Chemical Equilibrium

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Equilibrium is a state in which there are no observable changes as time goes by. Chemical equilibrium is achieved when:

the rates of the forward and reverse reactions are equal and the concentrations of the reactants and products remain constant Physical equilibrium H2O l! H2O g!

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"2O# g!

Chemical equilibrium 2"O2 g!

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"2O# g!

2"O2 g!

equilibrium

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%tart with "2O#

equilibrium

equilibrium

%tart with "O2

%tart with "O2 & "2O#

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constant

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"2O# g! K' -"O2.2 -"2O#.

2"O2 g! ' #.() * $+,)

K'

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a/ 0 b1 cC 0 d2 -C.c-2.d -/.a-1.b

Law of Mass Action

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K 33 $ K 44 $

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5ie to the right 5ie to the left

K'

-C.c-2.d -/.a-1.b

a/ 0 b1

cC 0 d2

Equilibrium 7ill
6avor products 6avor reactants

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Homogenous equilibrium applies to reactions in which all reacting species are in the same phase.

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-"O2.
2

"2O# g!

2"O2 g! Kp '

Kc '

2 P "O
2

-"2O#.

P "O

9n most cases Kc Kp

a/ (g) 0 b1 (g)

cC (g) 0 d2 (g)

Kp ' Kc(RT)n

n ' moles of gaseous products 8 moles of gaseous reactants ' c 0 d) 8 a 0 b!

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Homogeneous Equilibrium
CH)COOH aq! 0 H2O l! CH)COO, aq! 0 H)O0 aq! -H2O. ' constant

-CH)COO,.-H)O0. K: c ' -CH)COOH.-H2O.

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-CH)COO,.-H)O0. ' K: Kc = c -H2O. -CH)COOH. ;eneral practice not to include units for the equilibrium constant.

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-COCl2. +.$# ' ' 22+ Kc ' -CO.-Cl2. +.+$2 * +.+?# Kp ' Kc(RT)n

n ' $ 8 2 ' ,$

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CO g! 0 Cl2 g! R ' +.+@2$

<he equilibrium concentrations for the reaction between carbon mono*ide and molecular chlorine to form COCl2 g! at =#+C are -CO. ' +.+$2 M> -Cl2. ' +.+?# M> and -COCl2. ' +.$# M. Calculate the equilibrium constants Kc and Kp. COCl2 g!

T ' 2=) 0 =# ' )#= A

Kp ' 22+ * +.+@2$ * )#=!,$ ' =.=

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PO2 ' $?@ * +.#++!2C +.2=+!2 ' )#= atm

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Kp '
2 P"O PO 2 2 P"O 2

<he equilibrium constant Kp for the reaction 2"O2 g! 2"O g! 0 O2 g! is $?@ at $+++A. 7hat is the equilibrium pressure of O 2 if the P"O 2' +.#++ atm and P"O ' +.2=+ atmB

PO2 ' Kp

2 P"O 2

P"O

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Heterogenous equilibrium applies to reactions in which reactants and products are in different phases.

-CaO.-CO2. K: c ' -CaCO). Kc ' -CO2. ' K: c *

<he concentration of solids and pure liquids are not included in the e*pression for the equilibrium constant.

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-CaCO). -CaO.

CaCO) s!

CaO s! 0 CO2 g! -CaCO). ' constant -CaO. ' constant Kp ' PCO2

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CaCO) s!

CaO s! 0 CO2 g!

PCO 2 does not depend on the amount of CaCO) or CaO

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PCO 2 ' Kp

Consider the following equilibrium at 2D? A: "H#H% s! "H) g! 0 H2% g! <he partial pressure of each gas is +.2(? atm. Calculate Kp and Kc for the reactionB Kp = P H % ' +.2(? * +.2(? ' +.+=+2 "H P
) 2

Kc ' +.+=+2 * +.+@2$ * 2D?!,2 ' $.2+ * $+,#

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Kp ' Kc(RT)n Kc ' Kp(RT)-n

n ' 2 8 + ' 2

T ' 2D? A

/01 C02 /01

C02 E06 E06

K: c K: c: Kc

-C.-2. K: c ' -/.-1.

-E.-6. K:: c ' -C.-2.

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Kc ' K: c * K: c:

-E.-6. Kc ' -/.-1.

9f a reaction can be e*pressed as the sum of two or more reactions> the equilibrium constant for the overall reaction is given by the product of the equilibrium constants of the individual reactions.

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"2O# g! K' -"O2.2 -"2O#.

2"O2 g! ' #.() * $+

,)

2"O2 g! -"2O#.

"2O# g!

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$ ' 2$( K: ' ' 2 K -"O2.

7hen the equation for a reversible reaction is written in the opposite direction> the equilibrium constant becomes the reciprocal of the original equilibrium constant.

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7riting Equilibrium Constant E*pressions

$. <he concentrations of the reacting species in the condensed phase are e*pressed in M. 9n the gaseous phase> the concentrations can be e*pressed in M or in atm. 2. <he concentrations of pure solids> pure liquids and solvents do not appear in the equilibrium constant e*pressions. ). <he equilibrium constant is a dimensionless quantity. #. 9n quoting a value for the equilibrium constant> you must specify the balanced equation and the temperature. ?. 9f a reaction can be e*pressed as a sum of two or more reactions> the equilibrium constant for the overall reaction is given by the product of the equilibrium constants of the individual reactions.
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Chemical Ainetics and Chemical Equilibrium

/ 0 21 kf kr /12 ratef ' kf -/.-1.2 rater ' kr -/12.

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Equilibrium ratef ' rater kf -/.-1.2 ' kr -/12. kf -/12. ' Kc ' kr -/.-1.2

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Qc 3 Kc system proceeds from right to left to reach equilibrium Qc ' Kc the system is at equilibrium Qc 4 Kc system proceeds from left to right to reach equilibrium

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IF

<he reaction quotient (Qc) is calculated by substituting the initial concentrations of the reactants and products into the equilibrium constant Kc! e*pression.

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Calculating Equilibrium Concentrations

$. E*press the equilibrium concentrations of all species in terms of the initial concentrations and a single unEnown x> which represents the change in concentration. 2. 7rite the equilibrium constant e*pression in terms of the equilibrium concentrations. Anowing the value of the equilibrium constant> solve for x. ). Having solved for x> calculate the equilibrium concentrations of all species.

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/t $2@++C the equilibrium constant Kc! for the reaction 1r2 g! 21r g! 9s $.$ * $+,). 9f the initial concentrations are -1r2. ' +.+() M and -1r. ' +.+$2 M> calculate the concentrations of these species at equilibrium. 5et x be the change in concentration of 1r2 1r2 g! ,x 21r g! +.+$2 02x 9nitial M! +.+()

Change M!

Equilibrium M! -1r.2 Kc ' -1r2.

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+.+() , x

+.+$2 0 2x %olve for x

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+.+$2 0 2x!2 ' $.$ * $+,) Kc ' +.+() , x

9nitial M! Change M!

Equilibrium M!

/t equilibrium> -1r. ' +.+$2 0 2x ' ,+.++D M or +.++@## M /t equilibrium> -1r2. ' +.+(2 8 x ' +.+(#@ M
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1r2 g! ,x 21r g! +.+$2 02x +.+() +.+() , x +.+$2 0 2x

+.+$2 0 2x!2 ' $.$ * $+,) Kc ' +.+() , x #x2 0 +.+#@x 0 +.+++$## ' +.++++(D) 8 +.++$$x #x2 0 +.+#D$x 0 +.++++=#= ' + 2 , b b 8 #ac x' ax2 0 bx 0 c '+ 2a x ' ,+.+$+? x ' ,+.++$=@

Le Chteliers Princi le
9f an e*ternal stress is applied to a system at equilibrium> the system adFusts in such a way that the stress is partially offset as the system reaches a new equilibrium position.

Changes in Concentration
"2 g! 0 )H2 g! Equilibrium shifts left to offset stress 2"H) g! /dd "H)

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Le Chteliers Princi le Changes in Concentration continued

Gemove /dd Gemove /dd

9ncrease concentration of product s! 2ecrease concentration of product s! 9ncrease concentration of reactant s! 2ecrease concentration of reactant s!

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a/ 0 b1 cC 0 d2 Change

Shifts the Equilibrium left right right left

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Le Chteliers Princi le Changes in Holume and Iressure

Change

9ncrease pressure 2ecrease pressure 9ncrease volume 2ecrease volume

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/ (g) 0 1 (g) C (g)

Shifts the Equilibrium

%ide with fewest moles of gas %ide with most moles of gas %ide with most moles of gas %ide with fewest moles of gas

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Le Chteliers Princi le Changes in <emperature

Change

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Exothermic Rx K decreases K increases colder

Endothermic Rx K increases K decreases

9ncrease temperature 2ecrease temperature

hotter

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uncatalyJed

Catalyst lowers Ea for both forward and reverse reactions. Catalyst does not change equilibrium constant or shift equilibrium.
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Le Chteliers Princi le /dding a Catalyst does not change K does not shift the position of an equilibrium system system will reach equilibrium sooner

catalyJed

Chemistry In Action 5ife at High /ltitudes and Hemoglobin Iroduction

Hb aq! 0 O2 aq!

Kc '

-Hb.-O2.

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HbO2 aq!

-HbO2.

Chemistry In Action <he Haber Irocess

"2 g! 0 )H2 g! 2"H) g! H+ ' ,D2.( EKCmol

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Le Chteliers Princi le
Change Equilibrium Constant no no no yes no

Concentration Iressure Holume <emperature Catalyst

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yes yes yes yes no

Change

Shift Equilibrium

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