Equilibrium)

Equilibrium)and)Le)Chatelier’s)principle)
!
Threshold)Questions)
1) Decide whether the following statements are true or false.

a) At the atomic level, no changes are occurring for a system that has reached chemical
equilibrium.

b) The concentrations of reactants and products remain constant over time for a system
that has reached chemical equilibrium.

c) When a reactant is added to a system initially at equilibrium, the forward reaction will
occur to consume all the added reactant and reach a new equilibrium.

d) A reaction reaches equilibrium when the concentration of products is equal to the

concentration of reactants.

e) When reactants are mixed together, the rate of the forward reached increases until an
equilbrium position is reached.

f) In an equilibrium system in which the forward reaction is endothermic, the reverse

reaction will be exothermic.

g) Equilibrium is reached when the rate of the forward reaction is equal to the rate of the
reverse reaction

h) A system that is at equilibrium has stopped reacting.

2) Sulfur trioxide dissociates reversibly 2SO3 (g) ⇌ O2 (g) + 2 SO2 (g) .

The$graph$shows$the$amount$of$SO3$(g)$present$in$a$sealed$container$at$400$°C.$

a) How long did it take for equilibrium to be established?

b) How many moles of O2 gas were in the container 8 minutes after the start?

c) Which reaction was occurring faster at the 8 minute mark?

2SO3 (g) → O2 (g) + 2 SO2 (g) or 2SO2 (g) + O2 (g) → 2 SO3 (g)

3) Use Le Chateliers' Principle to predict the effect (i.e. shift to the left, shift to the right, or no
effect) of each of the changes described below on the following reversible reaction at
equilibrium in a closed container:
 CO$(g)$+$H2$(g)$$⇌$$H2O$(g)$+$C$(s)$$ $ $ !H$=$–$131$kJ/mol$
a) decrease in concentration of H2 (g)

b) increase in concentration of CO (g)

c) decreasing the pressure (by increasing the volume of the container)

d) decreasing the temperature (without changing the volume of the container)decreasing

the pressure (by increasing the volume of the container)

e) addition of a catalyst (to accelerate the reaction)

f) adding additional C(s) to the container

4) Use Le Chatelier's Principle to predict the effect (i.e. shift to the left, shift to the right, or no
effect) of each of the changes described below on the following reversible reaction at
equilibrium in a closed container:

CaCO3$(s)$$⇌$$CaO$(s)$+$CO2$(g)$ !H$=$+$179$kJ/mole$
a) addition of extra CaCO3 (s)

b) removal of some CaO (s)

c) increasing the temperature

d) increasing the pressure by compressing the equilibrium mixture into a smaller volume

e) increasing the pressure (by adding some argon gas to the container)

5) When bromine is dissolved in water a reversible reaction forming hypobromite and bromide
ions occurs: Br2 (aq) + H2O (l) ⇌ Br" (aq) + OBr" (aq) + 2H+ (aq)

In$this$mixture$bromine$is$brown$while$all$ions$are$colourless.$$$Predict$the$effect$on$the$depth$
of$the$brown$colour$in$the$mixture$if:$
a) a small volume of concentrated hydrochloric acid solution is added

b) a small volume of concetrated sodium hydroxide solution is added

c) a small amount of solid sodium bromide is added

! )
Intermediate)Questions)
6) Ammonia gas is manufactured from nitrogen and hydrogen gases:

N2$ (g)$$+$ 3H2$ (g)$$$$⇌$$$$$2NH3$ (g)$$$ $ $ !H$$$=$ "$92$kJ/mol$

The$table$shows$the$percentage$of$a$mixture$of$1.0$mol$N2(g)$and$3.0$mol$H2(g)$$gases$that$are$
converted$into$ammonia$at$different$conditions:$
Conditions$ 1$atmos$ 50$atmos$ 100$atmos$ 200$atmos$ 600$atmos$
200$oC$ 15%$ 74%$ 81%$ 86%$ 95%$
o
400$ C$ 0.50%$ 15%$ 25%$ 36%$ 65%$
o
500$ C$ 0.10%$ 6.0%$ 11%$ 18%$ 42%$
Explain$how$these$data$illustrate$Le$Chatelier’s$principle.$$$
7) When 10.0 g of solid calcium hydroxide were shaken with one litre of water it was found
that 0.900 g of it dissolved forming a saturated (equilibrium) solution:

Ca(OH)2$ (s)$$$$⇌$$$$Ca2+(aq)$$+$$2OH"(aq)$$$$$!H$=$ –$12$kJ/mol$

(The$remaining$9.10$g$of$the$solid$rested$on$the$bottom$of$the$container).$Predict$the$effect$
(i.e.$more$solid$would$dissolve,$some$dissolved$compound$would$precipitate,$or$no$visible$
change)$of:$
a) adding another 1.00 g of Ca(OH)2 (s) to the saturated solution

b) adding some solid NaOH to the saturated solution

c) adding some solid CaCl2 to the saturated solution

d) adding some solid NaCl to the saturated solution

e) adding a small volume of concentrated HCl to the saturated solution

f) heating the saturated solution

8) Chromate ions (CrO42−) are yellow and dichromate ions (Cr2O72") orange in colour.
Chromate and dicchromate ions can interconvert according to the following reversible
reaction:

2CrO42"$(aq)$+$2H+$(aq)$$$$⇌$$Cr2O72Z$(aq)$+$H2O$(l)$
Describe$the$colour$changes$(yellow$to$orange,$orange$to$yellow,$remains$yellow$or$remains$
orange)$that$would$occur$when$the$following$changes$are$made$to$this$solution:$
a) A small volume of concentrated hydrochloric acid is added to a solution of
sodium chromate.

b) A small volume of concentrated sodium hydroxide solution was added a solution of

sodium chromate.

c) A small volume of concentrated hydrochloric acid is added to a solution of

sodium dichromate.

d) A small sample of solid sodium hydroxide is added to a solution of sodium dichromate.

e) Barium dichromate is soluble. Barium chromate is insoluble. What occurs when a

small sample of solid barium nitrate is added to a solution of sodium dichromate.

$ !
Advanced)Questions)
9) Some PCl5 (g) was placed in a sealed container and heated to decompose it.

$PCl5$ (g)$$⇌$$$Cl2$ (g)$+$PCl3$ (g)$ $$$ !H$=$+$88$kJ/mol$

The$concentrations$of$PCl5$(g)$and$Cl2$
!
(g)$were$monitored$separately$over$25$
minutes$and$various$changes$were$
made$to$the$gas$mixture.$
a) How long did it take for
equilibrium to be reached initially?

b) What change was made to the

mixture at the 7.5 minute mark?

c) What change was made to the

mixture at the 12.5 minute mark?

d) Identify two different changes that could be made made to the mixture at the 20
minute mark to cause the subsequent shifts shown between 20 to 25 minutes?

$
10) Some hydrogen iodide was introduced into a sealed container and heated to decompose it.

2HI(g)$$$$$⇌$$$$H2(g)$ +$ I2(g)$ !H$=$"52$kJ/mol$$

The$concentrations$of$hydrogen$iodide$and$iodine$ !
were$monitored$separately$over$100$minutes$and$
are$represented$in$the$graph.$
a) What was the initial concentration of HI (g)?

b) How long did it take for equilibrium to be

reached initially?

c) What change was made to the mixture at:

i) the 30 minute mark?

ii) the 50 minute mark?

iii) the 80 minute mark?

11) A mixture containing dinitrogen tetraoxide and

nitrogen dioxide was allowed to reach equilibrium in a sealed container: N2O4(g) ⇌
2NO2(g) !H = + 57 kJ/mol

Using$the$graph$paper$provided$below,$sketch$a$graph$of$concentration$of$N2O4(g)$and$NO2(g)$
separately$on$the$vertical$axis$vs.$time$on$the$horizontal$axis$showing$how$the$system$
responds$when$the$following$five$changes$were$made$at$oneZhour$intervals$in$the$order$listed:$
a) removal of some of the NO2(g) present

b) addition of some extra N2O4(g)

c) increase in the temperature without any change in volume

d) addition of a catalyst to the container

 e) increase in volume while maintaining the same temperature

Add$
!
[NO2]!
[Concentration,!molar]!

[N2O4]!

(a)! (b)! (c)! (d)! (e)! (f)!

Remove!some!! Add!some!! Increase!T! Add!a!! Increase! Argon!gas!
NO2! NO2! catalyst! volume! added!

$ $
The)equilibrium)constant)
Threshold)Questions)
1) Decide whether the following statements are true or false.

a) A high value of the equilibrium constant,Kc, indicates that the

forward reaction occurs much faster than the reverse reaction.

b) Increasing the temperature of the surroundings shifts the position of

equilibrium in favour of exothermic reactions.

c) The value of the equilibrium constant, K, depends on the

temperature of the equilibrium system.

d) The equilbrium constant for the reaction 2HI(g) ⇌ I2(g) + H2(g) has
no units.

e) The equilbrium constant for the reaction 2NO2(g) ⇌ N2O4(g) has units
of L/mole.

2) For each reversible reaction below write a mathematical expression relating the equilibrium
constant (Kc) to the equilibrium concentrations of the participants.

a) N2 (g) + O2 (g) ⇌ 2NO (g)

b) 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

c) N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

d) 4HCl (g) + O2 (g) ⇌ 2Cl2 (g) + 2H2O (g)

e) 3Fe (s) + 4H2O (g) ⇌ Fe3O4 (s) + 4H2 (g)

f) 2O3 (g) ⇌ 3O2(g)

g) CO2 (g) + C (s) ⇌ 2CO (g)

h) MgCO3 (s) ⇌ MgO (s) + CO2 (g)

i) Sn2+ (aq) + 2Fe3+ (aq) ⇌ Sn4+(aq) + 2Fe2+(aq)

j) Cu (s) + 2Ag+ (aq) ⇌ Cu2+(aq) + 2Ag(s)

3) At 525oC the value of Kc is 800 for the reaction between sulfur dioxide and oxygen gases:
2SO2(g) + O2(g) ⇌ 2SO3(g).
Evaluate Kc at 525oC for:

a) 2SO3(g) ⇌ 2SO2(g) + O2(g)

b) SO2(g) + ½ O2(g) ⇌ SO3(g)

c) SO3(g) ⇌ SO2(g) + ½ O2(g)

$ $
4) When heated, calcium carbonate decomposes according to:
CaCO3(s) ⇌ CaO(s) + CO2(g) for which Kc = 0.0034 (at 1073oC)

a) Write a mathematical expression in terms of concentration(s) to

represent the equilibrium constant Kc for this reaction.

b) Calculate the molar concentration of CO2(g) at equilibrium at

1073oC.

c) Would this concentration increase, decrease or be unchanged if

some of the CaO(s) was removed from the container without
changing the temperature?

d) What is the effect of adding some CaO(s) to the container on the

magnitude of the equilibrium constant Kc?

e) Would this concentration increase, decrease or be unchanged if the

temperature was increased to 2000 oC?

f) The decomposition of calcium carbonate is an endothermic process.

What is the effect of increasing the temperature of equilibrium
mixture on the magnitude of the equilibrium constant Kc?

5) 1.00 kg of cold water in a 100 litre tank was warmed to 25oC. Some of the water
evaporated until the space in the tank was saturated with water vapour; the pressure of
this vapour at 25oC was 3.17 kPa. The resulting equilibrium system can be represented by
the equation: H2O(l) ⇌ H2O(g).

a) Using the ideal gas law calculate the concentration of water vapour in
the tank at 25 oC.

b) Write a mathematical expression in terms of concentration(s) to

represent the equilibrium constant Kc for the reaction: H2O (l) ⇌
H2O (g)
and calculate the value at 25 oC of the equilibrium constant (Kc).

c) Would the value of Kc be smaller, larger or the same size as this if

this system was at equilibrium at 50 oC?

6) One litre of a solution containing 1.00 mol of iron(II) nitrate and 1.00 mol of
silver nitrate was prepared at 25oC. The reversible reaction takes place:

Fe2+(aq) + Ag+(aq) ⇌ Fe3+(aq) + Ag(s)

At equilibrium, the concentration of Ag+ (aq) ions was 0.42 M.

a) Calculate the concentrations of Fe2+(aq) and Fe3+(aq)

b) Calculate the value, at 25 oC, of the equilibrium constant Kc for this

reaction.

c) Some solid NaCl was added to the reaction mixture, reducing the
concentration of Ag+(aq) in the resulting equilibrium mixture to
0.100 Molar. Determine the concentrations of Fe2+ and Fe3+, at 25
o
C, in the resulting equilibrium mixture.

$ $
7) A mixture of 0.100 mole of NO(g), 0.0500 mole of H2(g) and 0.100 mole of H2O(g) was
placed in a 1.00 litre container and allowed to react according to:

2NO (g) + 2H2 (g) ⇌ N2 (g) + 2H2O (g) !H = −332 kJ/mol

When equilibrium was established at 27oC the concentration of NO (g) present in the
container was 0.0620 M.

a) Calculate the concentrations of the other three gases at equilibrium

at 27oC.

b) Evaluate Kc for the reaction at 27 oC.

c) Predict whether the value for an equilibrium constant for this

reaction occurring at
100 oC will be larger, smaller or the same as the value of the
equilibrium constant determined for the reaction occuring at 27 oC.
Briefly justify your answer.

) )
Intermediate)Questions)
8) At high temperatures the two isomers of 2"butene can interconvert:

cis"2"butene (g) ⇌ trans"2"butene (g)

a) Some pure cis-2-butene was heated to 307oC in a sealed tank and

then allowed to come to equilibrium with its trans isomer. At
equilibrium the tank contained 40.0 % of cis"2"butene and 60.0 %
trans"2"butene. Calculate the value of the equilibrium constant (Kc)
for the reaction shown above.

b) In another experiment some pure trans"2"butene was heated to

307oC in a sealed tank and then allowed to come to equilibrium with
its cis isomer. What was the composition of the gas mixture at
equilibrium?

c) Calculate the value of the equilibrium constant (Kc) at 307oC for the
reaction:

trans"2"butene (g) ⇌ cis"2"butene (g)

9) Fructose (fruit sugar) and glucose (corn sugar) are isomers of formula C6H12O6. When
dissolved in water they interconvert:

C6H12O6 fructose (aq) ⇌ C6H12O6 glucose (aq)

A chemist prepared a 0.244 M solution of fructose at 25oC and found that, at equilibrium,
its concentration was only 0.113 M.

a) Evaluate the equilibrium constant Kc for the interconversion as

written.

b) At equilibrium, what percentage of the fructose was converted to

glucose?

c) The chemist then prepared a 0.500 M glucose solution. Calculate the

equilibrium concentration of glucose in this solution at 25oC.

$ $
10) Three different experiments were performed on the reversible reaction:

H2(g) + CO2(g) ⇌ H2O(g) + CO(g)

The table shows the molar concentrations of the four gases present at equilibrium in three
different mixtures which were all at 825°C.

Concentration in the equilibrium mixture

Experiment [H2] [CO2] [H2O] [CO]

I 0.500 0.800 0.760 0.760

II 0.500 1.50 0.600 x

III 2.00 y 1.200 2.40

a) Evaluate Kc for this reaction at 825°C.

b) Evaluate x, the equilibrium [CO] in Experiment II.

c) Evaluate y, the equilibrium [CO2] in Experiment II.

d) Hydrogen and carbon dioxide gases, both at 1.00 M initial

concentrations, were sealed in a 100 litre tank and allowed to react
together. Calculate the concentrations of all four gases present in
the tank once equilibrium was reached

11) Steam reacts with carbon monoxide to produce hydrogen and carbon dioxide:

H2O(g) + CO(g) ⇌ H2(g) + CO2 (g)

The reaction is reversible. 3.00 moles of carbon monoxide and 3.00 moles of steam were
placed in a 100.0 litre container and allowed to react. At equilibrium it was found that only
1.00 mole of steam remained at 500 oC.

a) Calculate the number of moles of hydrogen gas which were present

in the equilibrium mixture.

b) Write a mathematical expression relating the equilibrium constant

(Kc) to the equilibrium concentrations of the four substances.

c) Evaluate Kc for the reaction shown above at 500 oC.

d) The container was then allowed to expand until its volume was
200.0 litres and equilibrium was re-established at 500 oC. Using Le
Chatelier’s principle predict whether the number of moles of steam
present was greater than, less than, or equal to 1.00 mole.

e) The mixture in (d) was then heated without any volume change.
When equilibrium was reached at 827 oC it was found that 1.50
moles of steam were present. Is this reaction between carbon
monoxide and steam exothermic or endothermic? Briefly justify your
answer.

$ $
12) H2 and I2 gases react together producing hydrogen iodide:

H2(g) + I2(g) ⇌ 2HI(g)

a) In one study of this reaction, 0.50 mole of H2(g) and 0.50 mole of
I2(g) were sealed in a 100 litre container. When equilibrium was
reached at 448oC there were 0.11 moles of each element present.
Calculate the number of moles of HI(g) also present in the mixture
and evaluate Kc at this temperature.

b) In a separate study, 1.00 mole of HI(g) was sealed in the container

and allowed to decompose into its elements. Calculate the number
of moles of HI(g) remaining when equilibrium was established at
448oC.

c) Predict the effect of increasing the volume of the container from 100
L to 200 L on magnitude of the equilibrium constant when this
reaction is performed at 448 oC. Provide a brief reason to support
your prediction.

Advanced)Questions)
13) The graph shows the variation in concentrations of the three gases present in a mixture of
phosgene (COCl2), carbon monoxide and chlorine over a period of 18 minutes. These gases
interact according to: CO(g) + Cl2(g) ⇌ COCl2(g) !H = –108 kJ/mol

a) The gas mixture was initially at equilibrium. 4 minutes later its temperature was
changed. Decide whether its temperature was increased or decreased and briefly
justify your choice.

b) What change was made to the mixture at the 10 minute mark? Briefly justify your
choice.

c) Write an expression relating the equilibrium constant (Kc) to the concentrations of the
gases in the mixture.

d) Calculate the value of the equilibrium constant (Kc) at the 13 minute mark.

e) What change was made to the mixture at the 14 minute mark? Briefly justify your
choice.

$ $
14) N2O4(g) decomposes according to: N2O4(g) ⇌ 2NO2(g).

Initially 1.00 mole of N2O4(g) and 1.00 mole of NO2(g) were placed in a 1.00 litre
container. At 60 oC the mixture reached equilibrium and was found to contain twice as
many NO2(g) molecules as N2O4(g) molecules.

a) Calculate the percent dissociation of N2O4(g) at 60 oC.

b) Calculate the value of Kc at 60oC.

c) The value of Kc at 25 oC is 0.0058. Is the decomposition reaction

(i.e. N2O4(g) → 2NO2(g)) exothermic or endothermic?

15) A mixture of 0.100 mole of NO(g), 0.0500 mole of H2(g) and 0.100 mole of H2O(g) were
placed in a 1.00 litre container and allowed to react according to:

2NO(g) + 2H2(g) ⇌ 2H2O(g) + N2(g)

The concentration of NO(g) present in the container was 0.062 M when equilibrium was
established at 27oC.

a) By completing the following RICE table, Determine the concentration

of the other three gases in the equilibrium mixture that was
established at 27oC

Reaction 2NO(g) + 2H2(g) ⇌ 2H2O(g) + N2(g)

Initial 0.100 0.0500 0.100

Change

Equilibrium

b) Write an expression relating the equilibrium constant (Kc) for this

reaction to the concentration of the gases in the equilibrium system.

c) Evaluate Kc for this reaction at 27oC.

d) Predict the effect increasing the pressure on the value of the

equilibrium constant for this reaction

e) The value of the equilibrium constant increased when the

temperature was decreased. Explain, using Le Chatelier’s
principle, how this information can be used to determine whether
this reaction is an endothermic or exothermic process.

16) Iron reacts reversibly with steam according to:

Fe(s) + H2O(g) ⇌ FeO(s) + H2(g)

1.00 mol of iron and 1.00 mol of steam were sealed inside a 50.0 litre tank at 777 oC.
When the reaction had reached equilibrium at this temperature the tank was found to
contain 0.60 mol of iron (II) oxide.

a) Calculate the number of moles of steam which were present in the

mixture at equilibrium.

b) Calculate the pressure inside the tank at equilibrium at 777 oC.

 c) Write an expression relating the equilibrium constant (Kc) to the
concentrations of the substances present in the mixture at
equilibrium.

d) Calculate the value of the equilibrium constant (Kc) for this reaction
at 777 oC.

e) At 800 oC the value of the equilibrium constant (Kc) for this reaction
is 1.42. Decide whether the reaction:

Fe(s) + H2O(g) ⇌ FeO(s) + H2(g)

is exothermic or endothermic and briefly justify your choice.

17) A 250.0 litre tank was initially filled with a gaseous mixture comprising 3.00 moles of SO2,
1.25 moles of NO2 and 0.50 mole of SO3.The tank was found to contain 1.50 moles
of SO3 (g) when equilibrium was established for the reaction:

SO2 (g) + NO2 (g) ⇌ SO3 (g) + NO (g)

a) How many moles of each of the other gases were present at

equilibrium?

b) Evaluate Kc for the reaction.

c) Some additional SO3 (g) was then added to the tank in (a) and the
mixture reached a new equilibrium at the same temperature.

This equilibrium mixture contained 0.50 mole of NO2 (g).

Analysis of the resulting equilibrium mixture showed that it contained 1.50 mol SO3(g).

Calculate the number of moles of the other 3 gases present in the mixture at
equilibrium.

18) When heated, nitrogen dioxide dissociates according to the following equation:

2NO2(g) ⇌ 2NO(g) + O2(g)

24.4 grams of pure nitrogen dioxide were heated to a constant temperature, T, in a flask
of volume 10.0 litres. An equilibrium mixture containing 1.4 grams of nitrogen dioxide was
formed

a) Calculate the number of moles of nitrogen dioxide that were present

in this equilibrium mixture.

b) Calculate the numbers of moles of nitrogen monoxide and oxygen

that were also present in this equilibrium mixture.

c) Write an expression for the equilibrium constant, Kc, for this reaction
in terms of the concentrations of the three gases.

d) Calculate the value of Kc at the temperature T.

e) The total pressure in the flask was 330 kPa. Calculate the value of the
temperature T in degrees Celsius.

$ $
19) The reversible reaction between iron(II) oxide and carbon monoxide is shown below:

FeO(s) + CO(g) ⇌ Fe(s) + CO2(g)

1.00 mol of iron(II) oxide and 1.00 mol of carbon monoxide were sealed inside a 55.0 litre
tank at 877 oC. When the reaction had reached equilibrium at this temperature the tank
was found to contain 0.25 mol of the iron(II) oxide.

a) Calculate the number of moles of carbon dioxide which were present

in the mixture at equilibrium.

b) Calculate the total gas pressure inside the tank at equilibrium at 877
o
C.

c) Write an expression relating the equilibrium constant (Kc) to the

concentrations of the substances present in the mixture at
equilibrium.

d) Calculate the value of the equilibrium constant (Kc) for this reaction
o
at 877 C.
o
e) At 1000 C the value of the equilibrium constant (Kc) for this reaction
is 1.68. Decide whether the reaction FeO (s) + CO (g) # Fe (s) +
CO2 (g) is exothermic or endothermic, and briefly justify your choice.

#
Solubility)equilibria)
Threshold)Questions)
1) Decide whether the following statements are true or false.

a) The molar solubility of a sparingly soluble compound is equal to its solubility product.

b) A saturated solution contains the maximum amount of solute that can dissolve in that
solution at that temperature.

c) Vigorously stirring a solution increases the amount of solute required prepare 1.00 L of
a saturated solution at room temperature.

d) A solution is unsaturated if added solute dissolves when more solute is added to the
solution.

e) The solubility of copper(II) hydoxide increases if the pH increases.

f) The solubility of silver chloride is larger in 0.100 M NaCl than in 0.100 M MgCl2.

g) Consider the following solubility data for a range of chromates at 25 oC:

Compound Ksp

Ag2CrO4 9.0 × 10−12

BaCro4 2.4 × 10−10

PbCrO4 1.8 × 10−14

The compound with the largest molar solubility is BaCrO4.

h) The solubility product of copper(II) hydroxide equal to 1.6 × 10−19. A solution of

0.0015 M copper(II) nitrate is prepared. A precipitate of copper(II) hydroxide forms
when sufficient solid NaOH is added to make the pH of the final solution equal to 8.00.

$ $
2) Complete the following table of aqueous solubilities of 1:1 electrolytes.

Solubility at 25oC Solubility at 25 oC

Compound Value of Ksp
(grams per litre) (moles per litre = M)

Silver bromide 0.00014

Lithium fluoride 1.1

Radium sulfate 6.1 × 10"6

Lead(II) carbonate 2.7 × 10"7

Barium carbonate 2.0 × 10"9

Lead(II) sulfate 1.6 × 10"8

Zinc carbonate 1.2 × 10"5

Copper(II) oxalate 4.4 × 10"10

3) Calculate the molar solubility of each of the following:

a) silver iodide (Ksp = 1.5 × 10–16)

b) strontium oxalate (Ksp = 5.6 × 10–8)

c) calcium carbonate (Ksp = 3.3 × 10–9)

d) lead chromate (Ksp = 1.8 × 10–14)

e) aluminium phosphate (Ksp = 9.8 × 10–21)

f) calcium phosphate (Ksp = 2.1 × 10–33)

g) calcium fluoride (Ksp = 3.9 × 10–11)

4) The value of Ksp for barium chromate (BaCrO4) is 2.4 × 10"10 at 25 oC. How many grams
of BaCrO4 are present in 10.00 L of a saturated solution of BaCrO4?

5) Calculate the equilibrium concentration of Cd2+(aq) ions in a saturated aqueous solution

made by shaking solid cadmium sulfide with water.
(The value of the solubility product for CdS at 25oC is 3.6 × 10–29)

# )
Intermediate)Questions)
6) Complete the following table of aqueous solubilities of a range of electrolytes.

Solubility at 25oC Solubility at 25 oC

Compound Value of Ksp
(grams per litre) (moles per litre = M)

Barium 2.55 × 10−4

hydroxide.8H20
Barium phosphate 3.40 × 10−23

Iron(III) phosphate 6.1 × 10"6

Barium carbonate 4.75 × 10−6

Lead(II) bromide 6.60 × 10"6

Lead(II) iodide 0.442

7) Solutions of silver nitrate and potassium chloride were mixed together. The resulting
mixture, at equilibrium with a precipitate of AgCl, was found to
contain 3.4 × 10–6 M Ag+(aq) ions and 5.0 × 10–5 M Cl–(aq) ions.

a) Evaluate Ksp for AgCl.

b) If a sample of solid silver chloride was shaken with water, calculate the concentration
of Ag+(aq) ions that would be present in the saturated solution.

c) Would a precipitate form if 1.00 L of a 3.4 × 10–6 M solution of AgNO3(aq) was mixed
with 1.00 L of a 5.0 × 10–5 M solution of NaCl(aq)?

8) Calculate the molar solubility of lead(II) sulfate (Ksp= 1.6 × 10"8 at 25 oC) in

a) pure water;

b) 0.10 M lead(II) nitrate solution;

c) 0.50 M sulfuric acid solution (assume the acid completely dissociates).

9) Calculate the molar solubility of silver iodide (Ksp = 1.5 × 10–16 at 25oC) in:

a) pure water;

b) 0.100 M silver nitrate solution;

c) 0.100 M sodium iodide solution.

10) Calculate the molar solubility of silver chromate (Ksp(Ag2CrO4) = 9.0 × 10−12) in

a) pure water;

b) 0.00200 M silver nitrate solution;

c) 0.02000 M sodium chromate solution.

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11) A saturated solution of barium sulfate has a concentration of 1.0 × 10–5 M at 25oC.
Calculate the molar solubility of BaSO4 in:

a) 0.500 M sodium sulfate solution;

b) 0.00200 M barium chloride solution;

c) 0.01000 M sodium chloride solution.

Advanced)Questions)
12) The solubility product constant (Ksp) of calcium chromate is 2.3 × 10–2. Assuming the
volumes are additive, will a precipitate form if:

a) 100 mL of 0.60 M calcium nitrate solution is mixed with 100 mL of

0.50 M sodium chromate solution?

b) 100 mL of 0.40 M calcium chloride solution is mixed with 300 mL of

0.080 M potassium chromate solution?

13) A student added 0.015 M potassium chromate (K2CrO4) solution dropwise from a burette to
100.0 mL of 0.012 M strontium chloride (SrCl2) solution with continual mixing. It was
found that 20.0 mL of the K2CrO4 solution were added before any precipitate of strontium
chromate appeared. Calculate

a) the concentration of Sr2+(aq) ions in the 120.0 mL of mixed solutions.

b) the concentration of CrO42–(aq) ions in the 120.0 mL of mixed solutions.

c) the value of Ksp for strontium chromate based on these results.

14) A solid mixture of barium sulfate (Ksp = 1.1 × 10–10) and calcium sulfate (Ksp = 2.4 × 10–5)
was shaken with a litre of water until no more of either solid would dissolve. Calculate the
molar solubility of both compounds in the solution.

Hint: Virtually all the sulfate ions in the solution come from the calcium sulfate
because it is much more soluble than the barium sulfate.

15) If dilute nitric acid solution is added to a mixture containing magnesium oxalate and
calcium oxalate, which of the two compounds is more likely to dissolve? (Ksp of MgC2O4 =
4.8 × 10–6, Ksp of CaC2O4 = 2.3 × 10–9).

16) In order to evaluate its solubility product, a student shook solid silver acetate (AgCH3COO)
with pure water to make a saturated silver acetate solution. Some copper wire was added
to100 mL of the saturated silver acetate solution to displace all the Ag+ (aq) ions as solid
silver metal:
Cu (s) + 2Ag+(aq) # 2Ag (s) + Cu2+(aq)
After drying, it was found that 0.460 g of silver were produced in this way.

a) Calculate the number of moles of silver produced by the reaction.

b) Calculate the concentration of Ag+(aq) ions that formed this solid.

c) Calculate the Ksp value of silver acetate using the result in (b).

# )
Acid>base)equilibria)
Threshold)Questions)
1) Decide whether the following statements are true or false.

a) The stronger the acid the weaker its conjugate base.

b) The conjugate base of a weak acid is a strong base.

c) Ammionia, NH3, is a stronger base than water therefore NH4+(aq) ion is a stronger acid
than H3O+ ion.

d) The conjugate base of H3O+ is OH−.

e) The conjugate base of a strong acid is a weak base.

f) The conjugate acid of a weak base is a strong acid.

2) You have 0.100 M solutions of three acids identified as HX, HY, and HZ. The pH of HX is
greater than the pH of HY, which in turn is greater than the pH of HZ.

a) Which of the acids is the least ionised in its solution?

b) Which acid has the largest Ka value?

3) Hydrofluoric acid is weak because it establishes the following equilibrium when in aqueous
solution:
HF(aq) ⇌ H+(aq) + F–(aq)
Predict how, if at all, the number of undissociated HF (aq) molecules in one litre of HF
solution would change if:

a) some solid sodium fluoride was added

b) a drop of concentrated hydrochloric acid was added

c) some solid sodium hydroxide was added

d) some solid sodium chloride was added

e) some solid lead nitrate was added (lead fluoride is virtually insoluble).

4) The Ka value of nitrous acid (HNO2) is 1.51 × 10–5 at 25oC.

a) Write an ionic equation to represent the ionisation of nitrous acid in water.

b) Write an expression for the dissociation constant (Ka) of nitrous acid.

c) Calculate the pH of an aqueous 0.15 M nitrous acid solution.

5) A certain acid (HX) is 1.25 % ionised in a 1.00 M solution of the acid. Calculate:

a) the pH of the acid solution

b) the dissociation constant (Ka) of the acid.

c) Calculate the pKa of the acid.

6) a Complete the following table for the weak acids listed.

b) List these five acids in decreasing order of strength.

c) List the five conjugate bases in decreasing order of strength.

7) Ka for butanoic acid is 1.51 × 10–5 at 25°C. In a 0.150 M aqueous solution of

butanoic acid (C3H7COOH) what is:

a) the concentration of undissociated butanoic acid?

b) the concentration of hydronium ion?

c) the concentration of butanoate anion?

d) the pH of the solution?

Hint: This style of problem is best answered by completing a RICE table

8) For hydrazoic acid (HN3) the value of Ka is 1.91 × 10–5. Calculate the pH and the
percentage dissociation of:

a) 1.00 M hydrazoic acid solution

b) 0.10 M hydrazoic acid solution

c) 0.0010 M hydrazoic acid solutio

d) Using Le Chatelier’s principle, explain why the % dissociation increases as the acid
becomes more dilute.
9) a Complete the following table for the weak bases listed.

b) List these three bases in decreasing order of strength.

c) List the three conjugate acids in decreasing order of strength

Intermediate)Questions)
10) A solution containing 2.34 grams of NH4Cl in 250 mL of solution has a pH of 5.0.Using
these data calculate the value of:

a) Ka for NH4+

b) pKa for NH4

c) Kb for NH3

d) pKb for NH3

11) The pH of a 0.10 M sodium cyanide (NaCN) solution is 11.20 at 25oC. Calculate:

a) the Kb and pKb for the cyanide CN– ion.

b) the percentage of CN–(aq) ions which undergo hydrolysis in this solution.

c) the Ka and pKa for hydrocyanic acid (HCN).

12) The bicarbonate ion (HCO3") can function as a Bronsted-Lowry acid

(for which Ka = 4.6 × 10–11) or a Bronsted-Lowry base (Kb = 2.2 × 10–8).

a) Write an ionic equation to represent bicarbonate ion in water acting as a Bronsted-

Lowry acid.

b) Write an ionic equation to represent bicarbonate ion in water acting as a Bronsted-

Lowry base.

c) Would a solution of sodium bicarbonate in water have a pH greater than, less than or
equal to 7.0? Provide a brief explanation to support your answer.

13) Butanoic acid is a weak acid in water. Its Ka value is 1.51 × 10–5 at 25oC.

a) Write an expression for the dissociation constant (Ka) of butanoic acid.

b) Calculate the pH of an aqueous 0.150 M butanoic acid solution.

c) Calculate the pH of a solution containing 0.150 mole of butanoic acid and 0.150 mole
of sodium butanoate mixed together in one litre.
14) A simple way to measure the pKa of a weak acid HB is to add exactly half the number of
moles of a strong base (such as NaOH) as there are moles of weak acid and measure the
pH of the resulting solution with a pH meter.
Explain why this method avoids having to perform equilibrium calculations.

Advanced)Questions)
15) If ammonia is added to a magnesium sulfate solution a white precipitate forms.

a) Identify this precipitate and explain its formation.

b) Explain why this precipitate disappears if some ammonium sulfate is added to the
mixture.

16) A buffer solution is often a mixture of a weak acid and its conjugate base.

a) Calculate the pH of a solution made by mixing 1.00 L of 0.200 M hydrofluoric acid

(Ka = 6.7 × 10–4) and 1.00 L of 0.200 M sodium fluoride

b) If 0.0100 mol of hydrochloric acid was added to the solution in (a) it would not react
with the hydrofluoric acid present. However the H+ ions added would react with the
fluoride ions according to:
F"(aq) + H+ (aq) ! HF (aq)
Calculate the number of moles of fluoride ions and the number of moles of hydrofluoric
acid molecules present in the mixture after the hydrochloric acid has been added.

c) Assuming the total volume is unchanged, calculate the pH of the mixture in (b) and
compare it with that in (a).

d) If 0.0100 mol of sodium hydroxide was added to the solution in (a) it would not react
with the fluoride ions present. However the OH" ions added would react with the
hydrofluoric acid according to:
HF(aq) + OH"(aq) ! F"(aq) + H2O(l)
Calculate the number of moles of fluoride ions and the number of moles of hydrofluoric
acid molecules present in the mixture after the sodium hydroxide has been added.

e) Assuming the total volume is unchanged, calculate the pH of the mixture in (d) and
compare it with that in (a).

17) 20.0 mL of 0.100 M acetic acid CH3COOH (Ka = 1.74 × 10–5) solution is titrated against
0.100 M sodium hydroxide solution. Calculate the pH of the mixture after each of the
following volumes of sodium hydroxide has been added:

a 0 mL;
!
b 10.0 mL;
c 19.0 mL;
d 20.0 mL;
e 21.0 mL;
f 30.0 mL
g Use these data to sketch a titration curve.

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