CHEMICAL EQUILIBRIUM

14.1 THE CONCEPT OF EQUILIBRIUM AND THE EQUILIBRIUM CONSTANT Many chemical reactions do not go to completion but instead attain a state of chemical equilibrium. Chemical equili !ium" A state in which the rates of the forward and reverse reactions are equal and the concentrations of the reactants and products remain constant. Equilibrium is a dynamic process the conversions of reactants to products and products to reactants are still going on, although there is no net change in the number of reactant and product molecules. For the reaction: N2O4(g) 2NO2(g)
N
2

O
4

Forward rate
Rate

concentration

N O
2

Reverse rate
time time

The Equili !ium C#$%&a$& "

c

For a reaction:

A + bB

C +

C !c K D !d Equilibrium constant: c = A!a B!b "he equili !ium c#$%&a$&' (c' is the ratio of the equilibrium concentrations of products over the equilibrium concentrations of reactants each raised to the power of their stoichiometric coefficients.

La) #* ma%% ac&i#$ # "he value of the equilibrium constant e$pression, %c, is constant for a given reaction at equilibrium and at a constant temperature. "he equilibrium concentrations of reactants and products may vary, but the value for % c remains

the same. Other Characteristics of Kc &' Equilibrium can be approached from either direction. (' %c does not depend on the initial concentrations of reactants and products. )' %c does depend on temperature. Magnitude of Kc *f the %c value is large +%c ,, &', the equilibrium lies to the right and the reaction mi$ture contains mostly products. *f the %c value is small +%c --&', the equilibrium lies to the left and the reaction mi$ture contains mostly reactants. *f the %c value is close to & +..&. - %c - &.', the mi$ture contains appreciable amounts of both reactants and products.
Chemical Equilibrium Notes

&

14.2 WRITING EQ I!I"RI M CON#T$NT E%&RE##ION#

Ca'cu'ating E(ui'i)riu* Constants+ Kc

%c values are listed without units don/t include units when calculating %c. *f equilibrium concentrations are 0nown, simply substitute the concentrations into the equilibrium constant e$pression1 Exam l!: For the reaction, CO + 3H2 CH4 + H2O, calculate %c from the following equilibrium concentrations1 23! 4 ...5&) M6 7(! 4 ..&8)9 M6 27:! 4 ...)8; M6 7(3! 4 ...)8; M.

H#m#+e$e#u% equili !ium1 reactants and products e$ist in a single phase. For the gas phase reaction1 <(3:(g) (<3((g) "he equilibrium constant with the concentrations of reactants and products e$pressed in terms of molarity, %c, is1 <3( !( KC =
<(3: !

,a% Pha%e E-.!e%%i#$% ca$ al%# e e-.!e%%e/ 0 (. "he %p e$pression is written using equilibrium partial pressures of reactants = products. For the reaction given above, the %p e$pression is1 ><3 $ ><3

(. 4
>
<(3:

K is r!lat!d to Kc

Since pressure and molarit are related ! the "deal #as $a%, the &ollo%in' e(uation relates )p and )c: *n K " Kc#R$% %here R = +.+,2? atm % mol

. / = temperature in )el0in

n = moles o& 'aseous products 1 moles o& 'aseous reactants Note that )c = )p %hen the num!er o& 'as molecules are the same on !oth sides.

He&e!#+e$e#u% Equili !ia a$/ S#l1e$&% i$ H#m#+e$e#u% Equili !ia He&e!#+e$e#u% equili !ia1 reactants and products are present in more than one phase.
&ur! solids and liquids: concentrations o& pure solids and li(uids are &i2ed ! their densit and molar mass 3!oth constants4 and do not 0ar %ith the amount. Density Molar Mass
M = m o &.) l = g 7 ml m L l &L m o 7 l g

56=M=

 /hus, the concentrations o& solids and li(uids are incorporated in the ) c 0alue. the are not part o& the 0aria!le )c e2pression:

'mit conc!ntration t!rms (or solids and liquids (rom K c and K !x r!ssions) onl* includ! t!rms (or +as!s #+% and aqu!ous substanc!s #aq%, 3Cu(s) + 2NO3 (aq) + ,H (aq )
: +

82ample. 9rite the )c e2pression &or the &ollo%in' reaction: 3Cu (aq) + 2NO(g) + 4H2O(l)
2+

M#/i*0i$+ Equili !ium C#$%&a$& E-.!e%%i#$%" A. 2hanging stoichiometric coefficients1 -4 2SO2 + O2 24 SO2 + & ( "& %e multipl an e(uation ! a &actor, %e must raise its ) to that po%er to 'et the ne% ). ;. Re0ersin' the reaction: 34 2SO3 2SO2 + O2
)3 =

2SO3 O2 SO3

)= )2 =

) is the reciprocal o& the ) 0alue &or the re0erse reaction. C. <ddin' 8(uations &or =ultiple 8(uili!rium Reactions: -. 2. 3. < + 2; < + > C ; )- = )2 = C )3 =

2< + ; + >

9hen %e add e(uations to 'et a ne% e(uation, the ne% ) is the product o& the other )?s. 82ample.2H2(g) + O2(g) 2H2O(g) N2(g) 3H2(g 2NH3(g) + ) Calculate the 0alue o& )c &or 4NH3(g) )c = -.@2-+ )c = -.A2-+ + 3O2(g)
2 2@

2N2(g) + BH2O(g)

Chemical Equilibrium Notes

14.3 THE RELATIONSHIP BETWEEN CHEMICAL KINETICS AND CHEMICAL EQUILIBRIUM For the reaction N2O4(g) 2NO2(g) Rate o& &or%ard reaction = Rate o& re0erse reaction C&5N2O46 = 2 Cr5NO26 k NO( !( Rearran'e:
f

N(O k = = r )c :! /hus, the e(uili!rium constant is simpl the ratio o& the &or%ard and re0erse rate constants %hich are !oth constant 0alues at a 'i0en temperature. 14.4 W,$T -OE# T,E EQ I!I"RI M CON#T$NT TE!! #.

P!e/ic&i$+ &he Di!ec&i#$ #* Reac&i#$ "he !eac&i#$ qu#&ie$&' Q' is the resulting value when we substitute reactant and product concentrations into the equilibrium e$pression. &. *f A , %, the reaction will go to the left. @ "he ratio of products over reactants is too large = the reaction will move toward equilibrium by forming more reactants. (. *f A - %, the reaction will go to the right. @ "he ratio of products over reactants is too small = the reaction will move toward equilibrium by forming more products. ). *f A 4 %, the reaction mi$ture is already at equilibrium, so no shift occurs. Exam l!: For the reaction, ; 2<, ) c = 2. Buppose ).. moles of A and ).. moles of C are introduced into a (... ? flas0. +a' *n which direction will the reaction proceed to attain equilibriumD +b' Eill the concentration of C increase, decrease or remain the same as the system moves towards equilibriumD

Calcula&i$+ Equili !ium C#$ce$&!a&i#$% se ICE Ta)'es To #o'/e E(ui'i)riu* &ro)'e*s 0or Kc Or E(ui'i)riu* $*ounts1 &. I 2 i$i&ial c#$ce$&!a&i#$1 *nitial concentration of reactants are usually given6 initial >roduct!/s are assumed to be . unless otherwise specified. (. C 2 cha$+e i$ c#$ce$&!a&i#$ 1 Assign change as the variable $6 use the stoichiometry of the reaction to assign changes for all species. ). E 2 equili !ium c#$ce$&!a&i#$" E 4 * F 2 <ote, values in *2E tables can be in terms of moles or Molarity +or atm for % p', but values used in the %c e$pression must be in terms of Molarity +or atm for %p'.

Chemical Equilibrium Notes

82ample: 9hen +.2A+ mol SO 2 and +.2++ mol O2 are placed in a -+.+ $ 0essel at -+++ ), the e(uili!rium mi2ture %as &ound to contain +.-B2 mol SO 3. Calculate )c &or this reaction: 2SO2(g) + O2(g) 2SO3(g)

Me&h#/ &# *i$/ equili !ium c#$ce$&!a&i#$%

&' Set up the "C8 ta!le. (' Set up the )c e2pression. su!stitute e(uili!rium concentrations &rom the "C8 ta!le into )c. )' Sol0e &or 2. plu' the solution &or 2 !acC into the e(uili!rium concentration e2pressions.

Pe!*ec& %qua!e .!# lem &# %#l1e *#! /aCe the s(uare root o& !oth sides %hen the math e2pression is a per&ect s(uare. 82ample. <t 43+ DC, )p = A4.3 &or the &ollo%in' reaction: H2(g) "2(g) + 2H"(g) < mi2ture o& H2 at a pressure o& +.A++ atm and "2 at a pressure +.A++ atm is placed in o& a container at 43+ DC. Calculate the e(uili!rium partial pressures o& H", H2 and "2.

Qua/!a&ic F#!mula E-am.le

For this reaction, H2(g) + F2(g) 2HF(g), )c = -.-A2-+ at a certain temperature. Suppose 3.+++ moles o& H2 and B.+++ moles o& F2 are placed in a 3.+++ $ container. 9hat are the e(uili!rium concentrations o& H2, F2 and HFE
2

Chemical Equilibrium Notes

-.,/ 0AC$'R1 $HA$ A00EC$ CHEMICAL EQUILIBRIUM Le Cha&elie!3% P!i$ci.le" "& a s stem at e(uili!rium is distur!ed ! an e2ternal stress, the s stem adFusts to partiall o&&set the stress as the s stem attains a ne% e(uili!rium position. Cha$+e% i$ C#$ce$&!a&i#$ <ddin' a reactant or product, the e(uili!ria shi&ts a%a &rom the increase in order to consume part o& the added su!stance. Remo0in' a reactant or product, the e(uili!ria shi&ts to%ard the decrease to replace part o& the remo0ed species. 8.'. For H2 + "2 2H", does the e(uili!ria shi&t le&t or ri'ht i& %e: a4 add H2E !4 remo0e "2 E a4 !4 Cha$+e% i$ 4#lume a$/ P!e%%u!e ;ecause the pressure o& 'ases is related directl to the concentration ! G = nHI, chan'in' the pressure ! increasin'Hdecreasin' the 0olume o& a container %ill distur! an e(uili!rium s stem. "& G increases 3I decreases4, the s stem shi&ts to the side %ith a smaller num!er o& 'as molecules 3this e&&ecti0el re:esta!lishes e(uili!rium ! decreasin' the pressure4. "& G decreases 3I increases4, the s stem shi&ts to the side %ith a 'reater num!er o& 'as molecules. 82ample: For N2(g) + 3H2(g) 2NH3(g), does the e(uili!rium shi&t le&t or ri'ht i& the pressure is increasedE

Cha$+e% i$ Tem.e!a&u!e
Heat can !e considered a reactant in an endothermic r2n and a product in an e2othermic r2n. 8ndothermic 3H J +4 82othermic 3H K +4 R + Heat R Grodu cts Groducts + Heat

Recall that !oth )c and the position o& the e(uili!rium s stem %ill 0ar %ith temperature: @ )c is lar'er %hen the reaction shi&ts ri'ht. /his occurs i& / is increased &or an 8ndothermic Reaction or / is decreased &or an 82othermic reaction. )c is smaller %hen the reaction shi&ts le&t. /his occurs i& / is decreased &or an

8ndothermic Reaction or / is increased &or an 82othermic reaction. 82ample. "& the temperature is decreased &or the reaction: 2CO 2 2CO + O2, *H = ABB CL. a4 9ill the e(uili!rium shi&t le&t or ri'htE !4 >oes ) c !ecome lar'er or smallerE Effect of a Catalyst Catal sts lo%er 8a &or the reaction, so a catal st decreases the amount o& time taCen to reach e(uili!rium &or !oth the &or%ard and re0erse reactions. /he catal st does not a&&ect the e(uili!rium concentrations o& reactants and products in the e(uili!rium mi2ture. thus, the )c 0alue does not chan'e. Choosing Optimum Conditions $e Chatelier?s principle can !e used to select optimum conditions to &orm a su!stance. e.'. /o &orm more NH3, predict the optimum conditions &or temperature and pressure. N2(g) + 3H2(g)
Chemical Equilibrium Notes

2NH3(g)

H = :M-., CL
B