.

CHEMICALEQUILIBIURM

CHEMICALEQUILIBRIUM
PART1:

EQUILIBRIUM
LAWANDEQUILIBRIUM
CONSTANT

Obiectives
.
.
.
.

Explain, in tems of rates of fonyad and reversereactions,what is meant by a reversiblereaciion and

dynamicequilibrium:
Deduceexpressionsfor equilibdumconstanbin termsof concentration,
lG,and partialpressures,lg;
Calculatethe valuesof equilibriumconstanbin termsof concentrations
or padialpressuresfrom appmpriate
data;
Calculatethe quantitiespresentat equilibrium,
givenappropriatedata:

Textsand References

\*

.
.
.

A-LevelGuides,Chemistry,
J G R Bdggs,Longman,
3d ed,ChapterI
A-LevelChemistry,E N Ramsden,StanteyThomes(Publishers)Ltd,2med, pg 19t206
Chemistryin Aciion,MichaelFreemantle,MacmillanEducationalLtd,pg 250- 2*,25&261

IRREVERSIBLE
REACTION
.
.
.

Manychemicalreactionsgo to comoletion.
This meansthat the reactioncontinuesuntil one of the reactantsis completely
used up in the reaction.Whenthis happensthe reactionstops-- lt has gone to
completion.
Suchreactionsare irreverciblereactions.
A +B )C +D

This can be represented

graphically:
c

.9
E
{)
o

Examples:
0) F'!

t",r!

(t\ cacDg.

AJC/JC,1

.,"*;I +w lvrl
z{tl

a,

taClz

t.ns

r.rt

+ (Az +

>o

CHEMICALEQUILIBIUR'N

REVERSIBLE
REACTION
.

ManJ othe-r,reactions. lo ,ort go t

a.,.plctn,r
productsof the reactionthemserves
reaa@ctanis.

'

such chemicalreactionsthat take placein both directionsare calledreversible

reactions.Thisis indicatedby the reversiblesign,' !; ".
A tB

&'*'d "r'
<br.lultl

, because
- the

C+ D

,r |i

Thiscan be represented
graphically:

c
o
o

Aftertimet, forwardand backward(reverse)reactionsoccurat the sanra,L

Boththe concentrations
ofthe reactants
(A andB) andproducts
(c andD) remain
arttdnt
.
. Thereare still certainquantitiesof reactantsremaining
(i.e.concentrations
of A andB * 0).
The system is said to reach

Examplesof
reversiblereactions:

OH 2 ra r
@ rro3

<
F-

'

:ut
,Jo:

oz

Otherexamples:

(1,

AJC/JC1

CHEMICAL EQWUAIURM

DYNAMIC
EQUILIBRIUM
.
.
.

In a reversiblereactionbothforwardand backwardreactionscontinueindefinitely
andthe systemis saidto reachdynamicequilibium.
Dynamicequilibrium
In an equilibriummixture,both the fonrard and backward
a
o
o
place.
o
reactionsare stilltaking

Systemdoesnotundergoanyobservablechange.
i.e.Concentration
of eachspecies(equilibrium
mixture)

remainsconstant.
I

t-

(*la o( &"oa

rih i Rrtr e{ gr.g

"o4rl

oo

o
o

,.rrr

Equilibrium
canonlybe achievedin a closedsvstemin whichthereis no exchange
of matteror energybetweenthe systemand its surroundings.

EQUILIBRIUM
LAWANDEQUILIBRIUM
CONSTANT,
K

The behaviorof a reversiblereactionat equilibriumcan be describedin termsof

equilibrium law. This enablesthe calculationof a quantityknown as the
equilibriumconstant,K.

K givestheequilibrium
concentration
of reactants
andproducts.

K can be expressedin termsof:

(1)Concentrations;
(2) Partialpressuresof gases;and
(3) Rateconstants.

(1)

K in terms of Concentrations
Consider
an equilibrium
system:
a A +b B s cC+dD
A, B, C and D represent
chemicalsubstances,
a, b, c and d representstiochiometric
coefiicients.
ay,'Lt"rlvt

La,r

fc l' I s J '
'

AJC/JC1

fr ] ' [ Bl'

3
I I = eqm concin mol dm

CHEMICAL EQUILIBIURM

The aboveis a mathematicalexpressionof the

lad
which relates the concentrationsof reactantsand procluctsIn an equilibrium
mixture.
The expressionshowsthat no matterwhatstartingconcentrations
are for A, B, C
and D, whenequilibrium
is established,
the aboveratioof concentrations
will be
aalarl

It is possible to determine the concentrationsof the substances

through
experiments.
K" is called the
a

(2)

.uiriLr:,r!,

oe.r+.*

K" is a constantat
( ,*t t-Unitof l(" is

for the reaction.

K in terms of Paftial pressures

(Applicableto reactionsinvolvinggases.)

aA (S)
t.e.

K r,

+ bB (S) s
?'

c.

oe
'A

9b
' ,E

cc (s) +

dD (s)

WhereP^is the partialpressureof

A, etc.
(Unitof gas: atmorpa)

Unitof Ko

l"n + o,\'-^'o-t

Partialpressures
of gasescanbe calculated
usino
Pr= Xr.x P1

Pr = Totalpressure
of gases
p = Molefractionof X = nx/nr

(x
(X
"P) ' Dp)

Hence,Kocan also be
expressedin terms of 1 and p:

(3)

( x , p) ^( X"t ) t

K in Termsof RateConsfants
K may be derivedfromkineticsif we knowthe rateequationsfor bothforward
and
reversereactions.
tl

e .g . A

B5C
tb

AJC/JC1

CHEMICAL EQUILIBIURM

. rf.orr

ol 'S,parl .cac{ioy , 1.
k1[tl[o)
' fub + asvs< nocl.t:* , r" = kb fc]
' At

4clrb,t,a

of 6,we'A

th7- .t*
Yt

alt

Grqx

'l.acloat

qQ .+al',

f ,

uaItft s] , rr[.]
t c 1 / 1 g 1 1 6 e 1=) F r /Ku
t(

= kl
/Kb

' Y.,;r',;
:;
)'4 z o'w

t,

Note: This expressionis only true if the chemicalreactionproceedin a single step. Many '1 "n
reactionsdo notproceedin onestepbut proceedthrougha complicated
mechanism.
O

Why doesthe expression

: K = k/k applicable
to onlysinglestepreactions?

POSITION
OF EQUILIBRIUM
.

Definesas the proportionof productsto reactantsin theequilibriummixture.

p+n
| ,\,,r

.,

tP)fs'l

't= 6Li

lf conversionof P andQ intoR andS is sma//,the p.o.m.liesto the /eft

r +A

, +S
,1

\--

K +3
(r

at

Jh4.rt )

lf conversionof P andQ intoR andS is large,the p.o.m.liesto the nght:

f+ A

P +S
l*

iI

l^ ' . )

Changein conditionse.g.pressure,temperature
etcwill affectthe p.o.m.
NOTES ON EQUILIBRIUM CONSTANTS KCAND KP
.

Equilibrium
lawonlyappliesto systemat equilibrium.

( and [$ are only affectedby_t"rr+".e_J_Theeffectof temperature

dependson theenthalpy
changeofthe reaction,
AH.

Magnitudeof G and Ko providesa usefulindicationof the e)dentof a chemical

reaction.

AJC/JC,1

CHEMICALEQUILTBruRM

Reactionhas a skong@
positionof equilibrium
liesto theright.
composition
willconsistof largely
reactants;
positionof equilibrium
liesto the left.
10-3<K <103

Significantamou@

P.o.m. can be affectedby

ca,rtt.7-t.'o,,cr.
. However,K is only affectedby temperatura

'

K for a reactionindicatesthe extentof a reaction,butgivesno

information
:-'
the rateof reaction.rt teilsus howfar but not howfast-thereactiong;;;. about

Examples:
(1)

Givethe( andunitsforthefollowing
reactions:
pcts

(b) PCl3+ Cl, [r.r:] [c1,]

tpttcf

[-r r."'r1[,,] r"-f

. r.t

Lu-rJ

l;r,il

f^r t*"t]
=

' L^au'zJ

(2)

f,,".,rr"-{l
--

;=
lillca*

L.c/i'''l
t
J

l * tt-,).' )

A sealedflaskcontained
2 moresof iodine,19mores
of hydrogen
iodideand4 moresof
hydrogen_at
equiribrium.
carcurate
theequiiibriu;
tt
for
thereaction.
Givethe
unitsforK.
""".tr.i,
Solution:
b+ tt"r va.,,.c ol rt
nr .

^,,r.
(*t7

ol ,i,l
o*

ot

.ri.

4,".

2HI

fl61g 51 1.
rt

-'s
-

t7

t4Z

'n

t (c

,H I,

.4L

l,tr 7,
K.'F;m

AJC/JC1

H2+

[,r ]'

>t.

tiilil

: 45, rs

lo

m q,*tr

CHEUTCALEQUIUBIURIt'

3(a)

Whena mixtureof 50 g ethanoicacid and 20 g ethanolis allorcd to readt equilihium at

constanttemp,it ls that 0.469mol of ethancicacida.s foundto be gesent. Calorlatethe
equilibriumconstantfor the Baction at this tempratw.

Solution
CH3COTH(4
t;l

CTH5OH(r)

to

tr$',

0o

ff'o.r13

ft. o,ers

ar ,\0r.,al .

0.033- r

o..fJt - I

.0, rfrl

O,8t3-,
(A'r"\,t-'e
qPrtq

o..+tl t
4 .tc.t&.,

,-

oo

r E o,'l+
V f.t)

0',.*h

o.rb+,/v

o' + r\lv

a.a-thh

cH3corqHs(4 + HzO(4

,o

Id tl f ur.J ,
.4h

o,tt.

/v

fttr"o,"x3l[u'01
[crrr a, n][6Hsc*r]
Io 3.+II o.rr+l

I J I LT J :

+.02 I

l+lt+]
(b)

3.fl) molesof ethanoland 1.00 mde of ethanoicacidweremixedtogetherat the

producedat equilibrium.
Calculatethe amountof ethylethanoate
sametemperaturc.
Solution
: i.

-tn
-*

(0 +CrHsOH(/)
CH3CO2H
!

'.ol|r.

'

-r,Q
lc t

l ,o o - >

t. o0 - r

t!

tr@ ' a )
v

t1.c-r)

lU. .l

fel, to, u] fa,$ ruJ

t+l[+]

l0.ortc+ ra.of - o
+.42 0<l\ v s.1o!
fL

lclr^,..

AJC/JC1

o0
tr

[cx1o1c,ns] frl no1

Fc ;.{.or :

3, oo

r. oo

' * ) t< ;

cH3corcrHs(4 + HrO(4

\,,.- *. 4 ..r *
o..y ,..o g

c{, (ad

',Et .l
o. {ot

ctll &o. tr
,.,rllr

. fd ur.l

CHEMICAL EQUILIBIURM

(4)

Dissociationof NaOr
0.05 mol N2o1is introducedinto a vesselof 1 dm3 at 25"c. The totar pressure
at
equilibrium
is 142.5kpa. Calculatel$ for the dissociation
of N2Oa.
NzOr(9)

2NOdg)

Solution:
To caVdh r,r0at

gcst'.r ,

Pi o+

^LO4

i
lrv ? o.l h

1 V' n r1

It,r.

_ o .o s x c ..)l r:4 1

r
(o.rf ,r.,

1 r tg r
= t..t rr x |0s Pa
1z

Ne 01 l9)
triid

li nel I

| ' t .4 r

(P r' - P)

p
P{,,

'

tq t, S - v t ,i
ta

?|t . . a +.

Kr'

t? ' b

t2 r,1 -

.:P

l,a 3 q tlo l- ?

t\r.3.i -9) + e?

-_

o.og

PLaoq s

:N 02 ft)

.
tf ,(

!4).!

rP.

_ tt .g l < ?a
3 1 .2 l Po
'

r! j , , 876

tD,

tr7 2t

P.r,
"{

1 0 3 ,3

/,

= t3't+

lt.tkla
-

Self-DirectedLeaming:
(5)

The equilibrium
mixturein a flaskwasfoundto consistof o.s0moleof so2, 0.12mole
Ozand 5.0.
weregaseo;s.The pressuiein the
Toles of SO3.All threesubstances
was8.0x 105
Pa.
Calculatethe partialpressuresof SO2,02 andSO3in the flask.
(il
(b)
Writean expression
for Kofor the equilib,rium:
'2SO,(g) + o, (g) S
2SOs(g)
(c)
calculate the varue of G for the mixtuie in the flask. state the units.
Ans: 5.85 x 1O'3Pa'1

AJC/JC1

CHEMICAL EQUILIBIURM

Self-Directed Learning:
(6)

The equilibriumconstantK for the esterificationreaction= 4.00. Calculatethe mass

ethanolthat mustbe mixedwith 2.0 mol of ethanoicacidto produce1.5 mol of ethyl

ethanoateat equilibrium.
cH3corH(4+c2H5oH(4

HzO(4
CH3COTCTH5(/)+

Ans:121.0 o

PRINCIPLE
LE CHATELIER'S

PART2:
Obiectives:

State Le Chatelieis Principleand applyit to deducequalitatively(fromappropriateinformation)the effectsof

presure,on a systemat equilibrium:
changesin temperature,concentration,
Deducewtrethercfrangesin temperature,concenfationor pressureor the presenceof a catalystaffect the
valueof the eouilibrium
consiantfora readion:

.
.

LE CHATELIER'S
PRINCIPLE
Summarizesthe effect on the compositionof an equilibriummixture when
conditions
arechanged.
Staftr
[i,e.

-lrat

a'c|t

clor{rr b

g.rrtn

so'ic

rrft

rv' p?ri hL'i/ m

{o

rr rubj.c+ad

vnl Sdo yg r.rth 4t .t"d\'rt

chet'0(

f.t.tJqr

, atc.)

ih

,.4}i'{<r"'r
- +ra

Note: The systemcannotcompletely

cancelthe changein the erternalfactor,but it movesin
the direclionthatwill minimizethe change.

FACTORSAFFECTING
POSITION
OF EQUILIBRIUM
1.

lnfluencein Concentration

When the concentrationof the reactant is increasedor decreasedin an

equilibrium
occursso as to &rrrcr d 'tnd.a'd$au.lg
system,reaction
lL.
.

co^ar.tro,{,oon ut

To ' wt.rr
AJC/JCI

*| t

1i"c+ r^folqnC

changz ^n

coq.'*V'5t"vti
e

CHEMICALEQUTUBruRM

Example:

Hr+lz

-+lr. irtru*

,to
'rAue
j!b!_
-r=

grs Ar,a

fur&.I,
H-

i^

no4

.r oeht6

fA']

e+l6\^

sL,p6

pctu,.

a5.

HI

{arourrl

t4 a !_ zn-----------.-:
L

New eqm composition : t H,1 D FArf

rnr*.,r i

ft)

Lt cx,,r<s

.9
E
o

By LCP,to reducetfreAecr
to producemoreH2.
ga$-a/d,
=)

Art

rct'eAx^ la,or,'.t .
!:

r-=+

lHr

Neweqm composition: fx,-l * furl 4.,.ol. ., L!r1;nr*,

K" : ,a.star+

2.

lnfluence in Pressure

when totalpressure
is changed,concentration
of ail speciesin thecontainer
wirl
changeto reducethechangein pressure.
lncreasein pressure(by decreasingthe vorume)brings morecures
croser
together.To rerievestress of additionarpressure,ieactionoccurs produce
to
er.rrr

*'olqrl.r

Of gasgs.

Hence,increasein pressurefavorsthe reactionthat producesfewermorecures

of
gasesandviceversa.
Example:

AJC/JC1

Nz+3Hz

2NHJ

10

CHEMICAL EQUILIBIURM

Totalmoles:

plt

9n<. *\t

llt

*r

rye {on

Pressure on {rrc dgh,|

n& I lg r-cP , ep'l{{.u
t
lrtc{

nvrrlcr cf trolc..to

;",15
, ' lr , il',,.,
'. i .,: " .:.,,...,,,,

Etfect

i:::;1,i,._'.t:

so ar to

...

l^as + gr.,v*lrlrr cq^.fq^f +. a gartr h r

,,lr 3h$t .t +"
J5!L
, ,.,hrch nA*ce 'l*
lhr- atat

&.C!4,.

p^..${n

Jt E',.raaf n.b&.or,tl'
.ila + 3Hz r.rlle
:5

( P*,)
( pu) ( p,J
New eqm compositioni 4r, I ltx" I o'.^r. \ 4,,p,i" 14at'
K": ,axa*.

Sincethe leftsideof the equationhas4 particlescomparedto 2 particleson

the rightside,by LCP,eqmwillshiftsto the lult
to increasethe total
Pressure no. of molecules
so as to increasethe totaloressure.

ba<Y,,t l ea,&r
lo,",t d ,
d:. r 3$ r- '-r,!--- L\tH A

New eqm crmposition i (*, a ltr, iv,crc.s ,j n\1r )c.re'e

G: r.-rtor't

NOTE: Changein pressurehasno effecton the p.o.mfor gaseousreadionsif the

no.of moleculesin bothsidesof the equationis the same.
Example:
3.

Hu+ lz

2Hl

Influence in Temperature

When an equilibriums)Nstem
is subjectedto an increasetn temperature,the
brn
AnA

rcacuo.a

Example:

ot;v

t*

v{.. Vtrt(.

Nzor

2NO2 AH>O(Foruardreactionis endothermic)

(Backwardreactionis exothermic)

Change

Effect

Temperature 4

aht.

u",

ar.tro'f

$,b*n
,rsqtk

(h*fr
th

+- @,t4 noa g-dr4c

b $, .@
s*q&oo
&
0+ rr4(ra$ ad t rno t
a la

tvt

alr $,,y1)

-[le

tf*tn

A Yt.

o l!{-

6o(l,o)r" rcX
AJCiJCI

11

11

cd71' -

lA, o

CHEMICALEQUILIBIURM

:+

hrr.rad
Nl.ll-

,tn 1hsF rqtor.rA .

,^101
:=r

Neweqmcomposition
: [^r,o.]

Aac,eot,

r^.,r r *

iv' ( z .34.

@ ill

Temperature l,y
Byr-vr,
LCP,equlllDnum
equitibriumGhifts
snlTISIO
toGe
Ine

E\t)]

l?+l

tO prOdUCemOre reaCtantSGin;

thebackward
readionresultsin r;te;Gd;;;"rgi

temperature.

"nJi";"

to increase
the

ra.nb,^ lceer
r.lr 9" ..:1p,

$(r.I(n$

New eqm composition :

fu o,l'

f^lno.]

i,.61ta,.t, fi.ro:f d"rar:..

r,ilr dec+r

lC = Ifr;lNote:
a

fncreasein temperaturefavors the

ca[4ra1,q rector

Decreasein temperature
favorsthe ..orr,r,.,r.F,
Positionof equilibrium
andK
.rn"^".,
.

Reason for changes in K:

RecallK canbe expressed
as rateconstants,
K = k/k.
Increasein temperatureincreasesthe rate constantsand rates

reactions
rhroush
qi[fpq!nqgl.

of both forwardand backward

[kr = Ae-Emr,k. = Ae'm where Er + EJ

4.

Influenceof Catalyst
Lt4t

rateof reaction.

po ridt

t)

affect the positionof equilibriumand K.

Reason:
catalystlowersthe activationenergyof bothforwardandbackward
reactions:
:)

iv\ c'\1 ..r

r4+(

= ftrJ,L\ar- \
,Pt4'\'r

AJC/JC1

{^a

lr,{"

.h,oO

^41?rrL 0cr,{r, \rt

/ uoff,,I,.'a

.r"a^c,.r

.,r<r,r}.dirrt

cir.ctlg

.pa'c o a+ o,*r.flt r,rr

CHEMICALEQUIUBIURIT

5.

lnfluenceof lnerl Gas (atconstanttemperature)

1.

At constantvolume

Total pressureof the systemincreasesdue to increasein numberof gaseous

particles.
After additlonof lnert oasea(a I

OmlnalSvstem

@ o@
o@

@
@

00f-->

oa

@O

o@

\9

Equilibrium
System: @
.

(^o
,,60

Concentrations
or partialpressuresof reactantsandproductsremain ur'rlonttA
+ No alft,t en +lu prrtrora ee qrr'!b;ut' , aa| K.

2.
.

At constant pressure
To maintaina constantpressure,reactionvolume must increase.
After additionof inert qasesfll I

OrqinalSvstom

(^lrl

:@

mr--->

@:

io

oi"

a
@

Partialpressureofeach gasesdecreases.

Thiseffectis the sameas if the volumeincreasesis broughtby

,. l.r^'.4

+'r. taaprl

(effectdue to pressure).
lftsaac
System reacts to increase partial pressures of reactants/productsby favoring
oroductionof more molectrles

Positionof equilibriumwill shift in the directionproducing

AJC/JC1

'rc ,'lr.rc,rr..

CHEMICALEQUIUBTURM

SUMMARYOF THE EFFECTSOF CHANGINGCONDITIONS

ON AN
EQUILIBRIUM
SYSTEM
Considerthe reaction:

aA +
Changesimposeclon the
systemat Equilibium

bB

cc

Equilibium positionshifts

Concentrations
of
A and/orB increase
Concentrations
of
C and/orD increase
Pressureincreases

lf (c+d) < (a+b): To right

Verylittleeffect,if any,on
reactionsin liquidsolution.

lf (a+b) < (c+d): To tefl

Temperature
increases

lf fonrvard
reactionis
exothermic: To left

K decreased o Rate of both forwardand

If forwardreactionis
endothermic:
To right

K increased

.
.

Additionof catalyst

backwardreactions
increases.
Hence,equilibrium
is
achievedfaster.
K is also affectedby
temperature.

Equilibrium
is achievedfaster
dueto loweringof E".

Presenceof inertgas:
1. Constant
volume

No change

2. Constanttotal
pressure

lf (ctd) < (a+b): To Ieft

No change

lf (a+b)< (crd): To right

AJC/JC1

14

2. Volumemustincrease:
=) partialpressures
of
reactantVproducts
decrease)

CHEUICALECNI'UB'Uffi

(7)

The equlllbriummixturein a 2.oodmsflask at soo oc urasfoundto consistof 0.6q) mot

of SO2,0.200mol of Ozand 4.80 mol of SOa.
Calculatethe equilibriumconstantlG at S00.C for the Eaction.
2 S Oz(g )+Od s)s2 SOg( g)

(i)
Solutlon:
(i)

2sodg)
qf

etlt

Or(S)

2sO.(S)

a t00

0. lar

$+g

.+,80

PYr plT,
r ,3 t+Jl rrr.l -l

F'

ro.ro. tltar.+) talA + 90)

9!'rrt s|rt 4 4.

Iq ,rl

Pdttal R'Dr1r +

rrot P A

(o . a o ) ( & ai )( + 1t)
z , oc (o.t)t

0. ,

g.+)b x rrt ta
.qhr f'lt tllna?)
I,oo l,, rlt

( t s+ .:* r rot)t

p',t

,x?

(ii)

tgl.>* sttl 0a

ET_

6rr.et rro,)9(o.rrtrrot)

'

4'1b x,o-s qo-t

,

Howmarrymolesof 02 mustbe addedinto the flask at 50O"C in orderto

increasethe amountof SO3to 5.0Omoles?
lo\r.r {

llrrr . el'

rl 0 r,l t
O f r 1 .:
. r t - . + . *, .

o ,L c
g .4 ,

(c.

A"JClJC1

l tl d

:50s f5)

o r.o

4.tto

Irc fi

* .Fl,

(ry)(ryI'(+)

= 6+o

-l

15

l-'3

CHEI(ICALEQUI'-'BIUR',

e|lr} 5

L**ro h rt,L

a r01q) r

ot

llFGro
= o'{t

dr. xfo rrl r

T
. otor tr rt,r
:
. ?2

9,

? :Jor r { l
*.n +o'Lg
Oo
-9,

,.tc. g-{9rr)
{c 'l
-5

go
1

{.,O. I

-!]!,

()'

(ry)"(+)-- { ro

Kct

134,15

u t9 .l

3 '-6
I '

(iiD

lf 2.00 mol of SO2ard 1.00mol of 02 are mixedand allou/edto read at S(D"C.

wttat mustthe total pressurebe for 80 % conversionto SO3?
zl0r tl) +

. 7,*n
, fr

o,t&t/

rf
q

rl

( aa n l \

r,or
,.(. -t.Lc
. ,,.to

i*

Qt3)

10" Q)

l,oo

(t+)
"- =o-2o

{d.
a(o&)
:1.61

o ,tto + o ,to .

t.60

? ,.2 0
^

ft=T

tlr lT
(!,t

)(l ,$ r)(tb + o ?3)

" +.ol ( ,.t ?. I

AJC;/JC1

16

CHEMICAL EQUILIBIURM

HOMOGENOUS
EQUILIBRIA
substancespresentin onephaseonly.
Equilibrium
reactionsin whichparticipating
Examples: Reactions
in liquidor gasphase.
(/) +
CHgCOzH
NzOa(g)

(/) s
CTHsOH

+ HzO(/)
CHsCOzCzHs(D

2NO2(s)

HETEROGENOUS
EQUILIBRIA
.

phase.
present
participating
indifferent
substances
Equilibrium
reactions
inwtrich
Ca4J: ts't

Example:

ao o (s) r

co:. (j)

-""'>
fcaol p...
h-

(n31
lf a

?,- . lgli..^

Note: Whatis meantby the concentrations

of pure solid/liquid?
.
.
.
.

=
Concentration
of a puresolid/liguid
*Cgry (a constant)
Amount of solid/liquidmay change,but concentrations
of pure solids/liquids,
and of
solventsof dilutesolutionsare constant.
lt is obviouslysensibleto combineanyconstantswithK itself.
Therefore,crncentrations
of pure solid/liquiddo not appearin the equilibriumconstant
exoression.

The equilibriumconstantexpressionfor a heterogeneous

reactionis written in
such a way that the concentrations
of solids/pure liquidsare excludedin the
exDression.
Examples:

AJC/JC1

K . = [c o,]

or

l(t -- ?ro,

CHEMICALEQUTUBURU

(8) A mixtureof ironand steam

at 600 .c. The equilibrium
_wasallowedlo reachequilibrium
pressuresof hydrogenandsteam
were3.2kpa and2:4 kpa respectivery.
c"i*i"-r.e (,.
3Fe (s) +

4HrO(g)

Solutlon:

1o \.
(p=

FqOa(s)

4Hz(9)

( r .r )

:_

(P *" Jt

(9)

= ttb

'l

Thesolubilityof the silverharidesin waterdecreases

in theorderAgcr > AgBr> Agr.
Becauseof thisdifi.*19 in solubility,bromideionswill displacecilorideiins frori'sotio
silverchloride.Theequilibrium
constantlC for thisreaciion:
AgCt(s)

Br (aq) g

AgBr(s)

Ct(aq)

is 360 at 2s8K. rf 0-100mordmi Br (aq) is addedto soridAgcr, what wi[

be the
equilibrium
@ncentrations
of Br(aq)and'Ci(aq).
Solutlon:
A6cl ls) .

Bv- lq)

Itriltrt corc I
At A

c q-

Ag Br b)
-

a, log

"

{
o'l- i

IAr'

.l6b
16 -rlor
,[

fu..

.+

r-^r^l 0I

-- 36t,
t z

o,oe{\)

.l

.F

g/ -

orr" t

o, oqq?a

,,olJ\-l

v.t _ 5 sqq*L
2.?? r 1e.e ,.;g-3

AJC/JC1

cr- tq,,,
o

,' l !o -i

'

1B

CHEMICAL EQUIUAIURM

PART3: HABERPROCESS
Obiectives
.

Describeand explainlhe conditionsusedin lhe Hab.process.as an exampleof the importance

of an
understanding
of chemicalequilibrium
in thechemical
industry.

THEHABERPROCESS
T F r it z Habers tu d i e d th e N 2 (g } + 3 H ,(g ))2 N H :(g)cqui l i bri umi nt}reearl y
19O0s and concluded that direct ammonia sjmthesis should be possible.
E
Howevcr, it was not until l9l4 ttrat the cngineering problems and catal56t
question had been solved by Carl Bosch, and arnmonia production began just
E
in
time for ttle atart of World War I. Ammonia is the starting matcrial to makc
-E
nitric
acid, a vital material in t}re manufacture of the e.folosives TNl and
f
E nit r ogly c c r i n .T h e re fo rc ,th i s i s tl ro u g h tt obethefi rstl .argc.scal euseofa
synthetic chemical for military purposes.
m
Haber's contract with t}re manufacturer of ammonia called for him to receive 1
A Fritz Haber (1868-1934) pfennig per kilograrn of ammonia, and he aoon
-untom:natcly,
became not only famous but rictrhc joined the Gcrman
E
Chemical
Warfare
Servicc
at
tlrc
start
of
World
War
1
and became its director
-L
E
in 1916. The primary mission of tfie service was to develop gas warfare, and in
-r-1915 he supervised the frrst use of Clz at tie battle of Ypres. Not only was this a tragedy of modern
warfare but also to Haber personally. His wife pteaded with him to stop his work in this area, and when
he refused, she committed suicidc.
IE

In 1918 he was awarded the Nobel Prize for the ammonia qmthesis, but ttte choice was criticized because
of his role in chemica-l warfare.
After world war 1, Haber did some of his best work, continuing on in thermodynarnics (Bom-Haber
99!el Jvas a product of tllis period). However, because he had a Jewish background, Haber left Gerrnany
in 1933, worked for a time in Englald, and died in Swi rland in 1934.

THE MODERNMANUFACTURING
PROCESS
Manyimportantindustrialreactionsare reversiblereactions.
Two importantprinciplesin choosinga processfor industrialreactionsare:
(1) Efficientand(2) Economicallyviable
Theconditions
in an industrial
reversible
reaction
aimto:
o Produe maximumamountof product(highyield);
o Usingminimumamountof time;
o At minimumcost.
Thecostcanbe minimized
by:
o Usingcheapestreagenfs(air, water);
o Makingreadionas rapidas possible(catalyst);
o Avoidingveryhigh temperature/pressure,
if possible.

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19

CHEMICAL EQUILIBIURM

THEHABERPROCESS
Nz(g) +

3Hz(g) I

aH = 46 kJmol-l

2NH3(g)

Nitrogen from
fractional
distillation of liquid
alr

trr#--lqffidm

&d

tI from
"r*"*" 1I
I

gas
synthesls

OF AMMONIA
OPTIMUMCONDITIONS
FORSYNTHESIS
Conditionsfor the synthesisof ammoniahaveto be carefullychosenif the processis to
be efficientandthuseconomically
viable.
3 mostimportant
are:(1)yield,(2)rateof reactionand(3)energy.
considerations
(1)

Effect of Pressure:High Pressure

Desired

Out

Reason

) lncreaserateof
reaction

F An increasein pressurebringsgas
molecules
closertogether.Theycollide
and hencereac{ionis
morefrequently
faster.

D Pos'rtion
of equilibrium > Accordingto LCP,highpressureincreases
shiftedto the right
the relativeamountsof NH3at equilibrium,
(higheryield)
sincethefoMardreac{ionresultsin a
decreasein the no.of molesof gas (4 mol
) 2 mol).

Undesired ) Noteconomically
viable

AJC/JC1

plantandmaintenance
) Costof industrial
becomemoreexpensive,
e.g.pipeshaveto
be tougherto withstandhighpressure.

20

CHEMICALEQUILIBIURM

betweenhighyieldandlowcost.
Compromise

.
(21

EffectofTemperature: LowTemperafrtre
Desired

Outeome.'.',,...:,

virtuallyzero

(3)

t.,. :.,:.rrijliii:.r..:

tbvors
to LCP,lowertemperature
F Positionof equilibrium > According
production
heat
to
counteract
of
more
the
right
to
the
shifted
Hence,the exothermic
the lowtemperature.
(higheryield)
reaction(fonnardreaction)is favored.

Undesired > Rateof reactionis

ReaSOn

no.of energetic
> At lowtemperature,
whichleadto chemicalreaction
collisions
reduced.
aredrasticallv

betweenhighyieldandlowrate.
Compromise

Catalyst
Reason
Desired

. :..
:,,.,
a:,ti-.ltr.

F Increaserate of
reaction

> Catalystlowersactivationenergyof reaction

andhenceincreasethe no.of effective
collisions.

) Synthesiscanbe
caniedoutat a lower
temperature.

> Highrateableto achieveat low

temperature.

Conclusion
.

Accordingto the principlesof kineticsand chemicalequilibrium,the following

of NH3:
conditionswouldfavorthe manufacture
(1) Highpressure
(2) Moderotetemperoture
(3) Useof catolyst
Hence, optimum conditionschosen that compromisesbetween kinetics and
chemicalequilibrium
for HaberProcessare:
(1) Pressure :200 - 300otm
rote of reocfion.
(2) Temperature
: 450 - 500'Cis usedto obtqinreasonable
by cddifion
(3) Catalyst
: FinelydividedFecotolyst.Efficiencyis enhonced
promoters:
AlaOrondKzO.
of
of smollomount

YIELDOF AMMONIA
.

yieldof NHris only10 - 15%.

Despitetheseoptimumconditions,

AJC/JC1

CHEMICAL EQUILIBIURM

Thisyieldcan be increasedby allowingliquidNH3formedto be drawnoff the

systemso thatpositionof equilibrium
is shiftedto the rightin favorof production
of moreammonia.
unreactednitrogenandhydrogencan be recycled.Ail reactantgaseseventua[y
convertedto NH3.

'

USESOF AMMONIA
.. - .
.

Make feftilizefsi
o.ro,i r $+rcr.r , aurrritrr,l iaa+c
Makg nitfic acid: r, ,qr\! r{$! t a. y sxt c,, ryo1p (ilrl
,

l.[rt.

,r"o. ca^ U

.r,tl

ieF

,^'..'iqr

rr,,6

Makesyntheticfibres: ngn^, .400^_

Self-Directed
Learning
Exercise:
The HaberProcess.
for the production
of ammoniafromits elementscanbe represented
by the
equation:
Nz(g) +
3Hdg) s
2NH3(g)
ln the process,a mixtureof nitrogenandhydrogenis passedovera catalyst.TheNH3is
remov_ed
ftom.theproductsandunreacted
gasespassedthroughthe rea&ionveir"r
tiT:-j:
gasis removedfrJmthereactionvesJetlwhereit accumuiate"s;,
"g"in.
1,",T Statethe
ll": catalyst
?19o1
(axt)
normallyusedin the Haberprocess
(ii) Whatare the sourcesof the nitrogenandhydrogen?
(iiD Suggestwherethe argoncomesftom.
(iv) \a/hyis the NH3removedfromthe productsbeforepassingthe unreacted
nitrogen
andhydrogenoverthe catalystagain?
(b)

Figurebelowshowsthepercentage
of NH.in the equiribrium
mixtureunderdifferent
conditions.

Prgssuray'alm

(i) Vvhichtemperature,
200oCor S00oC,producesa largerpercentage
of NH3in the
equilibrium
mixture?stateonedisadvantage
of using-atemperature
wefiberowsoo oc.
(ii) \A/hichpressure,s0 or 1SOatm,produces largerpjrcent"ie
of NH3in fhe
equilibrium
mixture?
Stateone disadvantage
of usinga pressure
- greaterthan200atm.

AJC/JC1

22