Equilibrium & The Gaseous State

(12)1, 8
The gas-phase reaction of carbon monoxide with hydrogen forming methanol is an example
of an equilibrium. The reaction was investigated by mixing 2.0mol of H
2
(g) with 1.0mol of
CO(g) and allowing equilibrium to be established.

() ()

()
Initial moles 2.0 1.0 0
At equilibrium, x mol of H
2
had reacted with CO.
What are the amounts, in moles, of each of the components of the equilibrium mixture?
H
2
(g) CO(g) CH
3
OH(g)
A

(12)1, 9
Pyruvic acid is a weak acid that is an important intermediate in many biological processes.
CH
3
COCO
2
H
Pyruvic acid
Which graph best represents the change in pH that occurs when a sample of pyruvic acid is
titrated with NaOH(aq)?


(12)1, 10
Stomach juices have a pH of 1.0.
Aspirin is a monobasic (monoprotic) acid represented by HA (K
a
= 1 x 10
-4
moldm
-3
) which
dissociated into ions H
+
and A
-
.
What are the relative concentrations of H
+
, A
-
and HA when aspirin from a tablet enters the
stomach?
A. [HA] > [H
+
] = [A
-
]
B. [H
+
] = [A
-
] > [HA]
C. [H
+
] > [A
-
] > [HA]
D. [H
+
] > [HA] > [A
-
]
(12)1, 11
A 1dm
3
solution was made by mixing 0.0040mol of HCl(aq) and 0.0025mol of NaOH(aq).
What was the pH of the resulting solution?
A. 2.19
B. 2.40
C. 2.60
D. 2.82
(11)1, 4
A given mass of ideal gas occupies a volume V and exerts a pressure p at 27C.
At which temperature will the same mass of the ideal gas occupy the same volume V and
exert a pressure 2p?
A. 54C
B. 54K
C. 600C
D. 600K

(11)1, 11
Soft drinks often have sodium citrate added to them to act as a buffer.
Which statement about buffer solutions is correct?
A. The pH of a buffer solution changes slightly when very large amounts of acid or base
are added.
B. The pH of a buffer solution increases very slightly when small amounts of acid are
added.
C. The pH of a buffer solution increases very slightly when small amounts of base are
added.
D. The pH of a buffer solution remains unchanged when small amounts of acid or base
are added.
(10), 1, 7
The value of pV is plotted against p for three gases, an ideal gas and two non-ideal gases,
where p is the pressure and V is the volume of the gas.

Which gas shows the greatest deviation from ideality?
A. Ammonia
B. Ethene
C. Methane
D. Nitrogen

(10)1, 13
At a total pressure of 1.0atm, dinitrogen tetraoxide is 50% dissociated at a temperature of
60C, according to the following equation.

What is the value of the equilibrium constant, K
p
, for this reaction at 60C?
A.

B.

C.

D.
(10)1, 36
Two students separately have available equal volumes of 0.1moldm
-3
silver nitrate, sodium
ethanoate and potassium bromide.
The first student, on mixing the sodium ethanoate and silver nitrate, obtains a white
precipitate. On adding potassium bromide to this mixture, the precipitate turns cream.
The second student adds the silver nitrate to the potassium bromide and obtains a cream
precipitate. On adding the sodium ehtanoate to this mixture, there is no further change.
Which statements about these observations are correct?
1. Silver ethanoate is insoluble.
2. Silver bromide is less soluble than silver ethanoate.
3. Ethanoate can oxidise bromide.
(09)1, 7
Use of the Data Booklet is relevant to this question.
Which expression gives the pressure exerted by 1.6 x 10
-3
mol of N
2
in a container of volume
3.0dm
3
at 273C?
A.

B.

()

C.

D.

()

(12)2, 3
Fifty years ago, students of A-level chemistry carried out qualitative inorganic analysis in
their practical sessions. This method included precipitating cations as chlorides, sulfides, etc.,
and used the concept of solubility product, K
sp
.
a) [5]
i. Write an expression for K
sp
of PbCl
2
, stating the units.

ii. The solubility of PbCl
2
is 4.7gdm
-3
.
Calculate the solubility product of PbCl
2
.
Give your answer to two significant figures.
When 2.0moldm
-3
hydrochloric acid is added to separate samples of aqueous silver nitrate
and aqueous lead(II) nitrate, AgCl and PbCl
2
are precipitated.
b) [7]
i. When the HCl(aq) is added to AgNO
3
(aq), what will be seen in the container
immediately, and after one hour in daylight?

ii. How would you confirm the original precipitate was AgCl by adding a single
reagent to it?
Describe what you would see and give an equation with state symbols for the
reaction that occurs with the reagent you have chosen.

iii. When concentrated hydrochloric acid is added to the precipitate of PbCl
2
, the
precipitate dissolves.
Suggest, with an ionic equation, an explanation for this observation.

Selective precipitation of sulfides may be used to separate the cations present in a solution
containing Cu
2+
, Ni
2+
and Zn
2+
.
The reagent used is hydrogen sulfide which behaves as a dibasic (diprotic) weak acid when in
aqueous solution.

()

()

() K
a
= 9.1 x 10
-8
moldm
-3

And

()

()

() K
a
= 1.0 x 10
-15
moldm
-3

Metal sulfides are precipitated by the following reaction.

()

() ()

Relevant K
sp
values are given in the table.
salt K
sp
/mol
2
dm
-6

CuS 6.3 x 10
-36

NiS 4.0 x 10
-21

ZnS 1.6 x 10
-24


The results of passing hydrogen sulfide through separate solutions of Cu
2+
, Ni
2+
, and Zn
2+
are
shown in the table below.
M
2+
being tested
H
2
S passed through an
acidic solution of M
2+

H
2
S passed through a
neutral solution of M
2+

H
2
S passed through an
alkaline solution of
M
2+

Cu
2+

Black precipitate of
CuS
Black precipitate of
CuS
Black precipitate of
CuS
Ni
2+
No precipitate No precipitate
Black precipitate of
NiS
Zn
2+
No precipitate
White precipitate of
ZnS
White precipitate of
ZnS

d) Use the data given above to give an explanation for each of the following questions.
You should give equations where appropriate. You are not expected to do any
calculations in this part. [6]

i. Why is CuS the only sulfide of these three precipitated in acid solution?

ii. Why is NiS precipitated in alkaline solution and not in neutral or acidic
solution?

iii. Why is ZnS precipitated in both neutral and alkaline solution?
(11)2, 2
Phosphorus(V) chloride, PCl
5
, is a white solid which sublimes at 160C.
When gaseous phosphorus(V) chloride is heated in a closed container, the following
equilibrium is established.

()

()

()
a) Write an expression for K
c
for this equilibrium, stating the units. [2]
Phosphorus(V) chloride dissolves in some polar solvents without reaction and such solutions
conduct electricity. This is due to the presence of the two ions [PCl
4
]
+
and [PCl
6
]
-
.
b) Draw the structure and suggest the shape of each of these ions. [3]
(11)2, 3
This question refers to the equilibrium previously.

()

()

()
In an experiment, 1.00mol of PCl
5
vapour was heated in a closed 5.00dm
3
flask at 500K until
equilibrium had been established.
The gases in the flask were then rapidly cooled, causing the formation of crystals of PCl
5
and
liquid PCl
3
. The chlorine gas present was pumped away and collected.
The amount of chlorine collected was x mol.
An excess of water was then very carefully added to the two remaining compounds, under
suitable conditions, causing the following reactions to occur.

You may assume that both H
3
PO
4
and H
3
PO
3
behave as dibasic (diprotic) strong acids.
a) Determine, in terms of x, the number of moles of H
+
that will be formed after the
addition of water to the mixture of PCl
3
and PCl
5
. [4]
The resulting solution was made up to 1.00dm
3
in a standard flask. 25.0cm
3
of this solution
was titrated with 4.00moldm
-3
NaOH and required 37.4cm
3
for neutralisation.
b) [4]
i. Calculate the total amount, in moles, of H
+
ions present in the 1.00dm
3

standard flask.

ii. Use your answers to 3(a) and 3(b)(i) to calculate the amounts, in moles, of
PCl
5
, PCl
3
and Cl
2
in the original equilibrium at 500K.

c) Use your answers to question 2(a) and 3(b)(ii) to calculate a value for K
c
for the
equilibrium. [2]

(11)3, 3
Parts of this question are concerned with the salts of the Group II elements. You may find this
following information to be useful.
Salts of Group II elements with divalent anions (i.e. those with a charge of 2-) tend to
be insoluble.
These salts become more insoluble down the group.
Salts of Group II elements with monovalent anions tend to be soluble.
The hydrogencarbonates of Group II elements do not exist in the solid state.
Carbon dioxide reacts with solutions of carbonate ions according to the following
equilibrium

()

()

()

()
You should use the above information and the ideas behind Le Chateliers principle and
solubility product, K
sp
, to explain your answers.
a) Mineral waters often contain the chlorides and hydrogencarbonates of Group II metals.
Solutions of these salts are formed when rainwater percolates through the roacks of
hills and mountains, and emerges as springs in the hillside. [9]

One such mineral water has the following composition.
Ion Concentration /gdm
-3

Ca
2+
0.0080
Mg
2+
0.0049
Cl
-
0.0071
HCO
3
-
0.036

i. Calculate the concentrations of these ions in moldm
-3
, and hence suggest the
formulae of the salts that could exist in the solution, and their relative amounts.

When a sample of the mineral water was partially evaporated, a mixture of white
solids was formed, and a solution containing a single salt remained.

ii. Suggest the identity of the first solid to be precipitated. Explain your answer.

iii. Suggest the composition of the rock through which the rainwater had
percolated, and explain how the mineral water had been formed.


b) One of the most common phosphorus-containing rocks is fluorapatite, Ca
5
(PO
4
)
3
F.
The first step in the production of phosphate as a mineral supplement for animal feed
is defluorination, which is achieved by heating the rock in a rotary kiln at 1500C
with silica and steam. [5]

The following equation represents this process.

i. Complete the balancing of the above equation by deducing values for a, b, c, d,
e and f.

ii. Write the expression for the solubility product of calcium phosphate, stating
its units.

iii. The value of K
sp
for calcium phosphate is 1 x 10
-26
. Calculate [Ca
2+
] in a
saturated solution of calcium phosphate. Show your working clearly.

c) [6]
i. Describe how separate samples of PCl
3
and PCl
5
can be made in the laboratory.

When reacted with SO
3
, PCl
3
produces a compound G with M
r
= 153.5, and a
byproduct H. G is also produced when PCl
5
is reacted with a small amount of H
2
O.
ii. Suggest a formula for G, and describe its shape.

iii. Suggest the identity of the byproduct H and construct equations for the
production of G from PCl
3
and from PCl
5
.