Unit 15 Equilibrium

I. The Concept of Equilibrium

Chemical equilibrium occurs when a reaction and its reverse reaction proceed at the same rate.

A. The Concept of Equilibrium

When CO and H2O are mixed, they immediately begin to react to form H2 and CO2.This leads to a decrease in the concentrations of the reactants, Beyond a certain time, indicated by the dashed line, the concentrations of reactants and products no longer changes and equilibrium has been reached the concentrations of reactants never go to zero; the reactants will always be present in small but constant concentrations

B. A System at Equilibrium

Once equilibrium is achieved, the amount of each reactant and product remains constant.

C. Depicting Equilibrium
In a system at equilibrium, both the forward and reverse reactions are being carried out; as a result, we write its equation with a double arrow N2O4 (g) 2 NO2 (g)

II. Equilibrium constant Expression that relates the concentration of products to reactants in terms of a constant K A. Variations of K Kc for concentrations expressed in mol/L Kp for partial pressures of gases Ksp for solubility product, which has no denominator because the reactants are solids Ka is acid dissociation constant for weak acids Kb dissociation constant for weak bases Kw the ionization of water (Kw= 1 x 1014)

B. Equilibrium expression aA + bB cC + dD Keq= [C]c [D]d [A]a [B]b 1) [A], [B], [C], and [D] are molar concentration or partial pressures at equilibrium 2) Products are in the numerator, and reactants are in the denominator 3) Coefficients in the balanced equation become exponents in the equilibrium expression 4) Solids and pure liquids are ignored 5) Units are not given for Keq

What Are the Equilibrium Expressions for These Equilibria?

C. Calculating equilibrium constant If the concentrations at equilibrium are as follows: [O2]= 2.0 x 108M, [SO2]= 3.4 x109M and [SO3]= 0.971M then what is the equilibrium constant?

Kc=

(0.971)2 (2.0 x 108) x (3.4 x 109)2

= 4.2 x 1024

D. Keq and gases Kc and Kp of gases can be related using following formula: Kp= Kc (RT)n Kp= partial pressure constant (atm) Kc= molar concentration constant (M) R= 0.0821 L atm/ mol K T= temperature (K) n= (moles of product gas moles of reactant gas)

Question: For the following equilibrium Kp= 1.90 C (s) + CO2(g) 2 CO (g)

Calculate Kc for this reaction at 25C. Kc= Kp

(RT)n Kc= 1.90 . [(0.0821 L atm/ mol K)(298K)]2-1

=0.0777

III. What Does the Value of K Mean?

If K >> 1, the reaction is product-favored; product predominates at equilibrium.

If K << 1, the reaction is reactant-favored; reactant predominates at equilibrium.

A. K for reverse reaction

The equilibrium constant of a reaction in the reverse reaction is the reciprocal of the equilibrium constant of the forward reaction.

N2O4 (g) 2 NO2 (g)

[NO2]2 2 NO2 (g) Kc = [N O ] = 0.212 at 100C 2 4 [N2O4] 1 Kc = N2O4 (g) = [NO2]2 0.212 = 4.72 at 100C

B. Effect of increasing amount of chemicals on K

The equilibrium constant of a reaction that has been multiplied by a number is the equilibrium constant raised to a power that is equal to that number.
N2O4 (g)
2 N2O4 (g)
[NO2]2 2 NO2 (g) Kc = [N O ] 2 4
= 0.212 at 100C

[NO2]4 4 NO2 (g)Kc = [N O ]2 = (0.212)2 at 100C 2 4

C. K for multi-step reactions

The equilibrium constant for a reaction made up of two or more steps is the product of the equilibrium constants for the individual steps. Basically like Hesss law with the way the reactions are added up but instead of adding the equilibrium constants, you multiply them to get equilibrium constant for final reaction

Example: HCrO4 + Ca2+ H+ + CaCrO4 Rxn1: HCrO4 H+ + CrO42 Ka= 3 x 107 Rxn 2: CaCrO4 Ca2+ + CrO42 Ksp= 7.1 x 104 What is the K for the overall reaction if the K values for the multistep reaction is given.

Keq= (Ka) (1/Ksp)= Ka/Ksp since the second reaction needs to be flipped to get the final reaction.
Keq= 3 x 107 /7.1 x 104 = 4. 23 x 104

IV. Reaction Quotient

Determined exactly as equilibrium constant with initial conditions instead of equilibrium conditions Allows prediction of direction of reaction For the reaction: aA + bB cC + dD Q= [C]c [D]d [A]a [B]b [A], [B], [C], and [D] are initial molar concentrations or partial pressures if Q is less than the calculated K for the reaction, rxn. proceeds fwd. generating products if Q is greater than K, the rxn. proceeds backward, generating reactants if Q=K, the reaction is already at equilibrium

If Q = K, the system is at equilibrium.

If Q > K, there is too much product and the equilibrium shifts to the left.

If Q < K, there is too much reactant, and the equilibrium shifts to the right.

Question: Using the equilibrium constants and reactions below, determine whether or not each of the following systems is in equilibrium, predict whether it will proceed in the forward or reverse direction. 1) H2(g) + I2 (g) 2HI (g) Kc= 49 [H2] = 0.10M [I2]= 0.10M [HI]= 0.70M Q= 49 so reaction in equilibrium 2)HF(aq)+ H2O(l) F(aq)+H3O+(aq) Kc=6.8x104 [HF]= 0.20M [F]=2.0 x 104M [H3O+]=2.0 x 104M Q= 2 x 107 Q < Kc so reaction must go in fwd. direction to reach in equilibrium

V. Equilibrium Calculations To solve equilibrium questions, we need to construct a equilibrium table

Reaction Initial condition Change Equilibrium Answer

There are 4 types of questions you may be asked

Type 1 Solving for equilibrium constant NO2(g) + SO2(g) NO(g) + SO3(g) Assume that a 4.00L flask is filled with 1 mole of each of the four compounds. The equilibrium concentration of NO2 is 0.261M. What is Kc equal? The molarity of each compound is 1.00mol/4.00L= 0.250M .

Reaction Initial condition Change

NO2(g) SO2(g) NO(g) SO3(g)

0.250M 0.250M 0.250M

0.250M x
0.250 x

+x

+x

Equilibrium 0.250+x 0.250+x 0.250 x

Answer
0.261

Since 0.250+ x= 0.261 then x= 0.011M

Reaction

NO2(g) SO2(g) NO(g) SO3(g)

0.250M x
0.250 x

0.250M 0.250M 0.250M Initial condition +x +x x Change Equilibrium 0.250+x 0.250+x 0.250 x

Answer

0.261

0.261

0.239

0.239 = 0.839

Kc= [NO] [SO3] [NO2][ SO2]

= (0.239) (0.239) (0.261) (0.261)

Type 2 Finding equilibrium conc. of all species Br2 + Cl2 2BrCl The above reaction has an equilibrium constant of 6.90 and has 0.100 mol of BrCl introduced into a 500mL flask. What is the equilibrium concentration of all reactants and products? [BrCl]= 0.100mol/0.500L= 0.200M Reaction Initial condition Change Equilibrium Answer Br2 0 +x X Cl2 0 +x X 2BrCl 0.200M 2x 0.2002x

Kc= [BrCl]2 [Br2] [Cl2] 6.90= (0.200-2x)2 x2 Take square root of both sides 2.63= 0.2002x2.63x= 0.200 2x 4.63x= 0.200 x = 0.0432 Reaction Initial condition Change Equilibrium Answer Br2 0 +x X 0.0432 Cl2 0 +x X 0.0432 2BrCl 0.200M 2x 0.2002x 0.114

Type 3 Quadratic equation Br2 + Cl2 2BrCl 0.200M Br2 and 0.300M Cl2 is mixed with an equilibrium constant of 6.90. What is the equilibrium concentrations of all species? Reaction Initial condition Change Equilibrium Answer Br2 0.200M Cl2 0.300M 2BrCl 0

-x 0.200x

-x 0.300X

+2x 2x

Kc= [BrCl]2 [Br2] [Cl2] 6.90= (2x)2 . (0.200x) (0.300x) Square root cant be taken since denominator not an exact square. Multiplying denominator yields

6.90= (2x)2 . (x2 0.5x +0.06)

6.90 x2 3.45x + 0.414= 4x2 2.90x2 3.45x +0.414= 0

Using quadratic to solve x= b b2 4ac 2a Substituting into equation gets x=(3.45) (3.45)2 4(2.90) (0.414) 2(2.90) x= 3.452.66 5.8 x= 1.05 or 0.136

Plugging in both values in for x we see that only 0.136 is reasonable since 1.05 gives a negative answer which is impossible

Reaction Initial condition Change Equilibrium Answer

Br2 0.200M -x 0.200x 0.064

Cl2 0.300M -x 0.300X 0.164

2BrCl 0 +2x 2x 0.272

Type 4 Assuming If the equilibrium constant is less than 103 and the initial concentrations of reactants are given we can avoid doing quadratics 2SO3 (g) 2SO2 (g) + O2(g) If 2.00 moles of SO3 is placed in a 1.00L flask and the equilibrium constant is 2.4 x 1025 then what is the concentration of all species at equilibrium.

Reaction Initial condition Change

2SO3 0.200M

2SO2 0

O2 0

-2x

+2x

+x

Equilibrium
Answer

0.2002x

2x

Kc= [SO2]2 [O2] [SO3]2 2.4 x 1025= (2x)2 (x) (2.00M2x)2 Since Kc is small we can assume that very little product is produced and that 2x subtracted from 2.00M will still be 2.00M

2.4 x 1025= (2x)2 (x) (2.00M)2 9.6 x 1025= 4x3 2.4 x 1025= x3 6.2 x 109M= x
Checking to see assumption is correct: 2.00M 6.2 x 109M= 2.00M so assumption valid

Reaction Initial condition Change Equilibrium Answer

2SO3 0.200M

2SO2 0

O2 0

-2x 0.2002x 2.00

+2x 2x 1.24 x 108

+x x 6.2 x 109

Question: At 2000oC the equilibrium constant is 2400. 2NO(g) N2(g) + O2(g) If [NO]init = .2M, determine the [NO]eq, [N2]eq and [O2]eq. Reaction Initial condition Change Equilibrium Answer 2NO 0.200M N2 0 O2 0

-2x 0.2002x

+x x

+x x

Kc= [N2] [O2] [NO]2 2400= x2 . (0.2002x)2 48.99= x . 0.2002x

48.99(0.2002x)= x 9.80 97.98x= x 9.80= 98.98x 0.099= x

Reaction Initial condition Change Equilibrium Answer

2NO 0.200M -2x 0.2002x 0.0022

N2 0 +x x 0.099

O2 0 +x x 0.099

VI. Le Chteliers Principle

If a system at equilibrium is disturbed 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. Physical stresses include changes in temperature, pressure and volume Chemical stresses include the addition or removal of one or more of the products or reactants

A. Effect of Concentration
Even though concentrations may change, the value of Kc or Kp would remain the same since the ratios of products to reactants is the same 1) Decreasing concentration shift to produce more of whatever substance is decreased causing concentration of other side of arrow to decrease 2) Increasing concentration shift to consume substance that increased which will increase concentration of substance on other side of arrow

N2 (g) + 3H2 (g) 2NH3 (g) 1) What would happen if you increase the concentration of hydrogen gas? 1) shift to right 2) shift to left 3) nothing shift to right to consume hydrogen 2) What would happen to the concentration of ammonia? 1) increase 2) decrease 3) nothing increase 3) What would happen to the concentration of nitrogen? 1) increase 2) decrease 3) nothing decrease 4) What would happen if the concentration of nitrogen decreased? 1) shift to right 2) shift to left 3) nothing shift to left to increase nitrogen conc. 5) What would happen to the concentration of hydrogen? 1) increase 2) decrease 3) nothing increase 6) What would happen to the concentration of ammonia? 1) increase 2) decrease 3) nothing decrease

B. Effect of Pressure Only significant for gases Pressure can be changed by changing the volume of the container or by adding or removing either the reactants or products or adding an inert gas Nothing will happen if you have same number of moles of reactants as products 1) increasing pressure (decreasing volume) - reaction will go in direction that produces fewer moles of gas 2) decreasing pressure (increasing volume) -reaction will go in direction that produces more moles of gas

N2 (g) + 3H2 (g) 2NH3 (g) 1) Which direction will the reaction shift if the pressure increases? 1) right 2) left if pressure increases than rxn. will shift to side with fewer moles which is right side 2) Which direction will the reaction shift if the pressure decreases? 1) right 2) left Rxn. will shift to left since fewer moles 3) Which direction will the reaction shift if the volume decreases? 1) right 2) left If volume decreases than pressure increases and reaction will shift to right

C. Temperature Easiest way to handle is to treat temperature as a chemical and put the word temperature on reactant side if the reaction is endothermic and on product side if the reaction is exothermic Ex. N2 (g) + 3H2 (g) 2NH3 (g) + 300kJ

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

(g) If the temperature is increased in above reaction then the reaction will shift to right if the temperature is decreased, the reaction shifts to left.

Question: The reaction below is exothermic in forward direction. N2 (g) + 3H2 (g) 2NH3 (g) 1) Which direction will the reaction shift if the temperature is increased? 1) left 2) right 2) Which direction will the reaction shift if the temperature is decreased? 1) left 2) right

Question: At elevated temperatures, SbCl5 gas decomposes into SbCl3 gas and Cl2 gas as shown by the following equation: SbCl5(g) SbCl3(g) + Cl2(g) (a) An 89.7 gram sample of SbCl5 (molecular weight 299.0) is placed in an evacuated 15.0 litre container at 182C. 1. What is the concentration in moles per litre of SbCl5 in the container before any decomposition occurs? 89.7g SbCl5 x 1 mole = 0.300 mol 299 g M= 0.300mol = 0.0200M 15L

2. What is the pressure in atmospheres of SbCl5 in the container before any decomposition occurs?

P = nRT = 0.300mol (0.0821) 455K V 15L = 0.747 atm

(b)If the SbCl5 is 29.2 percent decomposed when equilibrium is established at 182C, calculate the value for either equilibrium constant Kp or Kc, for this decomposition reaction. Indicated whether you are calculating Kp or Kc. SbCl5 SbCl3 + Cl2 If 29.2% of the SbCl5 is decomposed than that means that 29.2 % of it converts into the products and 70.8% of it stays as SbCl5 [SbCl3] = [Cl2] = (0.0200 mol/L)(0.292) = 5.84 x10-3M [SbCl5] = (0.0200 mol/L)(0.708) = 1.42 x10-2M
K c [ SbCl 3 ][ Cl 2 ] [ SbCl 5 ]

( 5 . 84 0 1

3 2

1 . 42 0 1

2 . 41 0 1

(c)In order to produce some SbCl5, a 1.00 mole sample of SbCl3 is first placed in an empty 2.00 litre container maintained at a temperature different from 182C. At this temperature, Kc, equals 0.117. How many moles of Cl2 must be added to this container to reduce the number of moles of SbCl3 to 0.700 mole at equilibrium? Since you start with 1 mole of SbCl3 and end up with 0.700 at equilibrium then the amount of change in the reaction was 0.300 mol which you subtract from product side and add to reactant side

[SbCl3] = 0.700mol/2l= 0.350M

[SbCl5]= 0.300/2L= 0.150M

Change = 0.300/2L= 0.150M Reaction Initial condition Change Equilibrium Answer SbCl5 0 +0.150M 0.150M SbCl3 0.500M -0.150M 0.350M Cl2 x 0.150M x 0.150M

K= 0.117= (x 0.150M) (0.350M) 0.150M 0.0176= 0.350x 0.0525 0.0701=0.350x x= 0.200M of Cl2 Since they are looking for moles we multiply by volume to get 0.200M(2L)= 0.400moles