Equilibrio Qumico

17-1

Kinetics applies to the speed of a reaction, the concentration of product that appears (or of reactant that disappears) per unit time. Equilibrium applies to the extent of a reaction, the concentration of product that has appeared after an unlimited time, or once no further change occurs. At equilibrium: rateforward = ratereverse

A system at equilibrium is dynamic on the molecular level; no further net change is observed because changes in one direction are balanced by changes in the other.

17-2

Reaching equilibrium on the macroscopic and molecular levels.

N2O4(g) 2NO2(g)

17-3

Equilibrium Equal
the rates of the forward and reverse reactions are equal at equilibrium but that does not mean the concentrations of reactants and products are equal some reactions reach equilibrium only after almost all the reactant molecules are consumed- we say the position of equilibrium favors the products. some reactions reach equilibrium only after small percentage of the reactant molecules are consumed- we say the position of equilibrium favors the reactants.
17-4

If rateforward = ratereverse then kforward[reactants]m = kreverse[products]n

kforward kreverse

[products]n [reactants]m

= K

the equilibrium constant

This is also known as the LAW OF MASS ACTION.

The values of m and n are those of the coefficients in the balanced chemical equation. Note that this is equilibrium, not kinetics. The rates of the forward and reverse reactions are equal, NOT the concentrations of reactants and products.

17-5

The range of equilibrium constants

K = [Productos]m [Reactivos]n

small K

large K

intermediate K

17-6

Q - The Reaction Quotient

At any time, t, the system can be sampled to determine the amounts of reactants and products present. Q is calculated in the same manner as K
Q= [C]c[D]d [A]a[B]b

We use the molar concentrations of the substances in the reaction. This is symbolised by using square brackets - [ ]. For a general reaction aA + bB cC + dD where a, b, c, and d are the numerical coefficients in the balanced equation, Q (and K) can be calculated as 17-7

Calculate K for each experiment K. Compare equilibrium concentrations.

Initial and Equilibrium Concentration Ratios for the N2O4-NO2 System at 2000C(473 K)

Initial Experiment [N2O4] [NO2] 1 2 3 4 0.1000 0.0000 0.0500 0.0750 0.0000 0.1000 0.0500 0.0250

Equilibrium [N2O4]eq [NO2]eq 3.57x10-3 9.24x10-4 2.04x10-3 2.75x10-3 0.193 9.82x10-2 0.146 0.170

[NO2]eq2 [N2O4]eq 10.4 10.4 10.4 10.5

=K

17-8

Sample Problem 17.1

Writing the Reaction Quotient from the Balanced Equation

PROBLEM: Write the reaction quotient, Qc, for each of the following reactions: (a) The decomposition of dinitrogen pentoxide, N2O5(g) NO2(g) + O2(g) (b) The combustion of propane gas, C3H8(g) + O2(g) CO2(g) + H2O(g) PLAN: Be sure to balance the equations before writing the Qc expression. SOLUTION: 42(g) + O2(g) (a) 2N2O5(g) NO Qc = [NO2]4[O2] [N2O5]2 [CO2]3[H2O]4 (b) C3H8(g) + 5O2(g) 3 CO2(g) + 4 H2O(g) Qc = [C3H8][O2]5

17-9

Calculating Variations on Q and K

[C]c[D]d aA + bB cC + dD

cC + dD aA + bB cC + dD

Qc =

[A]a[B]b

Q = 1/Qc Qc = (Qc)n

aA + bB

For a sequence of equilibria, Koverall = K1 x K2 x K3 x

17-10

Sample Problem 17.2

Writing the Reaction Quotient for an Overall Reaction

PROBLEM: Understanding reactions involving N2 and O2, the most abundant gases in air, is essential for solving problems dealing with atmospheric pollution. Here is a reaction sequence between N2 and O2 to form nitrogen dioxide, a toxic pollutant that contributes to photochemical smog. (1) N2(g) + O2(g)

2NO(g)

Kc1 = 4.3 x 10-25 Kc2 = 6.4 x 109

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

(a) Show that the Qc for the overall reaction sequence is the same as the product of the Qcs of the individual reactions. (b) Calculate the Kc for the overall reaction. PLAN: Write the sum of the overall reactions; write the Qc. Write the Qcs for the individual reactions and then multiply the expressions. We are given the Kcs for the individual reactions, so we multiply those values.

17-11

Sample Problem 17.2 SOLUTION: (a) [NO2] Qc =

2 2

Writing the Reaction Quotient for an Overall Reaction Qc1 = Qc2 = [NO]2 [N2][O2] [NO2]2 [NO]2[O2] [NO2]2 [NO]2[O2] = [NO2]2 [N2] [O2] 2

(1) N2(g) + O2(g)

2NO(g) 2NO2(g)

(2) 2NO(g) + O2(g) N2(g) + 2O2(g) Qc1x Qc2 (b) Kc = =

[N2][O2]

2NO2(g)
[NO]2 [N2][O2]

Kc1 x Kc2 = (4.3 x 10-25) x (6.4 x 109) = 2.8 x 10-15

17-12

Sample Problem 17.3

Determining the Equilibrium Constant for an Equation Multiplied by a Common Factor

PROBLEM:

For the ammonia formation reaction N2(g) + 3H2(g)

2NH3(g)

the equilibrium constant, Kc, is 2.4x10-3 at 1000K. If we change the coefficients of the equation, which well call the reference (ref) equation, what are the values of Kc for the following balanced equations? (a) 1/3N2(g) + H2(g) PLAN:

2/3NH3(g)

(b) NH3(g) 1/2N2(g) + 3/2H2(g)

Compare each equation to the reference. Keep in mind that changing the coefficients will be reflected in a power change in Kc and a reversal of the equation will show up as an inversion of Kc. SOLUTION:

(a) The reference equation is multiplied by 1/3, so Kc(ref) will be to the 1/3 power. Kc = [Kc(ref)]1/3 = (2.4x10-3)1/3 = 0.13 (b) The reference equation is reversed and halved, so Kc(ref) is to the -1/2 power. Kc = [Kc(ref)]-1/2 = (2.4x10-3)-1/2 = 20.

17-13

Heterogeneous Equilibrium
When all reactants and products are in one phase, the equilibrium is homogeneous. If one or more reactants or products are in a different phase, the equilibrium is heterogeneous. Consider:
experimentally, the amount of CO2 does not seem to depend on the amounts of CaO and CaCO3. Why?

17-14

The reaction quotient for a heterogeneous system.

solids do not change their concentrations

17-15

Heterogeneous Equilibrium
Neither density nor molar mass is a variable, the concentrations of solids and pure liquids are constant. (You cant find the concentration of something that isnt a solution!) We ignore the concentrations of pure liquids and pure solids in equilibrium constant expressions.

17-16

17-17

Expressing Equilibria with Pressure Terms Kc and Kp

PV = nRT

P=

n V

RT

P RT

n V

=M

P M so for Qp = p(NO2)2 p(NO) x p(O2)

2

2NO(g) + O2(g) Qc =

2NO2(g)
[NO2]2 [NO]2 x [O2]

Kp = Kc (RT)n(gas)

17-18

Sample Problem 17.4 PROBLEM:

Converting Between Kc and Kp

A chemical engineer injects limestone (CaCO3) into the hot flue gas of a coal-burning power plant for form lime (CaO), which scrubs SO2 from the gas and forms gypsum. Find Kc for the following reaction, if CO2 pressure is in atmospheres.

CaCO3(s) PLAN:

CaO(s) + CO2(g)

Kp = 2.1x10-4 (at 1000K)

We know Kp and can calculate Kc after finding ngas. R = 0.0821 L*atm/mol*K. ngas = 1 - 0 since there is only a gaseous product and no gaseous reactants. Kc = Kp/(RT)n = (2.1x10-4)(0.0821 x 1000)-1 = 2.6x10-6

SOLUTION:

Kp = Kc(RT)n

17-19

Comparing Q with K tells us whether the system:

has come to equilibrium (Q = K) or the reaction has to proceed further from reactants to products (Q < K) or in the reverse direction from products to reactants (Q > K).

17-20

Reaction direction and the relative sizes of Q and K.

Reaction Progress

Reaction Progress

reactants

products

Equilibrium: no net change

reactants

products

17-21

Sample Problem 17.5 PROBLEM:

Comparing Q and K to Determine Reaction Direction

For the reaction N2O4(g) 2NO2(g), Kc = 0.21 at 1000C. At a point during the reaction, [N2O4] = 0.12M and [NO2] = 0.55M. Is the reaction at equilibrium. If not, in which direction is it progressing?

PLAN:

Write an expression for Qc, substitute with the values given, and compare the Qc with the given Kc. Qc = [NO2]2 [N2O4] = (0.55)2 (0.12) = 2.5

SOLUTION:

Qc is > Kc, therefore the reaction is not at equilibrium and will proceed from right to left, from products to reactants, until Qc = Kc.

17-22

How to solve Equilibrium Problems

In order to study hydrogen halide decomposition, a researcher fills an evacuated 2.00 L flask with 0.200 mol of HI gas and allows the reaction to proceed at 453 oC.
Concentration (M) 2 HI (g) H2 (g) + I2(g)

Initial Change () Equilibrium

0.100 -2x 0.100 -2x

0 +x x

0 +x x

At equilibrium, [HI] = 0.078 M, Calculate Kc

Kc = 0.020
17-23

Using Equilibrium Constant to Determine Quantities

Si la constante de equilibrio es 6.90 y se aaden 0.100 moles de BrCl en un envase de 500 mL. Determina la conentracin en equilibrio para cada especie siguiendo la siguiente reaccin.
Concentration (M) Br2 (g) + Cl2(g) 2 BrCl (g)

Initial Change () Equilibrium

0 +x x

0 +x x

0.200 -2 x 0.200-2x

17-24 [Br2] = 0.0432 M, [Cl2] = 0.0432 M, [BrCl] = 0.114 M

Using Equilibrium Constant to Determine Quantities

Si la constante de equilibrio es 6.90 y se aaden 0.200 M de Br2 y 0.300 M de Cl2. Determina la conentracin en equilibrio para cada especie siguiendo la siguiente reaccin.
Concentration (M) Br2 (g) + Cl2(g) 2 BrCl (g)

Initial Change () Equilibrium

0.200 -x 0.200-x

0.300 -x 0.300- x

0 +2 x 2x

17-25 [Br2] = 0.0432 M, [Cl2] = 0.0432 M, [BrCl] = 0.114 M

[ BrCl ]2 K c= [ Br 2 ] [ Cl 2 ] 2x 6.90 = 0.200 x 0.300 x 2x 6.90= 2 x 0.50 x 0.06 6.90 x 2 3.45 x 0.414 = 4x 2 2.90 x 3.45x 0.414 =0
2 2 2

b b 2 4ac x= 2a x =1.05 or 0.136

Se puede eliminar 1.05 porque al utilizarlo nos da un nmero negativo y no hace sentido. Por lo tanto x = 0.136 M

17-26

[Br2] =0.064 M, [Cl2] = 0.164 M, [BrCl] = 0.272 M

Si Kc = 2.4 x 10-25 y son colocados 2.00 moles de SO3 en un envase de 1.00 L. Calcula la concentracin de todas las especies en equilibrio.
Concentration (M) 2 SO3(g) 2SO2 (g) + O2(g)

Initial Change () Equilibrium

2.00 -2x 2.00 -2x

K c= [ SO 2 ]2 [ O 2 ] [ SO 3 ]2 2x x = 2 2.00 x
2

0 + 2x 2x

0 +x x

2.4 10

25

17-27

Si asumimos que el cambio no cambia suficiente la concentracin de SO3 se puede descartar x

2 2x x 2.4 10 25= 2 2.00

4 x =9.6 10

25

La asuncin es vlida siempre y cuando el cambio en la concentracin sea menor que 5%. Es decir: % error = 6.2 x 10-9 =3.1 x 10-7 % 2.00

x 3= 2.4 10 25 9 x =6.2 10

[SO3] =2.00 M, [SO2] = 1.24 x 10-9 M, [O2] = 6.2 x 10-9 M

17-28

Sample Problem 17.9 PROBLEM:

Calculating Equilibrium Concentration with Simplifying Assumptions

Phosgene is a potent chemical warfare agent that is now outlawed by international agreement. It decomposes by the reaction

COCl2(g) CO(g) + Cl2(g) Kc = 8.3x10-4 (at 3600C) Calculate [CO], [Cl2], and [COCl2] when the following amounts of phosgene decompose and reach equilibrium in a 10.0-L flask. (a) 5.00 mol COCl2 PLAN: (b) 0.100 mol COCl2

After finding the concentration of starting material, write the expressions for the equilibrium concentrations. When solving for the remaining amount of reactant, see if you can make an assumption about the initial and final concentrations which could simplifying the calculating by ignoring the solution to a quadratic equation. (a) 5.00 mol/10.0 L = 0.500M (b) 0.100 mol/10.0 L = 0.0100M

SOLUTION:

Let x = [CO]eq = [Cl2]eq and 0.500-x and 0.0100-x = [COCl2]eq, respectively, for (a) and (b).

17-29

Sample Problem 17.9 continued Kc = [CO][Cl2] [COCl2] (a)

Calculating Equilibrium Concentration with Simplifying Assumptions Kc = 8.3x10-4 = (x) (x) (0.500-x)

assume x is << 0.500 so that we can drop x in the denominator

-4

8.3x10 =

(x) (x) (0.500)

4.15x10-4 = x2

x 2 x 10-2 (0.500 - x) = 4.8x10-2

CHECK: 0.020/0.500 = 0.04 or 4% percent error (b) Kc = 8.3x10 =

-4

(x) (x) (0.010 - x)

Dropping the -x will give a value for x = 2.9x10-3M. (0.010 - x) 0.0071M CHECK: 0.0029/0.010 = 0.29 or 29% percent error Using the quadratic formula produces x = 2.5x10-3 and 0.0100-x = 7.5x10-3M

17-30

Sample Problem 17.10 Predicting Reaction Direction and Calculating Equilibrium Concentrations PROBLEM: The research and development unit of a chemical company is studying the reaction of CH4 and H2S, two components of natural gas. CH4(g) + 2H2S(g) CS2(g) + 4H2(g) In one experiment, 1.00mol of CH4, 1.00mol of CS2, 2.00mol of H2S, and 2.00mol of H2 are mixed in a 250-mL vessel at 9600C. At this temperature, Kc = 0.036 (a) In which direction will the reaction proceed to reach equilibrium? (b) If [CH4] = 5.56M at equilibrium, what are the equilibrium concentrations of the other substances? PLAN: Find the initial molar concentrations of all components and use these to calculate a Qc. Compare Qc to Kc, determine in which direction the reaction will progress, and draw up expressions for equilibrium concentrations. SOLUTION: [CH4]initial = 1.00mol/0.25 L = 4.0M [H2S]initial = 2.00mol/0.25 L = 8.0M [CS2]initial = 1.00mol/0.25 L = 4.0M [H2]initial = 2.00mol/0.25 L = 8.0M

17-31

Sample Problem 17.10 Predicting Reaction Direction and Calculating Equilibrium Concentrations continued Qc = [CS2][H2]4 [CH4][H2S]
2

[4.0][8.0]4 [4.0][8.0]
2

A Qc of 64 is >> than Kc = 0.036 = 64 The reaction will progress to the left.

concentrations initial change equilibrium

CH4(g) + 2H2S(g) CS2(g) + 4H2(g) 4.0 +x 4.0 + x 8.0 + 2x 8.0 + 2x 4.0 -x 4.0 - x 8.0 - 4x 8.0 - 4x

At equilibrium [CH4] = 5.56M, so 5.56 = 4.0 + x and x = 1.56M Therefore [H2S] = 8.0 + 2x = 11.12M [CS2] = 4.0 - x = 2.44M [H2] = 8.0 - 4x = 1.76M

17-32

Steps in solving equilibrium problems

PRELIMINARY SETTING UP 1. Write the balanced equation. 2. Write the reaction quotient, Q. 3. Convert all of the amounts into the correct units (M or atm). WORKING ON A REACTION TABLE 1. When reaction direction is not known compare Q with K. 2. Construct a reaction table. Check the sign of x, the change in the quantity.

SOLVING FOR X AND EQUILIBRIUM QUANTITIES 1. Substitute the quantities into Q. To simplify the math, assume that x is negligible. [A]ini - x = [A]eq = [A]ini Solve for x. 5. Find the equilibrium quantities Check that assumption is justified (<5% error). If not, solve quadratic equation for x. Check to see that calculated values give the known K.

17-33

LeChateliers Principle
When a chemical system at equilibrium is subjected to a stress, the system will return to equilibrium by shifting to reduce the stress.
If the concentration increases, the system reacts to consume some of it. If the concentration decreases, the system reacts to produce some of it.

17-34

PCl3(g) + Cl2(g)

PCl5(g)

17-35

Aumentar []

Disminuir []

The Effect of Added Cl2 on the PCl3-Cl2-PCl5 System

Concentration (M) Original equilibrium Disturbance New initial Change New equilibrium

PCl3(g) 0.200

Cl2(g) 0.125 +0.075

PCl5(g) 0.600

0.200 -x 0.200 - x

0.200 -x 0.200 - x

0.600 +x 0.200 + x (0.637)*

*Experimentally determined value.

17-36

Sample Problem 17.11 Predicting the Effect of a Change in Concentration on the Equilibrium Position PROBLEM: To improve air quality and obtain a useful product, chemists often remove sulfur from coal and natural gas by treating the fuel contaminant hydrogen sulfide with O2; 2H2S(g) + O2(g) 2S(s) + 2H2O(g) What happens to (a) [H2O] if O2 is added? (c) [O2] if H2S is removed? (b) [H2S] if O2 is added? (d) [H2S] if sulfur is added?

PLAN: Write an expression for Q and compare it to K when the system is disturbed to see in which direction the reaction will progress. SOLUTION: Q = [H2O]2 [H2S]2[O2] (a) When O2 is added, Q decreases and the reaction progresses to the right to come back to K. So [H2O] increases.

17-37

Sample Problem 17.11 Predicting the Effect of a Change in Concentration on the Equilibrium Position continued 2 Q = [H2O] [H2S]2[O2] (b) When O2 is added, Q decreases and the reaction progresses to the right to come back to K. So [H2S] decreases. (c) When H2S is removed, Q increases and the reaction progresses to the left to come back to K. So [O2] increases. (d) Sulfur is not part of the Q (K) expression because it is a solid. Therefore, as long as some sulfur is present the reaction is unaffected. [H2S] is unchanged.

17-38

Effect of a Change in Pressure (Volume)

Pressure changes can occur in three ways:
Changing the concentration of a gaseous component Adding and innert gas (ine that foes not take part in the reaction) Changing the volume of the reaction vessel

17-39

Adding an Inert Gas

Adding an inert gas has no effect on the equilibrium position. Adding an inert gas does not change the volume, so all reactant and product concentrations remain the same.

17-40

Changing Pressure by Changing Volume

A change in volume results in a change in concentration A change in pressure due to a change in volume does not alter Kc.

17-41

 If the volume become smaller (pressure is higher), the reaction shifts so that the total number of gas molecules decreases. If the volume become larger (pressure is lower), the reactions shifts so that the total number of gas molecules increases. If ngas = 0, there is no effect on the equilibrium position.
17-42

The effect of pressure (volume) on an equilibrium system.

+

lower P (higher V) more moles of gas

higher P (lower V) fewer moles of gas

17-43

Sample Problem 17.12 PROBLEM:

Predicting the Effect of a Change in Volume (Pressure) on the Equilibrium Position

How would you change the volume of each of the following reactions to increase the yield of the products. (a) CaCO3(s) CaO(s) + CO2(g) (b) S(s) + 3F2(g) SF6(g) (c) Cl2(g) + I2(g) 2ICl(g)

PLAN:

When gases are present a change in volume will affect the concentration of the gas. If the volume decreases (pressure increases), the reaction will shift to fewer moles of gas and vice versa.

SOLUTION: (a) CO2 is the only gas present. To increase its yield, we should increase the volume (decrease the pressure). (b) There are more moles of gaseous reactants than products, so we should decrease the volume (increase the pressure) to shift the reaction to the right. (c) There are an equal number of moles of gases on both sides of the reaction, therefore a change in volume will have no effect.

17-44

The Effect of a Change in Temperature on an Equilibrium

Only temperature changes can alter K.

Consider heat as a product or a reactant.

A temperature rise will increase Kc for a system with a positive H0rxn.

N2H6CO (s) 2 NH3 (g) + CO2 (g) N2H6CO (s) + calor Hrxn = +33 kJ/mol

2 NH3 (g) + CO2 (g)

A temperature rise will decrease Kc for a system with a negative H0rxn.

CH4 (g) + 4 Cl2 (g) CCl4 (l) + 4 HCl (g) Hrxn = -397 kJ/mol

CH4 (g) + 4 Cl2 (g) CCl4 (l) + 4 HCl (g) + calor 17-45

Sample Problem 17.13 Predicting the Effect of a Change in Temperature on the Equilibrium Position PROBLEM: How does an increase in temperature affect the concentration of the underlined substance and Kc for the following reactions? (a) CaO(s) + H2O(l) (b) CaCO3(s) PLAN:

Ca(OH)2(aq) H0 = -82kJ

CaO(s) + CO2(g) H0 = 178kJ

(c) SO2(g) S(s) + O2(g) H0 = 297kJ Express the heat of reaction as a reactant or a product. Then consider the increase in temperature and its effect on Kc.

SOLUTION: (a) CaO(s) + H2O(l) Ca(OH)2(aq) heat An increase in temperature will shift the reaction to the left, decrease [Ca(OH)2], and decrease Kc. (b) CaCO3(s) + heat CaO(s) + CO2(g) The reaction will shift right resulting in an increase in [CO2] and increase in Kc. (c) SO2(g) + heat S(s) + O2(g) The reaction will shift right resulting in an decrease in [SO2] and increase in Kc.

17-46

The vant Hoff Equation: The Effect of T on K

ln

K2 = K1

H0rxn R

1 T2

1 T2

R = universal gas constant = 8.314 J/mol*K K1 is the equilibrium constant at T1

17-47

Effect of Various Disturbances on a System at Equilibrium

Disturbance Concentration Increase [reactant] Decrease [reactant] Increase [product] Decrease [product] Pressure Increase Pressure (decrease V) Toward formation of fewer mole gas None Decrease Pressure (increase V) Toward formation of more moles gas None Increase Pressure (adding inert gas, no change V) Temperature Increase T Toward absorption of heat Increase if endotermic Decrease if exotermic Decrease T Catalyst added Toward release of heat Increase if exotermic Decrease if endotermic None; forward and reverse equilibrium attained sooner; rates increase equally None, concentrations unchanged None Net direction of Reaction Effect on Value of K None None None None

17-48

None

Sample Problem 17.14 Determining Equilibrium Parameters from Molecular Species PROBLEM: For the reaction X(g) + Y2(g) XY(g) + Y(g) H>0 the following molecular scenes depict different reaction mixtures. (X = green, Y = purple)

(a) If Kc = 2 at the temperature of the reaction, which scene represents the mixture at equilibrium? (b) Will the reaction mixtures in the other two scenes proceed toward reactant or toward products to reach equilibrium? For the mixture at equilibrium, how will a rise in temperature affect [Y2]? [XY][Y] SOLUTION: The equilibrium constant, K, is . [X][Y2] scene 1: Qc = (5)(3)/(1)(1) = 15 scene 2: Qc = (4)(2)/(2)(2) = 2.0 scene 3: Qc = (3)(1)/(3)(3) = 0.33

17-49

Sample Problem 17.14 Determining Equilibrium Parameters from Molecular Species continued

Qc = 15

Qc = 2.0

Qc = 0.33

(a) In scene 2 Qc = Kc, so it represents the system at equilibrium. (b) In scene 1 Qc > Kc, so the system will proceed to reactants to reach equilibrium while in scene 3 Qc < Kc, so the system will proceed to products. (c) If H > 0, heat is a reactant (endothermic). A rise in temperature will favor products and [Y2] will decrease as the system shifts to products.

17-50