Topic 7/17 Equilibrium

7.1 Dynamic Equilibrium KEY

1. Define the term equilibrium.

Forward and reverse reactions occurring at the same time

2. How does the term “dynamic” apply to equilibrium?

Reaction does not stop but change is occurring at same rate, therefore cannot tell the difference
in concentration or macroscopic properties

3. What is true about rates of reaction at equilibrium? About concentrations at equilibrium?

Rates are equal Concentrations are not necessarily equal. Kc>1 more product, Kc<1 more
reactants, Kc=1 equal concentrations

4. Which statement concerning a chemical reaction at equilibrium is not correct?

a. The concentrations of reactants and products remain constant
b. Equilibrium can be approached from both directions
c. The rate of the forward reaction equals the rate of the reverse reaction
d. All reaction stops - DYNAMIC

5. Which statements are correct for a reaction at equilibrium?

i. The forward and reverse reactions both continue
ii. The rates of the forward and reverse reactions are equal
iii. The concentrations of reactants and products are equal – not necessarily
a. I and II only
b. I and III only
c. II and III only
d. I, II and III only

6. Which statement is always true for a chemical reaction that has reached equilibrium?
a. The yield of product(s) is greater than 50% - cannot determine
b. The rate of the forward reaction is greater than the rate of the reverse reaction - nope
c. The amounts of reactants and products do not change
d. Both forward and reverse reactions have stopped - nope
7. Which statement(s) is/are true for a mixture of ice and water at equilibrium?
i. The rates of melting and freezing are equal
ii. The amounts of ice and water are equal – not necessarily
iii. The same position of equilibrium can be reached by cooling water and by heating ice
a. I only
b. I and III only
c. II only
d. III only

8. Using the general reaction below, where j-m represent coefficients and A-D represent chemical
formulas, create an equilibrium expression.

j A(g) + k B(g)  l C(g) + m D(g)

l m
[C] [D ]
K c= j k
[ A] [B]

9. How are equilibrium expressions different than rate laws?

Exponents are the coefficients whereas in rate laws the exponents have to be determined
empirically

10. Write an equilibrium expression for the reaction: 2 H2 (g) + O2 (g)  2 H2O(g)
[ H 2 O ]2
K c= 2
[ H 2 ] [O 2]

11. If the equilibrium concentrations of the reactants and products in #10 are 0.10 M, 0.30 M, and 0.25 M
respectively at 25 C, calculate the value of the equilibrium constant.

[ 0 . 25 ] 2
K c= 2 = 20.8 – favor products
[ 0 .10 ] [ 0 .30 ]

12. Write the equilibrium expressions for the following chemical reactions:
a. Fluorine gas and chlorine gas combine to for ClF3
3 F2(g) + Cl2(g) ↔ 2 ClF3(g)
2
[ ClF 3 ]
K c= 3
[ F 2 ] [ Cl 2 ]

b. NO dissociates into its elements

2 NO ↔ N2 + O2
K c =( [ N 2 ][ O 2 ] )/¿
 c. Methane, CH4, and steam react to form carbon monoxide and hydrogen

2 CH4 + O2 ↔ 2 CO + 4 H2
[ CO ]2 [ H 2 ] 4
K c= 2
[ CH 4 ] [ O 2 ]

13. When the following reactions reach equilibrium, does the equilibrium mixture contain mostly
reactants or mostly products at the specified temperature? Assume that the value of Kc given
corresponds to the temperature of the reaction mixture.
a. N2(g) + 2 H2(g) ↔ N2H4(g) Kc = 7.4x10-26 Reactants
b. N2(g) + O2(g) ↔ 2NO(g) Kc = 2.7x10 -18
Reactants
c. 2 NO(g) + O2 ↔ 2 NO2(g) Kc = 6.0x10 13
Products

14. The equilibrium constant for the reaction: H2O(g) + Cl2O(g) ↔ 2HOCl(g) is 0.0900 at
298K. Determine whether the following sets of conditions represent an equilibrium mixture for the
reaction at this temperature. For those not at equilibrium, determine in which direction the reaction
will proceed.
2
[ HOCl ]
Q=
[ H 2O ] [ Cl 2 O ]
a. 0.100, 0.100, 1.00 (following order of reaction) 1, above Kc  move back to reactants
b. 0.49, 0.040, 0.042 0.09, same  at equilibrium
c. 0.19. 0.00033, 0.083 109.87, above Kc  move back to reactants

15. At a given temperature, the reaction 2 SO2(g) + O2(g) ↔ 2 SO3(g) has a value of Kc = 278.
Determine values of Kc for the following reactions at this temperature.
a. 4 SO2(g) + 2 O2(g) ↔ 4 SO3(g)
Doubling reaction  Kc2  77,284
b. 2 SO3(g) ↔ 2 SO2(g) + O2(g)
Reverse reaction  Kc’ = 1/Kc  0.0036
c. SO3(g) ↔ SO2(g) + ½ O2(g)
Reverse reaction and halving reaction  revered above  √0.0036 = 0.06

16. Equilibriums can shift in different directions if a “stress” is applied to the system. What are three of
these stresses, and how do they affect equilibrium?

Change in concentration, change in pressure, change in tempeature

17. For the reaction, 2 H2 (g) + O2 (g)  2 H2O(g) + 250 kJ, how will the equilibrium be affected if:

a. the temperature of the reaction is increased?

Increase temperature, decrease products because endo reaction wants to take in heat
 b. additional hydrogen gas is added?
Increase reactant concentration, increase products, added reactants – reaction removes it
c. the pressure is decreased?
Decrease pressure, increase reactants because there are more gas molecules

18. Why is there no change in equilibrium when the pressure of the reaction below is increased? Assume
all reactants and products are in the gaseous state.

NO (g) + CO2 (g)  NO2 (g) + CO (g)

Same number of molecules on both sides of the reaction

19. What will happen to the position of equilibrium and the value of the equilibrium constant when the
temperature is increased in the following reaction?
Br2(g) + Cl2(g) ↔ 2 BrCl(g) ∆H = +14kJ

Position of Equilibrium Value of Equilibrium Constant

Shifts towards the reactants Decreases
Shifts towards the reactants Increases
Shifts towards the products Decreases
Shifts towards the products increases

20. The reaction: 2CO(g) + O2(g) ↔ 2CO2(g) ∆H = -566 kJmol-1 takes place in catalytic
converters in cars. If this reaction is at equilibrium, will the amount of CO increase, decrease, or stay
the same when:
a. The pressure is increased by decreasing the volume? Decrease CO concentration
b. The pressure is increased by adding O2(g)? Decrease CO concentration
c. The temperature in increased? Increase CO concentration
d. A platinum catalyst is added? No change

21. Predict how you would expect the value for Kc for the Haber process to change as the temperature is
increased. Explain the significance of this in terms of the reaction yield.

Exothermic for the forward reaction (-93 kJmol-1)

Increasing temperature favors the endothermic reaction (reverse reaction), which causes the
value of Kc to decrease

22. In carbonated drinks containing dissolved carbon dioxide under high pressure, the following
dynamic equilibrium exists.

CO2(aq) CO2(g)

Describe the effect of opening a carbonated drink container and outline how this equilibrium is
affected.
CO2(g) escapes with decreased pressure (bubbles form), which causes the equilibrium to shift
right to replace the lost CO2(g)
17.1 The equilibrium Law
23. The dissociation of hydrogen iodide into its elements takes place in a 1.0 dm3 container at 440°C.
When 1.0 mole of hydrogen iodide is used, it is found to have decreased to 0.78 moles at equilibrium.
a. Calculate the equilibrium constant for this reaction at this temperature

R 2HI ↔ H2 + I2
I 1.0 0.0 0.0
C -2(0.11) +0.11 +0.11
E 0.78 0.11 0.11

[ H 2 ][ I 2 ] ( 0.11 ) ( 0.11 )
K c= 2
= 2
=0.0198=1.99 x 10−2
[ HI ] 0.78
b. Deduce whether the dissociation reaction is endothermic or exothermic, given that at 600°C
the value of Kc is 0.04

endothermic = Kc increases, therefore favor products. Increase temperature, need to

favor products  need heat to make more (endothermic)

24. The reaction N2(g) + O2(g) ↔ 2 NO(g) is carried out in a closed container
with initial concentrations of both reactants of 1.6 mol dm . Kc for the reaction is 1.7x10-3. Calculate
-3

the concentration of NO(g) at equilibrium.

R N2 + O2 ↔ 2NO
I 1.6 1.6 0.00
C -x -x + 2x
E 1.6 – x -x + 2x
1.6

[ NO ]
2
( 2 x )2
K c= 1.7 x 10−3= 2 0.004352=4 x
2 2
0.001088=x 0.033 = x
[ N 2 ][ O2 ] ( 1.6 )

NO = 2(0.033) = 0.066 mols dm-3

25. The production of ammonia is an important industrial process.

N2(g) + 3H2(g) 2NH3(g)

a. The reaction used in the production of ammonia is an equilibrium reaction. Outline the characteristics of
a system at equilibrium.
1) Macroscopic properties remain constant
2) Concentration remain constant
3) Forward and reverse reaction rates same
b. Deduce the equilibrium constant expression, Kc, for the production of ammonia.

[ NH 3 ] 2
K c= 3
[ N 2 ][ H 2 ]
3
c. 0.20 mol of N2(g) and 0.20 mol of H2(g) were allowed to reach equilibrium in a 1 dm closed container.
–3
At equilibrium the concentration of NH3(g) was 0.060 mol dm . Determine the equilibrium
concentrations of N2(g) and H2(g) and calculate the value of Kc.

R N2 + 3H2 ↔ 2NH3
I 0.20 0.20 0.00
C -0.03 -3(0.03) +2(0.03)
E 0.17 0.11 0.60

[ 0.060 ] 2
K c= 3
=15.9( products favored )
[ 0.17 ] [ 0.11 ]
d. Predict and explain how increasing the temperature will affect the value of Kc.

ΔH = -93 kJmol-1

Increase temperate in exothermic reaction, reaction shifts to favor the endothermic process
which is the reactants side, causing Kc to decrease

26. The reaction CO(g) + H2O(g) ↔ H2(g) + CO2(g) was studied at 550°C.
a. When 4.0 moles of Co and 6.4 moles of H2O were introduced into a 1dm3 vessel, the
equilibrium mixture was found to contain 3.2 moles of both H2 and CO2. Calculate the
concentrations of CO and H2O at equilibrium and the value of Kc.

R CO(g) + H2O(g) ↔ H2(g) + CO2(g)

I 4.0 6.4 0.0 0.0
C -3.2 -3.2 +3.2 +3.2
E 0.8 moles 3.2 moles 3.2 3.2

[ CO 2 ][ H 2 ] ( 3.2 ) ( 3.2 )
K c= = =4.0 ( products favored )
[ CO ][ H 2 O ] ( 0.8 ) ( 3.2 )

b. At the same temperature and pressure, a different experiment was found to have 4.0 moles of
both Co and H2O, and 3.0 moles of both H2 and CO2 present in the mixture after a period of
reaction. Show mathematically that this mixture had not reached equilibrium, and in which
direction it will react.

[ CO 2 ] [ H 2 ] ( 3.0 )( 3.0 )
Q= = =0.56
[ CO ][ H 2 O ] ( 4.0 )( 4.0 )
 Does not equal above Kc at equilibrium, need to increase Kc, therefore reaction will
move to products side

27. Which of the following correctly describes the entropy and free energy of a system at equilibrium?
Entropy S Free Energy G
a. Maximum value maximum value
b. Minimum value maximum value
c. Maximum value minimum value
d. Minimum value minimum value

28. What is the sign for ΔGθ for a reaction when:

a. Kc = 1 zero
b. Kc > 1 negative
c. Kc < 1 positive

29. The following reaction 2 Al(s) + Fe2O3(s) ↔ 2 Fe(s) + Al2O3(s) has a free energy change of
ΔG = -8.40 kJmol . Calculate the value of the equilibrium constant of this reaction at 298K.
Θ -1

∆ Gθ =−RTln K c
−8400=−( 8.314 )( 298 ) ln K c
3.39=ln K c
3.39
e =K c =29.7

30. The ionization of water has an equilibrium constant 1.00x10-14 at 298K.

H2O(l) ↔ H+(aq) + OH-(aq)
a. Calculate ΔGθ for this reaction at this temperature.

θ
∆ G =−RTln K c
∆ Gθ =−( 8.314 ) ( 298 ) ln ( 1.00 x 10−14 ) =79,867=79.9 kJ mol−1

At 313K the equilibrium constant has a value of 2.92x10-14. What can you conclude about the enthalpy
change ΔH of the reaction?

θ
∆ G =−RTln K c
∆ G =−( 8.314 ) ( 298 ) ln ( 2.92 x 10 ) =77,212=77.2 kJ mol
θ −14 −1

ΔG is decreasing ,there for ΔH isbecoming more negative