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EQUILIBRIUM

1. The graph at the right shows the


concentrations of reactants and
products in a mixture of two
gases A2 and B2 that are reacting
to form another gas, AB.
A2 + B2

AB
Concentration
(mol/L)

2 AB

B2

10
Time (min)

A2
20

(a) What happens to the concentrations of A2 and B2 as the reaction proceeds?


The concentrations both drop.
(b) Since rate depends on concentration, what happens to the rate of consumption of A2 and B2 as the
reaction proceeds?
The rate decreases.
(c) In principle this simple reaction ought to be reversible; that is, two molecules of AB can collide to
form A2 and B2. What is the initial concentration of AB and what will be the rate of the reverse
reaction at the beginning?
The initial concentration is 0 mol/L.
The initial rate of reactin is 0 mol/Ls.
(d) What happens to the concentration of AB and therefore the rate of the reverse reaction as time
passes?
[AB] increases and therefore the reverse rate increases.
(e) The overall rate of reaction is the net result of the forward rate and the reverse rate. According to
the slope of the concentration/time graph what eventually happens to the overall rate of reaction.
The overall rate of reaction falls to zero.
(f) Does this mean that the reactions have stopped? Describe an experiment that could be done to
verify your answer.
No, the 0 slope does not mean that the reaction has stopped and to test this, add more
reactant or product and observe if the reaction continues (equilibrium verified) or it does
nothing (complete reaction verified).
2.

After 20 minutes this closed system has come to chemical equilibrium. Also, conditions such as
temperature or pressure, which might affect the rates of the reactions, are constant. Under these
circumstances the concentrations (and properties related to concentration such as density and colour)
will be constant. Predict what would happen to the concentrations over the next 20 minutes if an
additional 2 mol/L of B2 is suddenly injected into the reacting mixture. Explain your predictions in
terms of collision theory.

The sudden increase in B2 concentration will result in additional A2 - B2 collisions which


will produce additional AB. As a result there will be a decrease in A2 concentrations, a
sudden increase followed by a decrease in B2 concentrations and an increase in AB
concentrations. The rise in [AB] would result in increased reverse reaction slowing the
[A2] and [B2] decrease until rate forward = rate reverse and the new equilibrium is
reached.
3.

This same reaction could be carried out in a process where A2 and B2 are added and AB is removed
continually at the same rate. This would also result in constant concentrations of reactants and products.
(a) Why should this be called a steady state rather than a dynamic equilibrium?
Since the forward rate does not match the reverse rate, the constancy of concentrations is a
result of removal of products and the addition of reactants rather than an equilibrium.
(b) What would be the advantages of such a process for commercial production of a substance in
industry?
This process allows the continuous production of product rather than a batch mode in which
the process must be started and stopped to remove product.

4.

To ensure that a system is at equilibrium one must test its reversibility. If the system can be shown to
change concentrations when some factor such as pressure or temperature is altered, and then return to the
original concentrations when the original conditions are re-established, then it is demonstrated that the
reaction is readily reversible. Otherwise, apparently constant concentrations in a system could be due to
a high activation energy, and a correspondingly slow reaction rate.
(a) In a reaction similar to that above, two other substances may combine as shown in the equation
X2 (g)

Y2 (g)

2 XY(g)

When 6 moles of X2 , 4 moles of XY and 2 moles of Y2 were compressed into a one litre steel
cylinder at 35C, the concentrations were found to remain constant, and no significant amount of
product was detected. What test would you do to determine whether this system is at equilibrium?
If it were at equilibrium under these conditions, what would you observe?
Change the temperature and measure the new reactant and product concentrations. If the
system is an equilibrium one, the concentrations will have changed.
If it was at equilibrium there would be no visible change of macroscopic properties.
(b) When methane gas is mixed with air in a steel cylinder at room temperature the concentration does
not change over a long period of time. What could be done to determine whether the mixture is at
equilibrium?
Change the pressure or temperature. If the system is an equilibrium one, the concentrations
will have changed. What do you expect to observe? Unless the temperature and/or the
pressure is raised a great deal, expect no change since the activation energy for this reaction is
quite high and the reaction is very exothermic. Once the rection is triggered it will be
explosive as the released enthalphy sustains the reaction. Since the reverse activation energy
is even larger than the forward one, little reverse reaction is expected. The reaction essentially
goes to completion.

THE EQUILIBRIUM CONSTANT


1. What happens to the equilibrium constants of the reactions below as the temperature increases? Heat of
reaction may be calculated from the Hf values given in appendix in the textbook.

(a) 2 NH3

N2

+ 3 H2

H = (1 mol(0) + 3 mol(0)) - (2 mol(-45.9 kJ/mol) = +91.8 kJ (endothermic)


Ea is largest in the direction and the reaction is most affected by a temperature increase
Keq which equals the ratio kf /kr increases.
(b) 2 CO(g)

O2 (g)

2 CO2 (g)

H = (2 mol(-393.5 kJ/mol)) (2 mol (-110.5 kJ/mol)) + = -566.0 kJ (exothermic)


Ea is largest in the direction and the reaction is most affected by a temperature increase,
Keq which equals the ratio kf /kr decreases.
2. What happens to the equilibrium constants of the following reactions as the temperature decreases?
(a) N2H4

H2

2 NH3

H = (2 mol(-45.9 kJ/mol)) - (1 mol(50.6 kJ/mol + 1 mol(0)) = -142.4 kJ (exothermic)


Ea is largest in the direction and the reaction is most affected by a temperature decreaaes,
Reverse of #1 - Keq increase.
(b) 16 H2S

8 SO2

16 H2O

+ 3 S8

H = (16 mol(-285.8 kJ/mol)) - (16 mol(-20.6kJ/mol) + 8 mol(-296.8 kJ/mol)) = -1868.8 kJ (exo),


Ea is largest in the direction and the reaction is most affected by a temperature decreaaes,
Reverse of #1 - Keq increase.
3. The value of Keq depends on how the chemical equation is written. Reversing the equation gives the
inverse of the equilibrium constant. Changing the molar coefficients in the equation alters the powers in
the equilibrium law expression. If the equilibrium constant, Keq = 40, for the reaction
A2 (g)

B2 (g)

2 AB(g)

(a) What is the equilibrium constant for the reaction


2 AB(g)

A2 (g)

B2 (g)
1
1
If Keq 40 then Keq'

0.025
Keq 40

(b) What is the equilibrium constant for the reaction


1
2 A2 (g)

1
2 B 2 (g)

If Keq = 40 then Keq"

AB(g)

Keq =

40 = 6.32

4. The yield of products at equilibrium is related to the magnitude of Keq. A large Keq corresponds to a
relatively large amount of products at equilibrium. For which reaction below is a greater percentage of
reactant converted to product; that is, which has the greater yield at equilibrium?
+1
-1
(a) HC2H3O2 (aq) H(aq) + C 2H3O (aq)
Keq = 1.8 x 10-5
3+
-1
2+
(b) Fe(aq) + SCN (aq) FeSCN(aq)
Keq = 300
Reaction (b) will have the greater yield
5. Only substances appearing in the equilibrium law expression will be those in solution. Solids are omitted.
Write equilibrium law expressions for the following reactions:
(a) CaCO3 (s)

CaO(s)

CO2 (g)

Keq = [CO2]
(b) NH3 (g)

K eq

HCl(g)

NH4Cl(s)

1
[NH 3 ][HCl]

6. The equilibrium law as explained in this course applies only to dilute solutions. Since the concentration
of the solvent in a dilute solution is large and nearly constant, the solvent is not usually included in the
equilibrium law expression. Write equilibrium law expressions for the following reactions:
(a) H2SO4 (aq)

K eq
(b) NH3 (aq)

K eq

H2O(l)

-1
HSO4(aq)

+1
H 3O(aq)

[HSO 41- ][H 3O ]


[H 2SO 4 ]
H2O(l)

+1
NH4(aq)

-1
OH (aq)

[NH 4 ][OH ]
[NH 3 ]

7. When 0.40 moles of N2 is placed in a 5.0 L container with 0.20 moles of H2 it reaches an equilibrium in
which there is 0.10 mol H2. The reaction equation is

N 2 (g)

(a)

I 0.40
C -x
E 0.40 - x

3 H 2 (g)

0.20
- 3x
0.10

n H (0.20 0.10 ) mol 0.10 mol


2

2 NH 3 (g)
0
2x
2x

Calculate the number of moles of H2


consumed in reaching equilibrium.

(b) Calculate the number of moles of N2 consumed in reaching equilibrium.


n N 2 0.10 mol H 2 x

1 mol N 2
0.033 mol
3 mol H 2

(c) Calculate the number of moles of NH3 produced in reaching equilibrium.


n NH 3 0.10 mol H 2 x

2 mol NH 3
0.067 mol
3 mol H 2

(d) Calculate the equilibrium concentrations of the reactants and products.

(0.40 0.033 ) mol


0.073 mol/L
5.0 L
(0.20 0.10 ) mol
[H 2 ]
0.020 mol/L
5.0 L
0.067 mol
[NH 3 ]
0.013 mol/L
5.0 L
[N 2 ]

(e) Write the equilibrium law expression for this reaction.


K eq

[NH 3 ]2
[N 2 ][H 2 ]3

(f) Calculate the equilibrium constant for this reaction.

K eq

[NH 3 ]2
(0.013) 2

290
[N 2 ][H 2 ]3 (0.073)(0.020 )3

Keq and ICE Problems Worksheet


1. Calculate the equilibrium constant, Keq, for the following reaction at 25 C, if [NO]eq = 0.106 M,
[O2]eq = 0.122 M and [NO2]eq = 0.129 M.
(Answer: Keq = 12.1)
2 NO (g)

E 0.106

[NO 2 ]2
2 NO2 (g) ; K eq
[ NO]2 [O 2 ]

O2 (g)
0.122

0.129

[0.129] 2
K eq
12.1
[0.106 ]2 [0.122 ]
2. Given the balanced equation and the value for Keq from #1, calculate new value of Keq for the
following:
(Answer: a. Keq = 1.87, b. Keq = 0.0826, Keq = 0.287)
a. NO (g)

O2 (g)

NO2 (g)

Multiply original reaction by , then K'eq K eq

1/ 4

b. 2 NO2 (g)

2 NO (g)

4 12.1 1.87

O2 (g)
1

-1
Multiply original reaction by -1 then K'eq K eq (12.1) 0.0826

c. NO2 (g)

NO (g)

O2 (g)

Multiply original reaction by - then K'eq K eq

1 / 2

1
0.287
12.1

3. Find the equilibrium constant, Keq, for the following equilibrium. The initial concentrations of AB and
A2D are 0.30 M before they are mixed and when equilibrium is reached, the equilibrium concentration of
A2D is 0.20 M. Be sure to show an ICE table for your calculation.
(Answer: Keq = 0.80)
I
C
E

2 AB (g) +
0.30
+2x
0.30 + 2x

C2D (s)
n/a

A2D (g) + 2 CB (s)


0.30
n/a
-x
0.30 x = 0.20

[A 2 D] 0.30 - x 0.20 x 0.10


[AB] 0.30 2(0.10) 0.50
[A D] 0.20
K eq 2 2
0.80
[AB]
0.50 2

4. If 0.50 mol of NO2 is placed in a 2.0L flask to create NO and O2, calculate [ ]eq if Keq = 1.2 x 10-5.

2 NO O 2 ; K eq =

2 NO 2

[NO ]2 [O 2 ]
[NO 2 ]2
= 1.2 x 10 -5

I 0.25

C -2x

+2x

+x

Q 0 K eq

E 0.25 - 2 x

+2x

+x

100 Rule applies


0.25
= 20 833 100
1.2 x 10 -5

0.25 - 2 x 0.25

5. For the system, if we start with 0.100mol/L of CO2 and H2, what are the concentrations of the reactants
and products at equilibrium given that Keq = 0.64 at 900K?

CO 2

I 0.100
C -x
E 0.100 - x
K eq
(0.100

H2

0.100
-x
0.100 - x
(x)(x)

- x)(0.100 - x)

CO

H 2 O

K eq

[CO][H 2 O]
0.64
[H 2 ][CO 2 ]

Q 0 Keq
100 Rule - doesn't apply

0
0
x
x
x
x
0.64 then

x2
0.64
(0.100 - x) 2

x
0.80
0.100 - x
x 0.080 - 0.80x
1.80x 0.080

and

x 0.044

[CO] eq [H 2 O]eq 0.044 M and [CO 2 ]eq [H 2 ]eq 0.100 - 0.044 0.056 M
(0.044) 2
Check : Q
0.62
(0.056 ) 2
6. For the system, if we start with 0.010 mol/L of H2 and I2 and 0.096 mol/L of HI, what are their
concentrations at equilibrium given that Keq = 0.016?

2 HI
I

0.096

H2
0.010

C - 2x

E 0.096 - 2x

0.010 x

I2

K eq

[H 2 ][I 2 ]
0.016
[HI] 2

0.010 2
0.010
Q
0.010 Keq
0.096 2
x
100 Rule
0.010
0.010 x
0.625 doesn't apply
0.016

(0.010 x)(0.010 x)
K eq
0.016
(0.096 - 2x) 2

then

(0.010 x) 2
0.016
(0.096 - 2x) 2

0.010 x
0.126
0.096 - 2x
0.010 x 0.012 - 0.252x
1.252x 0.002
x 0.0016
[HI]eq 0.096 - 2(0.0016) 0.093 M and [H 2 ]eq [I 2 ]eq 0.010 0.0016 0.012 M
(0.012) 2
Check : Q
0.017
(0.093 ) 2
7. At 650C, the reaction below has a Keq value of 0.771. If 2.00 mol of both hydrogen and carbon dioxide
are placed in a 4.00 L container and allowed to react, what will be the equilibrium concentrations of all
four gases?

H2

I 0.500
C -x
E 0.500 - x

CO 2

CO

0.500
-x
0.500 - x

0
x
x

[CO][H 2 O]
0.771
[CO 2 ][H 2 ]

H 2 O

K eq

0
x
x

Q 0 Keq
100 rule
doesn't apply

(x)(x)
K eq
0.771 then
(0.500 - x)(0.500 - x)

x2
0.771
(0.500 - x) 2

x
0.878
0.500 - x
x 0.439 - 0.878x t hen

x 0.234

[CO] eq 0.260 M , [H 2O]eq 0.234 M and [H 2 ]eq [CO 2 ]eq 0.500 - 0.234 0.266 M
(0.234) 2
Check : Q
0.774
(0.266 ) 2

8. Carbonyl bromide, COBr2, can be formed by reacting CO with Br2. A mixture of 0.400 mol CO, 0.300
mol Br2, and 0.0200 mol COBr2 is sealed in a 5.00L flask. Calculate equilibrium concentrations for all
gases.

CO
I 0.0800
C x
E 0.0800 x
K eq

Br2

0.0600
x
0.0600 - x

COBr 2

K eq

[COBr 2 ]
0.680
[CO][Br 2 ]

0.00400
Q 0.83 Keq
-x
100 Rule - doesn't apply
0.00400 - x

0.00400 - x
0.680
(0.0800 x)(0.0600 x)
0.00400 - x 0.680 (0.0048 0.14x x 2 )
0.00400 - x 0.0033 0.095x 0.680x 2

0.680x 2 1.095x - 0.0007 0


a 0.680 b 1.095 c - 0.0007
- 1.095 1.20
1.36
- 1.095 1.096
x
1.36
x 0.0007 or x - 1.611 (no negatives)
[CO] eq 0.0807 M, [Br2 ]eq 0.0607 M and [COBr 2 ]eq 0.00400 0.0007 0.0033M
x

Check : Q

(0.0033)
0.674
(0.0807 )(0.0607 )

DETERMINATION OF Keq
OBJECTIVE:
Determine the equilibrium constant for the reaction
3+
-1
2+
Fe(aq) + SCN (aq)
FeSCN (aq)
INTRODUCTION:
Iron(III) ion reacts with thiocyanate ion to produce a coloured complex ion.
3+
Fe(aq)

-1
SCN (aq)

2+
FeSCN (aq)

The intensity of the colour of the solution depends on two things, the concentration of the coloured species and the
path length through which light travels in the solution. For example, light traveling through a 3 cm depth of a 0.1
mol/L solution of this ion will appear to have the same colour intensity as light traveling through a 1 cm depth of a
0.3 mol/L solution. Therefore, if the depth of two solutions is adjusted until they appear to have the same colour
intensity, the ratio of their concentrations will be inversely proportional to the ratio of their depths:
C1 D2
C2 = D1
If the concentration of one solution is known then concentration of the other may be calculated. The equilibrium
concentrations may be used to calculate the value of the equilibrium constant for this reaction. Then predictions may
be made about the equilibrium concentrations in other solutions.
To prepare a solution with a known concentration of the coloured complex, a dilute solution of thiocyanate ion is
reacted with a concentrated solution of iron (III) ion. It may be assumed that the large excess of iron (III) ion causes
most of the thiocyanate ion to be converted to the coloured complex. Therefore, for this mixture the equilibrium
concentration of the coloured complex will be equal to the initial concentration of the thiocyanate ion.
PROCEDURE:
(a) Line up five clean test tubes all of the same diameter, and label them. Add 5.0 mL of 0.002 mol/L potassium
thiocyanate solution to each of these five test tubes. To test tube (1) add 5.0 mL of 0.2 mol/L iron (III) nitrate
solution. This tube will be used as the standard.
(b) Measure 10.0 mL of 0.2 mol/L iron (III) nitrate solution in a graduated cylinder, and fill to the 25.0 mL mark
with distilled water. Pour the solution into a clean dry beaker to mix it. Measure 5.0 mL of this solution and pour
it into test tube 2. Save the remainder of this solution for Part (c).
(c) Pour 10.0 mL of the diluted iron (III) nitrate solution from the beaker into your graduate. Discard the remainder.
Again fill the graduate to the 25.0 mL mark with distilled water, and pour the solution into a clean dry beaker to
mix. Pour 5.0 mL of this solution into test tube 3. Continue dilution in this manner until you have 5.0 mL of
successively more dilute solution in each test tube.
(d) Now compare the solutions in each of the test tubes with the standard tube (1) in order to determine the
concentration of the coloured complex ion. Wrap a strip of paper around test tubes (1) and (2) to exclude light
from the side. Look vertically down through the solutions toward a diffused light source. If the colour
intensities appear the same, measure the depth of each solution to the nearest millimetre and record this. If the
colour intensities do not appear the same, remove some of the solution form the standard tube with a dropper
until the colour intensities are the same. Put the portion you removed into a clean dry beaker, since you may
have to use some of this solution later. The matching may be accomplished by removing more standard than
seems necessary and then replacing part of it drop by drop. When the colour intensities are the same in each
test tube, measure the depth of both solutions to the nearest millimetre. Repeat the procedure comparing test
tubes (1) and (3), (1) and (4), (1) and (5).

CALCULATIONS

1. Remember that the solution in test tube (1) was taken as the standard. The equilibrium concentration of coloured
complex in this solution is very nearly equal to the concentration of thiocyanate in the mixture before the reaction
began. However, a calculation is necessary since the 0.002 mol/L solution of thiocyanate used was diluted by the
addition of the other solution even before the reaction occurred. The initial concentration of thiocyanate in the
mixture is found by multiplying its concentration before mixing (0.002) by the dilution factor, (initial
volume/final volume), which in this case is (5/10). Therefore for the standard solution (1), the equilibrium
concentration of the coloured complex was
[FeSCN2+]eq = 0.002 x (5/10) mol/L.

2. The initial concentration of thiocyanate ion in each test tube was


[SCN-1]in = 0.002 x (5/10) mol/L.

3. The initial concentration of the iron (III) ion was different in each test tube since this solution was diluted
repeatedly by a factor of (10/25) in preparing the other solutions. In addition, the iron (III) ion was further diluted
by mixing with the thiocyanate solution.
[Fe3+]in = 0.2 x (10/25) n-1 x (5/10) mol/L

where n is the test tube number.

4. The equilibrium concentration of the coloured complex in each test tube is equal to the assumed concentration in
(1) multiplied by the ratio of depths which you measured in your experiment.

5. The amount of thiocyanate ion consumed is equal to the amount of coloured ion produced. Therefore to get the
equilibrium concentration of thiocyanate ion, subtract the equilibrium concentration of the coloured product from
the initial concentration of the thiocyanate ion.

6. Similarly, subtract the equilibrium concentration of the coloured product from the initial concentration of ferric
ion to get the equilibrium concentration of ferric ion.

7. Write the equilibrium expression for this reaction.


8. Calculate the values for the equilibrium constant from the data for the second through fifth test tubes.
9. Summarize your calculations in the data table below.
1

Initial [SCN-1]

0.00100

0.00100

0.00100

0.00100

0.00100

Initial [Fe3+]

0.100

0.0400

0.0160

0.00640

0.00256

Depth of Standard ( D1)

5.20

4.60

3.90

2.70

1.50

Depth of Sample (D2)

5.20

5.20

5.20

5.20

5.20

Depth Ratio (D1/D2)

N/A

0.8846

0.75

0.5192

0.2885

Equilibrium [FeSCN2+]

0.001

Equilibrium [SCN-1]

~0

8.85x10-4
1.15x10-4

7.50x10-4
2.50x10-4

5.19x10-4
4.81x10-4

2.88x10-4
7.12x10-4

Equilibrium [Fe3+]

N/A

3.91x10-2

1.53x10-2

5.92x1--3

2.27x10-3

Keq

N/A

197

196

182

178

CONCLUSION:
What is the average Ke value for the mixtures in test tubes 2 to 5?

197 196 182 178


188
4

LE CHATELIER'S PRINCIPLE
1. The graph at the right shows the
affect of adding more reactant, B2,
(at time = 20 minutes) to a system
initially at equilibrium with
concentrations of 6 mol/L, 2 mol/L
and 4 mol/L respectively for A2, B2
and AB.

[A 2 ]
[AB]

4
Concentration
(mol/L)
2

[B 2 ]

0
15

20

The reaction is

25
Time
(min)

30

35

A2
+ B2
2 AB
Use collision theory to explain the change in concentrations.
The addition of B2 results in an increased number of collisions between the reactants which causes a
decrease in the concentrations of A2 and B2 and an increase in the concentration of the product AB. As.
the reactants are consumed the forward reaction rate decreases and as the product is produced, the reverse
reaction rate increases until the forward and reverse rates become equal and equilibrium is reestablished.
2. If pressure on the system is increased, the equilibrium will shift to reduce the number of moles of gas in
the mixture, thus lowering the pressure again. What would be the affect on the yield of products of
increasing the pressure in each of the following systems at equilibrium?
(a) 3 H2 (g)

N2 (g)

2 NH 3 (g)

Increased pressure results in a greater increase in reactant particle collisions than products and a greater
increase in the forward reaction than the reverse and requires a reduction in gaseous moles which is the
product side therefore increased products
(b) 2 NaCl(s)

H2SO4 (l)

2 HCl(g)

Na2SO4 (s)

Increased pressure results in an increase in product collisions and an increase in the reverse reaction and
requires a reduction in gaseous moles which is the reactant side therefore decreased products
(c) SO3 (g)

CaCO3 (s)

CaSO4 (s)

CO2 (g)

Since the gaseous moles are the same for reactants and products therefore nothing happens
3. If the temperature is raised, the equilibrium will shift in the endothermic direction to consume some of
the added heat. What would be the affect of raising the temperature on the concentrations of products in
each of the following systems at equilibrium? Explain using Collision Theory.
(a) HCl

NH3

NH4Cl

heat

To absorb the increased heat the reverse reaction must proceed therefore product concentrations decrease,
OR since exothermic, activation energy in the reverse is larger and therefore the reverse reaction
increases more than the forward and product concentrations decrease.
(b) 1/2 N2

3/2 H2

NH3

H = -46.2 kJ/mol NH3

To absorb the increased heat the reverse reaction must proceed therefore product concentrations decrease,
OR since exothermic, activation energy in the reverse is larger and therefore the reverse reaction
increases more than the forward and product concentrations decrease.
(c) C2H4 (g)

heat

C2H2 (g)

H2 (g)

To absorb the increased heat the forward reaction must proceed therefore product concentrations
increase, OR since endothermic, activation energy in the forward is larger and therefore the forward
reaction increases more than the reverse and product concentrations increase.
4. Of course, lowering the concentration, pressure or temperature will have the opposite affect to the
changes described above. Each question below refers to the reaction:
N2O4 (g)

heat

2 NO2 (g)

(a) What is the affect on the yield of products of decreasing the pressure? Increase
(b) What would be the affect of decreasing the temperature?

Decrease

(c) What would be the affect of removing the NO2 as it is formed?


5. H2(g)

Cl2(g)

Increase

2 HCl(g)

What direction will the equilibrium shift when the partial pressure of hydrogen is increased?
It will shift to the right to decrease the pressure of hydrogen.
6. 3 H2(g)

N2(g)

2 NH3(g)

Given that this reaction is exothermic, what direction will the equilibrium shift when the temperature of
the reaction is decreased?
It will shift to the right so that the heat thats being removed will be replaced.
7. 2 NO2(g)

N2O4(g)

If a large quantity of argon is added to the container in what direction will the equilibrium shift?
It wont shift, because the partial pressures of each gas will be the same.
8. NH4OH(aq)

NH3(g)

H2O(l)

In what direction will the equilibrium shift if ammonia is removed from the container as soon as it is
produced?
It will shift to the right in an effort to increase the quantity of ammonia present.
9. 2 BH3(g)

B2H6(g)

If this equilibrium is taking place in a piston with a volume of 1 L and I compress it so the final volume is
0.5 L, in what direction will the equilibrium shift?
It will shift to the right so the volume of the gases in the equilibrium will also be decreased.

PART 1 Equilibrium Involving Thymol Blue


Tb2- (blue) + H3O+ HTb 1- (yellow) + H2O
HTb 1- (yellow) + H3O+ H2Tb (red) + H2O
[ ]

[ ]

[ ]

visible change

[H3O+]

[Tb2-]

[HTb 1-]

yellow

HCl 2nd

[H3O+]

[HTb2-]

[H2Tb ]

red

NaOH 1st

[OH-]

[H3O+] &
[H2Tb]

[HTb 1-]

yellow

NaOH 2nd

[OH-]

[H3O+] &
[HTb 1-]

[Tb2-]

blue

[ ]

visible change

nothing

slightly lighter
yellow/orange
due to dilution

stress
Starting blue
HCl

1st

shift direction

PART 2 Equilibrium involving Thiocyanatoiron (III) Ion


Fe3+(aq) + SCN-(aq) FeSCN2+(aq)
stress

[ ]

[ ]

shift direction

HCl

[Cl-] on both
sides

nothing

Fe(NO3)3

[Fe3+]

[SCN-]

[FeSCN2+]

Dark
orange/red

KSCN

[SCN-]

[Fe3+]

[FeSCN2+]

Dark
orange/red

NaOH

[OH-]

[Fe3+] &
[FeSCN2+]

[Fe3+]

yellow

no change

PART 3 Equilibrium Involving Copper Complexes


Cu(H2O)42+ (aq) + 4 NH3 (aq)

Cu(NH3)42+ (aq)

[ ]

[ ]

NH3 1st

[NH3]

[Cu(H2O)42+]

[Cu(NH3)42+] Blue precipitate

NH3 2nd

[NH3]

[Cu(H2O)42+]

[Cu(NH3)42+]

Darker blue
precipitate

HCl

[H3O+]

[NH3] &
[Cu(NH3)42+]

[Cu(H2O)42+]

Light blue
solution

stress

shift direction

[ ]

+ 4 H2O
visible change

Ksp PROBLEM SET #1


1. Write the solubility expression for the following:
(a) Zn(OH)2
(b) Ca3(PO4)2
(c) Fe2(SO4)3
(a) Zn(OH) 2 (s) Zn 2 (aq)
2 OH -(aq) ;

(b) Ca 3 (PO 4 ) 2 (s)

3 Ca 2 (aq)

(c) Fe 2 (SO 4 )3 (s)

2 Fe 2 (aq)

Ksp [Zn 2 ][OH - ]2

2 PO 43-(aq) ; Ksp [Ca 2 ]3[PO 43- ]2


3 SO 42-(aq) ;

Ksp [Ca 2 ]2[SO 42- ]3

2. Calculate the solubility of Mg(OH)2 in g/L given that Ksp = 5.6 x 10-12. (6.5 x 10-3 g/L).
Mg(OH)2

Mg2 (aq)

2 OH -(aq) ; K sp [Mg 2 ][OH - ]2


2x
5.6 x 10 12

x
K sp [Mg 2 ][OH - ]2 5.6 x 10 12 ; (x)(2x) 2 5.6 x 10 12 ; 4x 3 5.6 x 10 12

ICE

x 1.12 x 10 4 [Mg 2 ] molar solubility


1.12 x 10 4 mol Mg(OH)2
58.33 g
then, solubility of Mg(OH)2
x
6.5 x 10 3 g/L
L
mol Mg(OH)2

3. The solubility of SrF2 is 7.3 x 10-3 g/100 mL. Calculate Ksp. (7.8 x 10-10)
2 F-(aq) ; K sp [Sr 2 ][ F- ]2
x
2x
7.3 x 10 3 g 1 mol SrF2 1000 mL 1 mol Sr 2
molar solubility x
x
x
x
5.81 x 10 4 mol/L
100 mL
125 .62g
1L
1 mol SrF2

SrF2
ICE

Sr 2 (aq)

then, K sp [Sr 2 ][ F- ]2 (5.81 x 10 4 )(2 x 5.81 x 10 4 ) 2 7.8 x 10 10

4. The solubility of Cu(IO3)2 is 3.245 x 10-3 mol/L. Calculate Ksp. (1.367 x 10-7)
Cu(IO 3 ) 2

Cu 2 (aq)

2 IO3-(aq) ; K sp [Cu 2 ][ IO3- ]2

2x
K sp [Cu 2 ][ IO3- ]2 (3.245 x 10 3 )(2 x 3.245 x 10 3 ) 2 1.367 x 10 7

ICE

5. The solubility of PbI2 is 0.058 g/100mL. Calculate the Ksp for PbI2. (8.0 x 10-9)
PbI2
ICE

Pb 2 (aq)
x

molar solubility x

2 I-(aq) ; K sp [Pb 2 ][I - ]2


2x

0.058 g 1 mol PbI2 1000 mL 1 mol Pb 2


x
x
x
1.26 x 10 3 mol/L
100 mL
461 .00 g
1L
1 mol PbI2

then, K sp [Sr 2 ][ F- ]2 (1.26 x 10 3 )(2 x 1.26 x 10 3 ) 2 8.0 x 10 9

6. Calculate the molar concentration of Ba2+ ion in a saturated soln of Ba(IO3)2, if the Ksp = 1.15 x 10-9.
(6.6 x 10-4 mol/L)
Ba(IO 3 ) 2

Ba 2 (aq)

2 IO3-(aq) ; K sp [Ba 2 ][IO 3- ]2


2x
1.15 x 10 9

ICE

K sp [Ba 2 ][IO 3- ]2 1.15 x 10 9 ; (x)(2x) 2 1.15 x 10 9 ; 4x 3 1.15 x 10 9


x 6.6 x 10 4 [Ba 2 ]

7. The solubility of Cd(OH)2 is 2.01 x 10-4 g/100mL. Calculate Ksp. (1.04 x 10-14)
2 OH -(aq) ; K sp [Cd 2 ][OH - ]2
ICE
x
2x
2.01 x 10 4 g 1 mol Cd(OH) 2 1000 mL
1 mol Cd 2
x
x
x
x
1.373 x 10 5 mol/L
100 mL
146 .43 g
1L
1 mol Cd(OH) 2
then, K sp [Cd 2 ][OH - ]2 (1.373 x 10 5 )(2 x 1.373 x 10 5 ) 2 1.04 x 10 14

Cd(OH) 2

Cd 2 (aq)

8. The Ksp for Silver Phosphate is 2.8 x 10-18. Calculate the solubility in g/100 mL.
(7.49 x 10-4 g/100 mL)
Ag3PO 4

3 Ag (aq)

PO 43-(aq) ; K sp [Ag ]3[PO 43- ]


x
2.8 x 10 18

3x

ICE

K sp [Ag ]3[PO 43- ] 2.8 x 10 18 ; (3x) 3 (x) 2.8 x 10 18 ; 27x 4 2.8 x 10 18


x 1.79 x 10 5 [PO 43- ] molar solubility
then, solubility of Ag3PO 4

1.79 x 10 5 mol Ag3PO 4


418.58 g
x
7.49 x 10 3 g/L
L
mol Ag3PO 4

7.49 x 10 4 g/100 mL

9. The solubility of Mg(OH)2 is 9.0 x 10-4 g/100 mL at 18C. Calculate Ksp. (1.5 x 10-11)
2 OH -(aq) ; K sp [Mg 2 ][OH - ]2
ICE
x
2x
9.0 x 10 4 g 1 mol Mg(OH)2 1000 mL
1 mol Mg2
x
x
x
x
1.54 x 10 4 mol/L
100 mL
58.33 g
1L
1 mol Mg(OH)2
then, K sp [Mg 2 ][OH - ]2 (1.54 x 10 4 )(2 x 1.54 x 10 4 ) 2 1.5 x 10 11
Mg(OH)2

Mg2 (aq)

Ksp PROBLEM SET #2


1. If 0.010 mg of NaCl is added to 200. mL of a 2.0 x 10-5 M AgNO3 will a precipitate form? Ksp AgCl =
1.8 x 10-10. (Q = 1.71 x 10-11)
Na

NaCl

1.0 x 10 -5 g x

M 58.44 g/mol
AgNO3

Ag

Cl -

1mol NaCl
1
x
8.56 x 10 -7 mol/L
58 .44 g
0.200 L

NO 3-

2.0 x 10 -5
Ag

Cl - ; K sp [Ag ][ Cl - ] 2.0 x 10 3
Q (2.0 x 10 -5 )(8.56 x 10 -7 ) 1.71 x 10 -11
Q Ksp no ppte will form

AgCl

2. If one gram of AgNO3 is added to 50. mL of a 0.050 M HC2H3O2 which is soluble, will a precipitate
form? Ksp for AgC2H3O2 is 2.0 x 10-3. (Q = 5.9 x 10-3)
HC 2H3O 2 H

C 2H3O 20.050 mol/L


AgNO3

Ag

NO31mol AgNO3
1
M 169.88 g/mol
1.0 g x
x
0.118 mol/L
169 .88 g
0.050 L
AgC2H3O 2 H C 2 H3O 2- ; K sp [H ][C 2 H3O 2- ] 2.0 x 10 3
Q (0.118 )(0.050 ) 5.9 x 10 -3
Q Ksp ppte will form

3. In each of the following cases, show whether a precipitate will form under the given conditions:
(a) 10. mL of 0.10 M AgNO3 is added to 600. mL of a 0.010 M Na2SO4 solution. Ksp for Ag2SO4 is
1.5 x 10-5. (Q = 2.65 x 10-8)
Na 2SO 4 2 Na

SO 42C 0.010 mol/L, V 0.600 L

Ag

n 6.00 x 10 -3 mol

NO3-

AgNO3

Ag2SO 4

C 0.10 mol/L,
2 Ag
1.00 x 10 -3 mol
0.610 L
1.64 x 10 -3

n 1.00 x 10 -3 mol
SO 4 2- ;
K sp [Ag ]2[SO 4 2- ] 1.5 x 10 5
6.00 x 10 -3 mol

V 0.010 L

0.610 L
9.84 x 10 -3

Q (1.64 x 10 -3 ) 2 (9.84 x 10 -3 ) 2.65 x 10 -8

Q Ksp no ppte will form

(b) 1.0 g of Pb(NO3)2 is put in 100. mL of 0.010 M HCl. Ksp (PbCl2) = 1.2 x 10-5. (Q = 3.02 x 10-6)
Pb 2

Pb(NO3 ) 2
m 1.0 g

2 NO 3-

1 mol Pb(NO3 ) 2
1
x
331.22 g
0.100 L
3.02 x 10 -2 M

C 1.0 g x

M 331.22 g/mol

Cl C 0.010 mol/L
PbCl 2 Pb 2 2 Cl - ;
K sp [Pb 2 ][Cl - ]2 1.2 x 10 5
Q (3.02 x 10 -2 )( 0.010 ) 2 3.02 x 10 -6
Q Ksp no ppte will form

HCl

(c) 1.0 milligram of CaCl2 and 1.0 milligram of Na2C2O4 are added to 1.0 litre of water. Ksp for
CaC2O4 is 2.0 x 10-9. (Q = 6.72 x 10-11)
CaCl 2
Ca 2 2 Cl 1 mol CaCl 2
1
C 1.0 x 10 -3 g x
x
9.01 x 10 -6 M
110.98 g
1.0 L
Na 2C 2O 4 2 Na C 2O 421 mol Na 2C 2O 4
1
C 1.0 x 10 -3 g x
x
7.46 x 10 -6 M
134.00 g
1.0 L
CaC 2O 4 Ca 2 C 2O 42- ;
K sp [Ca 2 ][C 2O 4- ] 2.0 x 10 9
Q (9.01 x 10 -6 )(7.46 x 10 -6 ) 6.72 x 10 -11
Q Ksp no ppte will form
4. Given that the Ksp for CaC2O4 is 2.0 x 10-9, calculate how many grams of CaC2O4 will dissolve in 1.0
litre of:
(a) water (m = 5.7 x 10-3g)
(b) 0.10 M Na2C2O4 (m = 2.6 x 10-6g)
(a) CaC 2O 4 Ca 2 C 2O 42- ;
K sp [Ca 2 ][C 2O 4- ] 2.0 x 10 9
ICE
x
x
(x)(x) 2.0 x 10 9 x 4.47 x 10 -5 molar solubility
m CaC O
2 4

4.47 x 10 -5 mol CaC 2O 4


128.1 g
x
x 1.0 L 5.7 x 10 3 g
L
1 mol CaC 2O 4

(b) Na 2C 2O 4 2 Na

C 2O 4 20.10

CaC 2O 4

Ca 2

ICE

C 2O 4 2- ;

K sp [Ca 2 ][C 2O 4- ] 2.0 x 10 9

0.10

(x)(0.10) 2.0 x 10 9 x 2.0 x 10 -8 molar solubility


mCaC O
2 4

2.0 x 10 -8 mol CaC 2O 4


128.1 g
x
x 1.0 L 2.6 x 10 6 g
L
1 mol CaC 2O 4

(c) 0.010 M CaCl2 (m = 2.6 x 10-5g)

(c) CaCl 2
CaC 2O 4
ICE

Ca 2

0.010
Ca 2

(d) 0.10 M NaNO3 (m = 5.7 x 10-3g)

2 Cl C 2O 4 2- ;

K sp [Ca 2 ][C 2O 4- ] 2.0 x 10 9

0.010

(0.010)(x) 2.0 x 10 9 x 2.0 x 10 -7 molar solubility


2.0 x 10 -7 mol CaC 2O 4
128.10 g
m CaC O
x
x 1.0 L 2.6 x 10 5 g
2 4
L
1 mol CaC 2O 4
(d) NaNO3
CaC 2O 4
ICE

Na

NO3-

0.10
Ca 2

0.10

C 2O 4 2- ;

K sp [Ca 2 ][C 2O 4- ] 2.0 x 10 9

There is no common ion, so the m CaC 2O 4 5.7 x 10 3 g as in (a).

5. Given the Ksp for PbI2 = 8.5 x 10-9, calculate how many grams of PbI2 will dissolve in 250. mL of the
following systems:
(a) water (m = 1.5 x 10-1g)
PbI2 Pb 2 2 I- ;
K sp [Pb 2 ][I - ]2 8.5 x 10 9

x
2x
(x)(2x) 2 8.5 x 10 9 ; 4x 3 8.5 x 10 9 ; x 1.29 x 10 3 molar solubility
1.29 x 10 3 mol PbI2
461.00 g
m PbI
x
x 0.250 L 1.5 x 10 1 g
2
L
1 mol PbI2

ICE

(b) 0.010 M Pb(NO3)2 (m = 5.3 x 10-2g)

(b) Pb(NO 3 ) 2 Pb 2 2 NO 3

(c) 0.010 M CaI2 (m = 2.5 x 10-3g)

0.010
PbI2
ICE

Pb 2

2 I- ;

K sp [Pb 2 ][I - ]2 8.5 x 10 9

2x

0.010

(0.010)(2x ) 2 8.5 x 10 9 ; x 4.6 x 10 4 molar solubility and m P bI2 5.3 x 10 2 g


(c) CaI 2

Ca 2

2 I0.020

PbI2

Pb 2

ICE

2 I- ;

K sp [Pb 2 ][I - ]2 8.5 x 10 9

0.020

(x)(0.020) 2 8.5 x 10 9 ; x 2.13 x 10 5 molar solubility and m P bI2 2.5 x 10 3 g

6. 75 mL of a 2.0 x 10-3 M AgNO3 solution is mixed with 45 mL of a 1.0 x 10-4 M NaCl soln. Will a ppte
form? Ksp AgCl = 1.8 x 10-10. (Q = 4.7 x 10-8)

NaCl

Na

Cl -

C 1.0 x 10 -4 mol/L, V 0.045 L

n 4.5 x 10 -6 mol

AgNO3 Ag

NO3C 2.0 x 10 -3 mol/L, V 0.075 L


Ag

Cl - ;

AgCl

1.5 x 10 -4 mol
0.120 L
1.25 x 10 -3

n 1.5 x 10 -4 mol
K sp [Ag ][Cl - ] 1.8 x 10 10

4.5 x 10 -6 mol
0.120 L
3.75 x 10 -5

Q (1.25 x 10 -3 )(3.75 x 10 -5 ) 4.7 x 10 -8

Q Ksp a ppte will form

7. How many grams of AgCl will dissolve in 100.0 mL of a 0.010 M NaCl soln. Ksp = 1.8 x 10-10. (m =
2.6 x 10-7g)
Na

NaCl

AgCl

Ag

ICE

Cl 0.010
Cl -

K sp [Ag ][Cl - ] 1.8 x 10 10

0.010
(x)(0.010) 1.8 x 10 10 ; x 1.8 x 10 8 molar solubility and m AgCl 2.6 x 10 7 g

8. 100. mL of a 0.010 M Mg(NO3)2 is mixed with 50. mL of a 0.010 M Ba(OH)2. Will a ppte form? Ksp
Mg(OH)2 = 5.6 x 10-12. (Q = 3.0 x 10-7)
Ba 2

Ba(OH) 2

2 OH C 0.010 mol/L (x 2), V 0.050 L

Mg(NO3 ) 2 Mg2 2 NO 3

C 0.010 mol/L,
Mg(OH)2

Mg2

1.0 x 10 -3 mol
0.150 L
6.67 x 10 -3

n 1.0 x 10 -3 mol

V 0.100 L

n 1.00 x 10 -3 mol

2 OH -

K sp [Mg 2 ][ OH - ]2 5.6 x 10 12

1.00 x 10 -3 mol
0.150 L
6.67 x 10 -3

Q (6.67 x 10 -3 )(6.67 x 10 -3 ) 2 3.0 x 10 -7

Q Ksp a ppte will form

9. Calculate the number of moles of AgCl that will dissolve in 1.0 litre of a 0.10 M CaCl2 solution. (m =
1.3 x 10-7g)
CaCl 2
AgCl
ICE

Ca 2

0.10
Ag
x

2 Cl

0.20
Cl - ;

K sp [Ag ][Cl - ] 1.8 x 10 10

0.20
(x)(0.20) 1.8 x 10 10 ; x 9.0 x 10 10 molar solubility and m AgCl 1.3 x 10 7 g

10. 50. mL of a 5.0 x 10-4 M Ca(NO3)2 is mixed with 50. mL of a 2.0 x 10-4 M NaF to give 100. mL of
solution. Will a ppte form? Ksp CaF2 is 3.9 x 10-11. (Q = 2.5 x 10-12)
NaF
Na
FC 2.0 x 10 -4 mol/L, V 0.050 L
Ca(NO 3 ) 2

Ca 2

n 1.0 x 10 -5 mol

2 NO 3-

C 5.0 x 10 -4 mol/L, V 0.050 L n 2.5 x 10 -5 mol


Ca 2

2 F- ;
K sp [Ca 2 ][ F- ]2 3.9 x 10 11
2.5 x 10 -5 mol
1.0 x 10 -5 mol

CaF2

0.100 L
2.5 x 10 -4

0.100 L
1.0 x 10 -5

Q (2.5 x 10 -4 )(1.00 x 10 -4 ) 2 2.5 x 10 -12

Q Ksp no ppte will form

11. Calculate the solubility of RaSO4 in mol/L in a 0.10 M Na2SO4 soln. Ksp RaSO4 = 4.3 x 10-11. (x =
4.3 x 10-10 M)
Na 2SO 4

2 Na

SO 420.10

RaSO 4

Ra 2

ICE

SO 42-

K sp [Ra 2 ][SO 42- ] 4.3 x 10 11

0.10

(x)(0.10) 4.3 x 10 11 ; x 4.3 x 10 10 molar solubility

12. A solution contains 0.010 moles of Cl- and 0.0010 moles of CrO4-2 per litre. Ag+ is added.
Which will ppte first AgCl or Ag2CrO4. Ksp AgCl = 1.8 x 10-10, Ksp Ag2CrO4 = 1.2 x 10-12. ([Ag+]
with Cl- is smaller than CrO42-, therefore AgCl will form a precipitate first)
Ag2CrO 4 2 Ag CrO 4 2- ; K sp [Ag ]2 [CrO 4 2- ] 1.2 x 10 12
ICE
0.0010
(x) 2 (0.0010) 1.2 x 10 12 ; x 3.5 x 10 5
AgCl
ICE

Ag
x

Cl -

K sp [Ag ][Cl - ] 1.8 x 10 10

0.010

(x)(0.010) 1.8 x 10 10 ; x 1.8 x 10 8


as [Ag ] is smaller for AgCl, it will precipitate first.

EQUILIBRIUM REVIEW
1. Two colourless solutions are mixed in a stoppered flask. As the reaction proceeds, the resulting solution
turns red, and a colourless gas is formed. After a few minutes, no more gas is evolved but the red colour
remains. What evidence is there that equilibrium has been established?
There are no macroscopic changes.
2. What evidence is there to indicate that equilibrium is a dynamic state?
The reaction can be shifted in either direction.
3. Using the Ideal gas law and the formula relating Concentration and moles, derive the relationship that
explains why pressure can be considered as a concentration unit for gases.

P=

n
RT or P = CRT
V

4. Write the equilibrium expressions (Ke or K) for each of the following reactions:
H2 (g) + F2 (g)

(a)

2 HF (g) ;

K eq =

(b)

4 NO (g) + 3 O2 (g) 2 N2O5 (g) ;

(c)

BaCO3 (s) BaO (s) + CO2 (g) ;

[HF] 2
[H 2 ][F2 ]
[N 2O5 ]2
K eq =
[NO] 4 [O 2 ]3

K eq = [CO 2 ]

Fe2+ (aq) + Cu (s) ;

(d)

Fe (s) + Cu2+ (aq)

(e)

HSO4- (aq) H+ (aq) + SO42- (aq) ;

(f)

2 CrO42- (aq) + H+ (aq) Cr2O72- (aq) + OH- (aq) ;

(g)

Ag2CO3 (s) 2 Ag+ (aq) + CO32- (aq) ;

[Fe 2 ]
[Cu 2 ]
[H ][SO 4 2- ]
K eq =
[HSO 4- ]
K eq =

K eq =

[Cr2O7 2- ][OH ]
[CrO 4 2- ]2 [H ]

K eq = [Ag ]2[CO 32- ]3

5. The equilibrium constants for three different reactions are:


(a) Keq = 1.5 x 1012 ;
In which reaction is there:

(b) Keq = 0.15;

(c) Keq = 4.3 x 10-15

(a) a large ratio of product to reactant? (a)


(b) a small ratio of reactant to product? (a)

6. When 0.035 mole of PCl5 is heated to 250C in a 1-litre vessel, an equilibrium is established in which
the concentration of Cl2 is 0.025 mol/L. Find the Keq.
PCl 5
ICE 0.035 - x
K eq

PCl 3
x

Cl 2 ;

K eq

0.025

[PCl 3 ][Cl 2 ]
(0.025)(0. 025)

0.063
[PCl 5 ]
(0.035 - 0.025)

[PCl 3 ][Cl 2 ]
[PCl 5 ]

7. Assume that the analysis of another equilibrium mixture of the system in Problem 6 shows that the
equilibrium concentration of PCl5 is 0.012 mol/L and that of Cl2 is 0.049 mol/L. What will be the
equilibrium concentration of PCl3? The reaction is carried out at 250C. Use Keq from question 6.
PCl 5
ICE 0.012
K eq

PCl 3

Cl 2 ;

K eq

[PCl 3 ][Cl 2 ]
0.063
[PCl 5 ]

0.049

[PCl 3 ][Cl 2 ]
(x)(0.049)

0.063 ; x [PCl 3 ] 0.015 M


[PCl 5 ]
0.012

8. How many moles of PCl5 must be heated in a 1-litre flask at 250C in order to produce enough chlorine
to give an equilibrium concentration of 0.10 mol/L? Use Keq from question 6.

PCl 5
ICE y - 0.10
K eq

PCl 3

0.10

Cl 2 ;

K eq

[PCl 3 ][Cl 2 ]
0.063
[PCl 5 ]

0.10

[PCl 3 ][Cl 2 ]
(0.10) 2

0.063 ; 0.063y - 0.0063 0.010 ; y 0.26


[PCl 5 ]
y - 0.10

9. Will there be a net reaction when 2.5 moles of PCl5 0.60 mole of Cl2, and 0.60 mole of PCl3 are placed
in a 1-litre flask and heated to 250C? If so, will PCl5 decompose, or will Cl2 and PCl3 react to form
more PCl5? Use Keq from question 6.

PCl 5

PCl 3

Cl 2 ;

K eq

[PCl 3 ][Cl 2 ]
0.063
[PCl 5 ]

ICE 2.5 - x
0.60 x
0.60 x
0.60 2
Q
0.144 Q K eq and the rxn will shift to the left until Q K eq
2.5
10. Under a given set of conditions, an equilibrium mixture:
SO2 (g) + NO2 (g) SO3 (g) + NO (g)
in a 1 litre container was analyzed and found to contain 0.300 mole of SO3, 0.200 mole of NO, 0.050
mole of NO2, and 0.400 mole of SO2. Calculate the Keq.
K eq

[SO 3 ][NO]
(0.300)(0. 200)

3.0
[SO 2 ][NO 2 ] (0.400)(0. 050)

11. At 55C, for the reaction


2 NO2 (g) N2O4 (g) : Keq = 1.15
(a) Write the equilibrium expression.
[N O ]
K eq 2 4 1.15
[NO 2 ]2
(b) Calculate the concentration of N2O4 present in equilibrium with 0.5 mole of NO2.

K eq

[N 2O4 ]
x

1.15 ; x 0.29 M
[NO 2 ]2 0.5 2

12. Calculate the Keq for the following reaction from the data given below.
CO2 (g) + H2 (g) CO (g) + H2O (g)
[CO] = [H2O] = 1.33 x 10-3 mol/L, [CO2] = [H2] = 1.17 x 10-3 mol/L
[CO][H 2O] (1.33 x 10 -3 )(1.33 x 10 -3 )
K eq

1.29
[CO 2 ][H 2 ] (1.17 x 10 -3 )(1.17 x 10 -3 )
13. One mole of pure NH3 was injected into a 1-litre flask at a certain temperature. The equilibrium mixture
below was then analyzed and found to contain 0.300 mol of H2:
2 NH3 N2 + 3 H2
(a) Calculate the concentration of N2 at equilibrium.
2 NH 3

N2

ICE 1.00 - 2x

3 H2 ;

K eq

3x 0.300 ;

[N 2 ][H 2 ]3
[NH 3 ]2
x 0.100 M [N 2 ]

(b) Calculate the concentration of NH3 at equilibrium.


[NH 3 ] 1.00 - 2x 1.00 - 0.200 0.80 M

(c) Calculate the equilibrium constant for this system at this temperature and pressure.
[N ][H 2 ]3 (0.100)(0. 300) 3
K eq 2

4.2 x 10 -3
[NH 3 ]2
0.80 2
(d) Which way would the equilibrium be shifted if 0.600 mole of H2 were injected into the flask?
The equilibrium will shift to the left, .
(e) How would the injection of hydrogen into the flask affect the equilibrium constant?
There would be no change to the equilibrium constant.
(f) How would the equilibrium constant be affected if the pressure of this system were suddenly
increased?
There would be no change to the equilibrium constant.
14. When 0.50 mole of CO2 and 0.50 mole of H2 were forced into a 1-litre reaction container, the following
equilibrium was established:
CO2 (g) + H2 (g) H2O (g) + CO (g) and Keq = 2.00.
(a) Find the equilibrium concentration of each reactant and product.

CO 2
ICE 0.50 - x
K eq

H2
0.50 - x

H 2O
x
x2

CO ;

K eq

[H 2O][CO ]
2.00
[CO 2 ][H 2 ]

[H 2O][CO ]
x
x

2.00 ;
2.00 ;
1.4
[CO 2 ][H 2 ] (0.50 x ) 2
0.50 - x
0.50 - x

(0.50 x)(1.4) x ; 0.7 - 1.4 x x ; 2.4 x 0.7 ; x 0.29


[H 2O] [CO ] 0.29 M and [CO 2 ] [H 2 ] 0.50 - 0.29 0.21 M

(b) How would the equilibrium concentrations differ if 0.50 mole of H2O and 0.50 mole of CO had
been introduced into the reaction vessel instead of the CO2 and H2?

CO 2
ICE

H2

H 2O

K eq

[H 2O][CO ]

[CO 2 ][H 2 ]

0.50 - x
(0.50 x ) 2

CO ;

K eq

[H 2O][CO ]
2.00
[CO 2 ][H 2 ]

0.50 - x
2.00 ;

0.50 - x
0.50 - x
2.00 ;
1.4
x
x

x2
0.50 x 1.4 x ; 2.4 x 0.5 ; x 0.21
[H 2O] [CO ] 0.50 - 0.21 0.29 M and [CO 2 ] [H 2 ] 0.21 M

15. The following equation represents a gaseous system at equilibrium:


2 H2O (g) + heat 2 H2 (g) + O2 (g)
Indicate in which direction the equilibrium will shift when the following changes are made:
(a)
(b)

The concentration of H2 is increased. To the left, .


The partial pressure (concentration) of H2O is increased.

(c)

The concentration of O2 is decreased. To the right, .

(d)
(e)

The temperature is increased. To the right, .


The total pressure is increased. To the left, .

To the right, .

16. Consider the following reaction:


N2O4 (g) 2 NO2 (g) ; H = +ve ; Keq = 0.87 at 55 C
What will be the effect of each of the following changes on the concentration of N2O4 at equilibrium:
(a)

increasing the pressure.

The [N2O4] will until Keq is reached again.

(b)

increasing the temperature.

The [N2O4] will until Keq is reached again.

(c)

increasing the volume.

The [N2O4] will until Keq is reached again.

(d)
(e)

adding more NO2 (g) to the system without changing P or T. The [N2O4] will .
adding a catalyst?
no change

17. Answer the same questions (a,b,c,e) for the following reaction as you did for the reaction given in
Problem 16 for the concentration of water.
H2 (g) + 1/2 O2 (g) H2O (g) ; H = -ve ; Keq = 1.0 x 1040 at 25 C
(a) [H2O] will (b) [H2O] will (c) [H2O] will (e) no change
18. How can you increase the concentration of the product in each of the following reactions by varying the
temperature and pressure?
(a)

4 NH3 (g) + 5 O2 (g)

(i) T

(ii) P

4 NO (g) + 6 H2O (g) ;

Br2 (g) + Cl2 (g) 2 BrCl (g) ;


(i) T
(ii) P
no change

(b)

H = +ve

BaSO4 (s) Ba2+ (aq) + SO42- (aq) ;


(i) T
(ii) P
no change

(c)

H = +ve

H = -ve

19. Write the equation for the chemical equilibrium that exists between undissolved and dissolved solute in a
saturated solution for each of the following slightly soluble sulfides.
T12S
Ksp = 1 x 10-24
CuS
Ksp = 1 x 10-35
T12S 2 Tl+ + S2CuS Cu2+ + S2Ksp = 1 x 10-48
HgS
Ksp = 1 x 10-52
Cu2S 2 Cu+ + S2HgS Hg2+ + S2Rank each of these sulfides in order of decreasing molar solubility in their saturated solutions.
T12S > CuS > Cu2S > HgS
Cu2S

20. 500 mL of a saturated solution of silver carbonate, Ag2CO3, is evaporated to dryness leaving 0.0698 g of
Ag2CO3. What is the Ksp of silver carbonate?
m Ag2CO 3 0.0698 g ; n 0.0698 g x

1 mol Ag2CO 3
2.531 x 10 -4 mol
275 .75 g

2.531 x 10 -4 mol
5.063 x 10 -4 M
0.500 L
Ag2CO 3 2 Ag

CO 32- ; K sp [Ag ]2[CO 32- ]


ICE
2(5.063 x 10 -4 )
5.063 x 10 -4
K sp [Ag ]2[CO 32- ] (1.013 x 10 -4 ) 2 (5.063 x 10 -4 ) 5.190 x 10 -10
then C

21. What mass of barium fluoride, BaF2, will dissolve in 500. mL of a 0.100 M NaF solution? The Ksp of
barium fluoride is 1.7 x 10-6. Fluoride ion is the common ion.
NaF

Na

BaF2

Ba 2

ICE

F0.100
2 F-

K sp [Ba 2 ][ F- ]2 1.7 x 10 6

0.100

(x)(0.100) 2 1.7 x 10 6 ; x 1.7 x 10 4 molar solubility and m BaF2 1.5 x 10 2 g

22. (a) Will a precipitate of BaF2 form when 0.035 mol of Ba2+ and 0.015 mol of F- are combined in 1.000
L of solution?
BaF2

Ba 2

2 F-

Ksp [Ba 2 ][ F- ]2 1.7 x 10 6

Q (0.035)(0. 015) 2 7.9 x 10 6 ; Q Ksp a ppte will form

Here is the same question, but asked in an alternate way:


Will a precipitate of BaF2 form when the following solutions are mixed?
700. mL of 0.050 M BaC12
NaF

BaCl 2

300. mL of 0.050 M NaF

Na FC 0.050 M ; V 0.300L then n 0.015 mol


Ba 2 2 Cl -

C 0.050 M ; V 0.700L then n 0.035 mol


BaF2 Ba 2
2 F- ;
K sp [Ba 2 ][ F- ]2 1.7 x 10 6
0.035 mol
0.015 mol
1.0 L
1.0 L
Q (0.035)(0. 015) 2 7.9 x 10 6 ; Q K sp a ppte will form

Ksp(BaF2) = 1.7 x 10-6.

Extra SCH 4U Review Questions


1. What is the solubility of PbCl2 in 0.10 M NaCl? (Ksp PbCl2 is 1.2 x 10-5).

NaCl Na 1

Pb 2 (aq)

PbCl 2

Cl10.10 M
2 Cl -(aq) ; K sp [Pb 2 ][ Cl - ]2

ICE

1.2 x 10 5

0.10

K sp [Pb 2 ][ Cl - ]2 1.2 x 10 5 ; (x)(0.10) 2 1.2 x 10 5 ; 0.01x 1.2 x 10 5


x 1.2 x 10 3 [Pb 2 ] molar solubility
then, solubility of PbCl 2 molar solubility x M P bCl2
1.2 x 10 3 mol PbCl 2
278.10 g

x
0.33 g/L
L
mol PbCl 2
2. What is the Keq for

2B

+ 2B AB2

; K eq

AB2

if [AB2]i = 0.20 M and [A]eq = 0.050 M?

[AB2 ]
[A][B] 2

x
2x
0.20 - x
0.050
[AB2 ]
(0.20 - 0.050)
0.15
K eq

150
[A][B] 2 (0.050)(2( 0.050)) 2 0.001

ICE

3. If 1.00 g of NaCl(s) is added to 500. mL of a 0.010 M Pb(NO3)2 will a precipitate form?


1.2 x 10-5).

Na

NaCl

M 58.44 g/mol
Pb(NO 3 ) 2

Cl 1.00 g x

Pb 2

1mol NaCl
1
x
3.42 x 10 -2 mol/L
58 .44 g
0.500 L

2NO 3

0.010
PbCl 2

Pb 2 (aq)

(Ksp PbCl2 =

2 Cl -(aq) ; K sp [Pb 2 ][ Cl - ]2

Q (0.010 )( 3.42 x 10 -2 ) 2 1.2 x 10 -5


Q Ksp no ppte will form

4. What is the [AB]eq in

AB

ICE 0.10 - x
0.10 - x
x
[AB]
(x)
K eq

101
[A][B] (0.10 - x) 2

AB

if [A]i = [B]i = 0.10 M (Keq = 101).

[AB]
101
[A][B]
100 Rule - doesn't apply

; K eq

x 1.01 - 20.2 x 101x 2


101x 2 - 21.2x 1.01 0
21.2 449.44 - 408.04 21.2 6.43

202
202
x 0.14 or x 0.073
x

[A]eq [B]eq 0.10 - 0.073 0.027 and [AB]eq 0.073


0.073
Check : Q
100 Q Keq
(0.027) 2
5. What is the solubility in g/100 mL of Ag2CO3 if the Ksp for Ag2CO3 is 8.5 x 10-12?

Ag2CO 3
ICE

2 Ag (aq)
2x

CO 3

-2
(aq)

; K sp [Ag ]2 [CO 3 ]
-2

8.5 x 10 12

K sp [Ag ]2 [CO 3 ] 8.5 x 10 12 ; (2x) 2 (x) 8.5 x 10 12 ; 4x 3 8.5 x 10 12


-2

x 1.29 x 10 4 [CO 3 ] molar solubility


-2

then, solubility of Ag2CO 3 molar solubility x M Ag2CO3

1.29 x 10 4 mol Ag2CO 3


275.75 g
0.1 L
x
x
0.0036 g/100 mL
L
mol Ag2CO 3 100 mL