Depictin g Equil ibr ium

Chem 229 Lecture Notes

Chapter 13
Chemical Equilibrium

Sug g ested Ho m ewo r k fo r Ch apter 13

In a chemical system at equilibrium, both the forward and reverse

reactions are running simultaneously. We write the chemical equation with a
double arrow () , this depicts a system at equilibrium.

Chemical reactions that proceed in both the forward and reverse direction
are said to be reversible. A B

Dynamic equilibrium is the condition where the rates of the forward and
reverse reactions are equal.

Equilibrium is macroscopically static & microscopically dynamic.

21,23,25,27,29,31,33,35,37,39,41,43,45,47,49,51,53,61,
63,65,67,69,81,87,91,93,95
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When a reaction begins (starting with A only), A

is consumed and B is formed. A B
The [A] decreases and the [B] increases.
As [A] decreases, the forward reaction rate
(ratef) decreases too.
As [B] increases, the reverse reaction rate
(rater) increases.
Eventually, when the [B] is high enough, B can
react to form A. B A

Over time, the (ratef) decreases and the (rater)

increases until the (ratef) = (rater). We call this
equilibrium. We write A B.
Look at the data for A B. How many seconds
did it take for this system to reach equilibrium
Notice that equilibrium does not mean that the
concentrations are equal.

Time (s)

[A]

[B]

0.400

0.000

10

0.208

0.096

20

0.190

0.105

30

0.180

0.110

40

0.174

0.113

50

0.170

0.115

60

0.168

0.116

70

0.167

0.117

80

0.166

0.117

Hypo thetical Reactio n :

2A B
Concentration vs. Time for

2A B

Concentration, M

Hypo thetical Reactio n 2 A B

Time, s

90

0.165

0.118

Show on the graph the time required for this system to reach equilibrium.

100

0.165

0.118

110

0.164

0.118

Once equilibrium is established, the rate of A molecules turning into B molecules

is the same as the rate of B molecules turning into A molecules.

120

0.164

0.118

130

0.164

0.118

140

0.164

0.118

150

0.164

0.118

Once equilibrium is achieved, the amount of each reactant and product remains
constant. On the molecular level, reactants are still becoming products, and
products are still becoming reactants, but they are doing so at the same rate.
Equilibrium on the molecular level is not static, it is a highly dynamic (always
changing) situation. Equilibrium, on the macroscopic level, appears to be static,
because the amounts of reactants and products isnt changing.
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A S ys tem at Equi l i br i um
R ates Become Equal

In 1864, Guldberg & Waage, observed that at a given temperature, a chemical

system reaches a state where a certain ratio of product and reactant
concentrations has a constant value.

Consider: N2O4 (g) 2NO2 (g)

This statement is called the Law of Chemical Equilibrium or the Law of

Mass Action.

Concentr ations Become

Constant

In i ti al an d Equi l i br i um Co n cen tr ati o n s fo r

H2( g ) + I2( g )
2 HI(g) @ 4 4 5 C

T h e E qui l i b r i um C o n s t an t , K eq

Keq can be called: K, Kc, Kp, Ksp, Kw, Ka, Kb etc.

In all cases, Keq is a ratio of (concentrations or partial pressures) of gas and

aqueous phase reactants and products (A,B,C,D), raised to their balancing
coefficients (a,b,c,d) at equilibrium.

Equilibrium can be reached from either direction.

The equilibrium constant depends only on the stoichiometry of the reaction, not
the reaction mechanism (kinetics).

aA + bB cC + dD

The concentrations of solids and liquids are essentially constant, relative to

themselves, during the reaction.

The concentrations of pure solids and liquids are not included in the equilibrium
expression because the concentrations of pure solids and liquids are constant
during a reaction. Even though pure solids and liquids do not appear in the
equilibrium expression, they must be present for equilibrium to be established.

Initial
(Four Trials, Varying Initial
Concentrations)

Equilibrium
(Equilibrium Position)

[H2]

[I2]

[HI]

[H2]

[I2]

[HI]

0.50

0.50

0.0

0.11

0.11

0.78

0.0

0.0

0.50

0.055

0.055

0.39

0.50

0.50

0.50

0.165

0.165

1.17

1.0

0.5

0.0

0.53

0.033

0.934

Equilibrium
Constant
(A Constant)

T he Equil ibr ium Co n s tan t: K p

T he Equil ibr ium Co n s tan t: K c

Consider: A reaction with gas phase reactants and products.

For gases, we can use their concentrations or their pressures when calculating K.

Because pressure is proportional to concentration for gases in a closed system,

the equilibrium expression can be written in terms of the partial pressure.

We call K, Kp, when the gas pressures (in atm) are used rather than the molarity.

Kc is often just called K

PA = partial pressure of gas A

A (aq) + 4B (aq) 2C (aq) + 3D (aq)

A (g) + 4B (g) 2C (g) + 3D (g)

2A (aq) + 5B (s) 3C (s) + 3D (aq)

2A (g) + 5B (s) 3C (l) + 3D (g)

Consider: A reaction taking place in aqueous solutions (aq)

Concentrations are given in molarity (M)

Molarity = moles of solute/liters of solution

M = mol/L

[A] = molarity of A

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Magn i tude o f the Equi l i br i um Co n s tan ts

Rel atio n ship Between Kc an d Kp

Large K: (K value with double digit powers of ten)

Derived from PV = nRT

Signifies that the reaction goes to completion.

Kp = Kc (RT)n

Almost all products, no reactants

2CO(g) + O2(g) 2CO2(g)

n = (mol of gaseous product) (mol of gaseous reactant)

R = 0.08206 Latm/Kmol

T = Kelvin temperature

Kc is 4.72 at 100C for 2NO2 (g) N2O4 (g). Calculate Kp.

K = 2.2 X 1022

@ 1000 K

Small K: (K value with double digit negative powers of ten) signifies the forward
reaction only occurs to a slight extent.

Almost all reactants, no products

N2(g) + O2(g) 2NO(g)

K = 1 X 10-30

@ 1000 K

Intermediate K:

11

Significant amounts of both reactants and products are present at equilibrium.

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

K=5

@ 1000 K
12

The equilibrium constant for a reaction written in reverse is the reciprocal of

the equilibrium constant for the original reaction.

2NO2 (g) N2O4 (g)

Kc = 4.72

N2O4 (g) 2NO2 (g)

Kc =

Solving Problems with K

1.

2. Write the K expression.

3. Determine what you are given and what you need to find.

Multiplying a balanced equation through by a factor n will result in a new

equilibrium constant that is raised to the nth power.

2NO2 (g) N2O4 (g)

Kc = 4.72

4NO2 (g) 2N2O4 (g)

Kc =

4. Solve.
5. Remember that:
K is unitless.
Solution concentrations are in molarity.

The equilibrium constant for a net reaction made up of two or more steps is the
product of the equilibrium constants for the individual steps.

A + B C + D
C + D E + F

K1

A + B E + F

K3

Gas pressures are in atmospheres.

Pure liquids and solids are not part of the K expression.

K2

K is the equilibrium constant (a constant), the only thing that can change K
(for a given reaction) is a change in
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Cal cul ati o n s wi th Equi l i br i um Co n s tan ts

1.

Write a balanced reaction.

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2.

Calculate the value of Kc for the decomposition of gaseous NH3 into hydrogen
and nitrogen gas at a certain temperature. Given: [NH3] = 3.1 X 10-2 M, [N2] =
8.5 X 10-2 M, [H2] = 3.1 X 10-3 M.

2.

Consider the gas phase reaction at 298 K, A + B

reaction, calculate [C] if [A]eq = [B]eq = 0.25 M.

The reaction 2 SO2(g) + O2(g) 2 SO3(g) is run at 25C. At equilibrium, a

2.0 L flask was found to have 0.35 moles of SO2, 0.70 moles of O2, and 1.40
moles of SO3. Calculate Kc. What is Kp for this reaction?

15

2C. If K = 9.24 for this

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Cal cul ati o n s U s i n g an ICE o r ICEE Char t

1.

2.

A mixture is initially 0.83 M in H2(g) and 1.3 M in I2(g) is heated to a constant

temperature and equilibrium is established. The equilibrium concentration of I2
is found to be 0.77 M. What is the equilibrium concentration of H2 and HI?
What is the equilibrium constant (K) for this reaction?
H 2( g ) + I 2( g ) 2 H I ( g )

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3.

2.0 atm of N2O4(g) is placed in a vessel with 2.0 atm of NO2(g) and a chemical
reaction was observed. After the system reaches equilibrium at a constant
temperature, 1.0 atm of N2O4(g) was detected in the reaction flask. What is
the equilibrium pressure of NO2(g) and what is the equilibrium constant for
the reaction N2O4(g) 2 NO2(g), at this temperature?

Carbon disulfide and chlorine react according to the reaction shown below.
When 1.0 mol of CS2(g) is placed in a 1.0 L vessel with 4.0 mol of Cl2(g) a
chemical reaction is observed. After the system reaches equilibrium, 0.50 mol
of CCl4(g) is detected in the reaction flask. What is the equilibrium
concentration of each species and what is the equilibrium constant for this
reaction at this temperature?
C S 2( g ) + 3 C l 2( g ) S 2C l 2( g ) + C C l 4( g )

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4.

A mixture of 9.2 moles of A, 10.1 moles of B, and 27.8 moles of C is placed in a

1.00 L container at 298 K. The reaction is allowed to reach equilibrium. At
equilibrium, 18.3 moles of B are found. Calculate the equilibrium constant for
the following reaction.
A (g) + 2 B (g) 3 C (g)

N 2O 4( g ) 2 N O 2( g )

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20

Pr edictin g the Dir ectio n o f the Reactio n : The

Reacti o n Quo ti en t, Q

As we already learned, we plug equilibrium concentrations (or pressures) into the

K expression to find the equilibrium constant, K.

Often, we are given initial (non-equilibrium) concentrations and the system may
have to shift to get to equilibrium.

We can plug the initial (non-equilibrium) values into an expression that looks just
like K, but we call it Q since the system is not at equilibrium.

Q is used to determine the direction (forward or reverse) that the reaction

must shift to get to equilibrium.

If or more of either the reactants or products has a concentration of zero, the

shift direction can be found without actually calculating Q.
A zero for one or more product(s) Rxn will shift to the RIGHT.
A zero for one or more reactant(s) Rxn will shift to the LEFT.

aA (aq)

bB (aq)

cC (aq)

dD (aq)

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1.

Gaseous carbon monoxide reacts with water vapor to produce carbon dioxide
gas and hydrogen gas. At 700 K, K = 5.1 for this reaction. Calculate the
equilibrium concentrations of all species if 1.0 mol of each component is mixed
in a 1.0 L flask.
CO (g) + H2O (g) CO2 (g) + H2 (g)

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Calculation of Q and comparing it to K will determine the direction of the shift

toward equilibrium.
If Q = K

The reaction is

____________________.

If Q < K

Too many reactants, not enough products. Shift

If Q > K

Too many products, not enough reactants. Shift

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2.

At 400K the K = 7.0 for the reaction given below. If the initial concentration
of [Br2] = [Cl2] = 1.0 M and [BrCl] = 4.0 M, determine the equilibrium
concentrations of all species.
B r 2( g ) + C l 2( g ) 2 B r C l ( g )

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1. A ddi ng o r r em o vi ng a r eactant o r pr o duct.

N 2(g ) + 3 H2(g ) 2 N H3(g )

Le Chtel ier s Pr in cipl e

Henri Le Chtelier, 1888: When a change in (concentration, temperature,

pressure or volume) is imposed on a system that is at equilibrium, the system
responds by attaining a new equilibrium position that minimizes the impact of
the imposed change.

a. Ammonia, NH3(g) is added.

Before addition

Immediately after addition

When a change is imposed on a system at equilibrium, the system will shift in the
direction that reduces the amount of the change. SHIFT to reactants (left or
backward) OR products (right or forward).

System shifts______________to restore equilibrium.

b. Nitrogen and/or hydrogen is added.
Before addition
Immediately after addition

Le Chteliers Principle can be used to qualitatively predict how a system can try
to restore equilibrium.

System shifts______________to restore equilibrium.

c. Ammonia, NH3(g) is removed.
Before removal

We will examine the following equilibrium stresses.

1.

Adding or removing a reactant or product.

2.

Changing volume on a gas phase reaction.

3.

Adding an inert gas.

4.

Changing the temperature.

Immediately after removal

System shifts______________to restore equilibrium.
d. Nitrogen and/or hydrogen is removed.
Before removal
Immediately after removal
System shifts______________to restore equilibrium.

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2. Ch ang i ng Vo lum e, Wh i ch Ch ang es th e P ar ti al

P r e s s ur e s N 2(g ) + 3 H2(g ) 2 N H3(g )

26

Consider each of the following equilibrium systems. Will decreasing

the vessel volume disrupt the equilibrium? If so, how can the system
minimize the stress?

The pressure that a gas exerts is due to the molecules/atoms colliding with the
walls the container.
more particles = more collisions =

1.

2SO2(g) + O2(g)

2.

PCl5(s)

3.

CO(g) + 2H2(g)

4.

N2O4(g)

5.

H2(g) + F2(g)

6.

H2O(l)

2 SO3(g)

PCl3(g) + Cl2(g)

a. The volume of the system is decreased.

CH3OH(g)

b. The volume of the system is increased.

Reactions Not Affected by Volume Changes

CO(g) + H2O(g) CO2(g) + H2(g)

H2(g) + Cl2(g) 2HCl(g)

These reactions have same number of gas molecules (moles of gas) in reactants
and products. Reducing or increasing the volume will cause equal stress on both
sides no net reaction will occur. Equilibrium is not affected by change in
pressure, therefore no shift is needed to restore equilibrium.

27

2 NO2(g)

2 HF(g)

H2O(g)
28

4. Ch ang i ng th e Tem per atur e

3. Ch ang i ng th e P r essur e (co nstant v o lum e) by addi ng

an i ner t g as do es no t di sr up t equi li br i um .
N 2(g ) + 3 H2(g ) 2 N H3(g )

Total pressure increases

Mole fraction decreases, proportionately

Concentration/Partial pressure of each component gas doesnt change

Pa = (moles a/total moles)PT

Q doesnt change

Q = K, the system is still at equilibrium.

No shifting necessary

Consider the addition of argon gas.

N 2(g ) + 3 H2(g ) 2 N H3(g )

H = -92.11 kJ/mol

Changing the temperature, changes the numerical value of K.

K is the ratio of products to reactants at equilibrium.

Therefore, changing the temperature changes the ratio of products to

reactants at equilibrium. Therefore, a shift is required to increase or decrease
the reactants or products.

Exothermic (H-). Products are favored at lower temperature.

Endothermic (H+). Products are favored at higher temperature.

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N 2( g ) + 3 H2( g ) 2 N H3( g )

30

Heat + C aC O3( s ) C aO( s )

+ heat

C O2( g )

T (C)

Kp

300

4.34 X 10-3

400

1.64 X 10-4

to _______________ therefore a shift to make _________ products &

450

4.51 X 10-5

_________ reactants occurs. SHIFT

500

1.45 X 10-5

550

5.38 X 10-6

600

10-6

2.25 X

Increasing the reaction temperature (on an endothermic reaction) will cause K

Decreasing the reaction temperature (on an endothermic reaction) will cause K

to _______________ therefore a shift to make _________ products &
_________ reactants occurs. SHIFT

Increasing the reaction temperature (on an exothermic reaction) will cause K to

_______________ therefore a shift to make _________ products & _________
reactants occurs. SHIFT

INCREASING TEMPERATURE ALWAYS FAVORS THE ENDOTHERMIC

DIRECTION (heat absorbing direction)

Decreasing the reaction temperature (on an exothermic reaction) will cause K to

_______________ therefore a shift to make _________ products & _________
reactants occurs. SHIFT

31

DECREASING TEMPERATURE ALWAYS FAVORS THE EXOTHERMIC

DIRECTION (heat releasing direction)
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Summary

Heat + CaCO3 (s) CO2 (g) +

1. Adding or removing a reactant or product: Q changes, K doesnt change,

reaction shifts to get Q = K.

CaO (s)

2. Changing the volume: This changes the concentration (partial pressure) of all
gaseous species. If the partial pressures change, Q will change. K doesnt
change, reaction shifts to get Q = K. Reactions with equal # of moles (of
gaseous reactants & products), are not affected by volume changes.
3. Changing the total pressure by adding an inert gas: This has no effect on the
partial pressures of the species involved. Neither Q nor K change. No shift is
required.
4. Changing the temperature: K changes K can increase or decrease, this
depends on whether the temperature goes up or down and whether the reaction
is exo- or endo- thermic. System shifts to get to the new K.
5. Catalysts: The use of a catalyst speeds up a reaction rate by providing a
different reaction mechanism with a lower activation energy. Since the
activation energy is lowered, the catalyst speeds up the reaction in both the
forward and reverse direction. The catalyst allows the system to reach
equilibrium sooner. But, the catalyst has no effect on the equilibrium position of
the system. K (equilibrium constant) is governed by the thermodynamics of the
reactants and products.
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The Haber Pr o cess: The S yn thesis o f A mmo n ia

fr o m Hydr o gen an d N itr o gen .

What can be done to maximize the

yield of the product?

N 2(g ) + 3 H2(g ) 2 N H3(g ) + h e a t

35

!
Consider this system at equilibrium where all three components are present.
(Necessary condition for equilibrium). If the equilibrium is disrupted by the stress,
indicate the direction of the shift to get back to equilibrium. And, mention
whether the PCO2 increases, decreases, or remains the same?
1.

The temperature is increased.

2.

The volume is decreased.

3.

More calcium carbonate is added.

4.

Neon gas is added.

5.

Carbon dioxide is removed.

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