Chemical Equilibrium
Whenever we hear the word Equilibrium immediately 2
picture arises in our wind an object under the influence of two
‘oppasing forees. For chemical reactions also this is Irae.
reaction also can exist in a state of equilibrium balancing
forward and hsckward reactions
Reversible and brreversibie reactions
A chemical reaction is said to have taken place wher the
concentration of reactants decreases, and the exncentration of
the products increases with time. The chemical reactions are
classified om the basis of the extent to which they proceed, inte
ze following hwo classes;
() Reversible reactions + Reaction in whieh entire
aman of the reactants is nol converted into products tered
ax reversibfe reuclion.
@ Characteristics of reversible reactions:
(a) These-reactions cum ie started from either sife,
(b) These reactions are never cormplete,
(e) These reactions have a tendency to attain a state of
equilibrium, in which Pree energy change is aera (= a),
(6) This sign (=) represents the reversibility of the
reselioa,
Gi) Examples of reversible reactions
(a) Neutralization tetieeen an acid and a base either of
thick or both are weak ea
CH COOH + Na OM = CH,COONG + FLO
b) Salt hydrolysis, ea,
oC +3H,0= Fe(OH)» 3HCL
fe) Thermal decampositian, #9.
Folgg = PElyg * Gayy
(a) Esterification, «9,
CH, COGH + Cy HOH = CH, COOH, + HO
(e) Evaporation af water in a closed vessel, eg.
HyOy = Og 0
(2) Irreversible reactions 1 Reaction in which entire
amount of the reactants is converted inte products is termed a
irreversible reactiam.
6) Charueteristies ofirreversible reactions
(a) These reactions proceed only in one dineetion (forward
irection),
(h) These reactions san proceed lo completion,
t
an irreversible reaction, AG <0,
(a) The arrow Cs) ts placed etween reactants and
protects,
Gi) Examples of irreversible reactions
(0) Neuiratiation betien strong avi and srg base
ats
NaCEl 4 HO NaCl 4 Hi,0 «07 bend
(8) Double decomposition reuctions or precipitation
reactions eg
FeCl HeSD gb HISD yy AA ZIICT g
(c) Thermaldecomporition. ©.
2KC1D,,, ME 2K, #0, t
(a) Reso reactions, e-,
SCI yt FHC 4 SCT 5 42, Chemical Equilibrium 305
Equiliprium and its dynamic nature
“Equilibritm is the state at which the concentration af
reactants und products do mot change wilh time. ic
concentrations of reactants an preducts Become constant.”
Prods
Tie Ellen ase
‘The important characteristics of equihriam state are,
(1) Rquirium state can be recognised by the constaney
of certain measurabie properties such as pressure, densi,
colour, consentration ets. by changing these conditions of the
syrlcmwe canconiral the exit to which. reaction praseed
(2) Equilibrium state can only be achieved in cle vessel.
() Equilibrium state is reversitein nature
(4) Eaquiitrium state also ciynamicin nature
(5) At equilibrium state,
‘Rate of forward reaction = Rate of backward reaction
(6) Atequilteiom state, sG-= 0, sathat AH = TAS
{Ss
i gem
t
a
ae
On the basis of observations of many equilibrium
reactions, two Narevgian chemists Goldherg and Wirage
suggested (3864) a quantitative relationship between the rales
of reactions and the concentration of the reacting subsiances,
‘This relationship is known as Jaw of mass action. It states that
“The rate of « chemical rection is directly proportional
lo the product of the molar concentrations of the reactants al a
constant temperature at angagiven time.”
‘The molarconcentration fe. mumber of males per litres so.
called actice mass. I is expremed by enclosing Ube symbols af
formulae of the sutstance in square brackets. Par example, molar
sombentration of A izexpremed ax LA].
Consider a simple reversible reaction
a+ Bf = oC+d! (Ata certain temperature)
Apcording ta law of mass acts
Rate of forward reaction = [AI"|a}* = AP at
Rate of backward reaction « [CFF = (CPL
Abeguilibriar ,
Rate of forward reaction = Rate of backward reactien
4 ,[aP Lat =a, (C1 1
hg fae
b 1A
‘Where, K_ iscalled equilibrium constant
In terms of partis pressures, equibbeium constant ix
denoted by Ki, and
x,
ee
Tnteems af mole fraction, equiBibrium cueetant is
enated by K, and
(ee) ear
"ka OP
tion between Ky, Kyand Ky
kK, = nen
yo KB
An = number af moet of gaseous products ~ number af
smcles of gasvous raclan in chemical equation,
‘Axa geaeral rule, the coauentration of pure solid and
pure liquids are not inched when writing an equisbeium.
equation.
Vale Taina
of
a Nowe
pe ‘nl
a ale bps
Characteristic of equi
(1) The vale of equiliwriumm constant i independent of
tee original concentration of reaciants,
(21 The equilibrium constant has @ definite value for
every reaction at a particular temperature. Hewerer, & varies
with change in temperature.
(9) Bor a reversible reaction, the equilibrium conten! for
the forward reaction is inverse of the equilibrium eametant fer
tine backward reaction,
Tn general, Kove
"Rect ate
(4) The vcine ofan equildhrium constant tells the extent
te which a reaction proceeds in the forward or reverse
direction.
(5) The equilibriun constant is independent of the
presence afeatalyst
(6) The value of equilibrium constant changes with the
change of temperature. Theemodynamically, it cin be shows
thal if K, and X, be the equilibrium constants of a reaetion at
absolute temperatures. 7 and J; IAAT is the beat of resection,
ateonstant volume, then
sag, = AM [Ll vane ttotrequation)
tah Bak, eT 306 Chemical Equilibrium
‘The eflect of temperature ean be studied in the following,
three eases
(When AN-0 ie. neither heat i eunloed nor
absorbed
eg Keg 5, <0 or tog & beg Kor k=
Thos, cquilheium constant remsins the some at sll
temperatures
Gi) When AM = suv ie, fat ie afacrbed, the reacties
endltermi: The temperature T,ichgher than 7;.
log K, - tog &, =e or lag K, >hog 0° & > K,
The value of equillbrivm onstant i higher at higher
(emporaare in gase of endother mie reactions
Gi) When ANT = ~ ve, i, heal i evolu, the reaction ix
cxaitermic. Thelempersture ; iskigherthan 7
egy ag 8 ove or ke
The value of equibrium constant i lower at higher
(emperatar in the case of exothermis reactions
(7) The value of the eqaitrium emetand depend ypom
(te stolchicmetry of the chemical equation.
Por the reaction
250,19 = 290.(0+ 0.49 and $0,(9 = 50,(941'20.18)
ag K, 06 > Ki
180, 10,) 150,110,"
Ke and At SO, MC;|
180, 180,)
Wado tnt
@) Similarly, if a particular equation is multiplied by 2,
the equilibrium constant for the new reaction (A) will be the
square af the equilibeum constant (K) for the original reasticn
ie, Rat
(Gi) If the chemical equation far a particular reaction is
written in two steps having equilibrium constants &, ard &,,
then the equilibrium constants are related ax A= Kix Ky
Applications of equilibrium constant
(2) Judging the extent of reaction
IC K, 210°, produds predominate over reuckants. If
A, is very large, the reaction proceeds almest all the way to:
completion.
GiLLE A, < 10-7, reactants predominate over products. If
A, te very small, the reaction proceeds hardy ata
(Gi) Wg, is an the range 10% ew 101, appreaciable
concentration of bath resctants and products are present.
:
Reaction, | sl
a
a
sos
‘tequila
(2) Predicting the direction of reaction The
concentration ratio, £e_,ratio of the product aff concentrations af
products i that of reactants is also known as concentration
quotient and is denoted by Q.
1)
[alla
may be noted that Q bocomes equal ta equilibria
constant (K) when the reaction is at the equilihrium state At
equilibrium, = K= K, =X, ‘Ths,
‘Concentration quatient, (=
GVIFQ > K, the reaction will promued in the direction af
reactanls (reverse reaclion).
(i) LEQ « K, the resetion will proceed in the disection af
the products (forward reactioa)
Gi) IQ = K, the reaction mixture ix alresdy at
ceaualitsriaum.
“Thus, a reaction fas a tervlency to form producesi€(Q © K
and ta form resctants if @ > K.
aff
Moacun-robes lh atin Pt
Oak ox
(areal rene) Sa (bteverse reaction)
Fig
of
‘The cquilibeium belwoen different chemical species
Present in the same or different phases is called chemical
equilibrium, There are twe-types ofchemical equilibriue,
(0) Homogencous equilibrium 1 The equilibrium
reactions in which all the reactants and the preducts are ir the
same phase are called homogeneous equilibrium reactions,
C:H,ONU le 0H, COOH) = CHCOOEH, De HEN
Nog BH igh = BN
250, (gh Oi =
(2) Heterogenous equilibrium : The equilibrium
reactions in which the reactants and the products are feesent
Uifferent phases are called elerayencons equilésriion reactions.
250,18
ENGHED, (1 NaC, hr CD.18 » HOL8
CHC 4 HOW = C2 agh BOW” (agp
CX00, {= CoO (sh CD, gh
2,00 = 4,08 ‘Table : 8.1 Homogeneous equilibria and equations for equilibrium constant (Hquilibrium pressure ix Patm ina V
Lfask)
fan=0; X= ameO: eK, ‘ar 30; KB
Wek = BHP Ngo 37h = 28H, 250;6O, = 250, FCI, © PCIe Ch
eo 4 om © 8 ® aoe @
Tata eke | 78 730 zo 7.
Moe at fo Ge [Ga a a ae
yates
“Tata make = Ga oa
-uilise
‘Ale ey fix
masses 7) (+
Nok acon toe a(tes)_* (zz) [=
wa-jtla-co-w |la-2) |a
Fart = aa Fe Ti) gin) Azz)
peste Res |) A)
x rer
(t-a)"
re ace
me
NHS ND HeSid | Cale Cong = 2001
“rita aie 7 =e =
ale eq = =e
“otal ce at eli = to ™
(iolid mot imetoded)
Mle ection zl 2 T
m2 2 a z
Taal SE - OF F
z 2 2
K, rl we 7
4 f-25 a
Relationship between equilibrium constant and
ao
AG fora reaction under any condition is related with Ao
by the lation, A= aca 2m &Tog
Standard free energy change of 9 reaction and its
coguilibrium constant are related ta each other at temperature T
bythe relation, AG = 2:03.87 ag Ke
For a general reaction al-+hit = C+aD
(acl tap
GaP tag?
Where @ represent the activity of the resctants and
products. Itis unit ess.
For pure sobids and Buide:
For gases: a= pressure of gasin afm.
For componenisia soluhon: a= molar eancemizaban,
Le-Chatelier's principle
Le-Chatetier and Braun (:8t4), French chernisis,
made certain generalizations to explain the effect of changes in
concentration, temperature or pressure on the state of system in
equilibrium. When a system is subjected to a change in one af
these factors, the equilibrium gets disturbed and the system
readjust itself until it returresto equiftrium. The generafiratin
iskaown as Le-Chatetier's principle. It may he stated a8:
"Ohenge in any of the factors that determine the
equiltrium conditions of e system wilt sft the equilibrium ie
such a manner ta reduce or to eounteract the effect of the
change.” 308 Chemical Equilibrium
‘The principle is very helpful in predicting qualicatively
the effect of change in concentration, pressure or lemperaure
fon a system in equiibeiv,
Gangs inpesed onthe | faquilibrmans positon mines Thay other palate
‘patem inequiiirinan
Tone ath mlfoe Berend an Toray Toone
me afd jr D Tate Tochange Te change
increta
Fresureinaenal | Torgunee aie ae Wie Anan Torche ‘Vey le oc, Way an
Tobit fe+.f)> Lae 8), t2, An= ine ee Lalla aes
Bo dhangeil (or dl (ar) ke ans 0
“Tapes cross "Toki AH =—ve(emtermi) Tale achieve ter
‘Toright it AH tue emathermi)
ETT aarp Sa oe
() Dissociation of phosphours pentachloride
Her's principle oe
‘The Le-Chaleliers principle has a greal significance For tbe
chemical, physieal systems and in every day life in a state af
cequilibrigm.
() Applications to the chemical equilibrium
(@) Synthesis of ammonia (Haber's process)
Nye 3éh, = 2ANy* 23kon! (exothermic)
(a) High pressure tun < 0}
(&) Law temperature:
(o) Exvessof Nand H,
(a) Removal of NE, favours forward resection.
(i) Formation of sulphur trioxide
= 250,448 teat (exnthermic)
fa) High pressure (an < 0}
(b) Low temperature
fe) Excess of SO, and Q,, Favours the reaction in
forward direction,
(Gil) Synthesis of nitric oxide
Noe O, = 2A0 = 43.2 kos! (endothermic)
(a) High temperature
(b) Excess of N, and O,
(6) Since reaction takws place without change in volume
- pressure hasno effect on equiltrium,
(iv) Formation ofmitragen diaxidle
2N0+ ND;+ FTE Keal
(a) High pressure
(b) Low temperature
(e) Excess af MO and Oy farours the reaction in forward
rection
Pet,
Ph, + Ch, 1S Beat
(a) Law pressuce or high volume of the container, An >0
(b) High temperature (c) Hucess of FE
(2) Applications to the physical equilibrium.
G) Melting af ice (lee — water system)
Water
cael
oF wheal
(In this reacting volume is decreased from 1.09 ce. to
Lone per gm.)
(a) At high temperature mare water is formed as it
sheorbs heat.
(O) AL high premure more water is farmed as it ix
accompanied by decrease in weilame.
(c) At higher pressure, melting point of ise is lowered,
while boiling point of waler is increased.
Gi) Melting afaulphur: §,. = Sy
(This renetion accompanies increase in vahame.)
(a) Al high temperature, move quid sulphur ix farmed.
(O) At bigher pressure, boas sulphur will melt ax melting
increases volume,
(c} AL higher pressuce, melting point of sulphar ix
increased
(ii) Boiling @f water (wxter- water vapour system)
Wane = Water Vapors kcal
ua ger beet
(00 is accompanied by absception of heat and increase in
volume)
(2) Al high temperature mare vapors are formed.
(BJA higher presture, vapours will be converted to guid
as it decreases volume.
(c} At higher pressure, boiling poinl of water is increased
(prineiple-af pressure axoker|
Givi Solubibiey of welte : If sciubibity of 2 salt ix
accompanied by abworption of bat its slubility increases with
rise in temperature; eg, NH,CI K,SO,, KV, ets
wx deat N54 (i) ——b AND ggg ~ 2 ead
(On the other hand if it ix accompanied by evolution af
heat, sclubiFity decreases with increase in temperature; e,,
Cat, CalCH),, NaOH, KOM ete.
COM 4 * Gai) ——r CHO aay # heal
Rolation between vapour density and
Degree of dissociation
Inthe flowing reversible chemical equation.
as
IniisImotl 4
At equilibrium (1-2) gr xedegree at
disacintion
‘Number of molesef A and 2 at equilibrium
ate eaye-lexy-1)
initial volume oft male of is V, then volume of
equilibrium mixture of 4 and is, = ly a1
Molar density before dissuviation,
Peach wel
250,
