Example3

Givethe mathematical expression for the equilibrium constant (K and k) for the reactions
H,(g) + 1(e)2HI(g)
(i) Ng) + 3H,C) 2NH,(g)
(ii) PCI{g) PCI,(g) +t CI,(g)
Solution. () [HI
Ke [H, I[l,] i K, = KRT)Ang = K,(RT-2 = K,
[NH,P
(ii) Ke ; K, = K(RT)Ang = K,RT -4 = K(RT)2

(iüi) K
[PCI,][Cl,] K, = KRT)Ang = K,(RT}-1 = K(RT)
(PCI] ;
Example4
The following concenirations were obtained for the formation of NH, from N, and H, at equilibrium at S00 K.
NAe)l = I:5x10- M; [H,(e)]= 3-0x102 M; NH,] = 1:2% 10-2 M. Calculate equilibrium constant.
Solution. N,(e) + 3H, (3) 2NH, (g)
[NH, [12x 10-2M? =3-55 >X 10² M
K, [N, I[H, ' [15x 1o MI[3-0 x10 Mö

Example 5
At 700 K, the equilibrium constant K,, or the reaction
280,49) 250, (g) + O,(g)
temperature
is 1-8 x 10 kPa. What is the numerical value in moles per litre of K for this reaction at the same
Solution. According to the available data,
(1·8 x 10KPa) = 1:78 x 105 atm
K, = 1:8 x 10-3 kPa =
(101-3k Pa atm)

R = 0-082 Latm K- mol-', N8 =3-2 = 1, T = 700 K

Using the relation K, =K (RT) A8
K, (1·78 x10atm)
K (RT)Ang (0-082 Latm K mol')x(700K) = 31 × 10-7 mol L-1:
Example 6
At 500°C, the equilibrium constant for the reaction
N,g) + 3H8) 2NH,(g) is 6-02 x 1O2 litre-2 mo2,
What is the value of K, at the same temperature ?
 ar
equilibrium constants
7.12
equations areto
" Whenever some chemical final equation. For
cquilibrium constant for the
be aAdded, their
example,
respective
mliplie
2NOR):K,
N, (e) + O,e)
2NO,(e) +0, (&) 2 NO,&) : K;
2NO,(8) ;Ky
Add: N,(&) +2 O,(e) [NO, or K, K, XK,
INO [NOJO,1. (N,J[O,1 expression ofthe

" Do not include the

the
IN,IO,1pure solids andpure liquids in
concentrations of
equilbrium constar
1200Kare given :
Example 7 reactions at O8
Equilibrum constants for lhe
following
+Ote K,= 64x 106
2H,O@ 2g) OeK, = 1·6x
2COe) + carried at the samne temperature
reaction
the
2C0219)
equilibriumconstant for the
Calculate the value of
Solution. The available data is : 64 X10o-8
2H,O(g) 2H,(g) + O,(e); K, == 16 X 106
2C0,(g) 2C0g) + 0,(e); K,
The equation we aim at :
H,(&) + CO,(g) cO(g) + H,O(g); K=?
2, we get
By reversing eqn. () and dividing it by
V64x108
H,(g) + 1/2 0,e)H,(g) ; K, =
By dividing egn. (i) by 2, we get v6x10-6
CO,e) cog) + 1/2 0,(e); K, =
By adding eqn. (ii) and egn. (i), we get, CO(g) + H,0g) K= K; x K , a h oaeto
H,e) + C0,e)
|l6x10-6
K=
= V25 = 5
or V6-4x10-8

Example 8
The equilibrium constant for the reaction :
Fet (aq) + SCN (aq) FeSCN* (aq)
equilibrium constant for the reaction ?
at 298 Kis 138. What is the value of the
2Fe*(aq) +25CN (aq)2FeSCNZ+ (aq) reactions may be written as :
two
Solution. The expressions for the equilibrium constants of the
[FeSCN* (aq)) -=138
K=
[Fe (aq)|[SCN (aq)]
(FeSCN?* (aq)) FeSCN (aq)
and
[Fe"aq)T' [SCN (aq) Fe* (aq)|[SCN (aq)l
= (K) = (138) = 19044
xa ple 9
The equilibrium constant for the reaction :
H,(g) + Ss) HS ($)
is 18-5 at 925 Kand 9-25 at 1000 Krespectively. Calculate the enthalpy of reaction.
 mol/L.
by
expressing For gaseous
7.13 same.
of the
terms
in the for
bar) considered.
are
concentrations denominator
(1
pressures
atmosphere.
are
solution
R8314
J
the
as of
states
J=71080-57 molar
or and in
bar nlace
the : numenator
K,
TT; kaare units.standard
taking PCH,COCH,8)
1000 2NO,(8)
Pa no reactions.
925 as the have casereactions
T, 2-303R x pressures mol/L
=
9-25, AH 1000 in
K, in
1000925 925
-92s1 and units
both following PO}(aq)pCO,) =
x N,O,(g)
determined the HAg) PO(aq)
- x x 8-314 partial bar, of K, no for Br(aq) K, H,(g)
K, 1000 1000 (mol/L)
(mol/L) 2HI(&);
exponents Ba0(s)
+
CO,(g) CH,COCH,(2)
3/2 BaO()
CO,(g)
+ Agt(aq)
+
Br(ag) and [AI*
(aq)TH,
(gJ2 [H,0*
(aq)[PO
(aq))
K, x 15 of :
=
(bar?
hasmolar) the + + = [Br(aq)) 3/2
[CH,COCH,(2)] [HPO
(aq))
K
183,T
925 AH×
75 8314x
×8-314 303 be termsreaction (bar) or for (ag) (aq) + (ag) K, + [H
(ag)j+
301x2- can (1
dimensionless H,0+ and APt(aq) H0+(aq)
if concentration Agt ARt
expressions [C0,(e)l(aq))
:
data AH x
2-303 2-303 Constant
(K) in the NO,
expressed
for
K, (N,041
pNO,pN,04 units L,8)
[Agt
available constantk, no
-0:301
=: has
+ constant CH,COCH,() = ==
108
18-5
9-25 AH Equilibrium
of and
be K, H,8) is
molar AgBr(s)
BaCO,(s) (aq) (aq)
+
H,0)BaCO,(5) K, K, (aq) =K, H,0() K,
K, AgBr(s)
solutlon.,
Constant constant
to equilibrium
canK, 3Ht
According units Equilibrium ofibrium 3H
example,Equiland
K, equilibrium
+ +
Units units theinilthearexample, that
notPlease +
brium the. 'siy
of
of units
ly,
Al(S)
reactions
10Examplthee )HPO()Solution.
Al()
(aq)
HPO
The for " wste
(1) fii)
()
 Reaction
o the direction
of Predicting
the Quotient- Reaction 10.
e
V123 K=
0-9 =
0,e) 1/2 2N,e)+ NOg)
reaction reverse the For
(036x
10 (e)) (e)][O, [N,
10-3
M) (4-41x M)x (8) [NO Ke
=1-23 (14x10-3
M)2
(JharkhBoyand 2NO(g) +O,e) N,g) Solution.
at
Kis 800 ,0,(g) ZNe)+ NOg)
iratithoennNs. for Kof
M10 44]x
respectively
M, 1o 0-36
x are NOg) and 0,(g)
x value Calculate,
the M.1O x14and eguilibrium or
the fvessel, sealed ain 800K At
+O&) N8)
equilibrium 2NO(g),
the Example
11
OMPCAHENION DINESH 7.14
 7.15
amplo
12
cyuilibrium
Jh constant at
298 Kfor the
Cu(s) + 2Ag* (aq)
Ina solution In reaction in astate of equllbriumis :
18x10'mol1-andthe which copperCut(aq) +2Ag (s)
has
displaced some silver lons from solution the concentration of Cu+ lonsis
For the
reuction,concentration 2AgtAg(aq)lonssis 3-0x10-mol
of
Solutton.
L-1, Is this system at equilibrium?
Theconcentration quotient Q, isCu(s)
: +
Cuz*(aq) +2Ag (s)

[Q (aq)l A()ICuaq)l
(Cu(s)[Ag*
(Ag(s)] = [Cu(s)] (a) [Ag(aq)l
ACcordingtothe available = 1mol L-]
Cuztdata,
(ag)) =18 X10-2 mol L-! and
[Agt(aq)]J==- 3-0 x10-9 mol L-!,
(1-8x102)
(3-0 ×10-9 =2 x 10!5
Sincethe value of the concentration quotient is the same as that of the equilibrium constant. the reaction is in a state of
ilibrium,
Brample13
for the process, 3/2 A B, at 298 K, AG° is 163 kJ mol-!. The Composition of the reaction mixture is (B] = 1 and
AJ= 10000. Predict the direction of the reaction and the relation between reaction quotient(0)and the equilibrium
constatn(K).
Solution. The reaction quotient (Q) for
the given reaction is :
3/2 A B; Q, = [B] 1
=10-6
(10000)3/2
AG° = - RT In K.= - RT X 2:303 x
log Ke
AGO
2:303 × log K, = (163 ×10°J mol')
RT (8314 JK- mol)x (298 K)

log K, (163 x10°J mol-') =-28:57

(2:303) x(8314 J K-mol-)x (298 K)
K, = 2-69 × 10-29
Since. O, > K the reaction will proceed more in the backward direction.
Example 14
The equilibrium constant for the reaction
H,g) +1(g) 2HI(g)
it0-35 at 298 K. In the following mixture at 298 K, has eguilibrium been reached?If not state on which side of the
equilibrium the system is
0 Pu, = 010 atm and py, = 0-80 atm and there is solid I, in the container.
) Pu. = 0-55 atm and pu, = -44 atm and there is solid I, in the container.
füi) PH, = 2-5 atm and Py, = 0:15 atm and there is solid I, in the container.
Solution. The equilibrium constant (K,) for the reaction is
H,(&) +1,&) 2HI (g)
p'HI(g) =0:35
Bp pH,(g) xpl, (8)
 rouibrium 7.17
bur exothermic reactions, AH willbe negutivo and will have a large magnitude for strongly
thKor Kwill have large magnltude for strongly or highly exothermic exothermic reaction. This
reaction.
ample1s
ahe cf A for the phosphorylation of glucose in glycolysis ls 13-8 kJimol. Caleulate the value of K, at 298.
AG
Solutlon. AG 2:303 RT log K or log K=
2-303 RT
AG 13-8 kJ mol-l;R 8314 J K- mot-;T- 298K
(13·8 x 10J mol-!)
log K = 3-581s
2"303 x (8-314 J K mol-) x (298 K)-2:418S
K=Antilog (3-5815) - 3-815 x 10-3

Eample16

Destandard Glbbs energy change at 300 Kfor the reaction 2A B+Cis 24942.J At agiven time, the composition

Amactionmixture is l4) - 1B] =2 and (C]-Predict the direction in which the reacion proceds.
[R=8314 JIK/mol]
Calotion. The equilibrium reaction is :
2A B+C
AG 2303 RT logK
AG =24942 J mol-;R=8314 JK- mol-;T=300 K.
(2494+-2 Jmol-)
log K, = (2303) x(8314 JK- mol-)(300 K)
=-0-434

K, =Antilog(-0-434) =0367
Now: B]=2 and(C]=;
BÊC]_ 2x%
For the reaction ; Q, = =4
[A'
Sinxe Q, > K,i;reaction is expected to proceed in the backward direction.
12. Problems on Equilibrium constant
We have studied in the characteristics of the equilibrium constant that its value does not depend upon the initial concentrations of the
racants and products involved in the reaction. However, its value depends upon their concentrations at the equilibrium point. Thus, if the
euilibrium concentrations of the species taking part in the reaction be known, then the value of the equilibrium constant and vice versa
an be calculated.
Example 17
Gihen the equilibrium ; N,OA8) 2NO,(:) with K, =015 atm at 298 K.
(a) What is K, using pressure in tor ?
0) What is K, using unis of moles per litre ?
(760 torr) x (0-15 atm)
Solution. (a) (1 atm)
= 114 x 10² torr
 DINESH COMPANION CHEMIST,

7.18 10-3molL-1
K, = K,(RTJAn (0-0821Latm(0-15 = 6-13 x
atm) 298K)2-1
K-'mol-!x
Kp
(RT)An
K concentration ?
depend uponthe units of
equilibrium constant
Example 18 reactions doesthe
following1
For which of theCOg) + H,Og) CO,(g) + H,(g)
(a) COg) + CI,(g)
COCI,(g) I2N,(g) + I/20,&) concentration becance the mumber of
() units of
NOg) constant depends upon
(c) equilibrium
value of
Solution. For reaction (b),
is not the same.
reactant and product moles
measured at 823 K.
Example 19 reactions have been
equilibrium constants for the
Co(s) + H,Og);K=67
The CoO(s) + H,(g) K=490.
CoOs) + CO(g) Cofs)+ CO,(g);
reaction.a
constantfor the
calculate the equilibrium ean.
From the data,
Hlg) COg) + H,0g) indicated, subtract second eqn. fronm first
CO,g) + value of K for the reaction
the
Solution. In order to find 67
CoO(s) + H &) Co(s) + H,O(g); K =
= 490
CoO(s) + COe) Cos) + CO,(&); K
67/490 = 0-137
Subtract: CO,(&) + H,e) Cog) + H,0(8) ;K =
equilibrium at 500 R.
Example 20
obtained for the formation of NH, from N, and H, at constant
The following concentrations were 10-2 M and [NHJ = 1:2 x 10 M. Calculate equilibrium
[N,] =15 x 102 M. H,J = 3-0 x N.C.E.R. T. Solved Examg
reaction is:
Solution. The equilibrium state for the
N,(g) + 3H,(g) 2NH, (g)
[NH,P (1-2 x 10 M?
10-2 M3 = 3:55 x 102.
K = (N, I[H, (1:5 x 10 M) x (3-0 x

Example 21
NO= 2-8 x 103 Min a enli
At equilibrium, the concentrations of N, = 3-0 x 10-3 M, 0, = 42 x 10-3 Mand
vessel at 800 K. What will be K, for the reaction ?
N, (g) + 0, (e) 2NO (g)
[NO (2-8 x 10 M?
Solution. KN,IO2] (3-0 x 10 M) × 4-2 X 10-3 M) =0-622
Example 22

For the reacion ; H,(g) +I(8) 2HI(g), K=553 at 699 K. In amixture consisting of 0-70 atm of HI and 00
each of H, and I, at 699 K, will there be any net reaction ? If so, will HI be consumed or formed ?
Solution. The reaction quotient (Q,) can be calculated as :

PL (0-70 atm)?
PH2 x Pi (0-02 atm) x (0-02 atm) = 1225
Since the value of Q, is more than that of K, the speed of the
equilibrium. reverse reaction must increase in order to au
 equilibriumis 7.19
ing
NAg) studied by
+ 3H,(R) taking l mole of N, and 3moles of H, In
frmed,at 2NH AR) a lL flask at a
NMe) equilibrium neutralised
is by 200 ml, of IM
glen lemperatur :
Sautlon.200 mL of IM HC) = 1 HCI. Clculate equilibrium
-x 200 constant.
HCI rcact in 1000 0-2 M
NH,evolvedin the equimolar proportion
reaction= 02 M to form
NHCI
N,(g) +3H,(g)
Ni.ofmolesof NH,(g) formed
2NH,(g)
= 02 M

No.ofmolesof N,(g)
022 -01M
reacted =
No.ofmolessof
H,(g) reacted =
molar concentration of
various
0-2x=0-3 M
Ie species the equilibrium point is :
at
Inicialmoles/litre N,&)
1 + 3H,(e) 2NH,8)
3
moleslitre at eqm. point 1- 0-1 0
3-0:3 0-2
ApplingLaw of chemical equilibrium : 2-7

[NH,(8) (0-2) 0-04

[N, (g)|[H, (8) 0-9 x(2.7)3 17.12:26 x 10-3
Eample24
issociates as ;
AB, AB,(g)AB(g) +
oquilibriumiS 700 mm of Hg, calculate Kp forB(g). If the initial pressure is 500 mm of Hg and the total pressure at the
the reaction.
Solution. Let us suppose that after
AB,(&)
dissociation, the decrease in vapour pressure of AB, 1S p mm.
Initial pressure 500 mm
AB(g) + B(g)
0 0
Eqm. presSure (500-p) mm pmm Pmm
Total pressure at equilibrium
= 500
(500 + p) =700 -p+p+p=
or p= 700 - 500(500+p)
= 200 mm
mm
. At eguilibrium pont, PAB2 =
(500-200) = 300 mm, pAR = 200 mm, P = 200mm
Anglving Law of chemical equilibrium :

K -PABPB (200 (300

mm) x(200 mm)
mm) = l33mm
PAB2
Eample25
Determine the concentration of CO, which will be in equilibrium with 2-5 x 102 mol L- of
reaction
CO at 100°C for the
Fe0(s) + COg) Fe(s) + COXg); K, = 5-0
Solution. For the reaction ;K (CO,] or 5 = [CO,1
[CO] (2-5x 10 mol L)
[CO,] = 5 x (2:5 x 10- mol L-l) = 12:5 x 10-2 mol L-1,
Eample 26
l, PCI, and Cl, are at equilibriumn at 500 Kand have concentration l59 Mfor PCl; 1-59 Mfor Cl, and l41 Mfor
l, Calculate K, for the reaction:
PCl, PCl, + CI,
Solution. K,, =[PCI,1[Clh]
(PCIs]
(1-59M) x (1-59M)
(1:41M).
= 1-79
 DINESH COMPANION CHEMISTRYt
7.20

into
Example 27 Some of the CO, is converted CO on
Avessel at 1000 Kcontains CO, under a pressure of 0-5 atm.
graphite. Calculate the value of K, if the total pressure of
equilibrium mixtureis 0-8 atm. ad itlon
Solution. The reaction taking place is :
CO,(g) + C(s) 2C08) the reaction=patm.
Suppose that the decrease in pressure of CO,(8) after taking part in
Then, increase in pressure of CO(g) = 2p atm
The partial pressures in the equilibrium mixture are
CO,) C) 200g)
At eqm. point: (05 - p) atm 2p atm
atm
Total pressure = (0:5 -p + 2p) = (0:5 + p)
But the actual pressure = 0-8 atm (given)
0:5 +p = 0-8 or p= 0-8-0-5 = 03 atm
According to the equation,
0-6atm x 0-6atm
(0-6atm) >x (0-6atm) =1-8 atm
(0-5atm -0-3atm) 0-2 atm
Pcoz(8)
Example 28
For the reactionK: =
CO424(g) at+600
H,0(g)co,(g) + H,(g) concentrations of CO, H, CO and H,0 at. 800 K, if onl,
K. Calculate the equilibrium
the value of K,
COand H, are present tinitially at a concentration of 0·1O Meach.
CO,(3) + H,(g)
(N.C.E.R.T. Solved Exama
Solution. COg) + H,0g) 0
Initial molar conc 01 M 0-1 M
rM xM
Eqm. molar conc : (0-1-x) (0-1 -)
[Co,][H>] (0-1 - x)
K, = [COJ[H,0] (0-1- )(0-1- x)

=(4-24)1/2 = 206
(0-1 - x' = 4-24 or (0-1 - x)
0-206
X= 2:06(0-1 - ) or 3-06x = 0-206 or x= 3-06 = 0-067
Eqm. conc. of CO = 01 - 0-067 = 0-033 M
Eqm. conc. of H,0 = 0-1-0-067 = 0-033 M
Eqm. conc. of CO, = 0-067 M
Eqm. conc. of H,0 = 0-067 M

Example 29
At certain temperature and under a pressure of 4 atm, PCL, is 10% dissociated. Caleulate the pressure at which POL.
will be 20% dissociated, temperature remaining constant.
Solution. Step I. Calculation of.
PCI,8) PCl, (8) + Clhíg)
Initial conc. 0 0
Eqm. conc. (1 - a)
Total number of moles in the equilibrium mixture =l-a+a ta= (1 + a) mol.
Let the total pressure of equilibrium mixture = P atm
(1-a)
Partial pressure of PCl, i.e. Prci = (1+a) x Patm.

Partial pressure of PCl, i.e. PrCl3 -xPatm.

(1+ a)
x Patm
Partial pressure of Cl, i.e. Prcn (1+a)
 brlum
7.21

K, = Prciy XPci2 1+a

Prcis I - ttm
1+a
10-0
Patm
P 4 atm and a = 10% = 01
100

Kp = (0-1) 1-(0-1)
x(0-1) x(4 atm) 0-04
=0-04 atm
0.99
Il,
Step
Calculation of P
Calculationof P under new conditions
a =0:2, K, = 0-04 atm ( temperature remains constant)

K,
a'p
1 - 2 or P
K,(1-a')

P= (0-04 atm) x(1- (0-2)) (0-04 atrm) x (0-96) = 0-96 atm.

(0-2) 0-04

hample
30
Vmol1of PCi, kept in 1 L closed reaction vessel was allowed to atain equilibrium at 380 K. Calculatethe composition
miktureat equilibrium, K, = 1:80. (N.C.E.R.T. Solved Example)
te
Solution, PCI, (g) PCl, (g) + Cl, (g)
Initial molar conc. 3-00
(3-0-)
Fam. molar conc.
[PCl,](Clh] or 1-80 X* 2
K,=
[PCI_] 3-x 3-x or = 540 - 1-80 x or + 1-80 x - 5-40 =0

otvb'-4ac -1:80 ± J1-80) - 4(-5-40)

2a 2
= 1:59(neglecting -ve value)
. At. equilibrium, (PCl_] = 3- 1:59 = 141 M;(PCI] = [C,] = 1:59 M
ample31
8o of N,0, was placed in 1 L reaction vessel at 400 K and allowed to attain equilibrium : N,0,
olnl pressure at equiltbrium was found to be 9-15 bar. Calculate K, K, and partial (g)2NOg).
pressures at equilibrium.
(N.C.E.R. T. Solved Example)
13-8
Solution. No. of moles of N,O, = mol = 0-15 mol (Molar mass of N,0, = 92 g mol-l)
92

nRT (0-15 mol) x (0-083 bar L molK)x400 K

PV = nRT or P = or P =
1L
= 4-98 bar

N,O, 8) 2 NO,
Initial pressure 4-98 bar 0
Eauilibrium pressure (4-98 - p) 2p
498-p + 2p =9-15 bar (Given) orp = 9-15 - 4-98 = 417 bar
(PN,o,eq = 4-98 4-17 = 0:81 bar;(PNO,eg =2 x4-17 = 834 bar
K, =Pýo, PN,o, = (8:34P10-81 =85-87,
K, = K (RTA".". 85-87 = K, (0-083 x 400)!
85-87
2-6
K, 0-083 x 400 =2-586 =
owlorum

No. ofmoles of
CaCO,(s) initially present Mass 7.23
Molar mass (20-0gmol-)
(100 g) = 02 mol
Percentage of CaCO, decomposed (0-132 mol)
Percentage of CaCO, left (0-2 mol) x 100 66%

Aample
34
undecomposed - 100
-66 =34%
J2molessof HI were heated in asealed bulb. at
20%, Calculate the 444°Ctillthe
obe number of moles of
determinethe value of equilibrium
constant. hydrogen iodide,equilibrium was
hydrogen andreached. Its degree of
Solutlon. Dissociation of HI iodine present at the dissociation was found
proceeds acçording to the following
equation: eguilibrium point and
2HI (g) H,) +H8)
No. of moles of Hl initially
present = 3-2 mol
Degree of dissociation (a) of HÊ 20%
No, of moles of HI
dissociated = 32×100
20
=0-64 mol
of moles of HI present at eg.
point =3-24 -0-64 = 2-56
No. of moles of H, present at eq. point
No. of moles of , present at eq. =0:32
molar concentration of point = 032
The various species at the
2HI (g) equilibrium point is :
Iuitialmoles: 3-2 H,)
0
+H8)
point : 0
Molesat eqm. 2-56 0-32 0-32
ApplyingLaw chemical equilibrium :

K= H2(8)l[L, (g)] (0-32 mol) x(0-32 mol)

2HI (g) 0-0156.
(2-56 mol) x(2-56mol)
Eumple35
eguilibriumn constant for the reaction
A,g) +B, (e) 2AB(g)
.12Kis S50. f one ltre flask
containing
how many moles offAB will be formed at 373oneK?mole of A, is connected to atwo litre flask containing two moles of Bz
Solution. Total volume available for reaction
The value of equilibrium mixture= = 3L
termoles of both the reactants A, and B, react constant 50
to form 2r moles of AB according to the
he molar Concentration per litre of the different species at equation given above. Therefore,
A,(g) equilibrium point is :
Initial moles/litre
B,(g) 2AB (g)
1 2
I-x
Moles/litre at equilibrium point 2x
3
3

Apolying Law of chemical equilibrium, K,= [AB

50 = 4x?O
(5)-(
(1-r)(2-x)
212 = 25 (2-3x +); 23r-75x + 50 = 0
75 +(75) -4 x 23 x 50 = 2-326 or 0-934
By solving quadratic equation, *x =
oSN 2x 23
Iit equation is of the type ar + br +c= 0 and the value of x is calculated as:
-btb-4ac
2a
 Example 37 Example36
H,O Let By know
that,WeStep Initial Value 7.24
Applying Solution.alcohol.
ethgofyl 4-0 is The ApplyingMoles/litretheatmoles/litre Therefore,
According Solution. to Z
substituting be
moles
wil the equilibrium
at I. Number 40% of
mol Initial
moles of x
bees Initial he 25°C. constant(K)
CalculationEquilibrium Law of .
Nocannot
CH,CtOOH The CH,COOH to Number dissociated
Step PCL,
formed. of Law equilibrium
molar the of of
the of point
CH,COOH moles of given
Calculate constant Chemical available Percentage moles I. were moles be
values conc./litre Number of more
of Chemical reaction
+ + of moles Calculation of
CH,COOH K, of intoheated
C,H,OH C,H,OH C;Hthe ,OH for in for data, of PCI, AB than
and the equilibrium, of of of PCl, formed
the K the to 1
K
CH,OH [CH,CcOOHI|C,H{0HÊ equilibrium, is weight relation, R K, the 0:8 moles PCI, PCL, initially ofand327°C and
: reaction 13·14
atm = 0622-08
==
0emol-l =
= =0-082 reaction reactants mole dissociated K,
A6omol-! (CH;COOCGH,[H;0] of (0267 (0-4
of dissociated
fo r =equal is
92g 120g ethyl K,(RT) PCI , present Cl,. in
2r
reacted 2 PCI,&) of
CHHCOOC,H, CH,CO0C,H, : L mol PCl, the da
mol atm and left = to
acetate A (0-6molL-)
L) Calculate
reacton. closed 2
= L-) =2-0-8 = = 0-934
X
be = 2 K- ; products wil 40% 2
x. 2mol mol that K, x(0-4 0-8 0
100 x40 2 mol the two 0-934
Therefore, x mol-!, PC,Cl(g,)(8)di+ssociate |=
(Molar (Molar + + (0-082 = = mol08=
H,0 wil H,0 molL) before
= T0-267 1:868
be = to12
L
equilibrium vessellitre
mass 4-0
according mass obtained atm 327°C= mol 20-8 the form mol
0-4 =
of of K-l L-', 0-267 = reaction 0:8 constants wheandn
C,H,OH CH,COOH
to when mol- (327 A mol
the and mole
120 x t = L-l at of
equation, 600 273) 2-1 the PCl, equllibarndiK,um
= = g
46 60 of K) = = k, DINESH
g g acetic 600 1, equilitbrium and
xmol-)
for waS
moles mol-!) K
0-8 8 the CHEMISTRY
COMPANION
acid mol reaction,
achieved
of point of
CH,CO0C,H, are
reacted isClh PCl
;
was
with fouN
 r2= or PCi
Solution.
conc. Poye Example 39 molefsh/itliatlre reaction
K= K Applying Eqm.amolar
rInitial
.PPCis = Total molconc. Total Solution. PrSovaemple eLet
that molar
conc. amountthe molar the
1 molar
Eqm.
conc.Initial
38Hence takingBy substi utingMoles/in
litre that
e
Px PrciPcig2 X no. no. the yolume
PrCis
lhatthe
(P+K,) Law (1+x) P(r) of for of.
(1+r) square equatiequilibrium
o()n, the point Concentration
K, ; of
P(1-1) moles PCl, moles pressure valuesthe of
Chemical ofroot, the
P=K, at at CHyC00C,H,
PPCl3 = eqm. (1-) PCI1, eqm.
(1+x)
(l+) P(r) P, necessary of
the
- P-x)1+ equilibrium, =
(1 + K, Kpoint= CH,COOH
different
mixture
K,; (1+)-Iti+) ChiI=P+K, - (1-0-5) 2 2 V 2
P(*) P(¢) MISCELLANEOUS
PROBLEMS
SOME PPCl, to formed2-x
P pPCI, 1-05 obtain
P+ PClCl, t or species
+
P=3K, pCl, X + 50% 4-2x=xor = = or
133 C,H,0H litres. V
K) = K, 0:5 (133 before
= (1 0 dissociation mol
K, +x) (05P1:5 +0-5 PCI,0 mol)
0-5 the
where X
mol. 150-5P Molarx 3x= reaction
= + (88
x 15 of CH,cOoc,Hs
is g
the mol. PCl, mol-l) mass or4 and
0-5 ofx=a at
degree at
-05p1-5 500 117-04 ethyl
= ne
of K acetal 1:33 = equiliH,b0riu+m
dissociation. is
numerically g
mol.
point
three can
be
times given
the as
value of follows 7.25
:
 DINESH COMPANION CHENAST
Eqilibrium
7.26
converted 7.27
Example 40 0-5 am.
CO, is
Some of the atm. tato CO on 0-6 x 208-5 +0-4x
Avessel at 1000 K contains CO, wiùh a pressure ofequilibriummirtureis
pressureof
graphite. Calculate the value ofK, if the total
0-8
addito Foran
idealgas, W = nRT W 1-4
137-5 +0-4 X = 148-92

Solution. The reaction taking place is : 200(e)

CO,(e) + C) part in the reaction = p atn. =RT
after taking PM =RT =
Suppose that the decrease in pressure of (&)
CO,
Then increase in pressure of CO(e) = 2p atm
dRT
The partial pressure in the equilibrium mixture are
de PM
2C0(3) I(atm) x (148-92 g
CO,(&) + C(s) RT mol) = 45374 L-1
(0-5-p) atm
2patm
(05 + p) atm EXAITIple
43
(0-082 atm K- mol) (400 K)
At eqm. point (05 -p t 2p) =
Total pressure = o168ofN,H,
pressure = 0-8 atm (given)
But the final 0-5 + p = 08 or p= 0-8-
0:5 = 0:3 atm
thathas
(hydrazine) dissolved in water and the total Volume is made upto S00 mL Calculate the percentage of
reacted' with are
water in
H,solution.
.Molarity of N,H, solution. The K, for NH, is 4-0 x 104 M.
Pog) solution
According to the equation, K Pco2 (s) Mass of N,H 1000
(0-6 atm) X (0-6
atn) Molar mass of NH, S00
atm)
(0-5 atrm - 0-3
0-6 atm x 0-6
atm
= 1:8atm (0-16g) y1000
32 g molrl = 0-01 M
S00
0-2 atm
Letx mole of N,H, be dissolved in water.
N,H, + H,0 N,H, + OH
Example 41 27°C and 760 torr. Calculate the Initialconc. 0-01 mol
dissociated in a sample of a gas at
Z0% of N,O, moecules are
epiibriHR Re.
2NO,8)
density Eqm. conc. (0-01 - ) mol
0
I mol Xmol

Solution. N,08) 0 K, [N,H}1TOH]

Initial conc. 1nol [N,H] (0-01 - )
0-2 x2 =0-4 mol =0-2)
(1-0-2) =08mol
Bqm conc. (degree of dissociation =20% 4-0 x 10-6 = [.0-01 -Ie 0-01]
= l12 mol.
Total mberof moles afer issociaion = 0-8 + 0-4 (0-01 - ) 0-01
nRT r=40 x 10-6 x 10-2 or I =(40 × 10812 = 2-0 x
Vohume of the equiibrium miture 104 mol.
P
mo:T=7°C = 300 K . Percentage of N,H reacted with water - (2-0 x 10 mol) 100
P=latrn, 1-2 moje R= -082 L atm K x = 2-0%
Substitutng the vabes in the above relaion : (0-01 mol)
K))
(1-2 mol) x (0-082L atn K mol')(300 = 29-52 L Example44
V
1(atm) at is the value of k for the reactionad 1473 K
+ 04 X 46 = 92-0g I{g) 2ig)
Ms of the equiliiiun mixture = 0-8 x 92
Mass (92g)=312 L when one mole oj todine gas is introduced into an evacuated one litre flask so that onty 5% of ügets issocitea
Density of the equilibrium mixture Vohume (29-52 L) Solution.
Initial no. of moles/Nitre 1
No. of moles/litre at equilibrium 1-0-05 0-05 x 2
Example 42
reaction : (. a= 5% = 005)
The degree of isociaior s Na 400R and 1-0 atn for the gaseous
= 0-95 =0-1
Applying Law of chemical equilibriun,
Pat) a) + a,)
Assuig ideal pas behaviou for all the gases, calculate the densiy of the equilibrium nirture t 400K e K Lg(0-1 molL'x0- Imol L =0-0105= 1-05 x 102 mol L
Iz(e)) (0-95 mol LL')
Solution. PCl{g) PCHe) + Cl(g)
PROBLEMs FOR PRACTICE
Eqn conc (1-04)
=06 mL 2moles of HI wben heated at 444°C nnil equilibrium is Teacbed were found o be 22% dissociated. Calculate the equilibriun
constant for the reacion. [Ans. K = 0-0198
Average noleculzr nass of mixure 2. The initial molar concentration of the reactants A and B were 0-1 M and 0-2 M respectively in the following eaction
0-6x Molecnlar mass of PCl, +0-4x Molecular as of PC, +0-4 Molecular mas of Cl, A+ B2c
0-6 +0-4 + 0-4 When equilibrium was attained, the concentiration of Ain the reacion miture was foand to be 0-06 M. Calculate the equilibriu
constant. [Ans. K,=0-67
 DINESH COMPANION CHEMSTS

reactants: enok
7.32 products
dividedby term raised t
concentration of
Example 46 expressed as the cC + dD
Equilibrium constant K, is reactionaA + bB MolL)
for are
concentration
stoichiometric coefficient,
(unitof
K, = 1AJ"(B
paragrap :
following on the basis ofabove reaction :
Answer the equilibriumconstantforthe
Write the
2NH, (g) reaction:
N, (g)+ 3H, (g) equilibriumconstantforthe
units of
(u) Writethe (8)2NO(g) equilibrium
constant?
N, &) + 0, onthe
effect of catalyst
(üi) What will be the
[NH,1
Solution. () K, = [N, I[H,
(molL-l;? equal moles.
and prodcets haveequilibrium
() K,=(mol L-)(mol L) reactants
the gaseous equilibrium. Therefore, constant has no nite
constant has no units since astate of
Equilibrium in
influencethe reaction
(üi) Acatalyst does not gasphase :
and oxygen in the
Example 47 sulphur trioxidefrom sulphurioxide
Forthe exothermicformation of 2s0,(8) 900Kand AH=-198kJ
250,(3) +0,(g)
= 40-5atm-lat
Kequilibrium constant forthe reaction. equal toK, at 900K.
() Write the
expressionfor the be greater than, less than or three gases is reduced,
(ü) At roOm
K,
temperature ( 300K) will if the volume of the vessel containing
equilibrium be affected
the
,kepiags
(üi) How will the What happens ? SOz O, and S0, at
equilibrium at
temperature constant ? flask containing
adding l mole of Helg) to a (P.ISA. Be
(iv) What is the effect of
temperature ? reaction is:
expression for the equilibrium constant (K,) for the
Solution. (i) The
= 40-5 atm-!
K, so,() XPoz ()
in nature. Therefore, the increei
forward reaction is exothermic and the backward reaction is endothermic than the value at 900 K
(i) The means that the K, at 300K will be
greater
temperature favour the backward reaction. This unit volume of the gases present will incee
volume of the vessel reduced, the number of moles per of moles per E
(iii) When the
must shift in that direction in which the number
According to the Le Chatelier's principle, the equilibrium
to the right or more of SO.(e) is formed.
volume decrease. Thus, the equilibrium gets shifted constant temperature will not affect the rh
mole of He(g) at
(iv) Since the volume of the flask is fixed, the addition of 1
of the equilibrium constant.
REVIEW PROBLEMS
1. Which type of substances participate in solid-gas equilibrium ? Give example.
2. Why does chemical reaction between ethyl acetate and water attain equilibrium even in an open container ?
3. How are K, and K, related to each other ?
4. Give expression for K, for the reaction :
Nag) + 3H,(g) 2NH,(g)
5. Does the value of equilibrium constant depend upon the initial molar conc. of reactant and product species ?
6. How does increase in temperature affect state of equilibrium if the forward reaction is exothermic in nature ?
7. Under what conditions can equilibrium be achieved between a solid and its liquid state ?
8. In a reaction Q, = K,. What does it indicate ?
 7,46 DINESH COMPANION
(i) ptB vahue of 0-2M
Ca(OH), solutlon
Ca(OH), is a diacid base and dissociates in solution as :
Ca(OH), Ca?t + 20H
Concentration of [OH] - 2 x 0-2 0-4M
pOH log (OH)=-log [0-4] -(- 0:3979) = 0:3979
pH 14- pOH 14 -0:3979 = 13-6021
Example 59
Asolution has
been prepared by dissolving 0-63 g of nitric acid in 100 mL. What is its pH yalue ?
completely dissociated.
of HNO / litre of solution
Assume that thg s
Solutlon. Molar concentration of the solution = AmountMolar mass of HNO, 0-63100063
100
1M
The complete dissociation of acid in solution is :
(aq)
HNO,(!) + H,0) H,0+ + NO, (aq)
0-1 M 0-1M
pH '= -log [H,0+] = - log [10-]=()(Hog 10) = 1
Example 60
Calculate the phl value of 0-20 Msolution of methyl amine (CH,NH,) at 298 K, given that its
44 X 10s, ionisation constan
Solution. Let abe the degree of ionisation of methylamine. The concentration of the various
and at the equilibrium point are : species before
CH,NH, + H,0) CH,NH,+ (aq) + OH (ag)
Initial molar conc. 02 0 0

Equilibrium molar conc. (0-2 -a)

Applying Law of chemical equilibrium,
(CH,NH,*IOH"] a. Xa
: 4-4 X 10-5 =
K, = (0-2-a)
[CH,NH,]
As methylamine is a weak base, a is very small. It can be neglected. Therefore, 0-2 -a = 0-2, Thus.
4-4 X10 0:2 or a = (0-2 x 4-4 X 10-5)/2 = 2-97 x 10-3
[OH-] = 2:97 x 10-3 M

K, (10x10-4M²)
x 10-12 M
[OH] (2-97x10-M) =3:37
pH =- log [H,0+]=- log (3-37 x 10-12)
= 12- log 3-37 = 12-0-53 = 11-47
Example 61
AL 298 K, the pH of a lemon juice is 2-32. Calculate its [H0t] and [OHJ.
Solution. pH of the solution = 2:32 ; - log [H,0*] = 2:32 or log [H,0+] = -232
[H,0]+ = Antilog(- 2-32) =Antilog (3-68) = 4-79 x 103
(1-0 x10-4M²)
[OH] [H,0*] (4-79 x 10³M) = 2-09 x 10-12 M e
 747

um

npl
6 e2

the
heplof following solutions :
fhydrogen chloride dissolved in 1-0 Lof water
fpotassium hydroride dissolved ln 1-0 Lof
In both the problems, he wster. water
soution. volume of the solution is the same as the volume of
Mass of hydrogen chloride =3-2 g
Molar mass of hydrogen chloride 36-5 g mol-!
ofmoles of hydrogen chloride (3:2g) 0-087n mol
No.
(36-5gmol-)
Volume of solution 10L
0-0877 mol) 0-0877 M
Molar concentration of solution 0-0877 mol L-!
(1-0L)
acidis strong and is completely ionised in solution as :
The (aq)
HCI H,0+ + CIt (aq)
0-0877 M
(H,0*] = 0-0877 M 10)
pH =- log [H,0+] =-log (0-0877)
( = - log(8-77 x
= (2- log 8-77) = (2-0-94) = 1-06
)
Mass of potassium hydroxide (KOH) = 0-28 g
Molar mass of KOH = 56-0 g mol
(0-28g)
No. of moles of KOH = 10 mol.
(S6-0g mo!-l, = 50 x
Volume of solution = 10L
(5-0x10'mol) L-l = 5-0 x 103 M
Molar concentration of solution = S-0x 10-3 mol
(1-0L)
base and is completely ionised in solution
KOH is a strong (aq)
KOH OH (aq) + K* (ag)
5-0x103M
[OH-(a)] = 5-0 × 10-3 M
K,(1-0x10-l4M')
- 2-0 X 10-12 M.
H,0*] OH (aq)l (5-0x10M) = (12 - log 2)
pH =-log [H,0+ = - log (2-0 × 10-12)
= 12-0-3010 = 11-699 11-7

Example 63 ne of the sotiee ?

drink is 3-8 x 1 M. What is the pH
The concentration of hydrogen in a sample of soft (N.C.E. R. T. Solved Erample)

Solution. pH = -log [H*] =- log (3-8 x 103)

=(3- log 3-8) = (3 -0:58) = 2-42
Erample 64
your answer.
Will the pH of water be the same 4°C and 25°C? Explain
Solution. In aqueous solution, [H+IOH]= K
For pure water, H*] = [OH] or (H] = JK
The value of K.. increases as the temperature increases.
Ku25'C) > Kur4 and also [H*l25" > [H*4c
1
Since pH = this means that pHsg <pHo*
[H]
 7.48 DINESH COMPANION
Example 65
Calculate the pH of l0 Macid solution.
(N.CER.T.
Solution. The molar concentration of the solution is 10-8 M. Therefore, ts PH value is CxDected
acidic medium pH cannot be 8. It must be less than 7, Actually, the solution is aqueous and it
ions released by the selfionisation of water, Their concentration is 10-7 M.
Thus, H,0*] given by acid 10- M
[H,0*] given by water 10-M
x 10-8 M
Total [H,0t] = 10 M+ 10-7 M= 10-8 (1 + 10) 11
Now, - log 11)
pH =- log [H,0*]= - log (11 x 10 M) = (8
= (8-1-0411) = 69586 6-96
Example 66
Calculate the pH of 10-10 MNaOH solution.
Solution. (OH] given by base = 10-10 M
(OH-]given by water = 107 M
Total [OH-1 = 10-10 M+ 10-7 M= 10: (10+1) = 1001 x 10-71M
pOH =-log (1-001 x 10-) = (7-log 1-001)
=7-0-0004 =69996; pH = 14 -69996 = 7-004
Example 67
An acid having pH = 6is diluted 100 times. Calculate the pll of the final solution.
Solution. pH of solution =6; [H,0+] = 10
After diluting the solution to 100 times.
(H,0+] = 10-/100 = 10-8 M
[H,0+] by the dissociation of water = 10 M
Total [H,0+) = 10-8 M+ 10-7 M= 10- (10-1 + 1) = 1·1 x 10-7 M
pH =-log(l-1x 10) =(7-log1-1) =(7-0-0414) =6-9586
Example 68
Equal volumes of three acid solutions with pH 3,4 and 5 are mixed in a vessel. What will be the H

C.B.S.E.ion(Pco.nMcenT)tr
in the mixture ?
Solution. For first solution,
pH =3 or -log [Ht] = 3 or log [Ht] = -3 = 3-0
(H"] = Antilog [H*] = Antilog (3-0) = 10-M
Similarly, for second solution, pH = 4 and [H+]= 10-4M
For third solution, pH = 5 and [H+] = 10-5M
Total [H] in the solution =(10-3 + 10+ + 105) = 10- (1+ 10-! + 10-3)
= 10-(1 + 0-1 + 0-01)= 1l1 x 103 M
Since equal volumes of the three solutions have been mixed. [H*]of the resulting solution
(1·11 x 10M) = 37 x 104 M
3

Example 69
Calculate the pH value of a solution obtained by mixing 50 mL of 0:2 NHCI solution with 50mL. of 0:l NL
solution.
Solution. When equal volumes of HCl and NaOH solutions are mixed, the volume becomes double andthe comee.
normality (or molarity) is reduced to half.
(0-2N) x (50mL)
Normality of HCl solution on mixing = = 0-1 N
(100 mL)
[H]in solution = 0-1 N = 01 M
(0-IN)x (50 mL.) =0-05 N
Normality of NaOH solution on mixing (100 mL)
 7.49
solution [OH] in solution =
after 0-05 N 0-05 M
neutralsolisatuitioonn =0:1-0-05
pH of
=- log [Ht] ==0-0S M
-log (0-05) =- log (5
g a n pT

suton.
leo

N HCI solution is added

=-(l0
to one litre
g5-2log 10) =(2-log
× 10)
5) =(2-0-6989)= 11301
resulting
Since of Caleulate the pH of the
solution. NaCl is a neutral
Concentration of HC) salt, its sodium chloride solution.
before dilution =solution HCl solution.
Concentration of
as such
will not give any H+ ions. It will simply dilute
HCl after 0-01 N
isa
monobasic acid. Itsdilution = 0-01/1000are=10N= 105
(HCI
molarity= and normality M.
(H,0+] 105; pH= -log the same)
Banple
71 (10-5 M) =() (-5) log 10=5
N
Whatwillbe the resultant pH of the solution when 200 mL of an aqueous solution of HCI (pH= 2) is mired with 300
mloffan aqueous solution
of
solution. pH HCI solutionNaOH (pH = 12-0) ?
=2; H,0+] in solution =
Numberoff moles of [H,0*] in
102 M
200 mL of HCI = 10-2 x 200 = 0-2 x 10-2 mol
Iof NaOH solution=
12; [0H]in solution =
solution 1000
10-2 M
Number offmoles of [OH] in 300 mL of
NaOH solution= 10-2 x 300 = 0-3 x 10-2 mol.
Total volume of the solution after mixing = 1000
Numberof moles of NaOH left in the (200 + 300) = 500 mL
solution after
= (0:3 x 10-20-2 x neutralisation
by the acid
10-2) = 0:1 × 10-2 mol
.[OH-]inthe resulting solution = 0-1 x102 x 1000
500
= 2.0 × 10- M
H,0+] = Ky (10-14 M²) = 5X 10-12 M
[OH] (2-0 × 10- M)
pH = -log [H,0+] = -log (5-0 x
= (12 - log 5) = (12-0-69897) =10-)
11:30103
Example72
paermineacidd
conjugate the4egree ootsation
of ammonia, andK,pHof a 0-05 Mammonia solution,
Given that Also caleulate ionisation constant of the
for NH, is 1-77 × 10-5.
on. Step I. Calculation of degree of ionisation (a).
The ionisation of NH, may be represented as
NH, + H,0 NH + OH
The dissociation constant for the base may be given as :
Ca? [ : a is very small for weak base]
K, = - Ca?
1-a
11/2 s11/2
= 0-018
0-05
Step II. Calculation of pH of solution
s, [OHF = Ca = 0-05 x 0-018 = 9-4 X 104 M
Ky 10-14
[Ht]=
[OH] 9-4 x104 = l06 x 10-11
pH =-log [H*] = - log (1-06 x 10-1l) = 10-97
Step III. Calculation of ionisation constant of conjugat acid NH ion
We know that for conjugate base-acid
10-14
K, x K, = K, or K, =Aw ; K= 1-77 x 10S = 5-64 x 10-10
Kp
 DINESH COMPANION CHEMISTR

7.50
01 M M
Example 73 solution containing
to precipitate from a
Calculate the pH at which Me{OH), Negùas
Ng(O), = 10x I , 10x O-!!
Solution. [Mg+]= 01 Mand K for Mg(OH),
The equilibrium in the saturated solution :
MgOH), M+20H
1-0x10-1-el0x1o-l0

10-10i2 = 105M
[OH = (10 x
We know that [H,0+] JOH] = K = 10l0-4
[OH)
10-4 0 0 M
,. H,0+] =
=- log [10-)
pH =-log[H,0+] 10 = 9.
=(-)(-9)log

Example 74 Üs Ky
aqueous solution of diethylamine is 12-0. Calculate
ThepH of0-05 M
Solution.
12-0 (given)
pH of solution =
But pH + pOH = 14 - 12 = 2
pOH = 14 - pH = 14
[OH (a2)) = 102 M
The dissociation of (C,H),NH is epresented as :
(CGH), NH+ H,0 (C,H), NH,t +OH
Initial no. of moles 005 M
0-01 M
(0-05 - 0-01) 0-01 M
No. of moles at the
= 0-04 M
equilibrium point
Applying Law of Chemical equilibrium,
[(ChHshNH,|[OH"] (0-01M) x (0-01M)
K [(C,Hs), NHÊ (0 04M)

= 2:5 x 103 M

Example
What 75will be the resultant pH of the solution when 200 mL of an aqueous solution of HCI (DH= 2-0) is mixeldwi

(pH = 12-0) ?
300 mL of an aqueos solution of NaOH
= 102 M
Solution. pH of HCIsolution = 2; [H,0+] in solution
10 x200 = 0-2 x 10-2 mol
H,0+]in 200 mL of HCI solution =
Number of moles of 1000

= 102M
pH of NaOH solution = 12: [OH] in solution
102 x 300
=0-3 X 10- mol.
Number of moles of [OH]in 300 mL of NaOH solution = 1000
mL
Total volume of the solution after mixing = (200 + 300) = 500
Number of moles of NaOH left in the solution after neutralisation
= (0:3 × 10-2-02 x 10-2) = 0-1 x 102 mol
 DINESH COMPANION CHEMIST

7.56 K, =18x15
at 298 K;
sodium acelate
Example 76 Msolutionof
of hydrolysis of01
Calculate the degree Calculation hydrolysis constant
weak
(K).
acid,
I. of and
Solutlon. Stepacetate is a salt of strong base 1·8x10-5=5-5x10-10
1·0x10-14
Since sodium
Ky
K, K,
of hydrolysisx (h. C=01M 10-5
Step II. Calculation of degree 10-10,
10-10,12 = 7-42x
K, = 55 5-5x10-10
= (55 X
0-1
Degree of hydrolysis (h)
given that
ammonium acetate
of
Example 77 of
decinormal solution
andK, = 10 x
14
Calculate the percentage
hydrolysis 1-80 x 15
1-75 x 10-5, K, =
K, =
(Ky). weak base,
Step I. Calculation of hydrolysis constant
weak acid and =3-175 x 10-5
salt of 1·0x10-14
Dnee ammonium acetate is a
Ky 105x1·80x 10
K.K, 1-75x
5"63 x 10-3
Calculation ofdegree ofhydrolysis (). = (31-75 x 10-)l2 =
Step II. (3-175x 10o
h =JK =
solution. Hydrolysis constant for
Example 78 hydrolysiS and pH of a 0:1
Msodium acetate sodium acetat
Calculatethe degree of
56 x 10l0,
degree of hydrolysis (h).
Solution. Step I. Calculation ofbase and weak acid.
strong
Sodium acetate is a salt of /5-6x10-10 = 748 x 10-5
01
solution.
Step II. Calculation of pHof the may be shown as follows :
acetate
The hydrolysis of sodium CH,COOH+ OH
CH,CO0 + H,0 Ch
Ch
X 10-6
C(1 - h)
xh= 0-1 X 7:48 x 10-5 = 7-48
[OH] = C
1-0x10-14 =1-33 x1oM
Kw
[H+] = [OH] 7-48x 10-6
x 101
pH - log [Ht] = - log [1-33
0-124 = 8-88.
= (9 - log 1-33] = 9 -
solutiomt
Example 79 the pH and hydroxyl ion concentration of 02 M aqueous
K, for butyric acid is 2-0 x 10-5, Calculate
butyrate.
Solutlon. Step I. Calculation of pH of the solution.
weak acid.
Sodium butyrate is a salt of strong base and
pH =-log
2
K, +log K, - log C]
2-0 X 10-5, C= 02 M
According to available data, K, = 1-0x 10-l4, K, =
10 +log(2-0x 10)-log(0-2)]
1
pH =-log
2

---14)-(6-log2)+0-698]=-1-14-4-699 +0-698] =9-0

Step II. Calculation of hydroryl ion concentration.
pH =9, pOH =pk, - pH = 14 -9 =5. [OH] = 10-sM
 7.57

ampl
B eo

a)Prove
ahatin the aqueous solution of NH Cl concentration of H,0* lons is K,
xC.

oulheratio of [HCO;] (K, =45 x 10)

Find
H,Co,1 in the 74. 2004)
agueous solution of carbonic acid whose pHis P.M.T.(Main)
(C.B.S.E.
solution.(a)
ionisationin aqueous
NH,CI + H,0 NH,OH + HCI
solution is
The
NH + Cl + H,0 NH,OH + H+ + CI
writtenag
be
Irmay
NHÀ + H,0 NH, + Hot
Initial molar COnc.: 1mol
Equilibriummolar 0
hydrolysis)
c(l-A) c.h = degree of
conc. of salt, h
conc.: C.h
(Here c =
Hydrolysis Constant (K,) [NH,IH,0jt c.hx c.h
(NH, c(1-)
Since.his very small. it can be neglected as compared to 1.

K, = ch2

com equilibrium reaction [H,0*] = ch =c=/K, xC

It is acidic buffer

pH = pK, + log (Conjugate

(Acid)
base)

pH =7-4 K, = 45 X 10-7 pK, =7- log 4:5

=635

pH = pkg + log [HCO3 1-4

[H,C031
= 6-35 + log [HCO]
[H,COj]
[HCO31 [HCO]
=7:4 -6-35 = 1-05 or [H,CO3]
log [H,CO3]
= Antilog 1-05 = 11-22.
PROBLEMS FOR PRACTICE
5-28. [Ans. h = 2:624 x 1041
28. Calculate the degree of hydrolysis of 0-02 M solution of ammonium chloride if its pH is
solution of ammonium acetate, given that K, = 1:752 x
Determine the hydrolysis constant and degree of hydrolysis of 0- 1 M
[Ans. K, = 3-28 x 10-5, h = 5-727 x 10-3)
"29.
10-5, K, = 1-74 x 10-5
[Ans. 1-312 x 101
30. Calculate the degree of hydrolysis of 0-04 M solution of NH,Cl of pH = 5-28.
31. Calculate the degree of hydrolysis and hydrolysis constant of 0-1 M solution of NH,CI. Given
K = 1x 10-14, K, = 1-75 x 10-5, [Ans. Kh = 5-714 X 10-10. h = 7-56 x 10-51