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[CH3COO-]eq = 0.600M -X
1972
Given a solution of ammonium chloride. What [OH-] = [CH3COOH] = X
X
2 −5 ( 0 . 50 − X ) ( 0 . 100 − X )
− 10 −5 1 . 8 ∞ 10 = ; X = 0 . 100 M
5 . 6 ∞ 10 = ; X = 9 . 66 ∞ 10 M
( 0 . 0600 − X ) ( 0 . 50 + X )
solution as shown by the following equation. Al(H2O)63+ + H2O --> [Al(H2O)5OH]2+ + H3O+
CH3NH2 + H2O <=> CH3NH3+ + OH-
Al3+ + 3 H2O --> Al(OH)3 + 3 H+
CO32- + H2O --> HCO3- + OH- at equil., (1.60 - 0.96) = 0.64 mol HCOOH and
HSO4- + H2O --> SO42- + H3O+ 0.96 mol HCOO-
+ −4 0 . 64 M −4
NH4+ + H2O --> NH3 + H3O+ [ H 3O ] = 1 . 8 ∞ 10 ∞ = 1. 2 ∞ M
0 . 96 M
1982 A
1982 D
A buffer solution contains 0.40 mole of formic acid,
A solution of barium hydroxide is titrated with 0.1-M
HCOOH, and 0.60 mole of sodium formate,
sulfuric acid and the electrical conductivity of the
HCOONa, in 1.00 litre of solution. The ionization
solution is measured as the titration proceeds. The data
constant, Ka, of formic acid is 1.8x10-4.
obtained are plotted on the graph below.
(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 bufferC o n d u c tiv ity , λ
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. 10 20 30 40 50 60 70 80
Answer:
Millilitres of 0.1-M H2SO4
(a) using the Henderson-Hasselbalch equation
(a) For the reaction that occurs during the titration
⊇[A − ] _
described above, write a balanced net ionic
pH = pK a + log ℑ
⊄[HA] ↓ equation.
(b) Explain why the conductivity decreases, passes
−4 ⊇ 0.60 _
= − log(1.8 ∞ 10 ) + log ℑ through a minimum, and then increases as the
⊄ 0.40 ↓
volume of H2SO4 added to the barium hydroxide
= 3.92 {other approaches possible} is increased.
(b) The pH remains unchanged because the ratio of (c) Calculate the number of moles of barium
the formate and formic acid concentration stays hydroxide originally present in the solution that is
the same. titrated.
(c) initial concentrations (d) Explain why the conductivity does not fall to zero
5 . 00 mL at the equivalence point of this titration.
1 . 00 M HCl ∞ = 0 . 0476 M
105 mL Answer:
100 mL (a) Ba2+ + 2 OH- + 2 H+ + SO42- --> BaSO4(s) + 2 H2O
0 . 40 M HCOOH ∞ = 0 . 38 M
105 mL (b) The initial conductivity is high because of the
- 100 mL presence of Ba2+ and OH- ions. The conductivity
0 . 60 M HCOO ∞ = 0 . 57 M decreases because Ba2+ forms insoluble BaSO4
105 mL
with the addition of SO42-. The conductivity also
concentrations after H+ reacts with HCOO- decreases because OH- combines with the addition
0.38M + 0.05M = 0.43M HCOOH of H+ ions by forming H2O.
0.57M - 0.05M = 0.52M HCOO -
Beyond the equivalence point conductivity
+ −4 0 . 43 M −4 increases as H+ and SO42- ions are added.
[ H 3 O ] = 1 . 8 ∞ 10 ∞ = 1. 5 ∞ M
0 . 52 M (c) # mol Ba(OH)2 = # mol H2SO4
(d) 0.800L × 2.00M HCOOH = 1.60 mol =0.1M × 0.04L = 0.004 mol
0.200L × 4.80M NaOH = 0.96 mol OH- (d) BaSO4(s) dissociates slightly to form Ba2+ and
SO42-, while the water ionizes slightly to form H+ MW =
g HX ( true value )
and OH-. mol HX ( calculated , and too large )
1983 B 1983 C
The molecular weight of a monoprotic acid HX was to (a) Specify the properties of a buffer solution.
be determined. A sample of 15.126 grams of HX was Describe the components and the composition of
dissolved in distilled water and the volume brought to effective buffer solutions.
exactly 250.00 millilitres in a volumetric flask.
(b) An employer is interviewing four applicants for a
Several 50.00 millilitre portions of this solution were
job as a laboratory technician and asks each how
titrated against NaOH solution, requiring an average
to prepare a buffer solution with a pH close to 9.
of 38.21 millilitres of NaOH.
Archie A. says he would mix acetic acid and
The NaOH solution was standardized against oxalic sodium acetate solutions.
acid dihydrate, H2C2O4.2H2O (molecular weight: Beula B. says she would mix NH4Cl and HCl
126.066 gram mol-1). The volume of NaOH solution solutions.
required to neutralize 1.2596 grams of oxalic acid Carla C. says she would mix NH4Cl and NH3
dihydrate was 41.24 millilitres. solutions.
(a) Calculate the molarity of the NaOH solution. Dexter D. says he would mix NH3 and NaOH
(b) Calculate the number of moles of HX in a 50.00 solutions.
millilitre portion used for titration. Which of these applicants has given an
appropriate procedure? Explain your answer,
(c) Calculate the molecular weight of HX.
referring to your discussion in part (a). Explain
(d) Discuss the effect of the calculated molecular what is wrong with the erroneous procedures.
weight of HX if the sample of oxalic acid
(No calculations are necessary, but the following
dihydrate contained a nonacidic impurity.
acidity constants may be helpful: acetic acid, Ka=
Answer: 1.8x10-5; NH4+, Ka = 5.6x10-10)
1.2596 g
g
Answer:
(a) mol H2C2O4.2H2O = 126.066 mol = (a) A buffer solution resists changes in pH upon the
9.9916x10 mol -3 addition of an acid or base.
H2C2O4 + 2 NaOH --> Na2C2O4 + 2 H2O Preparation of a buffer: (1) mix a weak acid + a
−3 2 molNaOH −2 salt of a weak acid; or (2) mix a weak base + salt
9 . 9916 ∞ 10 mol ∞ = 1 . 9983 ∞ 10 mol
1 molH 2 C 2 O 4 of a weak base; or (3) mix a weak acid with about
−2 half as many moles of strong base; or (4) mix a
1. 9983 ∞ 10 mol
M NaOH = = 0 . 4846 M weak base with about half as many moles of
0 . 04124 L strong acid; or (5) mix a weak acid and a weak
(b) mol HX = mol NaOH base.
0.03821 L x 0.4846 M = 0.01852 mol HX (b) Carla has the correct procedure, she has mixed a
0 . 01852 mol weak base, NH3, with the salt of a weak base,
∞ 250 . 00 mL = 0 . 09260 mol HX NH4Cl.
(c) 50 . 00 mL
15 . 126 g g
Archie has a buffer solution but a pH of around 5.
MW = = 163 . 3
0 . 09260 mol mol Beula doesn’t have a buffer solution, her solution
consists of a strong acid and a salt of a weak base.
(d) The calculated molecular weight is smaller than
true value, because: Dexter does not have a buffer solution, since his
measured g H2C2O4 is larger than true value, solution consists of a weak base plus a strong
base.
calculated mol H2C2O4 is larger than true value,
calculated mol NaOH is larger than true value, 1984 A
calculated M NaOH is larger than true value Sodium benzoate, C6H5COONa, is the salt of a the
calculated mol HX is larger than true value, weak acid, benzoic acid, C6H5COOH. A 0.10 molar
therefore, solution of sodium benzoate has a pH of 8.60 at room
temperature. strong base, the pH at the equivalence point is 7, so we
(a) Calculate the [OH-] in the sodium benzoate would choose an indicator that changes color at a pH
solution described above. = 7. {Many other examples possible.}
(b) Calculate the value for the equilibrium constant 1986 A
for the reaction: In water, hydrazoic acid, HN3, is a weak acid that has
C6H5COO- + H2O <=> C6H5COOH + OH- an equilibrium constant, Ka, equal to 2.8x10-5 at 25ºC.
(c) Calculate the value of Ka, the acid dissociation A 0.300 litre sample of a 0.050 molar solution of the
constant for benzoic acid. acid is prepared.
(d) A saturated solution of benzoic acid is prepared (a) Write the expression for the equilibrium constant,
by adding excess solid benzoic acid to pure water Ka, for hydrazoic acid.
at room temperature. Since this saturated solution
(b) Calculate the pH of this solution at 25ºC.
has a pH of 2.88, calculate the molar solubility of
benzoic acid at room temperature. (c) To 0.150 litre of this solution, 0.80 gram of
Answer: sodium azide, NaN3, is added. The salt dissolved
completely. Calculate the pH of the resulting
(a) pH =8.6, pOH =5.4
solution at 25ºC if the volume of the solution
[OH-] =10-pOH = 3.98x10-6M remains unchanged.
(b) [C6H5COOH] = [OH-] (d) To the remaining 0.150 litre of the original
− −6 2
[ C 6 H 5 COH ][ OH ] ( 3 . 98 ∞ 10 ) solution, 0.075 litre of 0.100 molar NaOH
Kb = =
[ C 6 H 5 CO 2 ]
−
( 0 . 1 − 3 . 98 ∞ 10
−6
) solution is added. Calculate the [OH-] for the
resulting solution at 25ºC.
= 1.58x10-10 Answer:
− 14
Kw 1 . 0 ∞ 10 −5
Ka = = = 6 . 33 ∞ 10 (a) HN3 <=> H+ + N3-
− 10
K 1 . 58 10 ∞
) + −
(c) b
Ka =
[H ][ N 3 ]
(c)
(d) Describe how the value of the acid-dissociation (d) from the titration curve, at the 12.5 mL volume
constant, Ka, for the weak acid HX could be point, the acid is half-neutralized and the pH =
determined from the titration curve in part (c). pKa. Ka = 10pKa
(e) The graph below shows the results obtained by (e) Y2- (could it be OH- ?)
titrating a different weak acid, H2Y, with the
standardized NaOH solution. Identify the negative
ion that is present in the highest concentration at 1998 D
the point in the titration represented by the letter Answer each of the following using appropriate
A on the curve. 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-
Answer
(a) • exactly mass a sample of KHP in the Erlenmeyer This, in turn, causes the Ksp of copper(II)
flask and add distilled water to dissolve the solid. hydroxide to be exceeded and the solution forms
• add a few drops of phenolphthalein to the flask.
a precipitate of Cu(OH)2.
• rinse the buret with the NaOH solution and fill. With the addition of more NH3, you form the
• record starting volume of base in buret.
soluble tetraamminecopper(II) complex ion,
[Cu(NH3)4]2+, which will cause the precipitate to
• with mixing, titrate the KHP with the NaOH
dissolve.
solution until it just turns slightly pink.
• record end volume of buret.
2000 D
• repeat to check your results.
mass of KHP 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-dis-
(b) molar mass KHP = moles of KHP
sociation constant, Kb, for NH3 in water is 1.8 × 10–5
since KHP is monoprotic, this is the number of
at 25°C.
moles of NaOH
moles of NaOH (a) Write the net-ionic equation for the reaction of
NH3(aq) with HCl(aq).
L of titrant = molarity of NaOH
(b) Using the axes provided below, sketch the
11
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). 9
11 7
pH
9 5
7 3
pH
5 1
0
0 10 20 30 40
3
Volume of 0.20
M HCl Added (mL)
[X ]X +
(e) very electronegative oxygen is able to draw elec- 0.50 mmol
trons away from the bromine and weaken the O– 30.0 mL
H bond, making it easier for the hydrogen ion “to 4.4× 10–10 =
20.0 mmol
leave”. 30.0 mL
O
Br O H X = 1.80× 10–9 = [OH–]
O
1×10−14
[H+] = = 5.6× 10–6; pH = 5.26
2003 A Required 1.8×10−9
C6H5NH2(aq) + H2O(l) C6H5NH3+(aq) + OH–(aq) (d) when neutralized, there are 2.5 mmol of
Aniline, a weak base, reacts with water according to C6H5NH3+ in 50.0 mL of solution, giving a
the reaction represented above. [C6H5NH3+] = 0.050 M
(a) Write the equilibrium constant expression, Kb, for this cation will partially ionize according to the
the reaction represented above. following equilibrium:
(b) A sample of aniline is dissolved in water to C6H5NH3+(aq) C6H5NH2(aq) + H+(aq)
produce 25.0 mL of 0.10 M solution. The pH of at equilibrium, [C6H5NH2] = [H+] = X
the solution is 8.82. Calculate the equilibrium
constant, Kb, for this reaction. [C6H5NH3+] = (0.050–X)
(c) The solution prepared in part (b) is titrated with X2
= Ka = 2.3× 10-5
0.10 M HCl. Calculate the pH of the solution (0.050 − X )
when 5.0 mL of the acid has been titrated. X = 1.06× 10–3 = [H+]
(d) Calculate the pH at the equivalence point of the pH = –log[H+] = 2.98
titration in part (c). (e) erythrosine; the indicator will change color when
(e) The pKa values for several indicators are given the pH is near its pKa, since the equivalence point
below. Which of the indicators listed is most is near pH 3, the indicator must have a pKa near
suitable for this titration? Justify your answer. this value.
Indicator pKa 2005 A Required
Erythrosine 3 HC3H5O2(aq) ↔ C3H5O2–(aq) + H+(aq) Ka = 1.34× 10–5
Litmus 7 Propanoic acid, HC3H5O2, ionizes in water according
Thymolphthalein 10 to the equation above.
(a) Write the equilibrium constant expression for the
Answer: reaction.
(a) Kb =
[CHN
6 H][O
5H] +
3
−
(b) Calculate the pH of a 0.265 M solution of
[C6H5N
H2] propanoic acid.