ITT CHNG CH 14 Chemical Equilibrium

Chemical Equilibrium
Pe U rs se o n W al IS u EL se Y on !!! ly .
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!
"2O# g!
Chemical equilibrium 2"O2 g!

$#.$
"2O# g!
2"O2 g!
equilibrium
%tart with "2O#
equilibrium
equilibrium
%tart with "O2
%tart with "O2 & "2O#
$#.$
constant
$#.$
"2O# g! K' -"O2.2 -"2O#.
2"O2 g! ' #.() * $+,)
K'
a/ 0 b1 cC 0 d2 -C.c-2.d -/.a-1.b
Law of Mass Action
$#.$
K 33 $ K 44 $
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
$#.$
Homogenous equilibrium applies to reactions in which all reacting species are in the same phase.
-"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!

$#.2
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.
-CH)COO,.-H)O0. ' K: Kc = c -H2O. -CH)COOH. ;eneral practice not to include units for the equilibrium constant.
$#.2
-COCl2. +.$# ' ' 22+ Kc ' -CO.-Cl2. +.+$2 * +.+?# Kp ' Kc(RT)n
n ' $ 8 2 ' ,$
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$ * )#=!,$ ' =.=

$#.2
PO2 ' $?@ * +.#++!2C +.2=+!2 ' )#= atm
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
$#.2
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.
-CaCO). -CaO.
CaCO) s!
CaO s! 0 CO2 g! -CaCO). ' constant -CaO. ' constant Kp ' PCO2
$#.2
CaCO) s!
CaO s! 0 CO2 g!
PCO 2 does not depend on the amount of CaCO) or CaO

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

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

,)
2"O2 g! -"2O#.
"2O# g!
$ ' 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.
$#.2
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.
$#.2
Chemical Ainetics and Chemical Equilibrium

/ 0 21 kf kr /12 ratef ' kf -/.-1.2 rater ' kr -/12.
Equilibrium ratef ' rater kf -/.-1.2 ' kr -/12. kf -/12. ' Kc ' kr -/.-1.2
$#.)
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
IF
<he reaction quotient (Qc) is calculated by substituting the initial concentrations of the reactants and products into the equilibrium constant Kc! e*pression.
$#.#
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.
$#.#
/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.
+.+() , x
+.+$2 0 2x %olve for x

$#.#
+.+$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
$#.#
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)
$#.?
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!
a/ 0 b1 cC 0 d2 Change
Shifts the Equilibrium left right right left

$#.?
Le Chteliers Princi le Changes in Holume and Iressure
Change
9ncrease pressure 2ecrease pressure 9ncrease volume 2ecrease volume
/ (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
$#.?
Le Chteliers Princi le Changes in <emperature

Change
Exothermic Rx K decreases K increases colder
Endothermic Rx K increases K decreases
9ncrease temperature 2ecrease temperature
hotter
$#.?
uncatalyJed
Catalyst lowers Ea for both forward and reverse reactions. Catalyst does not change equilibrium constant or shift equilibrium.
$#.?
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.
HbO2 aq!
-HbO2.
Chemistry In Action <he Haber Irocess

"2 g! 0 )H2 g! 2"H) g! H+ ' ,D2.( EKCmol
Le Chteliers Princi le
Change Equilibrium Constant no no no yes no
Concentration Iressure Holume <emperature Catalyst
yes yes yes yes no
Change
Shift Equilibrium
$#.?

ITT CHNG CH 14 Chemical Equilibrium

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ITT CHNG CH 14 Chemical Equilibrium

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Chemical Equilibrium

Chemical equilibrium 2"O2 g!

%tart with "O2

%tart with "O2 & "2O#

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

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

Law of Mass Action

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

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

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

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

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

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

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

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

/01 C02 /01

C02 E06 E06

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

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

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

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

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

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

7riting Equilibrium Constant E*pressions

Chemical Ainetics and Chemical Equilibrium

Calculating Equilibrium Concentrations

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

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

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

Le Chteliers Princi le Changes in Concentration continued

Shifts the Equilibrium left right right left

Le Chteliers Princi le Changes in Holume and Iressure

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

Shifts the Equilibrium

Le Chteliers Princi le Changes in <emperature

Endothermic Rx K increases K decreases

9ncrease temperature 2ecrease temperature

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

Chemistry In Action <he Haber Irocess

Concentration Iressure Holume <emperature Catalyst

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