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You are on page 1of 69

Chemical Equilibrium:

Gases & Heterogeneous

Dr. Kamyar Shameli,

Textbook Reference:

MJIIT-UTM •Chapter # 17

KL •Module # 5 (& Appendix

Equilibrium

2)

The Concept of Equilibrium

{Non-Equilibrium Reactions}: proceed in one direction, A B

2 NO (g) + O2 (g) 2 NO2 (g)

(clear gases) (red-brown gas)

{Equilibrium Reactions}: proceed in both directions, A ↔B

N2O4 (g) 2 NO2 (g)

(clear gas) (red-brown

2X

gas)

Chemical equilibrium occurs when a

reaction and its reverse reaction proceed

at the same rate.

Equilibrium

This does not mean chemicals are found

in same concentration!

The Equilibrium Constant (Keq)

N2O4 (g) 2 NO2 (g)

• Therefore, at equilibrium

Ratef = Rater

kf [N2O4] = kr [NO2]2

• Rewriting this, it becomes

kf [NO2]2

Keq = =

kr [N2O4]

The Equilibrium Constant is the ratio of theEquilibrium

The Equilibrium Constant (K)

• To generalize this expression, consider

the reaction

aA(aq) + bB(aq) cC(aq) + dD(aq)

• The equilibrium expression for this

reaction would be

[C]c[D]d

Kc =

[A]a[B]b

Equilibrium

where [X] = concentration of each chemical

in moles/ liter (M).

What Does the Value of K Mean?

10 x

aA + bB cC + dD

[C]c[D]d 10 = 10

Kc = [A]a[B]b Kc =

1

• If K >> 1, the reaction is product-favored; product

predominates at equilibrium.

aA + bB 10 x cC + dD

[C]c[D]d Kc = 1 = 0.1

Kc = [A]a[B]b 10

Equilibrium

predominates at equilibrium.

The Equilibrium Constant for Gases

[C]c[D]d

Kc =

[A]a[B]b

aA(g) + bB(g) cC(g) + dD(g)

Partial press: (75 torrs) (150 torrs) (300 torrs) (600 torrs) = total (1125 torrs)

concentration for gases in a closed

system, the equilibrium expression can

also be written

(PC)c (PD)d

Kp =

(PA)a (PB)b

where Kp = equilibrium constant for gases, and Equilibrium

Relationship between Kc and Kp

• ideal gas law:

[C]c[D]d PV = nRT

Kc = n

[A]a[B]b P= RT

V

n n

(PC)c (PD)d ( V RT )c

( V RT )d

Kp = =

( n ) a ( n ) b

(PA)a (PB)b V RT V RT

Plugging this into the expression for Kp

Where

Kp = Kc (RT)n ☺ Equilibrium

Equilibrium Can Be Reached from

Either Direction

@ 100°C

KC

[NO2]2

=

[N2O4]

2

2

[0.0172] [0.0243] [0.0310]2 [0.0310]2

Kc 0.212

[0.0014] [0.0028] [0.0045] [0.0045]

The ratio of [NO2]2 to [N2O4] remains constant at this temperature noEquilibrium

matter

what the initial concentrations of NO2 and N2O4 are.

Equilibrium Can Be Reached from

Either Direction

N2O4 (g) 2 NO2 (g)

2

[ NO 2 ] [0.0172 ] [0.0243] [0.0310 ]2 Equilibrium

2 2

Kc 0.212

[ N 2O4 ] [0.0014 ] [0.0028] [0.0045]

Manipulating Equilibrium Constants

RULE #1: Reciprocal Rule

the reciprocal of the equilibrium constant of the

forward reaction.

I [NO2]2

N2O4 (g) 2 NO2(g) K =

[N2O4]

= 0.212 at 100C

1

2 NO2 (g) N2O4(g) II

K =

[N2O4]

[NO2]2 =

0.212

Equilibrium

= 4.72 at 100C

Manipulating Equilibrium Constants

RULE #2: Coefficient Rule

If the coefficients of a chemical equation are

changed (increased or decreased) by a factor

n, then the value of K is raised to that power.

[NO ] 2

2

N2O4 (g) 2 NO2 (g) KI =

[N2O4]

= 0.212 at 100C

[NO2]4

2 N2O4 (g) 4 NO2 (g) KIII =

[N2O4]2

= (0.212) 2 at 100C

[ NO 2 ]2 Equilibrium

½N2O4(g) NO2(g) KIV = 0.212 at 100C

[N 2 O 4 ]

Manipulating Equilibrium Constants

RULE #3: Multiple Equilibria Rule

obtain a final resultant equation, the equilibrium

constant for the resultant equation is product of the

constants of the added equations.

4

[ C]

2 A(aq) + B(aq) ↔ 4 C(aq) KV

[A]2 [ B]

[ F]2

4 C(aq) + E(aq) ↔ 2 F(aq) K VI

[C]4 [ E]

[ F]2

2 A(aq) + B(aq) + E ↔ 2 F(aq) K VII Equilibrium

[A]2 [ B][ E]

Homogeneous

Reactions involving only gasses or only solutions

[NO2]2

N2O4 (g) 2 NO2(g) Kc = = 0.212 at 100C

[N2O4]

vs.

Heterogeneous

Reactions involving different phases (s, l, g, aq) of matter

Equilibria Equilibrium

The Concentrations of Solids and

Liquids Are Essentially Constant

PbCl2 (s) Pb2+ (aq) + 2 Cl−(aq)

Write the equilibrium expression!

Kc = [Pb2+] [Cl−]2

The concentrations of solids and liquids do not appear in

equilibrium expressions because their concentration does not

change.

Concentration of both solids and liquids can be obtained by

dividing the density of the substance by its molar mass—and

both of these are constants at constant temperature.

g g

D MM mol Equilibrium

Concentration ( M ) L

MM MM L L

What are the Equilibrium

Expressions for these

Heterogeneous Equilibria?

Kp

P CO2

2

PCO 2

K p PCO2

2

[Zn ]

Kc 2

[Cu ]

Equilibrium

CaCO3 (s) CO2 (g) + CaO(s)

K p PCO2

How does the concentration of CO2 differ in the two bell jars?

As long as some CaCO3 or CaO remain in the system, the

Equilibrium

Equilibrium Calculations

(1) Calculating Kc from experimental data: [ ]i & [ ]e

when Kc & [ ]i are known

ICE Tables:

[A] + [B] [C] + [D]

Initial I [A]i [B]i 0 0

- - + +

Change C change change change change

[C ]cequi[ D]equi

d

[C ]cequi[ D]equi

d

Kc Equilibrium

a

[ A]equi [ B]bequi [[ A]i change]equi

a

[[ B]i change]bequi

(1) Calculating Kc from experimental data: [ ]i & [ ]e

[HI]2

H2 (g) + I2 (g) 2 HI (g) Kc =

[H2] [I2]

A closed system initially containing 1.000 x 10−3 M H2 and 2.000 x 10−3 M

I2 at 448C is allowed to reach equilibrium. Analysis of the equilibrium

mixture shows that the concentration of HI is 1.87 x 10−3 M. Calculate Kc at

448C for the reaction taking place, which is

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At Equilibrium 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

Equilibrium

Stoichiometry tells us [H2] and [I2] decrease by half as much

…and, therefore, the equilibrium constant

[H2], M + [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At Equilibrium 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

[HI]2

Kc =

[H2] [I2]

(1.87 x 10-3)2

=

(6.5 x 10-5)(1.065 x 10-3)

Equilibrium

= 51

Calculating Kc from experimental data: [ ]i & [ ]e

@

100°C

+x - 2x x

+x - 2x

+x - 2x

-x + 2x

I 0.0 0.0200 [NO2]2

C +x - 2x

Kc = [N O ]

2 4

E 0.0014 0.0200-2x

Kc 0.212

[0.0014] [0.0028] [0.0045] [0.0045]

Equilibrium

The ratio of [NO2]2 to [N2O4] remains constant at this temperature no matter

what the initial concentrations of NO2 and N2O4 are.

2006B Q5

Practice Problem

{ }

Equilibrium

Equilibrium

Equilibrium

Equilibrium Calculations

(1) Calculating Kc from experimental data: [ ]i & [ ]e

[H2], M + [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change

At Equilibrium 1.87 x 10-3

when K & [ ]i are known

H2(g) + I2(g) ↔ 2HI(g)

I 0.00623 0.00414 0.0224 [HI ]2e

C -x -x + 2x K 51 =

[H 2 ]eEquilibrium

[I 2 ]e

E 0.00632- x 0.00414- x 0.0224 + 2x

(2) Calculating Equilibrium

Concentrations [ ]e when K & [ ]i are known

aA + bB cC + dD

I [A]i [B]i 0 0

C - ax - bx + cx + dx

E [A]i- ax [B]i- bx cx dx

K

[ A] a

equi

b

[ B]

equi ([ A]i ax) ([ B]i bx)

a b

ax bx c 0

2 b b Equilibrium

4ac 2

x

2a

Calculating Equilibrium Concentrations

when K & [ ]i are known

Problem: for the reaction H2(g) + I2(g) 2HI(g) , K= 54.3 @

430ºC. Suppose that the initial concentrations of H2, I2, and HI

are 0.00623 M, 0.00414 M, and 0.0224 M, respectively.

Calculate the concentrations of these species at equilibrium.

H2(g) + I2(g) 2HI(g)

K

C -x -x + 2x [H 2 ]e [I 2 ]e

E 0.00632- x 0.00414- x 0.0224 + 2x

ax 2 bx c 0

(0.0224 2 x) 2

Deciding if x is negligible: 54.3

([0.00632] - x) ([0.00414] - x)

54.3(2.58 x 1015 0.0104 x x 2 ) 5.02 x 10-4 0.0896 x 4 x 2 Equilibrium

2 -4

x

b b 2 4ac

2a

Problem: for the reaction H2(g) + I2(g) 2HI(g) , K= 54.3 @

430ºC. Suppose that the initial concentrations of H2, I2, and HI

are 0.00623 M, 0.00414 M, and 0.0224 M, respectively.

Calculate the concentrations of these species at equilibrium.

Deciding if x is negligible:

(0.0224 2 x) 2

54.3 [A]i

K [A]i x 100

([0.00632] - x) ([0.00414] - x) 100

0.000224 54.3 2.24

ax 2 bx c 0 1. Take the largest [A]i and multiply it by

100 and also divide it by 100.

2. Compare the answers of above to

50.3x 2 0.654 x 8.98 x 10-4 0 the value of K

YOU MUST USE QUADRATIC! 3. If comparison are not significant as

50.3x 2 8.98 x 10-4 compared to K, then x is negligible

and you can delete the x that is

50.3 50.3 subtracted from [A]I

4. If these calc values are significant

x 2 1.79 x 10 -5 compared to K, then x is notEquilibrium

negligible and you must use the

x 0.00423 quadratic to solve for x.

Calculating Equilibrium Concentrations

when K & [ ]i are known

ax 2 bx c 0 b b 4ac 2

x

50.3x 2 0.654 x 8.98 x 10-4 0 2a

0.654 (0.654) 2 4(50.3)(8.98 x 10-4 )

x

2(50.3)

x 0.0114 M or x 0.00156 M

[H2]i = 0.00623

[I2]i = 0.00414 E 0.00632- x 0.00414- x 0.0224 + 2x

would be more than original conc. x calc without quadratic:

[H2]e = 0.00623 – 0.00156) = 0.00467 M x 0.00423M

Equilibrium Calculations

(1) Calculating Kc from experimental data: [ ]i & [ ]e

[H2], M + [I2], M 2 [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change

At Equilibrium 1.87 x 10-3

[ HI ]2

K

e

when K & [ ]i are known

H2(g) + I2(g) 2HI(g) [HI ]2e

I 0.00623 0.00414 0.0224 K 51 =

[H 2 ]e [I 2 ]e

C -x -x + 2x

E 0.00632- x 0.00414- x 0.0224 + 2x Deciding if x is negligible:

Equilibrium

b b 4ac

2 [A]i

ax 2 bx c 0 x K [A]i x 100

2a 100

Le Châtelier’s Principle

{Equi.Intro1}

{Equi.Intro2}

by a change in temperature, pressure, or the

concentration of one of the components, the

system will shift its equilibrium position so

as to counteract the effect of the

disturbance.” [N2O4]

KC = [NO ]2

The effect of (1) Concentration 2

Henri Louis Le Chatelier

1850-1936

2 NO2 (g)

N2O4 (g)

(red-brown gas) (clear gas)

Equilibrium

The effect of (2) Pressure & Volume (3) Temperature

{L.C.&PressVol}

Le Châtelier’s Principle

The effect of (3) Temperature

2 NO2 (g)

N2O4 (g) + HEAT

(red-brown gas) (clear gas) H = -58.0 kJ

Why does heat

favor the formation

of NO2 over N2O4?

{Le Châtelier’s&Temp}

{Molecular Explanation}

Equilibrium

The Effect of Temperature Changes

Add heat (), which way will the equlibrium be shifted?

Co(H2O)62+(aq) + 4 Cl(aq) CoCl4 (aq) + 6 H2O (l)

(pink) + HEAT (blue) H= +

{CoCl}

Equilibrium

Briggs-Rauscher reaction

{ClockReaction}

Equilibrium

Le Châtelier’s Principle & the Haber Process

It was not until the early 20th century that this method was

developed to harness the atmospheric abundance of nitrogen

to create ammonia, which can then be oxidized to make the

nitrates and nitrites essential for the production of fertilizers and

ammunitions.

∆H = -92.4 kJ/n

@ 250 C

Equilibrium

Le Châtelier’s Principle & the Haber Process

Shift equilibrium to the right

Fe

N2 (g) + 3H2 (g) 2NH3 (g) by increasing press & conc. of

N2 + H2 and by removing NH3

from system

This apparatus helps

push the equilibrium to the

right by removing the

ammonia (NH3) from the

system as a liquid

Removed by liquefaction

Fe

Subs b. pt.

NH3 -33°C

N2 -196°C

Equilibrium

H2 -253°C

The Effect of Catalysts on Equilibrium

addition of a catalyst

catalyst affect

the equilibrium

between subs. A

and B?

• Equilibrium is achieved faster, but the equilibrium Equilibrium

composition remains unaltered.

Equilibrium Constant (K)

vs. Reaction Quotient (Q)

aA(aq) + bB(aq) cC(aq) + dD(aq)

At Equilibrium: At Non-Equilibrium:

[C]c[D]d [C]ic[D]id

K= Q=

[A]a[B]b [A]ia[B]ib

• To calculate Q, one substitutes the initial

concentrations on reactants and products into the

equilibrium expression.

• Q gives the same ratio the equilibrium expression Equilibrium

gives, but for a system that is not at equilibrium.

aA(aq) + bB(aq) cC(aq) + dD(aq)

K= Q= i i

i i

If Q < K? If Q < K, there is too much reactant, and the

equilibrium shifts to the right.

If Q > K? If Q > K, there is too much product and the Equilibrium

equilibrium shifts to the left.

Kc, Q and Spontaneity (ΔG)

[NH ] 2

[NH3]2eq Q= 3 i

KC =

[N2]eq[H2]eq [N2]i[H2]i

ΔG= -

Reverse Process

ΔG = + ΔG= -

Reverse Process

ΔG = +

Equilibrium

@ Equilibrium

K = Q, ΔG = 0

Free Energy (G) & Reaction Quotient

(Q) under non-Standard Conditions

Non-standard

conditions Non-standard conditions

products @ standard conditions (25ºC, 1 atm, 1M).

and under non-standard conditions of concentration, temperature and

pressure.

• If [Reactants]↑, then G = -

[ Products]p

• If [Products]↑, then G = + Q

[ Reactants]r

• If at Equilibrium , then G = 0 Equilibrium

Free Energy (G) & Equilibrium Constant (K)

at Equilibrium

At equilibrium, G = 0 and Q = K so……

G = G + RT ln Q

0 = G + RT ln K

Rearranging ……

K = eG/RT

G K Product formation

– >1 Product-favored @ Equilibrium

0 =1 [Products] = [Reactants] @ Equilibrium (RARE)

Equilibrium

Free Energy (ΔG), the Equilibrium

Constant (ΔK),and Temperature

Low Temp. How would T ↓or ↑ affect K?

2 NO2 (g) High Temp.

N2O4 (g) H = -58.0 kJ

(red-brown gas) (clear gas)

[ Products]p @ T ↓, K ↑ G°= -

K

G = - RT ln K [ Reactants]r @ T ↑, K ↓ G°= +

Low Temperature: High Temperature:

G°= - G°= +

Q=K

only mixture only Equilibrium

2003B Q1

2 HIH2 + I2

Equilibrium

2003B Q1 Kp = Kc(RT)Δn

Equilibrium

2000A Q1

Equilibrium

2000A Q1

Equilibrium

Equilibrium

Equilibrium

2004B Q1

Equilibrium

Equilibrium

2007B Q1

Equilibrium

2000 1

Equilibrium

Equilibrium

Equilibrium

2003 B

Equilibrium

Equilibrium

2004 B

Equilibrium

Equilibrium

2006 A

Equilibrium

Equilibrium

2006 (B)

Equilibrium

Equilibrium

Equilibrium

Equilibrium

Equilibrium

Equilibrium

Equilibrium

2007 (B)

Equilibrium

Equilibrium

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