Acid–Base

1970

(a) What is the pH of a 2.0 molar solution of acetic acid? Ka acetic acid = 1.810–5

(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 the hydrogen ion concentration of
the buffer solution.

(c) Suppose that 0.10 liter of 0.50 molar hydrochloric acid is added to 0.040 liter of the buffer
prepared in (b). Compute the hydrogen ion concentration of the resulting solution.

Answer:

(a) CH3COOH(aq) ↔ H+(aq) + CH3COO–(aq)

  Ka = 1.810-5 = 

  [H+] = [CH3COO–] = X

  [CH3COOH] = 2.0 – X, X << 2.0, (2.0– X) = 2.0

  1.810–5 =

  X = 6.010–3 = [H+];  pH = –log [H+] = 2.22

(b) 0.1 L  2.0 mol/L = 0.20 mol CH3COOH

  0.1 L  1.0 mol/L = 0.10 mol NaOH

  the 0.10 mol of hydroxide neutralizes 0.10 mol CH3COOH with 0.10 mol remaining with a
concentration of 0.10 mol/0.20 L = 0.5 M. This also produces 0.10 mol of acetate ion in 0.20
L, therefore, [CH3COO–] = 0.50 M.

  1.810-5 = 

  [H+] = 1.810–5 = pH of 4.74

(c) [CH3COOH]o = [CH3COO–]o

  = 0.50 M  = 0.143 M

  [H+]o = 0.50 M  = 0.357 M

  the equilibrium will be pushed nearly totally to the left resulting in a decrease of the
hydrogen ion by 0.143M. Therefore, the [H+]aq = 0.357M – 0.143M = 0.214M.

1970

H3PO2,H3PO3, and H3PO4 are monoprotic, diprotic and triprotic acids, respectively, and they
are about equal strong acids.

HClO2, HClO3, and HClO4 are all monoprotic acids, but HClO2 is a weaker acid than
HClO3 which is weaker than HClO4. Account for:

(a) The fact that the molecules of the three phosphorus acids can provide different numbers of
protons.

(b) The fact that the three chlorine acids differ in strengths.

Answer:

(a) the structure for the three acids are as follows:

 The hydrogen atom(s) bonded directly to the phosphorus atom is/are not acidic in aqueous
solution; only those hydrogen atoms bonded to the oxygen atoms can be released as protons.

(b) The acid strength is successively greater as the number of oxygen atoms increases
because the very electronegative oxygen atoms are able to draw electrons away from the
chlorine atom and the O–H bond. This effect is more important as the number of attached
oxygen atoms increases. This means that a proton is most readily produced by the molecule
with the largest number of attached oxygen atoms.

1970

A comparison of the theories Arrhenius, Brønsted and Lewis shows a progressive

generalization of the acid base concept. Outline the essential ideas in each of these theories
and select three reactions, one that can be interpreted by all three theories, one that can be
interpreted by two of them, and one that can be interpreted by only one of the theories.
Provide these six interpretations.

Answer:

Arrhenius

      acid = produce H+ ions in aqueous solution

      base = produce OH– ions in aqueous solution

Brønsted–Lowry

      acid = proton (H+) donor; base = proton acceptor

Lewis

      acid = e– pair acceptor; base = e– pair donor

Examples:

Interpreted by all three

      HCl + H2O → H+(aq) + Cl–(aq)

      NaOH + H2O → Na+(aq) + OH–(aq)

Interpreted by two

      NH3 + HCl ↔ NH4+ + Cl–

Interpreted by only one

      BF3 + NH3 → F3B:NH3

 1972 (repeated in gases topic)

A 5.00 gram sample of a dry mixture of potassium hydroxide, potassium carbonate, and
potassium chloride is reacted with 0.100 liter of 2.00 molar HCl solution

(a) A 249 milliliter sample of dry CO2 gas, measured at 22ºC and 740 torr, is obtained from
this reaction. What is the percentage of potassium carbonate in the mixture?

(b) The excess HCl is found by titration to be chemically equivalent to 86.6 milliliters of 1.50
molar NaOH. Calculate the percentages of potassium hydroxide and of potassium chloride in
the original mixture.

Answer:

(a) K2CO3 + 2 HCl → CO2 + 2 KCl + H2O 

  mol CO2 = = = 0.0100 mol CO2

  0.10 mol CO2   = 1.38 g K2CO3

   100% = 27.6% K2CO3

(b) orig. mol HCl = 0.100 L  2.00M = 0.200 mol

  reacted with K2CO3 = 0.020 mol

  excess HCl = 0.0866L  1.50M = 0.130 mol

  mol HCl that reacted w/KOH = 0.050 mol

  0.050 mol KOH = 2.81 g = 56.1% of sample

  the remaining KCl amounts to 16.3%

1972

Given a solution of ammonium chloride. What additional reagent or reagents are needed to
prepare a buffer from the ammonium chloride solution?

Explain how this buffer solution resists a change in pH when:

(a) Moderate amounts of strong acid are added.

(b) Moderate amounts of strong base are added.

(c) A portion of the buffer solution is diluted with an equal volume of water.

Answer:

Since ammonium chloride is a salt of a weak base, the weak base is needed, ammonia, NH3.

(a) When moderate amounts of a strong acid, H+, are added, the ammonia reacts with it. The
concentration of the hydrogen ion remains essentially the same and therefore only a very
small change in pH.

NH3 + H+ ↔ NH4+

(b) When moderate amounts of a strong base, OH–, are added, the ammonium ion reacts with
it. The concentration of the hydrogen ion remains essentially the same and therefore only a
very small change in pH.

NH4+ + OH– ↔ NH3 + H2O

(c) By diluting with water the relative concentration ratio of [NH4+]/[NH3] does not change,
therefore, there should be no change in pH.

1973
A sample of 40.0 milliliters of a 0.100 molar HC2H3O2 solution is titrated with a 0.150 molar
NaOH solution. Ka for acetic acid = 1.810–5

(a) What volume of NaOH is used in the titration in order to reach the equivalence point?

(b) What is the molar concentration of C2H3O2– at the equivalence point?

(c) What is the pH of the solution at the equivalence point?

Answer:

(a) MaVa=MbVb

  (0.100M)(40.0 mL) = (0.150M)(Vb)

  Vb = 26.7 mL

(b) acetate ion is a weak base with

  Kb = = 5.610–10

  [CH3COO-]o = = 0.0600 M

  [CH3COO–]eq = 0.600M –X

  [OH–] = [CH3COOH] = X

  5.610-10 = ; X = 9.6610-5 M

  0.0600M – 9.6610–5 M = 0.0599M [CH3COO–]eq

(c) [H+] = = 1.0410-10 M

  pH = –log [H+] = –log(1.04×10–10) = 9.98

1974 A

A solution is prepared from 0.0250 mole of HCl, 0.10 mole propionic acid, C2H5COOH, and
enough water to make 0.365 liter of solution. Determine the concentrations of H3O+,
C2H5COOH, C2H5COO–, and OH– in this solution. Ka for propionic acid = 1.3×10–5

Answer:

C2H5COOH + H2O ↔ C2H5COO– + H3O+

[C2H5COO–] = X
[C2H5COOH] = (0.10mol/0.365L) – X

[H3O+] = (0.0250mol/0.365L) + X

Ka = = 1.310-5 ; X = 5.210-5

[C2H5COO–] = 5.210–5M; [C2H5COOH] = 0.274M

[H3O+] = 0.0685M;

[OH-] = = 1.4610-13 M

1975 A

(a) A 4.00 gram sample of NaOH(s) is dissolved in enough water to make 0.50 liter of
solution. Calculate the pH of the solution.

(b) Suppose that 4.00 grams of NaOH(s) is dissolved in 1.00 liter of a solution that is 0.50
molar in NH3 and 0.50 molar in NH4+. Assuming that there is no change in volume and no
loss of NH3 to the atmosphere, calculate the concentration of hydroxide ion, after a chemical
reaction has occurred. [Ionization constant at 25ºC for the reaction NH3 + H2O →NH4+ + OH–;
K = 1.810–5]

Answer:

(a) = 0.20 M

  [H+] = = 510-14 ; pH = -log[H+] = 13.3

(b) [OH-] = - X

  [NH4+] = 0.50M – X; [NH3] = 0.50M + X

  1.810-5 = ; X = 0.100 M

  using the Henderson–Hasselbalch equation

  pH = pKa + log =  4.74 + log = 4.57

1975

Reactions requiring either an extremely strong acid or an extremely strong base are carried
out in solvents other than water. Explain why this is necessary for both cases.
Answer:

Water is amphoteric and can behave either as an acid in the presence of a strong base or as a
base in the presence of strong acid.

Water also undergoes autoionization.

1976

H2S + H2O ↔ H3O+ + HS– K1 = 1.010–7

HS– + H2O ↔ H3O+ + S2– K2 = 1.310–13

H2S + 2 H2O ↔ 2 H3O+ + S2– K = 1.310–20

Ag2S(s) ↔ 2 Ag+ + S2– Ksp= 5.510–51

(a) Calculate the concentration of H3O+ of a solution which is 0.10 molar in H2S.

(b) Calculate the concentration of the sulfide ion, S2–, in a solution that is 0.10 molar in H2S
and 0.40 molar in H3O+.

(c) Calculate the maximum concentration of silver ion, Ag+, that can exist in a solution that is
1.5×10–17 molar in sulfide ion, S2–.

Answer:

(a) H2S + H2O ↔ H3O+ + HS–

  = 1.010-7

  let X = [H3O+] = [HS–]

  = 1.010-7

   X is small, so (X-0.10) = 0.10;  X = 1.010–4 M = [H3O+]

(b) H2S + 2 H2O ↔ 2 H3O+ + S2–

  = 1.310-20 =; [S2–] = 8.110–21M

(c) Ag2S(s) ↔ 2 Ag+ + S2–; [Ag+]2[S2–] = 5.510–51

  [Ag+] = = 1.910-17 M

 
1977

The value of the ionization constant, Ka, for hypochlorous acid, HOCl, is 3.1×10–8.

(a) Calculate the hydronium ion concentration of a 0.050 molar solution of HOCl.

(b) Calculate the concentration of hydronium ion in a solution prepared by mixing equal

volumes of 0.050 molar HOCl and 0.020 molar sodium hypochlorite, NaOCl.

(c) A solution is prepared by the disproportionation reaction below.   Cl2 + H2O → HCl +

HOCl

  Calculate the pH of the solution if enough chlorine is added to water to make the
concentration of HOCl equal to 0.0040 molar.

Answer:

(a) HOCl + H2O ↔ H3O+ + OCl–

  3.210-8 =

  X = [H3O+] = 4.010–5M

(b) HOCl + H2O ↔ H3O+ + OCl–

  = 3.210-8 ; X << 0.010

  X = [H3O+] = 8.010-8M

(c) Cl2 + H2O → HCl + HOCl

  [HOCl] = [HCl] = 0.0040M

  HCl as principal source of H3O+

  pH = –log[H3O+] = 2.40

1978 A

A 0.682 gram sample of an unknown weak monoprotic organic acid, HA was dissolved in
sufficient water to make 50 milliliters of solution and was titrated with a 0.135 molar NaOH
solution. After the addition of 10.6 milliliters of base, a pH of 5.65 was recorded. The
equivalence point (end point) was reached after the addition of 27.4 milliliters of the 0.135
molar NaOH.

(a) Calculate the number of moles of acid in the original sample.

(b) Calculate the molecular weight of the acid HA.

(c) Calculate the number of moles of unreacted HA remaining in solution when the pH was
5.65.

(d) Calculate the [H3O+] at pH = 5.65

(e) Calculate the value of the ionization constant, Ka, of the acid HA.

Answer:

(a) at equivalence point, moles HA = moles NaOH

  = MbVb = (0.0274 L)(0.135 M) = 3.7010–3 mol HA

(b) molec. wt. = = 184 g/mol

(c) HA + OH– → A– + H2O

  initial: 0.00370 mol

  added: (0.0106L)(0.135M) = 0.00143 mole

  remaining: (0.00370 – 0.00143) = 0.00227 mol

(d) pH = –log[H3O+]; [H3O+] = 10–pH = 10–5.65 = 2.210–6M

(e) Ka = =1.410-6

1978 D

Predict whether solutions of each of the following salts are acidic, basic, or neutral. Explain
your prediction in each case

(a) Al(NO3)3         (b) K2CO3          (c) NaBr

Answer:

(a) acidic;   Al3+ + H2O ↔  AlOH2+ + H+;

  hydrolysis of Al3+;

  Al(OH2)n3+ as Brønsted acid, etc.

(b) basic;   CO32– + H2O ↔ HCO3– + OH– ; or

  hydrolysis of CO32– as conjugate to a weak acid, etc.

(c) neutral; Na+ from strong base; Br– from strong acid

1979 B

A solution of hydrochloric acid has a density of 1.15 grams per milliliter and is 30.0% by
weight HCl.

(a) What is the molarity of this solution of HCl?

(b) What volume of this solution should be taken in order to prepare 5.0 liters of 0.20 molar
hydrochloric acid by dilution with water?

(c) In order to obtain a precise concentration, the 0.20 molar hydrochloric acid is standardized
against pure HgO (molecular weight = 216.59) by titrating the OH– produced according to
the following quantitative reaction.

  HgO(s) + 4 I– + H2O → HgI42– + 2 OH–

  In a typical experiment 0.7147 grams of HgO required 31.67 milliliters of the hydrochloric
acid solution for titration. Based on these data what is the molarity of the HCl solution
expressed to four significant figures.

Answer:

(a) = 9.45 M

(b) MfVf = MiVi

  (0.20M)(5.0L) = (9.5M)(V)

  V = 0.11 L

(c) = 0.003300 mol HgO

  mol OH– prod. = 2 (mol HgO) = 0.006600 mol

  mol HCl req. = mol OH– prod. = 0.006600 mol

  molarity HCl = = 0.2084 M

1979 D
 NH4+ + OH– ↔NH3 + H2O

H2O + C2H5O– ↔ C2H5OH + OH–

The equations for two acid–base reactions are given above. Each of these reactions proceeds
essentially to completion to the right when carried out in aqueous solution.

(a) Give the Brønsted–Lowry definition of an acid and a base.

(b) List each acid and its conjugate base for each of the reactions above.

(c) Which is the stronger base, ammonia or the ethoxide ion. C2H5O–? Explain your answer.

Answer:

(a) acid = proton donor; base = proton acceptor

(b)  Acid Conjugate base

  1st reaction NH4+  NH3

        H2O OH–

  2nd reaction H2O OH–

        C2H5OH C2H5O–

(c) ethoxide is a stronger base than ammonia.

  A stronger base is always capable of displacing a weaker base. Since both reactions are
quantitative, in terms of base strength, OH– > NH3 in 1st reaction; C2H5O– > OH– in 2nd rxn.

1980 A

Methylamine CH3NH2, is a weak base that ionizes in solution as shown by the following
equation.

CH3NH2 + H2O ↔ CH3NH3+ + OH–

(a) At 25ºC the percentage ionization in a 0.160 molar solution of CH3NH2 is 4.7%. Calculate
[OH–], [CH3NH3+], [CH3NH2], [H3O+], and the pH of a 0.160 molar solution of CH3NH2 at
25ºC

(b) Calculate the value for Kb, the ionization constant for CH3NH2, at 25ºC.

(c) If 0.050 mole of crystalline lanthanum nitrate is added to 1.00 liter of a solution
containing 0.20 mole of CH3NH2 and 0.20 mole of its salt CH3NH3Cl at 25ºC, and the solution
is stirred until equilibrium is attained, will any La(OH)3 precipitate? Show the calculations
that prove your answer. (The solubility constant for La(OH)3, Ksp = 1×10–19 at 25ºC)

Answer:

(a) CH3NH2; 0.160M x 4.7% = 7.5×10–3 M ionizing

  (0.160M – 0.0075M) = 0.0152M @ equilibrium

  [CH3NH3+] = [OH–] = 7.5×10–3 M

  [H3O+] = = 1.310-12 M

  pH = –log [H3O+] = 11.89

(b) Kb = =3.710–4

(c) Kb =3.710–4 = ; X = 3.6910-4 = [OH-]

  Q = [La3+][OH–]3 = (0.050)(3.6910–4)3

  = 2.510–12

  Q > Ksp, therefore, La(OH)3 precipitates

1981 D

Al(NO3)3          K2CO3          NaHSO4          NH4Cl

(a) Predict whether a 0.10 molar solution of each of the

salts above is acidic, neutral or basic.

(b) For each of the solutions that is not neutral, write a

balanced chemical equation for a reaction occurring
with water that supports your prediction.

Answer:

(a) Al(NO3)3 – acidic K2CO3 – basic

  NaHSO4 – acidic NH4Cl – acidic

(b) Al3+ + H2O → Al(OH)2+ + H+

  Al(H2O)63+ + H2O → [Al(H2O)5OH]2+ + H3O+

   Al3+ + 3 H2O → Al(OH)3 + 3 H+

  CO32– + H2O → HCO3– + OH–

  HSO4– + H2O → SO42– + H3O+

  NH4+ + H2O → NH3 + H3O+

1982 A

A buffer solution contains 0.40 mole of formic acid, HCOOH, and 0.60 mole of sodium
formate, HCOONa, in 1.00 litre of solution. The ionization constant, Ka, of formic acid is
1.810–4.

(a) Calculate the pH of this solution.

(b) If 100. millilitres of this buffer solution is diluted to

a volume of 1.00 litre with pure water, the pH does not
change. Discuss why the pH remains constant on
dilution.

(c) A 5.00 millilitre sample of 1.00 molar HCl is added

to 100. millilitres of the original buffer solution.
Calculate the [H3O+] of the resulting solution.

(d) A 800.–milliliter sample of 2.00–molar formic acid

is mixed with 200. milliliters of 4.80–molar NaOH.
Calculate the [H3O+] of the resulting solution.

Answer:

(a) using the Henderson–Hasselbalch equation

  pH = pKa + log = -log(1.810-4) + log = 3.92

  {other approaches possible}

(b) The pH remains unchanged because the ratio of the

formate and formic acid concentration stays the same.

(c) initial concentrations

  1.00 M HCl 

  0.40 M HCOOH  = 0.38 M
   0.60 M HCOO-  = 0.57 M

  concentrations after H+ reacts with HCOO–

  0.38M + 0.05M = 0.43 M HCOOH

  0.57M – 0.05M = 0.52 M HCOO–

  [H3O+] = 1.810-4  = 1.510-4 M

(d) 0.800L  2.00M HCOOH = 1.60 mol

  0.200L  4.80M NaOH = 0.96 mol OH–

  at equil., (1.60 – 0.96) = 0.64 mol HCOOH and 0.96

mol HCOO–

  [H3O+] = 1.810-4  = 1.210-4 M

1982 D

A solution of barium hydroxide is titrated with 0.1–M sulfuric acid and the electrical
conductivity of the solution is measured as the titration proceeds. The data obtained are
plotted on the graph below.

Millilitres of 0.1–M H2SO4

(a) For the reaction that occurs during the titration

described above, write a balanced net ionic equation.

(b) Explain why the conductivity decreases, passes

through a minimum, and then increases as the volume
of H2SO4 added to the barium hydroxide is increased.

(c) Calculate the number of moles of barium hydroxide

originally present in the solution that is titrated.

(d) Explain why the conductivity does not fall to zero at

the equivalence point of this titration.

Answer:

(a) Ba2+ + 2 OH– + 2 H+ + SO42– → BaSO4(s) + 2 H2O

 (b) The initial conductivity is high because of the
presence of Ba2+ and OH– ions. The conductivity
decreases because Ba2+ forms insoluble BaSO4 with the
addition of SO42–. The conductivity also decreases
because OH– combines with the addition of H+ ions by
forming H2O.

  Beyond the equivalence point conductivity increases

as H+ and SO42– ions are added.

(c) # mol Ba(OH)2 = # mol H2SO4

  =0.1M  0.04 L = 0.004 mol

(d) BaSO4(s) dissociates slightly to form Ba2+ and SO42–,

while the water ionizes slightly to form H+ and OH–.

1983 B

The molecular weight of a monoprotic acid HX was to be determined. A sample of 15.126

grams of HX was dissolved in distilled water and the volume brought to exactly 250.00
millilitres in a volumetric flask. Several 50.00 millilitre portions of this solution were titrated
against NaOH solution, requiring an average of 38.21 millilitres of NaOH.

The NaOH solution was standardized against oxalic acid dihydrate, H2C2O4.2H2O (molecular
weight: 126.066 gram mol–1). The volume of NaOH solution required to neutralize 1.2596
grams of oxalic acid dihydrate was 41.24 millilitres.

(a) Calculate the molarity of the NaOH solution.

(b) Calculate the number of moles of HX in a 50.00

millilitre portion used for titration.

(c) Calculate the molecular weight of HX.

(d) Discuss the effect of the calculated molecular weight

of HX if the sample of oxalic acid dihydrate contained a
nonacidic impurity.

Answer:

(a) mol H2C2O4.2H2O = = 9.991610–3 mol

  H2C2O4 + 2 NaOH → Na2C2O4 + 2 H2O

9.991610–3 mol  = 1.998310–2 mol
 molarity of NaOH = = 0.4846 M

(b) mol HX = mol NaOH

  0.03821 L  0.4846 M = 0.01852 mol HX

(c)  250.00 mL = 0.09260 mol HX

  molec. wt. =

(d) The calculated molecular weight is smaller than true

value, because:

  measured g H2C2O4 is larger than true value,

  calculated mol H2C2O4 is larger than true value,

  calculated mol NaOH is larger than true value,

  calculated M NaOH is larger than true value

  calculated mol HX is larger than true value, therefore,

  molec wt. =

1983 C

(a) Specify the properties of a buffer solution. Describe

the components and the composition of effective buffer
solutions.

(b) An employer is interviewing four applicants for a

job as a laboratory technician and asks each how to
prepare a buffer solution with a pH close to 9.

Archie A. says he would mix acetic acid and

sodium acetate solutions.

Beula B. says she would mix NH4Cl and HCl

solutions.

Carla C. says she would mix NH4Cl and

NH3 solutions.

Dexter D. says he would mix NH3 and NaOH

solutions.
   Which of these applicants has given an appropriate
procedure? Explain your answer, referring to your
discussion in part (a). Explain what is wrong with the
erroneous procedures.

  (No calculations are necessary, but the following

acidity constants may be helpful: acetic acid, Ka=
1.8×10–5; NH4+, Ka = 5.6×10–10)

Answer:

(a) A buffer solution resists changes in pH upon the

addition of an acid or base.

  Preparation of a buffer: (1) mix a weak acid + a salt of

a weak acid; or (2) mix a weak base + salt of a weak
base; or (3) mix a weak acid with about half as many
moles of strong base; or (4) mix a weak base with about
half as many moles of strong acid; or (5) mix a weak
acid and a weak base.

(b) Carla has the correct procedure, she has mixed a

weak base, NH3, with the salt of a weak base, NH4Cl.

  Archie has a buffer solution but a pH of around 5.

  Beula doesn’t have a buffer solution, her solution

consists of a strong acid and a salt of a weak base.

  Dexter does not have a buffer solution, since his

solution consists of a weak base plus a strong base.

1984 A

Sodium benzoate, C6H5COONa, is the salt of a the weak acid, benzoic acid, C6H5COOH. A
0.10 molar solution of sodium benzoate has a pH of 8.60 at room temperature.

(a) Calculate the [OH–] in the sodium benzoate solution

described above.

(b) Calculate the value for the equilibrium constant for

the reaction:

C6H5COO– + H2O ↔ C6H5COOH + OH–

(c) Calculate the value of Ka, the acid dissociation

constant for benzoic acid.
 (d) A saturated solution of benzoic acid is prepared by
adding excess solid benzoic acid to pure water at room
temperature. Since this saturated solution has a pH of
2.88, calculate the molar solubility of benzoic acid at
room temperature.

Answer:

(a) pH =8.6, pOH =5.4

  [OH–] =10–pOH = 3.9810–6M

(b) [C6H5COOH] = [OH–]

  Kb = = 1.5810–10

(c) Ka = = 6.3310-5

(d) pH 2.88 = 1.3210–3M [H+] = [C6H5COO–]

      [C6H5COOH] = = 2.7510–2M

  total dissolved = (2.75×10–2M + 1.32×10–3M as ions) =

2.88×10–2M

1984 C

Discuss the roles of indicators in the titration of acids and bases. Explain the basis of their
operation and the factors to be considered in selecting an appropriate indicator for a particular
titration.

Answer:

   An indicator signals the end point of a titration by changing color.

   An indicator is a weak acid or weak base where the acid form and basic form of the
indicators are of different colors.

   An indicator changes color when the pH of the solution equals the pKa of the indicator. In
selecting an indicator, the pH at which the indicator changes color should be equal to (or
bracket) the pH of the solution at the equivalence point.

   For example, when a strong acid is titrated with a strong base, the pH at the equivalence
point is 7, so we would choose an indicator that changes color at a pH = 7. {Many other
examples possible.}
 

1986 A

In water, hydrazoic acid, HN3, is a weak acid that has an equilibrium constant, Ka, equal to
2.810–5 at 25ºC. A 0.300 litre sample of a 0.050 molar solution of the acid is prepared.

(a) Write the expression for the equilibrium constant,

Ka, for hydrazoic acid.

(b) Calculate the pH of this solution at 25ºC.

(c) To 0.150 litre of this solution, 0.80 gram of sodium

azide, NaN3, is added. The salt dissolved completely.
Calculate the pH of the resulting solution at 25ºC if the
volume of the solution remains unchanged.

(d) To the remaining 0.150 litre of the original solution,

0.075 litre of 0.100 molar NaOH solution is added.
Calculate the [OH–] for the resulting solution at 25ºC.

Answer:

(a) HN3 ↔ H+ + N3–

  Ka =

(b) [H+] = [N3–] = X

  2.810-5 = ; X = 1.210-3 M

  pH = –log[H+] = 2.93

(c) = 0.082 M

  2.810-5 = ; [H+] = 1.710-5 M

  pH = -log[H+] = -log(1.710-5) = 4.77

(d) (0.075 L)(0.100 M) = 0.0075 mol NaOH

  (0.150 L)(0.050 M) = 0.0075 mol HN3

  OH– + HN3 → H2O + N3– ; neut. complete

  N3– + H2O ↔ HN3 + OH– ; = = =

  X = [OH–] = 3.5×10–6M

 

1986 D

H2SO3 HSO3– HClO4 HClO3 H3BO3

Oxyacids, such as those above, contain an atom bonded to one or more oxygen atoms; one or
more of these oxygen atoms may also be bonded to hydrogen.

(a) Discuss the factors that are often used to predict

correctly the strengths of the oxyacids listed above.

(b) Arrange the examples above in the order

of increasing acid strength.

Answer:

(a) 1) As effective nuclear charge on central atom

increases, acid strength increases.  OR

  As number of lone oxygen atoms (oxygen atoms not

bonded to hydrogen) increases, acid strength
increases.   OR

  As electronegativity of central atom increases, acid

strength increases.

  2) Loss of H+ by a neutral acid molecule reduces acid

strength.   OR

  Ka of H2SO3 > Ka of HSO3–

(b) H3BO3 < HSO3– < H2SO3 < HClO3 < HClO4

  H3BO3 or HSO3–  weakest (must be together)

1987 A

NH3 + H2O ↔ NH4+ + OH– Ammonia is a weak base that dissociates in water as shown above.
At 25ºC, the base dissociation constant, Kb, for NH3 is 1.8×10–5.

(a) Determine the hydroxide ion concentration and the

percentage dissociation of a 0.150 molar solution of
ammonia at 25ºC.
 (b) Determine the pH of a solution prepared by adding
0.0500 mole of solid ammonium chloride to 100.
millilitres of a 0.150 molar solution of ammonia.

(c) If 0.0800 mole of solid magnesium chloride, MgCl2,

is dissolved in the solution prepared in part (b) and the
resulting solution is well–stirred, will a precipitate of
Mg(OH)2 form? Show calculations to support your
answer. (Assume the volume of the solution is
unchanged. The
solubility product constant for Mg(OH)2 is 1.5×10–11.

Answer:

(a) [NH4+] = [OH–] = X; [NH3] = (0.150 – X)

  Kb = ; 1.810-5 = ; X = [OH-] = 1.610-3 M

  % diss. =  100% = 1.1%

(b) [NH4+] = 0.0500 mol/0.100L = 0.500M

  [NH3] = 0.150M

  1.810-5 = ; X = [OH-] = 5.410-6 M

  pOH = 5.27; pH = (14 – 5.27) = 8.73

(c) Mg(OH)2 ↔ Mg2+ + 2 OH–

  [Mg2+] = (0.0800mol/0.100L) = 0.800M

  [OH–] = 5.410–6M

  Q = [Mg2+][OH–]2 = (0.800)(5.410–6)2 = 2.310–11

  Q > Ksp so Mg(OH)2 precipitates

1987 B

The percentage by weight of nitric acid, HNO3, in a sample of concentrated nitric acid is to be
determined.

(a) Initially a NaOH solution was standardized by

titration with a sample of potassium hydrogen phthalate,
KHC8H4O4, a monoprotic acid often used as a primary
 standard. A sample of pure KHC8H4O4 weighing 1.518
grams was dissolved in water and titrated with the
NaOH solution. To reach the equivalence point, 26.90
millilitres of base was required. Calculate the molarity
of the NaOH solution. (Molecular weight: KHC8H4O4 =
204.2)

(b) A 10.00 millilitre sample of the concentrated nitric

acid was diluted with water to a total volume of 500.00
millilitres. Then 25.00 millilitres of the diluted acid
solution was titrated with the standardized NaOH
solution prepared in part (a). The equivalence point
was reached after 28.35 millilitres of the base had been
added. Calculate the molarity of the concentrated nitric
acid.

(c) The density of the concentrated nitric acid used in

this experiment was determined to be 1.42 grams per
millilitre. Determine the percentage by weight of
HNO3 in the original sample of concentrated nitric acid.

Answer:

(a) 1.518 g  = 7.43410-3 mol NaOH required to neut.

  = 0.2764 M NaOH

(b) = 0.3134 M HNO3

  MfVf=MiVi; (0.3134M)(500mL) = (M)(10.00mL)

  M = 15.67 M HNO3

(c) % HNO3 in conc. sol’n =  100%

  grams HNO3 in 1 L conc. sol’n = = 987.5 g/mol

  grams sol’n in 1 L conc. sol’n = = 1420 g/L

  [HA] = = 0.04810 M

  K = = 1.310-10

  [A-] = = 0.0914 M

1988 D
 

A 30.00 millilitre sample of a weak monoprotic acid was titrated with a standardized solution
of NaOH. A pH meter was used to measure the pH after each increment of NaOH was added,
and the curve above was constructed.

(a) Explain how this curve could be used to determine

the molarity of the acid.

(b) Explain how this curve could be used to determine

the dissociation constant Ka of the weak monoprotic
acid.

(c) If you were to repeat the titration using a indicator in

the acid to signal the endpoint, which of the following
indicators should you select? Give the reason for your
choice.

      Methyl red Ka = 110–5

      Cresol red Ka = 110–8

      Alizarin yellow Ka = 110–11

(d) Sketch the titration curve that would result if the

weak monoprotic acid were replaced by a strong
monoprotic acid, such as HCl of the same molarity.
Identify differences between this titration curve and the
curve shown above.

Answer:

(a) The sharp vertical rise in pH on the pH–volume

curve appears at the equivalence point (about 23 mL).
Because the acid is monoprotic, the number of moles of
acid equals the number of moles of NaOH. That number
is the product of the exact volume and the molarity of
the NaOH. The molarity of the acid is the number of
moles of the acid divided by 0.30L, the volume of the
acid.

(b) At the half–equivalence point (where the volume of

the base added is exactly half its volume at the
equivalence point), the concentration [HX] of the weak
acid equals the concentration [X–] of its anion. Thus, in
the equilibrium expression = Ka, [H+] = Ka. Therefore,
pH at the half–equivalence point equals pKa.
 (c) Cresol red is the best indicator because it’s
pKa (about 8) appears midway in the steep equivalence
region. This insures that at the equivalence point the
maximum color change for the minimal change in the
volume of NaOH added is observed.

(d) 

1989 A

In an experiment to determine the molecular weight and the ionization constant for ascorbic
acid (vitamin C), a student dissolved 1.3717 grams of the acid in water to make 50.00
millilitres of solution. The entire solution was titrated with a 0.2211 molar NaOH solution.
The pH was monitored throughout the titration. The equivalence point was reached when
35.23 millilitres of the base has been added. Under the conditions of this experiment, ascorbic
acid acts as a monoprotic acid that can be represented as HA.

(a) From the information above, calculate the molecular

weight of ascorbic acid.

(b) When 20.00 millilitres of NaOH had been added

during the titration, the pH of the solution was 4.23.
Calculate the acid ionization constant for ascorbic acid.

(c) Calculate the equilibrium constant for the reaction of

the ascorbate ion, A–, with water.

(d) Calculate the pH of the solution at the equivalence

point of the titration.

Answer:

(a) (0.2211M)(0.03523L) = 7.78910–3 mol

  = 176.1g/mol

(b) at pH 4.23, [H+] = 5.8910–5M

  [A-] = = 0.06317 M

  [HA] = = 0.04810 M

K = = 7.710-5

(c) A– + H2O ↔ HA + OH–

  K = = 1.310-10
 (d) at equiv. pt.

  [A-] = = 0.0914 M

  [OH–]2 = (1.310–10)(9.1410–2) = 1.210–11

  [OH–] = 3.410–6M

  pOH =–log(3.410–6) =5.47; pH = (14–5.47)= 8.53

1990 D

Give a brief explanation for each of the following.

(a) For the diprotic acid H2S, the first dissociation

constant is larger than the second dissociation constant
by about 105 (K1 ~ 105 K2).

(b) In water, NaOH is a base but HOCl is an acid.

(c) HCl and HI are equally strong acids in water but, in

pure acetic acid, HI is a stronger acid than HCl.

(d) When each is dissolved in water, HCl is a much

stronger acid than HF.

Answer:

(a) After the first H+ is lost from H2S, the remaining

species, HS–, has a negative charge. This increases the
attraction of the S atom for the bonding electrons in
HS–. Therefore, the bond is stronger, H+ is harder to
remove, and K2 is lower.

(b) Polar H2O can separate ionic NaOH into Na+(aq) and

OH–(aq), giving a basic solution. In HOCl, chlorine has
a high attraction for electrons due to its greater charge
density. This draws electrons in the H–O bond towards
it and weakens the bond. H+ can be removed, making an
acidic solution.

(c) Water is a more basic solvent (greater attraction for

H+) and removes H+ from HCl and HI equally.

  Acetic acid has little attraction for H+, but the

H+ separates from the larger I– more easily than from the
smaller Cl–.
 (d) The bond between H and Cl is weaker than the bond
between H and F. Therefore, HCl is a stronger acid.

1991 A

The acid ionization constant, Ka, for propanoic acid, C2H5COOH, is 1.310–5.

(a) Calculate the hydrogen ion concentration, [H+], in a

0.20–molar solution of propanoic acid.

(b) Calculate the percentage of propanoic acid

molecules that are ionized in the solution in (a).

(c) What is the ratio of the concentration of propanoate

ion, C2H5COO–, to that of propanoic acid in a buffer
solution with a pH of 5.20?

(d) In a 100.–milliliter sample of a different buffer

solution, the propanoic acid concentration is 0.35–molar
and the sodium propanoate concentration is 0.50–molar.
To this buffer solution, 0.0040 mole of solid NaOH is
added. Calculate the pH of the resulting solution.

Answer:

(a)  = Ka

  [H+] = [C2H5COO–] = X

  [C2H5COOH] = 0.20 M – X

  assume X is small, therefore, 0.20 – X ~ 0.20

  = 1.310-5 ; X = 1.610-3 M = [H+]

(b) from (a), X = amount of acid that ionized, therefore,

    100% = 0.81% ionized

(c) @ pH 5.20, [H+] = antilog (–5.20) = 6.3110–6 M

   = Ka = 1.310-5

OR
 (c) Henderson–Hasselbalch

  pH = pKa + log

  5.20 = 4.89 + log

  log= 0.31 ; = 2.04

(d) [C2H5COO–] = 0.50 M; [C2H5COOH] = 0.35 M

  [OH–] = 0.0040 mol/0.100 L = 0.040 M

  this neutralizes 0.04 M of the acid, giving

[C2H5COOH] = 0.31 M and the propanoate ion increases
by a similar amount to 0.54 M.

  =1.310-5 ; [H+] = 7.510-6M

  pH = – log [H+] = 5.13

OR

(d) using [ ]’s or moles of propanoic acid and

propanoate ion...

  pH = pKa + = 4.89 + 0.24 = 5.13

1992 D

The equations and constants for the dissociation of three different acids are given below.

   HCO3– ↔ H+ + CO32– Ka = 4.2×10–7

   H2PO4– ↔ H+ + HPO42– Ka = 6.2×10–8

   HSO4– ↔ H+ + SO42– Ka = 1.3×10–2

(a) From the systems above, identify the conjugate pair

that is best for preparing a buffer with a pH of 7.2.
Explain your choice.

(b) Explain briefly how you would prepare the buffer

solution described in (a) with the conjugate pair you
have chosen.
 (c) If the concentrations of both the acid and the
conjugate base you have chosen were doubled, how
would the pH be affected? Explain how the capacity of
the buffer is affected by this change in concentrations of
acid and base.

(d) Explain briefly how you could prepare the buffer

solution in (a) if you had available the solid salt of the
only one member of the conjugate pair and solution of a
strong acid and a strong base.

Answer:

(a) Best conjugate pair: H2PO4–, HPO42–. When 7.2 = pH

= pKa for this pair when [H2PO4–] = [HPO42–].

(b) Dissolve equal moles (or amounts) of H2PO4–, and

HPO42– (or appropriate compounds) in water.

(c) pH not changed. Capacity of buffer would increase

because there are more moles of conjugate acid and
conjugate base to react with  added base or acid.

(d) Add strong base to salt of conjugate acid OR add

strong acid to salt of conjugate base.

  Add 1 mole conjugate acid to 1/2 mole strong

base OR 1 mole conjugate base to 1/2 mole strong acid.

  OR

  Use pH meter to monitor addition of strong base to

conjugate acid OR strong acid to conjugate base.

1993 A

CH3NH2 + H2O ↔ CH3NH3+ + OH–

Methylamine, CH3NH2, is a weak base that reacts according to the equation above. The value
of the ionization constant, Kb, is 5.2510–4. Methylamine forms salts such as
methylammonium nitrate, (CH3NH3+)(NO3–).

(a) Calculate the hydroxide ion concentration, [OH–], of

a 0.225–molar aqueous solution of methylamine.

(b) Calculate the pH of a solution made by adding

0.0100 mole of solid methylammonium nitrate to 120.0
 milliliters of a 0.225–molar solution of methylamine.
Assume no volume change occurs.

(c) How many moles of either NaOH or HCl (state

clearly which you choose) should be added to the
solution in (b) to produce a solution that has a pH of
11.00? Assume that no volume change occurs.

(d) A volume of 100. milliliters of distilled water is

added to the solution in (c). How is the pH of the
solution affected? Explain.

Answer:

(a) Kb =

        CH3NH2 + H2O ↔ CH3NH3+ + OH–

  [ ]i 0.225 0 0

  [ ] –X +X +X

  [ ]eq 0.225–X X X

  Kb = 5.2510-4 = ; X = [OH-] = 0.0106 M

(b) [CH3NH3+] = 0.0100 mol / 0.1200 L = 0.0833 M

  or CH3NH2 = 0.120 L  0.225 mol/L = 0.0270 mol

  Kb = 5.2510-4 = 

  X = [OH–] = 1.4210–3 M; pOH = 2.85; pH = 11.15

  OR

  pH = pKa + log= = 11.15

  OR

  pOH = pKb + log ; pKb = 3.28

  pOH = 3.28 + log = 2.85 ; pH = 11.15

(c) HCl must be added.

  Kb = 5.2510-4 = ; X = 0.0228 M

   0.0228 mol/L  0.120 L = 2.74×10–3 mol HCl

  OR

  11.00 = 10.72 + log ; log = 0.28

   = 1.905 = ; X = 0.0227 M

  0.0227 M  0.120 L = 2.73×10–3 mol HCl

(d) The ratio does not change in this buffer solution

with dilution, therefore, no effect on pH.

1993 D (Required)

The following observations are made about reaction of sulfuric acid, H2SO4. Discuss the
chemical processes involved in each case. Use principles from acid–base theory, oxidation–
reduction, and bonding and/or intermolecular forces to support your answers.

(a) When zinc metal is added to a solution of dilute

H2SO4, bubbles of gas are formed and the zinc
disappears.

(b) As concentrated H2SO4 is added to water, the

temperature of the resulting mixture rises.

(c) When a solution of Ba(OH)2 is added to a dilute

H2SO4 solution, the electrical conductivity decreases
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 changes only
by about 0.5 unit. After 10 more milliliters of 0.10–
molar H2SO4 is added, the pH changes about 6 units.

Answer:

(a) Zn is oxidized to Zn2+ by H+ which in turn is reduced

by Zn to H2. Identify H2(g) or Zn dissolving as Zn2+.

  Zn(s) + 2 H+(aq) → Zn2+(aq) + H2(g)

  Explicit: Redox or e– transfer or correctly identify

oxidizing agent or reducing agent.

(b) H2SO4 dissociates, forms ions or hydration “event”.

Bonds form, therefore, energy given off (connection).
 (c) BaSO4 (ppt) forms or H+ + OH– form water. Newly
formed water and ppt remove ions lowering
conductivity.

  Ba2+(aq) + OH–(aq) + H+(aq) + SO42–(aq) → BaSO4(s)+

H2O(l)

(d) First 10 mL produces solution of SO42– and OH– or

excess OH– or partial neutralization
(pH 13.0 → 12.6). [presence of HSO4– in solution voids this
point]

  Second 10 mL produces equivalence where pH

decreases (changes) rapidly (pH 12.6 → 7.0). [pH rises or
wrong graph, if used, voids this point]

1994 D

A chemical reaction occurs when 100. milliliters of 0.200–molar HCl is added dropwise to
100. milliliters of 0.100–molar Na3P04 solution.

(a) Write the two net ionic equations for the formation

of the major products.

(b) Identify the species that acts as both a Brønsted acid

and as a Brønsted base in the equation   in  (a), Draw
the Lewis electron–dot diagram for this species.

(c) Sketch a graph using the axes provided, showing the

shape of the titration curve that results when 100.
milliliters of the HCl solution is added slowly from a
buret to the Na3PO4 solution. Account for the shape of
the curve.

(d) Write the equation for the reaction that occurs if a

few additional milliliters of the HCl solution are added
to the solution resulting from the titration in (c).

Answer:

(a) PO43– + H+ → HPO42–; HPO42– + H+ → H2PO4–

(b) HPO42–

 
(c) 

(d) H+ + H2PO4– → H3PO4

1996 A

HOCl ↔ OCl– + H+

Hypochlorous acid, HOCl, is a weak acid commonly used as a bleaching agent. The acid–
dissociation constant, Ka, for the reaction represented above is 3.2×10–8.

(a) Calculate the [H+] of a 0.14–molar solution of HOCl.

(b) Write the correctly balanced net ionic equation for

the reaction that occurs when NaOCl is dissolved in
water and calculate the numerical value of the
equilibrium constant for the reaction.

(c) Calculate the pH of a solution made by combining

40.0 milliliters of 0.14–molar HOCl and 10.0 milliliters
of 0.56–molar NaOH.

(d) How many millimoles of solid NaOH must be added

to 50.0 milliliters of 0.20–molar HOCl to obtain a
buffer solution that has a pH of 7.49? Assume that the
addition of the solid NaOH results in a negligible
change in volume.

(e) Household bleach is made by dissolving chlorine gas

in water, as represented below.

Cl2(g) + H2O → H+ + Cl– + HOCl(aq)

   Calculate the pH of such a solution if the

concentration of HOCl in the solution is 0.065 molar.

Answer:

(a) Ka = = 3.2×10–8

   X = amount of acid that ionizes = [OCl–] = [H+]

   (0.14 – X) = [HOCl] that remains unionized

   3.2×10–8 =   ; X = 6.7×10–5 M = [H+]

 (b) NaOCl(s) +
H2O → Na+(aq) +
HOCl(aq) + OH–(aq)

   Kb = = 3.1×10–7

(c) [ ]o after dilution but prior to reaction:

   [HOCl] = 0.14 M    = 0.11 M

   [OH–] = 0.56 M    = 0.11 M

  Equivalence point reached. [OH–] ~ [HOCl]

   Kb = = 3.1×10–7

  [OH–] = 1.8×10–4 ; pOH = 3.7

  pH = 14 – 3.7 = 10.3

(d) at pH 7.49, the [H+] = 10–7.49 = 3.24×10–8 M

  when the solution is half–neutralized, pH = pKa and =

1

    50.0 mL = 10.0 mmol HOCl

  half this amount, or 5.0 mmol of NaOH added.

(e) 1 mol H+ for every 1 mole of HOCl produced

  [H+] ~ [HOCl] = 0.065 M

  pH = – log (0.065) = 1.2

1997 A

The overall dissociation of oxalic acid, H2C2O4, is represented below. The overall dissociation
constant is also indicated.

H2C2O4 ↔ 2 H+ + C2O42– K = 3.78×10–6

(a) What volume of 0.400–molar NaOH is required to

neutralize completely a 5.0010–3–mole sample of pure
oxalic acid?
 (b) Give the equations representing the first and second
dissociations of oxalic acid. Calculate the value of the
first dissociation constant, K1, for oxalic acid if the
value of the second dissociation constant, K2, is
6.40×10–5.

(c) To a 0.015–molar solution of oxalic acid, a strong

acid is added until the pH is 0.5. Calculate the [C2O42–]
in the resulting solution. (Assume the change in volume
is negligible.)

(d) Calculate the value of the equilibrium constant, Kb,

for the reaction that occurs when solid Na2C2O4 is
dissolved in water.

Answer:

(a) 5.00×10–3 mol oxalic acid      = 25.0 mL NaOH

(b) H2C2O4 ↔ H+ + HC2O4–

HC2O4– ↔ H+ + C2O42–

  K = K1  K2

  K1 =    =  = 5.91×10–2

(c) X = amt. ionized

  [H2C2O4] = 0.015 – X

  [H+] = 10–pH = 10–0.5 = 0.316 M

  [C2O42–] = X

  Ka =   = 3.78×10–6 = ;  X = 5.67×10–7 M

(d) Kb  =    = = 1.56×10–10

1998 D (Required) [repeated in lab procedures section]

An approximately 0.1–molar solution of NaOH is to be standardized by titration. Assume that

the following 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 standard)

(a) Briefly describe the steps you would take, using the

materials listed above, to standardize the NaOH
solution.

(b) Describe (i.e., set up) the calculations necessary to

determine the concentration of the NaOH solution.

(c) After the NaOH solution has been standardized, it is

used to titrate a weak monoprotic acid, HX. The
equivalence point is reached when 25.0 mL of NaOH
solution has been added. In the space provided at the
right, sketch the titration curve, showing the pH changes
that occur as the volume of NaOH solution added
increases from 0 to 35.0 mL. Clearly label the
equivalence point on the curve.

(d) Describe how the value of the acid–dissociation

constant, Ka, for the weak acid HX could be determined
from the titration curve in part (c).

(e) The graph below shows the results obtained by

titrating a different weak acid, H2Y, with the
standardized NaOH solution. Identify the negative ion
that is present in the highest concentration at the point
in the titration represented by the letter A on the curve.

Answer

(a) • exactly mass a sample of KHP in the Erlenmeyer

flask and add distilled water to dissolve the solid.

•  add a few drops of phenolphthalein to the flask.

•  rinse the buret with the NaOH solution and fill.

•  record starting volume of base in buret.

 with mixing, titrate the KHP with the NaOH solution
• 
until it just turns slightly pink.

•  record end volume of buret.

•  repeat to check your results.

(b)  = moles of KHP

   since KHP is monoprotic, this is the number of moles

of NaOH

     = molarity of NaOH

(c) 

(d) from the titration curve, at the 12.5 mL volume

point, the acid is half–neutralized and the pH =
pKa. Ka = 10pKa

(e) Y2– (could it be OH– ?)

1998 D

Answer each of the following using appropriate chemical principles.

(b) When NH3 gas is bubbled into an aqueous solution

of CuCl2, a precipitate forms initially. On further
bubbling, the precipitate disappears. Explain these two
observations.

In each case, justify your choice.

Answer

(b) A small amount of NH3 in solution causes an

increase in the [OH–].

  NH3 + H2O ↔ NH4+ + OH–

  This, in turn, causes the Ksp of copper(II) hydroxide to

be exceeded and the solution forms a precipitate of
Cu(OH)2.

  With the addition of more NH3, you form the soluble

tetraamminecopper(II) complex ion, [Cu(NH3)4]2+, which
will cause the precipitate to dissolve.
 

2000 D

A volume of 30.0 mL of 0.10 M NH3(aq) is titrated with 0.20 M HCl(aq). The value of the
base–dissociation constant, Kb, for NH3 in water is 1.8  10–5 at 25C.

(a) Write the net–ionic equation for the reaction of

NH3(aq) with HCl(aq).

(b) Using the axes provided below, sketch the titration

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).

(c) From the table below, select the most appropriate

indicator for the titration. Justify your choice.

Indicator pKa
Methyl Red 5.5
Bromothymol Blue 7.1
Phenolphthalein 8.7

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

0.10 M NH4Cl(aq) are mixed, is the resulting solution
acidic, neutral, or basic? Explain.

Answer:

(a) NH3 + H+  NH4+

(b)

(c) methyl red. The pKa of the indicator (where it

changes color) should be close to the pH at the
equivalence point. The equivalence point of a weak
base and a strong acid will be slightly acidic.

(d) basic. If equivolumes of a weak base, ammonia, and

the salt of a weak base, ammonium chloride, are mixed,
it will create a basic buffer solution.

2001 B
Answer the following questions about acetylsalicylic acid, the active ingredient in aspirin.

(a) The amount of acetylsalicylic acid in a single aspirin

tablet is 325 mg, yet the tablet has a mass of 2.00 g.
Calculate the mass percent of acetylsalicylic acid in the
tablet.

(b) The elements contained in acetylsalicylic acid are

hydrogen, carbon, and oxygen. The combustion of
3.000 g of the pure compound yields 1.200 g of water
and 3.72 L of dry carbon dioxide, measured at 750. mm
Hg and 25C. Calculate the mass, in g, of each element
in the 3.000 g sample.

(c) A student dissolved 1.625 g of pure acetylsalicylic

acid in distilled water and titrated the resulting solution
to the equivalence point using 88.43 mL of
0.102 M NaOH(aq). Assuming that acetylsalicylic acid
has only one ionizable hydrogen, calculate the molar
mass of the acid.

(d) A 2.00×10–3 mole sample of pure acetylsalicylic acid

was dissolved in 15.00 mL of water and then titrated
with 0.100 M NaOH(aq). The equivalence point was
reached after 20.00 mL of the NaOH solution had been
added. Using the data from the titration, shown in the
table below, determine

(i) the value of the acid dissociation constant, Ka, for

acetylsalicylic acid and

(ii) the pH of the solution after a total volume of 25.00

mL of the NaOH solution had been added (assume that
volumes are additive).

Volume of 0.100M NaOH pH

Added (mL)
0.00 2.2
2
5.00 2.9
7
10.00 3.4
4
15.00 3.9
2
20.00 8.1
3
25.00 ?
Answer:

(a)  100% = 16.3%

(b) 1.200 g H2O  = 0.134 g H

  n =   = = 0.150 mol CO2

  0.150 mol CO2  = 1.801 g C

  3.000 g ASA – (1.801 g C + 0.134 g H) = 1.065 g O

(c) 0.08843 L    = 0.00902 mol base

  1 mol base = 1 mol acid

    = 180 g/mol

(d) (i) HAsa ↔ Asa– + H+

    = 0.133 M

  pH = –log[H+]; 2.22 = –log[H+]

  [H+] = M = [Asa–]

  [HAsa] = 0.133 M – 6.03×10–3 M = 0.127 M

  K = =   = 2.85×10–4

  OR

  when the solution is half–neutralized, pH = pKa

  at 10.00 mL, pH = 3.44; K = 10–pH

  = 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 =

5.0×10–4 mol OH– remaining in (25 + 15 mL) of
solution; [OH–] = 5.0×10–4 mol/0.040 L = 0.0125 M

      pH = 14 – pOH = 14 + log[OH–] = 14 – 1.9 = 12.1

 
2002 A Required

  HOBr(aq) ↔ H+(aq) + OBr–(aq) K  = 2.3  10–9

a

Hypobromous acid, HOBr, is a weak acid that dissociates 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.

(b) Write the equilibrium constant expression for the

ionization of HOBr in water, then calculate the
concentration of HOBr(aq) in an HOBr solution that has
[H+] equal to 1.8  10–5 M.

(c) A solution of Ba(OH)2 is titrated into a solution of

HOBr.

(i) Calculate the volume of 0.115 M Ba(OH)2(aq) needed

to reach the equivalence point when titrated into a 65.0
mL sample of 0.146 M HOBr(aq).

(ii) Indicate whether the pH at the equivalence point is

less than 7, equal to 7, or greater than 7. Explain.

(d) Calculate the number of moles of NaOBr(s) that

would have to be added to 125 mL of 0.160 M HOBr to
produce a buffer solution with [H+] = 5.00  10–9 M.
Assume that volume change is negligible.

(e) HOBr is a weaker acid than HBrO3. Account for this

fact in terms of molecular structure.

Answer:

(a) pH = –log[H+]; 4.95 = –log[H+]

  [H+] = 1.12  10–5

(b) K  =  = 2.310–9

a

  [H+] = [OBr–] = 1.810–5 M

  = 2.310–9

  X = [HOBr] = 0.14 M

(c) (i) 65.0 mL         =

   = 41.3 mL

  (ii) pH > 7; salt of a weak acid is a weak base

(d) pH = pK  + log; [A–] =

a

  [OBr–] =  = 0.0736 M

  125 mL   = 0.00920 mol NaOBr

(e) very electronegative oxygen is able to draw

electrons away from the bromine and weaken the O–H
bond, making it easier for the hydrogen ion “to leave”.

 
 

2003 A Required

C6H5NH2(aq) + H2O(l) ↔ C6H5NH3+(aq) + OH–(aq)

Aniline, a weak base, reacts with water according to the reaction represented above.

(a) Write the equilibrium constant expression, Kb,  for

the reaction represented above.

(b) A sample of aniline is dissolved in water to produce

25.0 mL of 0.10 M solution. The pH of the solution is
8.82. Calculate the equilibrium constant,  Kb, for this
reaction.

(c) The solution prepared in part (b) is titrated with

0.10 M HCl. Calculate the pH of the solution when 5.0
mL of the acid has been titrated.

(d) Calculate the pH at the equivalence point of the

titration in part (c).

(e) The pKa values for several indicators are given

below. Which of the indicators listed is most suitable
for this titration? Justify your answer.

Indicator pKa
Erythrosine 3
Litmus 7
Thymolphthalein 10
 
Answer:

(a) Kb =

(b) pOH = 14 – pH = 14 – 8.82 = 5.18

  –log[OH–] = 5.18; [OH–] = 6.6110–6 M

  [OH–] = [C6H5NH3+]

  Kb = = 4.410–10

(c) 25 mL  = 2.5 mmol C6H5NH2

  5 mL  = 0.5 mmol  H+ added

  2.0 mmol base remains in 30.0 mL solution

  4.410–10 =

  X = 1.8010–9 = [OH–]

  [H+] = = 5.610–6; pH = 5.26

(d) when neutralized, there are 2.5 mmol of

C6H5NH3+ in 50.0 mL of solution, giving a [C6H5NH3+]
= 0.050 M

  this cation will partially ionize according to the

following equilibrium:

  C6H5NH3+(aq) ↔ C6H5NH2(aq) + H+(aq)

  at equilibrium, [C6H5NH2] = [H+] = X

  [C6H5NH3+] = (0.050–X)

  = Ka = 2.310–5

  X = 1.0610–3 = [H+]

  pH = –log[H+] = 2.98

(e) erythrosine; the indicator will change color when the

pH is near its pKa, since the equivalence point is near
pH 3, the indicator must have a pKa near this value.

 
2005 A Required

HC3H5O2(aq) ↔ C3H5O2–(aq) + H+(aq) Ka = 1.3410–5

Propanoic acid, HC3H5O2, ionizes in water according to the equation above.

(a) Write the equilibrium constant expression for the

reaction.

(b) Calculate the pH of a 0.265 M solution of propanoic

acid.

(c) A 0.496 g sample of sodium propanoate, NaC3H5O2,

is added to a 50.0 mL sample of a 0.265 M solution of
propanoic acid. Assuming that no change in the volume
of the solution occurs, calculate each of the following.

(i) The concentration of the propanoate ion, C3H5O2–

(aq) in the solution

(ii) The concentration of the H+(aq) ion in the solution.

The methanoate ion, HCO2–(aq) reacts with water to form methanoic acid and hydroxide ion,
as shown in the following equation.

HCO2–(aq) + H O (l) ↔ H2CO2(aq) + OH–(aq)

2

(d) Given that [OH–] is 4.1810–6 M in a

0.309 M solution of sodium methanoate, calculate each
of the following.

(i) The value of Kb for the methanoate ion, HCO2–(aq)

(ii) The value of Ka for methanoic acid, HCO2H

(e) Which acid is stronger, propanoic acid or methanoic

acid? Justify your answer.

Answer:

(a) = Ka

(b) let X be the amount of acid that ionizes, then

  X = [C3H5O2–] = [H+]

  0.265 – X = [HC3H5O2]

  = Ka = 1.3410–5
  X= 0.00188 M = [H+]

  [you can assume that 0.265 – X ≈ 0.265 in order to

simplify your calculations]

  pH = –log[H+] = 2.73

(c) (i) = 0.103 M

  since each sodium propanoate dissociates completely

when dissolved, producing 1 propanoate ion for every
sodium propanoate, and this is over 1000’s of times
larger than the propanoate ions from the acid, then
[C3H5O2–] = 0.103 M

  (ii) let X be the amount that ionizes, then:

  X = [H+]

  X + 0.103 = [C3H5O2–]

  0.265 – X = [HC3H5O2]

  = Ka = 1.3410–5

  X= 3.4310–5 M = [H+]

  [you can assume that 0.265 – X ≈ 0.265 and X + 0.103

≈ 0.103, in order to simplify your calculations]

(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 carbon

chain, the weaker the acid. Propanoic has 3 carbons,
whereas, methanoic has only 1. 
 
Beginning with the 2007 examination, the numerical problems, 1, 2, and 3, are Part A (part A).
Students may use a calculator for this part (55 minutes). Part B (40 minutes) is the three reactions
question (predict the products of a reaction, balance, and answer a short question regarding the
reaction) and the two theory questions. A laboratory question could be in either part A or B. NO
calculator is allowed in part B.

2007 part A, question #1

HF(aq) + H2O(l)  H3O+(aq) + F–(aq)  Ka = 7.2×10–4

Hydrofluoric acid, HF(aq), dissociates in water as

represented by the equation above.

(a) Write the equilibrium-constant expression for the

dissociation of HF(aq) in water.

(b) Calculate the molar concentration of H3O+ in a

0.40 M HF(aq) solution.

HF(aq) reacts with NaOH(aq) according to the reaction

represented below.

HF(aq) + OH–
(aq)  H2O(l) + F–(aq)

A volume of 15 mL of 0.40 M NaOH(aq) is added to 25 mL of 0.40 M HF(aq) solution.

Assume that volumes are additive.

(c) Calculate the number of moles of HF(aq) remaining

in the solution.

(d) Calculate the molar concentration of F–(aq) in the

solution.

(e) Calculate the pH of the solution.

Answer:

(a) 

(b) let X = [H3O+] = [F–]; let (0.40-X) = [HF]

  7.2×10–4 =; X = 1.7×10-2 = [H3O+]

(c) (0.40 M)(15 mL) = 6.0 mmol OH– neutralizes and

equal number of moles of HF
   (0.40 M)(25 mL) = 10. mmol HF

        4.0 mmol HF remains (or 0.0040 mol)

(d) 6.0 mmol OH– produces 6.0 mmol of F–, from a 1:1

stoichiometry in the equation

now in 40. mL of solution, [F–] = = 0.15 M

(e) = 0.10 M HF; let X = [H3O+]; 7.2×10–4 =; X

= 4.8×10–4

   pH = –log[H3O+] = –log(4.8×10–4) = 3.32

2009 part A, question #1

Answer the following questions that relate to the

chemistry of halogen oxoacids.

(a) Use the information the table below to answer part

(a)(i).

Acid Ka at 298 K

HOCl 2.9  10-8
HOBr 2.4  10-9

 (i) Which of the two acids is stronger, HOCl or HOBr?

Justify your answer in terms of Ka.

(ii) Draw a complete Lewis electron-dot diagram for the

acid that you identified in part (a)(i).

(iii) 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 (a)(i). Justify your
prediction in terms of chemical bonding.

(b) Write the equation for the reaction that occurs

between hypochlorous acid and water.

(c) A 1.2 M NaOCl solution is prepared by dissolving

solid NaOCl in distilled water at 298 K. The hydrolysis
reaction OCl-(aq) + H2O(l)  HOCl(aq) + OH-(aq) occurs.
 (i) Write the equilibrium-constant expression for the
hydrolysis reaction that occurs between OCl-(aq) and
H2O(l).

(ii) Calculate the value of the equilibrium constant at

298 K for the hydrolysis reaction.

(iii) Calculate the value of [OH-] in the 1.2 M NaOCl

solution at 298 K.

(d) A buffer solution is prepared by dissolving some

solid NaOCl in a solution of HOCl at 298 K. The pH of
the buffer solution is determined to be 6.48.

(i) Calculate the value of [H3O+] in the buffer solution.

(ii) Indicate which of HOCl(aq) or OCl-(aq) is present at

the higher concentration in the buffer solution. Support
your answer with a calculation.

Answer:

(a) (i) HOCl, larger Ka means higher percentage of

ionization and, therefore, a stronger acid

(ii) 

(iii) weaker, the H-O bond strength is stronger when the

other element bonded to the oxygen has a lower
electronegativity (iodine has a lower EN than chlorine).
Thus a H-O-I molecule holds on to its H more strongly
than HOCl and less H+ ionizes

(b) HOCl + H2O  OCl– + H3O+

(c) (i) & (ii) = 3.4  10-7

(iii) [HOCl] = [OH-] = X

  [OCl-] = 1.2 - X

  = 3.4  10-7 ; X = 6.4  10-4 M = [OH-]

(d) (i) pH = 6.48 = -log[H3O+] ; 3.31  10-7 M = [H+]

(ii) HOCl; pH = pKa + log

6.48 = -log (2.9  10-8) + log Q

 Q = 0.088, therefore, [HOCl] > [OCl-]

2009 part A, question #1, form B

1. A pure 14.85 g sample of the weak base ethylamine,

C2H5NH2 , is dissolved in enough distilled water to
make 500. mL of solution.

(a) Calculate the molar concentration of the C2H5NH2 in

the solution.

The aqueous ethylamine reacts with water according to

the equation below.

C2H5NH2(aq) + H2O(l)  C2H5NH3+(aq) + OH-(aq)

(b) Write the equilibrium-constant expression for the

reaction between C2H5NH2(aq) and water.

(c) Of C2H5NH2(aq) and C2H5NH3+(aq) , which is present

in the solution at the higher concentration at
equilibrium? Justify your answer.

(d) A different solution is made by mixing 500. mL of

0.500 M C2H5NH2 with 500. mL of 0.200 M HCl.
Assume that volumes are additive. The pH of the
resulting solution is found to be 10.93.

(i) Calculate the concentration of OH-(aq) in the

solution.

(ii) Write the net-ionic equation that represents the

reaction that occurs when the C2H5NH2 solution is
mixed with the HCl solution.

(iii) Calculate the molar concentration of the C2H5NH3+

(aq) that is formed in the reaction.

(iv) Calculate the value of Kb  for C2H5NH2 .

Answer:

(a) molarity = == 0.660 M

(b) Kb =

(c) C2H5NH2; weak base means Kb is very small so little

of the ethylamine dissociates
 (d) (i) pOH = 14 – pH = 14 – 10.93 = 3.07

  pOH = -log[OH–] = 3.07; [OH–] = 8.5110-4 M

  (ii) C2H5NH2(aq) + H+(aq)  C2H5NH3+(aq)

  (iii) (0.500 L)(0.200 M) = 0.100 mol H+ = # moles of

C2H5NH3+ since the stoichiometry is 1:1

   0.100 mol C2H5NH3+ /1 L of solution = 0.100 M

  (iv) [C2H5NH3+] = 0.100 M; [OH–] = 8.510-4

        Kb == 5.6710-4

Relevant information and Constants: 

 Kw = [H3O+][OH-] = 1.0 x 10-14  at 25oC; 

 Henderson-Hasselbalch equation:  pH = pKa + log();
 Gas constant,  R = 0.08206 L.atm/(K.mol)
 Quadratic equation: ax2 + bx + c = 0;       x =

Part A.  Multiple-choice questions (50 points).

1. The following reaction is carried out at a certain temperature:

             N2O4(g) ⇄ 2 NO2(g)

 Initially, the concentrations of NO2 and N2O4 are 0.000 M and 0.050 M,

respectively. If the concentration of NO2 at equilibrium is 0.044 M, what is the
equilibrium constant Kc for this reaction? 

 (a) 7.3    (b) 3.2 x 10-1  (c) 6.9 x 10-2  (d) 3.9 x 10-2 

2. For the reaction: H2(g)  +  I2(g) ⇄  2HI(g),  Kc = 54.0  at 427oC. 

 What is Kc for the reaction: HI(g)  ⇄ ½ H2(g)  +  ½ I2(g) at the same temperature? 

       (a) -27  (b) 0.136   (c) 3.7 x 10-2  (d) 9.26 x 10-3 

3. If the value of Kc for the reaction H2(g)  +  I2(g)  ⇄  2HI(g) is 54.0  at 427oC,
what is the value of Kp for this reaction at 427oC? 
 (a) 54.0  (b) 1.32  (c) 1.54  (d) 2.22 x 103 

4. For the reaction: CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g),   Ho = 206 kJ.

 Which of the following events will immediate occur to reach a new equilibrium
and what changes (if any) to the concentration of H2 if the equilibrium mixture is
transferred into a larger reaction vessel and the temperature is simultaneously
increased?  

 (a) A net reaction to the right will occur and [H2] will increase.

 (b) A net reaction to the right will occur but [H2] will not change.

 (c) A net reaction to the left will occur and [H2] will decrease;

 (d) A net reaction to the left will occur but [H2] will not change. 

5. For the reaction: CO(g) + H2O(g)  ⇄ CO2(g) +  H2(g); Ho = -41 kJ

 How would the concentrations of CO2 and H2 be affected if the equilibrium

mixture is compressed into a smaller reaction vessel and the temperature is
simultaneously increased? 

   (a) Both [CO2] and [H2] will increases; (b) Both [CO2] and [H2] will decrease;

   (c) Both [CO2] and [H2] will not change; (d) Changes on [CO2] and [H2] cannot
be predicted. 

6. The following equilibrium in aqueous solution involves the formation of

complex ion Cu(NH3)42+, which is dark blue, from Cu(H2O)62+, which is light blue.

             Cu(H2O)62+  +  4NH3  ⇄ Cu(NH3)42+  +  6H2O

 Which of the following statements is correct regarding the equilibrium if HCl is

added?

 (a) Equilibrium will not be affected because HCl reacts equally with both H2O and
NH3.

 (b) Equilibrium will shift right because HCl reacts more with H2O than it does to
NH3.

 (c) Equilibrium will shift left because HCl reacts more with NH3 than it does to
H2O.
 (d) The effect on this equilibrium by adding HCl cannot be predicted due to
insufficient information. 

7. The following decomposition of calcium carbonate has Kp = 1.16 at 800.oC.

             CaCO3(s)  ⇄   CaO(s)  +  CO2(g) 

 Suppose a 10.0-g sample of solid CaCO3 is placed in a rigid 5.0-L flask from
which the air has been completely removed. The sample is heated to 800.oC and
the reaction occurs until equilibrium is reached. What is the percentage by mass of
solid CaCO3 have decomposed at equilibrium? 

       (a) 66%        (b) 34%  (c) 13%        (d) 87% 

8. Which of the following is NOT a strong acid?

       (a) HClO4      (b) HNO3   (c) H3PO4         (d) H2SO4   

9. Identify an acid with a relatively strong conjugate base.

       (a) HCl  (b) HBr  (c) HI  (d) HCN 

10. Which of the following is NOT a conjugate acid-base pair?

       (a) H3O+ & H2O  (b) NH4+ & NH3 (c)  H2SO4- & SO42- (d) H2PO4- & HPO42-  

11. If the compound B(OH)3 is an acid, which of the following is its conjugate
base?

   (a) OH-  (b) H2O  (c)  B(OH)4-  (d) B(H2O)(OH)2+ 

12. Al(H2O)2(OH)4- is a Brnsted-Lowry base. Its conjugate acid is __________.

       (a) Al(H2O)3(OH)3  (b) Al(H2O)63+  (c) H3O+ (d) Al(H2O)2(OH)4+ 

13. Given the following ionizations of weak acids:

             HC2H3O2(aq) + H2O ⇄  H3O+(aq)  +  C2H3O2-(aq); Ka = 1.8 x 10–5.

                   HNO2(aq)  H2O ⇄  H3O+(aq)  +  NO2-(aq);  Ka = 4.0 x 10–4.

 Calculate Kc for the following equilibrium:

             HNO2(aq)  +  C2H3O2-(aq)  ⇄  HC2H3O2(aq) + NO2-(aq)

       (a) 7.2 x 10–9  (b) 4.2 x 10–4  (c)  4.5 x 10–2  (d) 22  

14. The following reaction has Kc = 0.25 at 25oC.

                   HCOOH (aq) + NaF(aq)  ⇄  HF(aq)  +  NaCHO2(aq)

 Based on the equilibrium constant value, which of the following statements is

correct?

       (a)  Formic acid (HCOOH) is a stronger acid than nitrous acid (HNO2);

       (b)  Nitrous acid is a stronger acid than formic acid;

       (c)  The nitrite ion (NO2-) is a stronger conjugate base than formate ion
(CHO2-);

       (d)  There is not enough information to tell. 

15. If water has auto-ionization constant, Kw = 5.5 x 10–14 at 50oC, what is the pH of
pure water at 50oC?

       (a) 7.00  (b) 6.63  (c) 7.37  (d) 13.26 

 

16. A solution has pH = 4.60. What is the concentration of OH- in this solution?

       (a) 2.5 x 10–5 M  (b) 4.6 M     (c) 9.4 M  (d)  4.0 x 10–10 M  

17. Hydrogen phthalate ion (HC8H4O4-) ionizes in aqueous solution to give

H3O+ and C8H4O42-. If 0.050 M solution of this ion (HC8H4O4-) is 0.88% ionized,
calculate its Ka value.

       (a) 4.4 x 10–4  (b) 3.9 x 10–6  (c) 7.7 x 10–6  (d) 1.9 x 10–7 

18. Which of these compounds will produce a neutral solution when dissolved in

water?

   (a) KNO3 (b) KCN (c) KHSO4  (d) KH2PO4  

19. Which of these compounds will produce an acidic solution when dissolved in

water?

       (a) NaNO2        (b) NaClO4   (c) Al(NO3)3        (d) Na2CO3

20. The aqueous solution of which compound is expected to have pH > 7?

   (a) NH4NO3 (b) Na3PO4  (c) KBr (d) None of them 

21. Which of the following substances will be a Lewis acid in an acid-base

reaction?

       (a) NH3 (b) BF3 (c) HF (d) H2O  

22. When sodium acetate (NaCH3CO2) is added to acetic acid solution, which of

the following will occur?

       (a) The degree of ionization of acid will increase and the pH of the solution
will increase;

       (b) The degree of ionization of acid will increase and the pH of the solution
will decrease;

      (c) The degree of ionization of acid will decrease and the pH of the solution
will also decrease;

      (d) The degree of ionization of acid will decrease but the pH of the solution
will increase; 

23. Which of the following will form a buffer solution?

       (a)  50.0 mL of 0.10 M HC2H3O2 + 50.0 mL of 0.10 M HCl;

       (b)  50.0 mL of 0.10 M HC2H3O2 + 50.0 mL of 0.10 M NaOH;

       (c)  50.0 mL of 0.20 M HC2H3O2 + 50.0 mL of 0.10 M NaOH;

       (d)  50.0 mL of 0.20 M HCl + 50.0 mL of 0.20 M NaCl. 

24. If a buffer solution contains sodium hydrogen sulfate, NaHSO4, as one of its
components, what other substance should also be present in the buffer? 

       (a)  H2SO4 (b) Na2SO4 (c) NaHSO3 (d) NaOH 

25. Which of the following indicators is the most suitable to use in a titration

between dimethylamine, (CH3)2NH, and HCl?  

 (a)  Phenolphthalein (pKa = 9.1)  (b) Phenol red (pKa = 8.0)

 (c)  Methyl orange (pKa = 3.5)  (d) All the above

 
 
 
 

Part B. For this section, be sure to show a complete solution to each problem.

B1. (15) Nitrosyl bromide decomposes according to the following equation.

             2NOBr(g)  ⇄ 2NO(g)  +  Br2(g)

 A 70.–g sample of NOBr was placed in an evacuated 1.00-L flask and no NO or

Br2 was initially present. When the reaction reached equilibrium, the reaction
mixture was found to contain 14 g of Br2. (a) Calculate the masses of NOBr and
NO, respectively, at equilibrium. (b) What is the equilibrium constant Kc for the
above reaction?

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 

B2. (12) The following equilibrium has been established at 373 K

             SO2Cl2(g) ⇄ SO2(g)  +  Cl2(g)

At 373 K, a 1.00-L reaction vessel is found to contain an equilibrium mixture

composed of 0.0106 mol of SO2Cl2 and 0.0293 mol each of SO2 and Cl2. (a)
Calculate the equilibrium constant Kc and Kp at 373 K for this reaction. (b) If a
1.00-L reaction vessel is initially charged with 1.50 atm of SO2Cl2 at 373 K, and no
SO2 or Cl2 is present, what are the partial pressures of each compound when
equilibrium is established?

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 

B3. (8) A 100.0-mL solution of hydrochloric acid has pH = 1.30. To what volume

must this solution be diluted in order to make a solution with pH = 2.00?

 
 
 
 
 
 
 
 
 
 
 
 

B4. (10) Lactic acid, HC3H5O3, has Ka = 1.4 x 10–4.

 (a) Calculate [H3O+] and the pH of 0.20 M lactic acid.

 (b) What is the percent ionization of lactic acid in the 0.20 M solution?

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
B5. (20) A phosphate buffer is prepared by mixing 400.0 mL of
0.30 M KH2PO4 and 600.0 mL of 0.25 M K2HPO4. (a) Calculate the molar
concentrations of H2PO4- and HPO42- in the buffer solution.

 (b) What is the pH of the buffer solution? (Ka of H2PO4- = 6.2 x 10–8)

 (c) Write an ionic equation that shows a buffering action against strong base.

 (c) How many grams of NaOH must be added to the buffer so that the pH
increases to 7.50? (Assume that the volume change due to the addition of solid
NaOH is negligible.)

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 

B6. (20) A 1.022-g sample of pure potassium hydrogen phthalate (KHC8H4O4;

molar mass = 204.22) is dissolved in de-ionized water to make a 100.0 mL
solution. This solution is then titrated with NaOH solution of unknown
concentration, added in small amounts, and the solution pH after each addition of
NaOH is measured using a pH meter. The pH values were plotted against volumes
of NaOH added to obtain a pH-titration curve. The graph shows that the equivalent
point for the titration occurs after 44.0 mL of NaOH is added, and the solution at
titration mid-point has pH = 5.41.
 

 (a) Calculate the molar concentration of NaOH. (b) What is the ionization
constant Ka for hydrogen phthalate ion (HC8H4O4-)? (c) Calculate the Kb value for
the phthalate ion (C8H4O42-), its molar concentration at equivalent point, and the pH
at equivalent point.

 The net ionic equation for the reaction of hydrogen phthalate ion with sodium
hydroxide is as follows:

                HC8H4O4-(aq)  +  OH-(aq)    H2O  +  C8H4O42–(aq)