agent.
.. O: . .:. .
(b) H2SO4 dissociates, forms ions or dydration O
ôeventö. Bonds form, therefore, energy given off . . ::.P. : O
. .: H
(connection). :O . .:
–
(c) BaSO4 (ppt) forms or H+ + OH- form water.
Newly formed water and ppt remove ions lower-
ing conductivity. 3– + 2–
PO4+ H ∅ HPO4
Ba2+(aq) + OH-(aq) + H+(aq) + SO42-(aq) -->
BaSO4(s)+ H2O(l) pH –
2– +
HPO4 + H ∅ H2PO4
(d) First 10 mL produces solution of SO 42- and OH- or
excess OH- or partial neutralization (pH 13.0 -->
0
12.6). [presence of HSO4- in solution voids this point] mL HCl
(c)
Second 10 mL produces equivalence where pH
decreases (changes) rapidly (pH 12.6 --> 7.0). [pH (d) H+ + H2PO4- --> H3PO4
ôrisesö or wrong graph, if used, voids this point]
1996 A
1994 D HOCl <=> OCl- + H+
A chemical reaction occurs when 100. milliliters of Hypochlorous acid, HOCl, is a weak acid commonly
0.200-molar HCl is added dropwise to 100. milliliters used as a bleaching agent. The acid-dissociation con-
of 0.100-molar Na3P04 solution. stant, Ka, for the reaction represented above is 3.2x10-8.
(a) Write the two net ionic equations for the forma- (a) Calculate the [H+] of a 0.14-molar solution of
tion of the major products. HOCl.
(b) Identify the species that acts as both a Bronsted (b) Write the correctly balanced net ionic equation
acid and as a Bronsted base in the equation in for the reaction that occurs when NaOCl is dis-
(a), Draw the Lewis electron-dot diagram for this solved in water and calculate the numerical value
species. of the equilibrium constant for the reaction.
(c) Calculate the pH of a solution made by combin- [H+] ~ [HOCl] = 0.065 M
ing 40.0 milliliters of 0.14-molar HOCl and 10.0 pH = - log (0.065) = 1.2
milliliters of 0.56-molar NaOH.
(d) How many millimoles of solid NaOH must be 1997 A
added to 50.0 milliliters of 0.20-molar HOCl to The overall dissociation of oxalic acid, H2C2O4, is rep-
obtain a buffer solution that has a pH of 7.49? As- resented below. The overall dissociation constant is
sume that the addition of the solid NaOH results also indicated.
in a negligible change in volume. H2C2O4 <=> 2 H+ + C2O42- K = 3.78x10-6
(e) Household bleach is made by dissolving chlorine (a) What volume of 0.400-molar NaOH is required to
gas in water, as represented below. neutralize completely a 5.00x10-3-mole sample of
Cl2(g) + H2O --> H+ + Cl- + HOCl(aq) pure oxalic acid?
Calculate the pH of such a solution if the concen- (b) Give the equations representing the first and sec-
tration of HOCl in the solution is 0.065 molar. ond dissociations of oxalic acid. Calculate the
Answer: value of the first dissociation constant, K1, for ox-
[OCl – ][H + ] alic acid if the value of the second dissociation
constant, K2, is 6.40x10-5.
(a) Ka = [HOCl] = 3.2x10-8
(c) To a 0.015-molar solution of oxalic acid, a strong
X = amount of acid that ionizes = [OCl-] = [H+] acid is added until the pH is 0.5. Calculate the
(0.14 - X) = [HOCl] that remains unionized [C2O42-] in the resulting solution. (Assume the
X2
change in volume is negligible.)
(d) Calculate the value of the equilibrium constant,
3.2x10-8 = 0.14 – X ; X = 6.7x10-5 M = [H+]
Kb, for the reaction that occurs when solid
(b) NaOCl(s) + H2O --> Na+(aq) + HOCl(aq) + OH-(aq) Na2C2O4 is dissolved in water.
K w 1 ∞1014 Answer:
= 8
Kb = K a 3.2 ∞10 = 3.1x10-7 2 mol H+

(c) [ ]o after dilution but prior to reaction: (a) 5.00x10-3 mol oxalic acid x 1 mol oxalic acid x
40 mL 1 mol OH 1000. mL NaOH
1 mol H+ x 0.400 mol NaOH =
[HOCl] = 0.14 M x 50mL = 0.11 M
10 mL = 25.0 mL NaOH
[OH-] = 0.56 M x 50mL = 0.11 M (b) H2C2O4 <=> H+ + HC2O4-
Equivalence point reached. [OH-] ~ [HOCl] HC2O4- <=> H+ + C2O42-
[OH – ]2 K = K1 x K2
Kb = 0.11 = 3.1x10-7 K 3.78 ∞106
5
[OH-] = 1.8x10-4 ; pOH = 3.7 K1 = K 2 = 6.40 ∞10 = 5.91x10-2
pH = 14 - 3.7 = 10.3 (c) X = amt. ionized
(d) at pH 7.49, the [H+] = 10-7.49 = 3.24x10-8 M [H2C2O4] = 0.015 - X
when the solution is half-neutralized, pH = pKa [H+] = 10-pH = 10-0.5 = 0.316 M
[OCl – ] [C2O42-] = X
and [HOCl] = 1 + 2
[H ] [C2 O4 2 ]
0.20 mol HOCl [H2 C2 O4 ]
Ka = = 3.78x10-6
1L x 50.0 mL = 10.0 mmol HOCl
[0.316]2 [X]
half this amount, or 5.0 mmol of NaOH added.
3.78x10-6 = [0.015 – X] ; X = 5.67x10-7 M
(e) 1 mol H+ for every 1 mole of HOCl produced
 Kw 1 ∞1014 (e) The graph below shows the results obtained by
K2 6 titrating a different weak acid, H2Y, with the stan-
(d) Kb = = 6.40 ∞10 = 1.56x10-10
dardized NaOH solution. Identify the negative ion
that is present in the highest concentration at the
1998 D (Required) [repeated in lab procedures section] point in the titration represented by the letter A on
An approximately 0.1-molar solution of NaOH is to the curve.
be standardized by titration. Assume that the follow-
ing materials are available.
• Clean, dry 50 mL buret
• 250 mL Erlenmeyer flask
• Wash bottle filled with distilled water
• Analytical balance
• Phenolphthalein indicator solution
• Potassium hydrogen phthalate, KHP, a pure solid
monoprotic acid (to be used as the primary stan- Answer
dard) (a) • exactly mass a sample of KHP in the Erlenmeyer
(a) Briefly describe the steps you would take, using flask and add distilled water to dissolve the solid.
the materials listed above, to standardize the • add a few drops of phenolphthalein to the flask.

NaOH solution. • rinse the buret with the NaOH solution and fill.

(b) Describe (i.e., set up) the calculations necessary • record starting volume of base in buret.

to determine the concentration of the NaOH solu- • with mixing, titrate the KHP with the NaOH so-

tion. lution until it just turns slightly pink.

(c) After the NaOH solution has been standardized, it • record end volume of buret.

is used to titrate a weak monoprotic acid, HX. • repeat to check your results.

The equivalence point is reached when 25.0 mL mass of KHP

of NaOH solution has been added. In the space
(b) molar mass KHP = moles of KHP
provided at the right, sketch the titration curve,
showing the pH changes that occur as the volume since KHP is monoprotic, this is the number of
of NaOH solution added increases from 0 to 35.0 moles of NaOH
mL. Clearly label the equivalence point on the moles of NaOH
curve. L of titrant = molarity of NaOH

equivalence point

(c)
(d) Describe how the value of the acid-dissociation
constant, Ka, for the weak acid HX could be deter-
mined from the titration curve in part (c).
(d) from the titration curve, at the 12.5 mL volume
point, the acid is half-neutralized and the pH =
11
pKa. Ka = 10pKa
(e) Y2- (could it be OH- ?)
9
1998 D
Answer each of the following using appropriate chem- 7
ical principles. pH
(b) When NH3 gas is bubbled into an aqueous solu- 5
tion of CuCl2, a precipitate forms initially. On fur-
ther bubbling, the precipitate disappears. Explain
these two observations. 3
In each case, justify your choice.
Answer 1
(b) A small amount of NH3 in solution causes an in- 0
crease in the [OH-]. 0 10 20 30 40
NH3 + H2O <=> NH4 + OH
+ - Volume of 0.20M HCl Added (mL)
This, in turn, causes the Ksp of copper(II) hydrox- (c) From the table below, select the most appropriate
ide to be exceeded and the solution forms a pre- indicator for the titration. Justify your choice.
cipitate of Cu(OH)2. Indicator pKa
With the addition of more NH3, you form the sol-
uble tetraamminecopper(II) complex ion, Methyl Red 5.5
[Cu(NH3)4] , which will cause the precipitate to
2+
Bromothymol Blue 7.1
dissolve.
Phenolphthalein 8.7

2000 D (d) If equal volumes of 0.10 M NH3(aq) and 0.10 M

A volume of 30.0 mL of 0.10 M NH 3(aq) is titrated NH4Cl(aq) are mixed, is the resulting solution
with 0.20 M HCl(aq). The value of the base-dis- acidic, neutral, or basic? Explain.
sociation constant, Kb, for NH3 in water is 1.8  10–5 Answer:
at 25C. (a) NH3 + H+  NH4+
(a) Write the net-ionic equation for the reaction of
NH3(aq) with HCl(aq).
(b) Using the axes provided below, sketch the titra-
tion curve that results when a total of 40.0 mL of
0.20 M HCl(aq) is added dropwise to the 30.0 mL
volume of 0. 10 M NH3(aq).
(b) (d) A 2.00  10-3 mole sample of pure acetylsalicylic
acid was dissolved in 15.00 mL of water and then
11
titrated with 0.100 M NaOH(aq). The equivalence
point was reached after 20.00 mL of the NaOH
9 solution had been added. Using the data from the
titration, shown in the table below, determine
7 (i) the value of the acid dissociation constant,
pH Ka, for acetylsalicylic acid and
(ii) the pH of the solution after a total volume of
5 25.00 mL of the NaOH solution had been
added (assume that volumes are additive).
3 Volume of
0.100M NaOH pH
Added (mL)
1
0 0.00 2.22
0 10 20 30 40 5.00 2.97
Volume of 0.20
M HCl Added (mL)
10.00 3.44
(c) methyl red. The pKa of the indicator (where it
15.00 3.92
changes color) should be close to the pH at the
equivalence point. The equivalence point of a 20.00 8.13
weak base and a strong acid will be slightly
25.00 ?
acidic.
Answer:
(d) basic. If equivolumes of a weak base, ammonia,
and the salt of a weak base, ammonium chloride, (a)  100% = 16.3%
are mixed, it will create a basic buffer solution. (b) 1.200 g H2O  + 16 g H2O) = 0.134 g H
n = = = 0.150 mol CO2
2001 B
0.150 mol CO2  = 1.801 g C
Answer the following questions about acetylsalicylic
acid, the active ingredient in aspirin. 3.000 g ASA – (1.801 g C + 0.134 g H) = 1.065 g
O
(a) The amount of acetylsalicylic acid in a single as-
pirin tablet is 325 mg, yet the tablet has a mass of (c) 0.08843 L  = 0.00902 mol base
2.00 g. Calculate the mass percent of acetylsali- 1 mol base = 1 mol acid
cylic acid in the tablet. = 180 g/mol
(b) The elements contained in acetylsalicylic acid are (d) (i) HAsa  Asa– + H+
hydrogen, carbon, and oxygen. The combustion
= 0.133 M
of 3.000 g of the pure compound yields 1.200 g
of water and 3.72 L of dry carbon dioxide, mea- pH = –log[H+]; 2.22 = –log[H+]
sured at 750. mm Hg and 25C. Calculate the [H+] = M = [Asa–]
mass, in g, of each element in the 3.000 g sample. [HAsa] = 0.133 M – 6.03  10-3 M = 0.127 M
(c) A student dissolved 1.625 g of pure acetylsali-
K = = = 2.85 10-4
cylic acid in distilled water and titrated the result-
ing solution to the equivalence point using 88.43 OR
mL of 0.102 M NaOH(aq). Assuming that acetyl- when the solution is half-neutralized, pH = pKa
salicylic acid has only one ionizable hydrogen, at 10.00 mL, pH = 3.44; K = 10–pH
calculate the molar mass of the acid.
= 10–3.44 = 3.6310-4
(ii) 0.025 L  0.100 mol/L = 2.50  10-3 mol OH-
 2.50  10-3 mol OH- - 2.00  10-3 mol neutralized (ii) pH > 7; salt of a weak acid is a weak base
= 5.0  10 mol OH remaining in (25 + 15 mL) (d) pH = pKa + log; [A–] =
-4 -

of solution; [OH-] = 5.010-4 mol/0.040 L =

0.0125 M [OBr–] = = 0.0736 M
pH = 14 – pOH = 14 + log[OH-] = 14 – 1.9 = 125 mL   =
12.1 = 0.00920 mol NaOBr
(e) very electronegative oxygen is able to draw elec-
2002 A Required trons away from the bromine and weaken the O–
HOBr(aq)  H+(aq) + OBr–(aq) Ka = 2.3  10–9 H bond, making it easier for the hydrogen ion “to
leave”.
Hypobromous acid, HOBr, is a weak acid that dissoci- Br
H
O
ates in water, as represented by the equation above.
(a) Calculate the value of [H+] in an HOBr solution
that has a pH of 4.95. 2003 A Required
(b) Write the equilibrium constant expression for the C6H5NH2(aq) + H2O(l)  C6H5NH3+(aq) + OH–(aq)
ionization of HOBr in water, then calculate the Aniline, a weak base, reacts with water according to
concentration of HOBr(aq) in an HOBr solution the reaction represented above.
that has [H+] equal to 1.8  10–5 M.
(a) Write the equilibrium constant expression, K b,
(c) A solution of Ba(OH)2 is titrated into a solution for the reaction represented above.
of HOBr. (b) A sample of aniline is dissolved in water to pro-
(i) Calculate the volume of 0.115 M duce 25.0 mL of 0.10 M solution. The pH of the
Ba(OH)2(aq) needed to reach the equivalence solution is 8.82. Calculate the equilibrium con-
point when titrated into a 65.0 mL sample of stant, Kb, for this reaction.
0.146 M HOBr(aq). (c) The solution prepared in part (b) is titrated with
(ii) Indicate whether the pH at the equivalence 0.10 M HCl. Calculate the pH of the solution
point is less than 7, equal to 7, or greater when 5.0 mL of the acid has been titrated.
than 7. Explain. (d) Calculate the pH at the equivalence point of the
(d) Calculate the number of moles of NaOBr (s) that titration in part (c).
would have to be added to 125 mL of 0.160 M (e) The pKa values for several indicators are given
HOBr to produce a buffer solution with [H +] = below. Which of the indicators listed is most suit-
5.00  10–9 M. Assume that volume change is able for this titration? Justify your answer.
negligible. Indicator pKa
(e) HOBr is a weaker acid than HBrO3. Account for
Erythrosine 3
this fact in terms of molecular structure.
Litmus 7
Answer:
(a) pH = -log[H+]; 4.95 = -log[H+] Thymolph- 10
thalein
[H+] = 1.12  10-5
(b) Ka = = 2.3  10-9 Answer:
+ −
[H+] = [OBr–] = 1.8  10-5 M [C 6H 5NH 3 ][OH ]
(a) Kb =
= 2.3  10-9 [C 6H 5NH 2 ]
X = [HOBr] = 0.14 M (b) pOH = 14 – pH = 14 – 8.82 = 5.18
(c) (i) 65.0 mL   -log[OH–] = 5.18; [OH–] = 6.6110–6 M
  €
[OH–] = [C6H5NH3+]
 = 41.3 mL
 −6 2 C3H5O2–(aq) in the solution
6.61×10 )
Kb = ( = 4.410–10
0.10 – 6.61×10 −6
(ii) The concentration of the H+(aq) ion in the so-
(c) 25 mL  = 2.5 mmol C6H5NH2 lution.
5 mL  = 0.5 mmol H+ added The methanoate ion, HCO2–(aq) reacts with water to
€ form methanoic acid and hydroxide ion, as shown in
2.0 mmol base remains in 30.0 mL solution
the following equation.
⎡ 0.50 mmol ⎤ HCO2–(aq) + H2O (l) ↔ HCO2(aq) + OH–(aq)
[X ] X +
⎣ 30.0 mL ⎦
4.410–10 = (d) Given that [OH–] is 4.1810–6 M in a 0.309 M so-
⎡20.0 mmol ⎤
lution of sodium methanoate, calculate each of
⎣ 30.0 mL ⎦ the following.
X = 1.8010–9 = [OH–] (i) The value of Kb for the methanoate ion,
1× 10−14 HCO2–(aq)
[H+] = –6
−9 = 5.610 ; pH = 5.26
1.8× 10 (ii) The value of Ka for methanoic acid, HCO2H
(d) when neutralized, there are 2.5 mmol of
(e) Which acid is stronger, propanoic acid or
C6H5NH3+ in 50.0 mL of solution, giving a methanoic acid? Justify your answer.
[C6H5NH3+] = 0.050 M
Answer:
this cation will partially ionize according to the (a) = K
a
following equilibrium:
(b) let X be the amount of acid that ionizes, then
C6H5NH3+(aq)  C6H5NH2(aq) + H+(aq)
X = [C3H5O2–] = [H+]
at equilibrium, [C6H5NH2] = [H+] = X
0.265 – X = [HC3H5O2]
[C6H5NH3+] = (0.050–X)
X2 = Ka = 1.3410–5
-5
= Ka = 2.310
(0.050− X ) X= 0.00188 M = [H+]
X = 1.0610–3 = [H+] [you can assume that 0.265 – X ≈ 0.265 in order
+
pH = –log[H ] = 2.98 to simplify your calculations]
(e) erythrosine; the indicator will change color when pH = –log[H+] = 2.73
the pH is near its pKa, since the equivalence point 1 m ol
is near pH 3, the indicator must have a pKa near 0.496 g ×
this value. (c) (i) 96.0 g = 0.103 M
0.050 L
2005 A Required since each sodium propanoate dissociates com-
– +
HC3H5O2(aq) ↔ C3H5O2 (aq) + H (aq) Ka = 1.3410 –5 pletely when dissolved, producing 1 propanoate
Propanoic acid, HC3H5O2, ionizes in water according ion for every sodium propanoate, and this is over
1000’s of times larger than the propanoate ions
to the equation above.
from the acid, then [C3H5O2–] = 0.103 M
(a) Write the equilibrium constant expression for the
reaction. (ii) let X be the amount that ionizes, then:
(b) Calculate the pH of a 0.265 M solution of X = [H+]
propanoic acid. X + 0.103 = [C3H5O2–]
(c) A 0.496 g sample of sodium propanoate, 0.265 – X = [HC3H5O2]
NaC3H5O2, is added to a 50.0 mL sample of a
= Ka = 1.3410–5
0.265 M solution of propanoic acid. Assuming
that no change in the volume of the solution oc- X= 3.4310–5 M = [H+]
curs, calculate each of the following. [you can assume that 0.265 – X ≈ 0.265 and X +
(i) The concentration of the propanoate ion, 0.103 ≈ 0.103, in order to simplify your calcula-
 tions]
(d) (i) [HCO2] = [OH–] = 4.1810–6 M
[HCO2–] = 0.309 - 4.1810–6
Kb = = =
= 5.6510–11
(ii) Ka = = = 1.7710–4
(e) methanoic acid is stronger;
the larger the Ka, the stronger the acid
OR
for monoprotic organic acids, the longer the car-
bon chain, the weaker the acid. Propanoic has 3
carbons, whereas, methanoic has only 1.