Introduction

11
(Physical equilibrium)

BA fav AIAJTRT (Solid-liquid equilibrium)

(a) 4[IAA I 5 (b) 4 311A AATt1

AI14T: H,0(s) H,o0)

301 UR (Liquid-vapour equilibrium)

511

A|A1<T: H,O() H,0(g)

475
476

7.1.3 7.1.5
AT ttt(Solid-y/apour equilibrium)

AIAGA, , *fA CO,, at\f o ) tCE, A4A

7.1,4 AA1T:L,(s) 1,(8)

p, 4w« p A1, w = kp [k=Mtt

ANT CO,
co,(a)
 477

H,O() H,08)

H,0(s) H,0()
I,(s) I,(8)
#) CO,(s) C0,(g)

AgCl(s) = AgCl(aq)

122 g Afezt (Reversible reactions)

AATTA NH,
GRAt: e A 350°C NO3 NH,CI AIA

aT4A Gog
NH, CI(vap) NH, (g) + HCI(g)|oÈ CI
+A9 TLa NH,, HCI 17 2y9 wAA0O NH,

(Irreversible and reversible reactions)

N,(8) +3H,(8) 2NH,(g): H,8) +1,(g)2HI(g):
sER (reversible reactions) PCI,(g) =PCl,(g) +Cl,(g): N,o,g)2NO,(8)

tug TAA REÍBS TT AfAT: H,(g) +I,(g)’ 2HI(g)

GR A0o Afat: 2HI(g) ’ H,(8) +I,(8)

2KCI0,(5) A2KCI(s) +30,(&)

444A fafers AA AgCl -

Afratto AAIAA (equilibriumn state) coeR|

N9,uq) + KCl aq)’AgCls)l+ KNO,{aq)

478
7.2.3

(CaO) 3 Co, 17 te : 7.3 (Chemical equilibrium)

CaCO,(s) Ca0(s) +CO,(8)

FoCA CAt D T,<*

r
A+BC+D
(A +
B’C-D)

oR XRIo AIPA0 (C+D’ A

+ B)
CaCO, Te A<FA: CaO(s) +CO,(g) ’ CaCO,(s)

3Fe(s)+4H,0(g) Fe,0,(s) +4H,(g)

C I D

|Fe,0,(s) +4H,(g) ’ 3Fe(s) +4H,0(g)] REÍbO IN AT|

H,O(g), Fe,0,(s) 9 H,(g) -GR afs GAT AIA|

A+B C+D A+BC+D

C+D
-’A+B

[HS '06]
7. Fe,0,(s) +3CO(g)-2Fe(s)+ 3C0,(g) Afsante tAt
 479

GATgfs AeE
stE8 (equlibrium concentration) aR AfPATAIG0A
s d (equilibrium mixture) 4(T |A
(re,

Grtst: TIA lmol PCI-(g) F 273°C GNOtT GGE AGT

chemical equilibrium) AT| Cl,(g) -G ART

tfAett PCI,(g).PCI,(g) 9
4
qRIsA 61.3%, 19.3% 3 19.3%| WIis 273°C GAot
ROAA 6 ta Imol PCl,(g) 3 lmol Cl,(g)

PCI,(g) +Cl,(g)=PCI,(g) IaMD9 ANATT PCI,(g).

19.3% 9
PCl,(g) 8 Cl,(g) -4 GHIA-RI0 ARIT 61.3%,

tta R (dynamic equilibrium)_ q1 23|.

CaCO,(s) CaO(s) +CO,(g) | I14N RÍSPAT

14c-aa
14,
17'co, s Ca0-43 YH AAA Ca"co
FAG AAtqt (Homogeneous equilibrium)
CaCO,-23S KKATG ALD CaO 9 CO,

GiEA*: O N,(8) +3H,(8) =2NH,(g)

250,(8)+0,(8) =2S0,(8)
y0TRA 3(Characteristics) 9 CH,COOH()+C,H,OH()=CH,CO0C,H,(9 +H,00)
PAG AIT (Heterogeneous equilibrium)
E Eof)

2Hg0(s) 2Hg() + 0,(g)

480

AC2N 7.3 7GTSrl constant) (T| [A) 3 [B]

11. 41afrs TAL A? [HS '07]
[HS 06)
[HS '09)
2A+ B ’ af4TTS SÁ
A+3B Af4TGTs Í
JA-) 250, 8) + O,(g) 250,(g) 3A +2B’RÍFAIatg
(1) 2Mg(s) + 0,(g) 2MgO(s) xA + yB + zC’ AA1G5
A(g) 2B(g) I ff EAAT faf T(A A(R)3 B(g)

T47 (mnin) 15
q:
30 45 60 75 90
A-R
B-
Et (molL-!) L.00 0.86 0.70 0.64 0.58 0.58 0.58
T(mol L ) 0.00 0.28 0.60 0.72 0.84 0.84 0.84
fafeufta
(0) f a t T41 A 1 ánt ACE? (i) 7A14414 A

4 X
(Law of mass action)
X

(P Waage) 1A14f4¢ FfeAT fA AA

fAfFALA IEL 4A

7.5
3 (Mathematical form of law of mass acó
MABI (Active mass) 4AT A1F, A 3B 3AA A8f fAfAT D oE
FA A 73 ASZT f 5 5A: aA+ bB dD+

(Tp)c[A]x (B]º 1,r(=k, [A]4 x [B]b R AYata

21A (rH)o[D] x (EJ° A1, rh=k,[D]d x (El'. G
|D) 4R E) SFCT AIAI1A A. B. D E 1

(partial pressure) A A1A1A I9. 4A TAfoÆ|BE TA

EILSÈ k,(AJª x[B)b = kh[D] x [E)*

K= [D]x(EJ
[AJa x (B]b [AJa x [B]b

Y4F| atA K

forfá2 yefafaftA s14, rc[A J[B] A1, r= k[AJ[B) (TGT, sifrfo

 481

aA+ bB dD+ eE A K(O

K |A1" x|Bjb

aA(g) + bB(g) dD(g)+ eE(g) H1II4TA (RO

b
PXPB
qIsAA, B, D E-4 WMF 5T°\|
dD+ eE NIIKIA (T0
aA + bB

K,

IsA A, B, D E-93 AIG-ATT|

Pco,(8)
|: [CaCO,(s)] = 1:(Ca O(s)] = 1] a K, =

H,O() H,0(8)
[H,0(8))
=[H,0(9))
[H,0(0)]

RR D EA: CaCO, (s) =CaO(s) +CO(8)

(CaO(s)][CO,(8)) =[CO,(8)] K,= PH,ot8)
[CaCO,(s)]

Ke
(Pco,)
[Co,12
2C0(g) +0,l8) 2C0,(8) K, = (PcoXPo,
[coj' x[0,]
[PCI,]x(CI,) Prci, XPci,
K= K, =
PCI,(g))=PCI,(g)
: +Cl,(8) [PCI] PPCI,

[NH,? (PNH,
Ng)+34,g) =2NH,(8) K, =
IN,]× [H,
Pn)x(Ps,)
[u,|/2 x(Br,l/2
HBrg)t K (HBr]
PBr
 482

HS(aq) +H*(aq) H,S(aq) Ke

[H,S]
(HS] x (H*]

4NH,(g) +50,(g) 4NO(g) +6H,0(g) [H,oj® x(NOj

K, =
(0,°(NH,J (PH,0PNo
C(s) +CO,(g)2CO(g)
K= [coj? - (CO!:C(s) = 1)
[C(s)|[CO,] [co,]
(Kp Po,(Pco(PNn
(H,1
Pco,
3Fe(s) +4H,O(g) K, = (Fe,0,(5)|[|H,'
Fe,0,(s) +4H,(8) [Fe(s)P[H,oj (H,01
(Fe 0,(s)] = 1 RR (Fe(s)] = 1
K (PH,
PH,0
(NH,]x(HI]
NH,I(S) NH,(g) +HI(g) K, =
(NH,I()) =[NH,]x[HI) K = PNH, X
: [NH,I(s)] = 1 PHI
afM A1q1N A(g), Bg),
D(g) E(g)
18. CaC0,(s) CaO(s) +C0,(g) 4tq414 (Hã
A134A qIFH PA PR" Pp pE A, 94 K,

20. fAafafs AfFAfas(A5 K, 3 K,

i) 2BrFs(g) Br,(g) +5F,(g) EG PV = nRT
(ü)
4HCI(g) +O,(g) 2cl,(g) +2H,0(g) A1, P =(RT = CRT C= ATA
(iü) P,(g) +30,(g)
(iv) CO(g) + P,0,(s) AAT FCA AË, p, = [AJRT, pp =
21. fAaffo 2H,(g)CH,0H() (B]RT. Pp =P
afATgfas ( K,-a ATTAT
(i) 2Ag* (aq) +Cu(s) ACT|
R PE =
(E]RT
(i) Aut (aq) + 2CN (aq) C2(ag) +2Ag(s)
PA PB Pp 8 Pp 4 AF1214
[Au(CN),J (aq)
(iü) 3Cu(s) +2NO, (aq) + 8H*

(iv) CL,(g) + 2Br (aq)

(a4)
3Cu2*(aq) +2NO(g) +4H,0(0)
K,
(DJRT}dx{[E)RT}_(D'x (E)RTd*0-"
{[AJRT}a x {[BJRT}b [AJ4 x (B]
Ky =K(RT)An; (TIA, An = AfA191
Br,() +2CI (aq)
76
(Relation between different equilibrium constants) i. Ky = K(RT)An
7.6.!
K, K,43 $(Relation between K, &K,)

144TA ATE: aA(g) +bB(g) dD(g) +eE(g)

A14I144TA A(g), B(g), D(g) 9 E(g) GAIAIA 1pg
A(AJ, [B). (D] [E] K, [D'x (E .-[1] afM An >0 21, G4
K,> K¢
[AJa x (B]b
 483

An

(4 + 6) -(4+5) = +1 K, = K(RT) K,> K,

+50,(g) e 4NO(g) +6H,0(g) K = K,(RT)2
(1+l) -0 = +2
(5)=
HCO,,
CaCO,(s) + CO,(g) +H,0(g)
Kp = K,(RT)-1/2 K,< K,
e0,g)
CO,(g) 1-(1+})= K,< K
0-(1+3) = -4 Kp = K,(RT)-4
P,O(s)
30,(8) 2-(1+ 1) =0 Ky = K(RTO K, = K
Ke0,48)2NO(g)
4-4 = 0 Kp = K(RT)0 K, = K,
LoitH,0(g)Fe,O,(s)+4H,(g)
+ K, = K,(RT) K, > K
HOg)

K,) K,, K, 9K,-44 TE: K, = K,(RT)an = K,(P)an| ETA

rK, R (Relation between K,, & 2A (H,(g) +1,(g) = 2HIg)
Bon], A K, =K, =K,
IRNIS NE: aA(g) + bB(g) dD(g) + eE(g)
7.6.4 ALAIMB (Characteristics)
.-[1]: K, = ...[2]
b

12
K NSFA A, B, D E - (AIG-yA|

PA = A XP,
**P. Pp= Ip XP R p; = XpXP (RIA P=

xgx P p X Ey (P)(d +e) -(a+b)

b GrtEat: PCl,(g) PCI,(g) +CL(g) afsIEA Ra 450K

=K, x (P) (d +e) - (a +b) A 4, 450K GON K, AA TRT 0.19 T|

...[3]

[NO,]? .--[1]
3 N,O,(g) 2NO,(8): a*a Ke, [N,0,]
KAó (Relation between k, and K)

aA(g) + bB(g) dD(g)+ eE(g) (NO,) -[2]

N K RT |1]: K, =K(P)an ..-[2]
ffarats - K,
2 4511 I*, aA + bB dD +eE AISNA YTNIINS KI
AA t, K,(RT)A" = K,(P)an
m ilAi E, maA + mbB màD +meE
484
ALS KF K' 5G K' = Km | agIA NAE 7.6.5
AUOA q4$ (Unit of equilibrium
aat AAE, aA+ bB
m
dD + eE
constant)
m m m
aHG ANYAF K" S, K" = Kl/m R

Grtkat: N,(g)+3H,(g) 2NH,(g) AfsATA GHa ziOAr = 0 A, AHHAD (K, K.)

AN*, K,= (NH,J2 1FA , 2 Ax#0 A, A0YTF

fayFA. 2NH,(g)N(g) +3H,(g) Ax = 0

Ax>0
atKa TYAE, K!N x(H K,-4A
(mol L-lyar
Ar<o
[2]
[NH,1² (molL
(atm )Ax
(atmj
(A, Kp

Gta: AfPAT O: A+
BC: A4SH45, K,=
Afs : C* D: t454*, K,= D [A][B]
fafFAT : A+ [C]
EafoA ÍAAO 519 (mneasured
BD;AASEKT
RÍFT O+ AfsAT : A+B D
= K4= [D]
[AJ[B] concentration, C)9 +t A

i. K xK, = x
[AJ[B)CjD) (DI
[AJ[B) = K 1pg (Co) IM (T 1molL-1) 4At
2|

Kc
Kp
3Fels)+4H,O(g)Fe,0,(s) +4H,(g)K =[H,0j (H,]1
Kp (PH Ax = 4
(PH,0) 4 = 0

NOCI(g) =NO(g) +Cl,(g) K, = (NO] × (CI,j/2

[NOCIJ K = PNOX (PCI,)2
Ax =1+-1=+(molL-ly/2(atm
PNOCI 2

N,(g)+3H,(g) 2NH,(g) Ke (NH;12 (PNH,

(N] x[H, K, = Ax = 2-(1+3) = -2 (mol L-!y2 (atm)-!
PN,× (PH,)
HAII: 2S0,(g) +O,(8) 2S0,(8)
An = 2-(2+ l) =
-1
25°C Gao11 250,(g) +O,(8) JoR, Kp = K(RTAn r'a
K, = 3× 1024
2S0,(g) Afgta 3 x 1024 = UT.
4, AA K-AA AA PS?
(HS '07) K(0.0821 x 298)
K, = 3 x 1024 x 0.0821 x 298 = 7.34> 1025
 485

(I,] = 0.6/5 = 0.12 mol L- R[HI] = = 0.7 mol L-l|

5
1.5 x 10-2
(0.7)2 =34.03
mol-' s-l| K (0.12) x (0.12)
4X10-3L
co(g) + Cl,(g) cocl,(8)
l.5x10-2 Lmol-l s-1
AHIAE, K= x 10-3Lmol-ls-l
8.33 CO(g), Cl,(g) a4R COCI,(g) -aA ARMF 5IY R1SPLA
1.8 0.12, 1.2 a7R 0.58 atm G, AISAta HA U A
2A+B 2 C RÍSPAIK
80x104Lmol-l
A17 1.24 Lmol-l, HI41A: 7G RIsPA0K (FO K, = Pcoci,
Pco XPc,
0.58 =4.03
0.12 x 1.2
I ,K=
81.0 dm3 qtOAA QpIE 1a lmol N,(g) 9 2 mol
10412 mol-2g
AY10X 1.24 L'molsl=9,92 x NH,(g) -4A (AG-RT 0.8| AecA H,(g)-9

N,(8)+ H,(8) NH,(8) RfFAA

AIA:RÍPAIK F9: N,(g) +3H,(g)2NH,(g)
AT qIA, lmol N,(g)= 3mol H,(g)= 2mol NH,(g)
3
.: 0.8mol NH,(g) = 0.4mol N,8)=x
2
0.8 = 1.2mol H,(g)
ISR N H.(g)9 IGRT = 2- 1.2 = 0.8 R
RAIA x , 94 K, = xatm-!
CAIGIK og0.8 mol L-! :: ldm3 =1L]
:molL-)= xLmol-1
, Aefs T A440°C GAo 2 mol HI(g) AI41A
3RI K, = K(RT)l
1
an= xL molx 2HI(g) H,(g) +l,(8). a2
0.0821 Latm mol-K-lxT [HS 10]
T= 1218 K. wTe, 12.18 KGAoR K, 8 K,-4 ARA0T
SIN: 7G AISPAIA (HA, K, =
A1500K [HI?
3;8) Br,(g) +5F,(8) AfpatbA 2 x 22 = 0.44mol
E3 K,= 2.6 x 10-9 AA K, 100

31FAK OAn = (1+ 5)-2 = +4 |

2mol HI(g)= lmol H,(g) = lmol I,(g)
26x 10- x (0.0821 x 1500) = 0.598 0.44mol HI(g) =0.22 mol H,(g) = 0.22mol I,(g)
DO 5L UINOLAKqIa H,(8) I,(8)-
T afaIA HI(g)
33 HI(g)-43 AA-7RI0 R1SCA 0.6, 0.6 9 3.5 2HI(g) H,(g) + I,(8)
0.22/V 0.22/V
H,l8) +1,(8) =2HI(g) fafstA K¹ A0N ttpg (molL-): (2-0.44)/ V
TA ? =1.56/ V
0.22,0.22
X
[HI2 (H,)x (14] = 0.0198
[H,II,]" K
[HI?
A ATATA M5- (H.1=0.D-0.12 mol L";
5
486
2 L-AA q1s l mol B- (HIG-RTT
PCL(g) A AfMZ GaotA GIT
AT A| 414TA
PCI-(2)-93 GATG-RI0 0.2 2, =2-0.175 -=0.175|
=
PCI;(g)= PCl,(g) +CI,(g) fafsAtA {4TAIA FO? gIA, lmol B= lmol C lmol A
L825mol B= 1.825 mol C=1.825mol A
1.825|
(PCI,]x(CI,] |
:. ArA1IN (B]=0.175molL-1,.[C]=3 l..825-175n0
(PCI) RLA =1+1.825 = 2.825 molL-1
Satg, ATAIT4TA PCI(g (ATGR0 =0.2 | 0R, K, = A ] 2.825
RAMSo PCl(g4 AA-RI =(1 -0.2) = 0.8 | (B]×(C] 0.175 x L.175 * 13.73
144* ug Imol PClg) -44 fAATATA 1 mol ATPAIA
1 mol Cl,(g) te tA 5A|ToAt, 0.8 mol PCl,{g)
PCl(g) - ALATTI
c
aA + bB|L + mM (44o E Ff
PCI(g) PCl,(g) + Cl,(g)
A1RTA SMEE (molL-): 02 = 0.1 = 0.4
0.8
0.4
CO(g) +H,O(g) CO,(g) + H,(g)
2

.
K, = (PCI;] x (CI,] 0.4 x 0.4
= l.6
(a) K,> K (b) K< K RR (c) K, = K, I
[PCI) (0.1)
(i) NH,(g) + HCI(g)NH,Cl(s)
(i) C(s) +CO,(g) +
CO,(g) +H,(g) CO(g)+ H,O(g) 1, 2Cl,(g)2C0CI,(g)
(ii) N(8) +O,(g) NO,(8)
AIFA 2atm latm | AIIT3 (iv) Fe(s) +
H,0(g)FeO(s) + H,(g)
CO.(g)-93 e f (v) CO(g) + 2H,(g) CH,OH()
PcoX PH,0 200°C GON
N,O,(g)2NO,(g) HIITAI0E At
14114TA CO,(g) -A ARME EI Pco,
(Pco) = 1.4 atm l 0.05 mol N,O,(g)
TR, CO,(g) sEr 7 =(21.4) atm = 0.05 mol NO,(g)- A
TSAA 41aT, 1 mol CO,(g) 0.6atm |fAÍPAR
l mol H,(g) -
l mol CO(g) lmol H,0(g) GeA 2A| AIN
T9AR,
A0AAÍFAeLs CO,(g)-A b E17 0.6 FA GION N(g) +3H,(g) 2NH,(g) F
atm 241, H,(g) - A{AA AA KEA, N,(g) +H,(g) NH(g)
Co,(g) + H,(g) CO(g) + H,O(g) 2H,(g) + O,(g)2H,0(g) RfFaIA
b1T (atn): 14 (1-0.6) = 0.4 R
0.6 0.6

K PcoX PH,O 0.6 × 0.6

=0.64
T& 2S0,(&) + 0,(g)2s0.(g) AfFK ONNS
1.4 x 0.4
Pcoz ) 4s0,(g) +
K12 B(g) + C(g) =A(g) | fAMZ G0A IL aOLAA (ü) 20,(g)4s0,lg)
2s0,(g) *2s0,(g) +O,(g)
aatE 4 1mol A(g),2 mol B(g) 3 3 mol (ii) so,(g) +0,(g)=so,(g) (iv)
C(g)
So,(g)2S0,8*
B(g) -A ATA-7A0 0.175 AgE GoA afIfDA A(g) +4B(g)AB,(g) I RfsFIA E AS B
AN

AB, Tpg A(g) Ce-

T93T QIE: () A K, = 2: ())
K, = 3 (iiü))
B+C:
(B] x (C] DB+E: K, = 4:
 487

A+2B A1PITA K.-9 AA o? K, -a AtAT: K,=

9 4 QLGT 2D
(ATGIA ttpg|
[D]o, 3 [EJ., sAYHNIIPT3N A, B, D 3 E-9
S RLF 29 % 1 t | Sp -3 S, 0
eE(g) AfAA AT TH6
ii] aA(g) + bB(g)dD(g)+
PD XPE IT [P,]. [Pg lPp!
a b
(Reaction quotient, 0) PXPB

K,-a ArfAtat: K, =
(PA), x (P.)
ARMF 5r|
(PpogPEFA AIIA|1A A, B, D 9 E
quotient)
1| I S t (FAOA oteA(Significance of reaction
3 9 AM fg AfsAT AIA AIA fAM{

fAtF1A S0), Q -9A AttATGIA A SSN, PA Q = 0 T|

S r i aA +bB dD+ eE 1SPA0A FT 56 AfE3IT

sTÈ, O. = D"x|E,IA (A], [B], [D] [E]
[AJa x [B]
G Yars G IFN A, B, D 8 E - CAGI ttp|

NO,8

Q>K
Q<K

D,(8)*0

(6)C=f-D
3B+E
A
488

GKa700 KDOtN H,(g)+l,(g) 2H1(g) APA

árE, K, =55.0| 700K DAOA AfArf®r afE
faf-a1ts
AA GT aN 1.8, 2.8

CASE 1 AfAtA AStRA

[HI? (0.4)2 =0.0317

|H,1,1 1.8 x 2.8

550K AsA PCI(8) =PCI,(g)- +

K,-aA AtA 0.08 || Clg) t

PCI(g) 3 Cl,(g)-a3
0.75 3 0.32 molL-l A,
PCI,g)-a1
41444, K, = (PCl,[PCI,]
) (Cl,)
[PCI,]=0.75 mol L-!, [Cl,]=0.32 molL-1
(ApplisatiYns of equilibrium constant) [PCI,] = Kx (PCI) = 0.08 y 0.75 =0.187 moll-!
[CI,) 0.32
T9R, T041T PCI, -41 t94 =0.187 mol L-!
2 2S0,(g)
+O,(8)250,(g)
-a 14I

0.8 atm G, AHAerA SO,(g)-9 RMs EN

(Pso,
(Pso,*Po,
eratgis, K,= 0.36, Pso, =0.15 atrn RPo. = 0.8
O ie AK:2CO(g) + (Pso,) = K, x(Pso,) = 0.36 x(0.15)x
727-C: K, = 2.3 x 1022 | K-a 0,(8)=2c0,(g):
afs G5 AIH =6.48 x 10-3 atm
ALÝt A1, Pso3 = 0.08 atm
oR, AS1A SO,(g) -9 NRE 5Y =0.08 atm
a1344fa (COg) 0,(g)] 19 AfAtto CASE 2 etA AfsPA1K
AAU01A
E K: 2NO,g)=N,g) +20,(g): GAot: 25C:
100°C GastA Azlg) +B,(8g)=2ABIg)-
3) 44 AHA K: H,\g) +1,(g) VP56F 2 mol B, t QNA QTfo 2L
2HI(g):
G1: 427°C: K, =55.0 | aA A141T a /
|AB]'
(A,]x(B,)
 = 20 <i, 21p = 23 r :: p = 238 atm
25-P
R AB
=(25 - 23.8) atm = 12 atm R Ng) - R&E E

2AB(g) =0,(g) ARAS EM = 23.8 = 119 atm

Azl8) + B,(g) 2
2

2-x 2r

+2L=3L I
=m
. K (A,] 3
o l L-!;

-molL-! R[AB] =(mol L-| 3

7.9 AG4a0A A049 (Free energy change
=50
42 = 50 AG) of a chemical reaction &equilibrum constant)
(1-r(2-x) KA*
AT AF TK AM~ aSTa A B RISA
. 46r-150x +100 = 0 TÀA1 gs D E T05 7:
z 4-50r- 150x+ 100
aÀ+ bB dD+ eE
B:(130-4x46 x 100 232 1, 0934
2x 46
AfEAiÍtA TR*, K= [eq = equilibrium]

--[1]
B3=L868 |
E- SA eA| RÍSAT l AT
AIFA A, B, D
2NO(g) Ng) +0,(g)

AG = AGo+ RT In D XE AG+ RTin Q .--[2)

EM 25 atm 3,t THIA NO, N, RO, 113 (A x[B}
ANIA Q= AfAI ATE (reaction quotient)
[AJ, (B], [D] [E) H YNs E6 AISH A, B,D S E
Ps
(PNo?

AfFA1ÍA AHIKAITA AG = 0 RQ= K (HIY4F)|

N(g) +0,(8) ATA [2) R TAET KE Y, 0 = AGO + RTInK
2NO(g)
25 AGO = -RT ln K--[3]1, AG = -2.303 RTlogK (4)
TAAZ (atm): 25 - p 2 2
K= e-AG°/RT ..-{5]
RAT Aã 2 mol NO(g)
o Sg) 31 mol 0,(g) TeA 2A| TAR, F4A
patm
. N2) [2] (3] R T1EAT HF I, AG = -RTIn K+ RTInQ
2
A1, AG = RT .-{6]
= 100 = 400
(25 - p
490

A(g) +B(g) D(g) A1FAIA HA rJT

PAP
Pp
K
PA XPR

K =Jo.6181 = 0.7862
(GT N| QRS AGO = -RTIn K. at K. = 2 298 KGAotA
K F K,
e-AG/RT
CO(g)+¿0,(8)=C0,(g) faon
(GT 5A| QA AGO =
-RTIn Kp'
K, AGO RIIsFCA -394.4 g
K =e-aG'/RT |
AGO = -RT InK, eAT4S RÍAf9 AfSFAtGitg CA
-137.3k]moi
aC =aGco,)-acco)-}aco,
AG® = -RT]n K, EAA 8 RfAE 9
=-394.4 -(-137.3) 0.0 =-257.1 kl mol
AfFATG1O a AAT GIA, AG=-RT In K.
7.9.! A. -257.1 x 103 J
AG = -RT lnK mol-l=-8.314J K- mol-! x Ay1.
AlAI se
(Significance of the relation, A1, In K, = 103.77 . K=1.166 × 1045
AGO = -RT In K)
298K TAoA N,O,(g)
2NO,(g) AA
fadA AIG 5I 2N 20 atm| TT
100 kJ mol-l AGAN,O
AGNO,) =50 kJ mot-!
iül AG0 -ag AtH
Nt* (AGO <0) LG K>1
|9HA

AGO = 0
AG°=2aG(NO,)-
AfAT AAAA CTD
AGN,0,)=2 x50 -100=0 kjma
G K= 1 2| ATLA AIAYKAA afAIGIA CAIG-RT =5 +5 = 10
5 x 20 = I

PNO, X 20 =10 atm

PN,o4
1 A(g) + 2B(g)
(PNO,)2 (10 =10
2D(g) 10
500K AGO = 2kJmol-' | aNAT G, AG PN,O,
= AG +
A(g) + B(g) D(g) AtA0A K,-aA AA AA A| ". AG = RTInp
0+8.314 x 298In 10 = 5.706 K)
H14A: a A(g)+ 2B(g) 2D(g) APAIA GLO AA | : AfFAIÍba a, AG = 0]
4A1A K, EA, OA AG = -RT ln K,, At HF YË, 2) IA3, AGO =
-RTln K,; ToR 0 =-RTIhk,
In K, = -4GO RT
2000 J mol-!
=-0.4811 (A, AG = 0] 1, K,2
8.314 JK-l mol!x 500K
Kp = 0.6181
 491

IAC2Y 7.7, 7.8 7.9 13 e 110

atftt (Expressions of equilibrium constant for
Some selected reactions)

e tA ABC+D
+ R1ATA AINSYAAA AT KI
(iü) 1RIA
A. AGO = -RTIn K,
CH,COOH() +C,H,OH() = CH,cOoC,H,() + H,0()
4At F, fg AO1A VL SIOA AD ZTS a mol
R AG = -RTIn K, O0R,
Xmol

CH,CO0C,H, 9 x mol fso a| AfsA1A TAA A

GA,
MNYAA AÍA 2x 10-3 | fFIt
TT A, CH,COOC,H, 9 H,0 fstbsI x mol TeA
MAB+C A1PA0IEA

x 10-4M
JA]= [B]= (C] = 3

CH,COOH() +C,H,OH() CH,co0C,H,(U) +H,o()

a
0 (CH,COOC,H;) X(H,0)
Ke (CH,COOH)X(C,H;0H)
(a-x) (b-x)

TNIQR NEa(mol L-l) (CH,COOH] -( 1c,H,0H) =(: ()x(9

Ka-x) x (b-x)
[CH,COOC,H,] =((H,0]=( ()(
FG N,
RUF (RT 1A, 2x mol NO Te IT

1: N,(g) + 0,(g) 2NO(g) | 4t AF,

RVAK ANOAA AÍb ta amol N, GR bmnol

O,(8) 2NO(g)
N,(8)
b 0
[NO2
(a-x) (b- x) 2x K= [N,]x [0,1
EK (mol L-)
[N,) =() (0,) =() [NOJ =( 4x2
A1, K= (a-x) x (b-x)
a-x+ b-x+ 2x = a + b 2x 2 x p²
(PNo a+b

|PN, P: Po, -(P: Pyo = P PN, XPo, a-z)px(b-xp

\a+ b \a+ b

412
A1, K,= a-x) x (b-x)

PCI,(g) TeYA
n. . PCI,(g) As 119A x mol PCI,(g) 8 x mol CI,(g)
PCI,(g) PCI(g)+(
MI41441 CfcutA A x mol
492
PCI,(g) PCLH(8) 4
Cl,(8)

.:. K,
(PCl,] × (CI,]
(1-x)
[PCI;]
ASTATA 19 (mol L- )
1-x + x+x = l+x Kp=
PpCls
Ppci, P: Ppci (P: Pcl, P
KpxP

P GAotA K
K,

ARZ AfPAt: N,(g) +

3H,(g)=2NH,(g) | 4aT A*, fPes
3 mol H,(g) RC M3 RfPAtf 3
FA0 EA|Gafs RfPaIfo
TAI1TA F0atAIA FEAM 2x mol NH,(g) TeA A, OAG H,(g) aR NH(g) - GIN Sg 3 UR

Ng(8) + 3H,(8) 2NH,(g)

3 0

(1-x) 3-3x = 3(1 - x) 23 (NH,?

AAIIPRIA (mol L-l) K=
(
AIPATA AB
IG-T-x+3-3x + 2x = 4-2x = 2(2-x) K=
4x2 y2
27(1 - x)4
PN, P: PH,-P:PNH,
= P
K= PN,PGH,
\2-x

x2-x)?
(1-x)p2
ffrAA OIÁAB (NH,co,NH,) -aA ot-fAAISA
fafPAT: NH,CO,NH,(9) 2NH,(g) +CO,(g) I
ieAIA A 2x mol NH,(g) 3 x mnol CO,(g) TeA
NH,CONH,(S) 2NH,(8) Co,(g)
0

(1-x) 2x
K= (NH,1² x [CO,]
TA11TIA S94 (mol L- ) (* (NH,co,NH,(9)) =1)
()
2x+x = 3x
K,= (PNH, XPco, -(
PNH, P=ipco,- P i K,=
 495

dxVod'rv-1-1. -1-a1-) -1

d'-d

D'-D
L I .
n
A nB

712
(Le Chatelier's principle)

frots fA -ofAItA 9 gA (Le Chatelier and Braun)

d
l: d'yV|I +a(n - 1)] 41, = |+ r(n-1) {1]
d
l" oln-1) (2]
d- d'
d'(n -1)
D- D'
D'(n - 1)

VTA n mol Imol B 14 Ç 53|

V IrTA gf8 4TCG Imol A

nA B
A+ B C+D

CTA-7°ST faf11: A+ B C+D

 494
G T RSP3IT (A+ B’C+ D)
X|AT TTP
(C+D ’A + B) 9cII A Ataty RAfDU
(C+D-A+ B), "
yoIN At Atax
(A+B ’C+ D)

Grea: AOr gr tAON N,(g) +3H,(g)=2NH5(8) B) 1/%

AfsPAIA
A+N0 (N,+3H, ’ 2NH,), Aio
fAf11: A+BeC+D

[Hl
[H)
[NH]
[NH,]
[N)
[N]

(2NH, ’ N, +3H,) 9X AM AatA RaÍDS ES

AfFAT: A+ B C+D

afa

ITA ATE: A+
BC+D
(Cleg X(Dlay
[AJpg X[B)eg
(TTA, eq = equilibrium aR [A)eg[B)g .(Cl
Afpat: A+B eC+D 041T RISP(4 A, B, C9 D-9 ATGIA
 495

[AJeg
[Cleg x[Dleq ..(2]
[A]x(Bleg

A)xBleg

N,(g) + 3H,(g) 2NH,(g) | aH

N,(g) G 3 ag H,(g) NLF 2 NH,(g) Ge AA 3A) R

g NH,(g) NLT Iug N,(g) 3 g H,(g) TeAA) |

4, UA RÍA1-MCoA C
0,<K
ArÁ C

equilibrium at constant temperature) AfAfs HD aRIIA 4 (Te AYT RfFAIN An = 0).

, a 4A1A FHTÍO afta GEA1: H, (g) + L,(g)

2HI(g).
N,(g) + O,(g) 2NO(g) 9 H,(g) + Cl,(g) 2HCl(g)
496

An
N,o,(g) :2NO,(g)
PCI(g) PCl,g)+ Cl,(g) +1

2S0,(g)+ 0,(g)2SO3(g)
Xe(g)+ 3F,(g) XeFsg) 3
A
C(s) +O,(g)co,8) 0

O H,(8)+ CO,g) CO(g) +H,0(g)

7.12.3
of temperature on equilibrium of achemical reaction)

GESY: 13 (Haber) fo

N,g)+3H,(g) 2NH,(g): AH= -22 kcal:

atto art RfsT: N,(g) +0,8) 1)

AH = + 44 kcal: aE H AfAtb 5 Or

NO-8
 497

F1AU (CoCI,) -t HCIa Gx

colH,0),1*(aq))+4CI (aq)[CoCI,)2(aq) +6H,0()

(E t ) AH>0 N

(A1 AH> 0)| A-ofAICAA fo

An - 9

An>0 PCI,(g) PCl,(g) +Cl,(g) 5SAML* TA rA

N,0,(8) 2NO,(8)

2 An< 0 N,(g) +3H,(g) 2NH,() 4 AAf,S A FIA

2S0,(g) +O,(g) 2S0,(g) 18TS1bo EN, A
(Efect of catalyst on equilibrium of a chemical reaction)

An=0 N,g) + 0,(g) 2NO(g)

2HI(g) H,(g) +1,(g)

2NOIE 0.63

CO(g) +H,O(g) CO,(g) +H,(g) | a AoN

eR (Efiect of addition of inert gas on equilibrium of a 3mol H,0(g) a4R 1mol CO(g)-4 AAT AREIÍbG
hemital reaction) afI1A IAIAATA AfPAI AA AIE ST 2.0 atm 4,

Ne, Ar, otf) (* uK

CO(g) + H,0(g) co,(g) + H,(8)

3 0 0

3-x
498

=l-x+3-x++x = 4 (PNo, (0.55 + 2p)²

4R UR51: K,=: (0.14 - p) =4.32
Pco = 4 x2 =-x);
PN,o4
At, 4p2 + 2.2p + 0.3025 = 4.32(0.14 - p)
A1, p+ 1.63p - 0.0755 = 0 :.p =
Pu,o= )x2 (3-*) 0.045 atm

Pco, -()x2 -
(0.14 - 0.045)
atm NO2
=

6fA, n = 0|
2 (0.55 +2 x 0.045) atm = 0.64 atm 0.093 atm
GE K, = K,=0.63
Pco, A(g) + 2B(g) Cg)
PcoXPH,0 AR pa = 0.5 atm |A4STTT

K,-4A
75% C(g) teA F3A1A
AlR, 0.63 =
(1 -x) x (3 x)
A14TA: RfA2 AfFAt: A(g)
12=0.631-2.52x +1.89 0.,25 atm
2B(g)
0.5 atm
46.81x 5.108 = 0 X= 0.681
0.25 -0.125 0.5 -2 x0.125
H11TR O H,(g) - HIG-IT =0.681 =0.125 atm
05 0z
=0.25 atm
Pco =1-0.681) = 0.1595 atm Pc 0.125
=0.15a
K, 0.125 x (0.25 )2
= 16

PH,o = (3-0.681 ) = 1.1595 atm 16 =

Px P0.1875
p = 0.802 atm
0.681
Pco, = 0.3405 atm
0.0625 x (p- 0.375)2
2 250°C baotA 7G fAfFA\A ATA414 K,-4
N,0,(8)*2NO,(g) | N,O,(8)
PCI(g)PCI,(g) + Cl,(g) IffsA-fÈA
NO,(g) -43 TRTF b ET 250 °C GotA A1qAA 50% PCI,-3
T3A 0.28 9R 1.l atm

RIPAT-MAA 5r P atm 4, ASIT1A PCl,g

KCATST AbLA|PCI-(g)-43 50% fACATGH AELA THKK3
(PNo, (1.1)2.=4.32
PN,0, 0.28
PCI,(g) PCI,(g) +Cl,(3)
a-0.5a = 0.5a 0.5a 0.5a
A04S04RTA ATs CIG a a R = 0.5a +0.5a +030
Tf ET TA TTFA 0.14 9 0.55 atm | 4 pLGT ISPA0K YIAS

-(0.5a) p-P P gar PC,"3

Ppcl, (1.5a)
Ppci, XPcl,
PpCls
At, 1.8 = P P= 5.4 atm
3
250C
N,O,(8) ZNO,(g) y0R, frAt-oDINA 5IY 5.4 atm
f¢ BIM(atm): 0.14-p 0.55 + 2p
 499

fafa Ao0 8 0.50 atm ATAS14T fo EA: NH,Cl(s) NH,(g) + HCI(g) 7

ITT (NH,)
To afoA NH HS
JÈTEQS (NH,HS) P= 24K, I
43. fA13FAIT: aX,(g) + bY,(g)cXY(g) + Ot- tAF bA
(H,S) 5H
(i) a, b Rc-g A(T F A|

NH, HS(s) -a fAfs311

() at1ofaAtAA foft Ago TAT|
(ii) H,(g) +I,(g) 2HI(g) AfsAos AIA URAA getT
(a) 5t R(b) p o4tat sAaA HI GAt1A Ay
N:NH,HS(s)-9T [HS 08)

: NH, HS(s) NH,(g) +H,S(g)

R

NH,(8) PCl,(g)=PCI, (g) +Cl,(&)

-
RCA NH, HS(s) 2BrF,(g) Br,(g) +5F,(g)

I*, NH,HS(s) -ds AATGLT Te# NH,(g) 9

LSg) afobs RF 5Y =p atm
8R, ARTA NH,(g) H,S(g)-9 R F 5t
+O-Q AfPAt J1RT3I
W A(g) + 2B(g)2D(g) + 3E(g)
NH,HS(S) NH,(g) +H,S(8)
0.5
SsÍYE ETY(atm):
AIA 5T (atm) : 0.5 + p p

=0.5 + p+p = 0.5 + 2p = 0.84

=05+2p = 0.84 T, p = 0.17 atm

= (0.5 +0.17) =0.67 atm

* PH.s = 0.17 atm

(a) PCI, (g) PCl,(g) + Cl, (g); AH>0
AtA K, = =0.67 >x 0.17
(b) 2S0, (g) +0,(g) 2s0,(g); AH<0

Sa:
PNH,XPH,S =0.1139 atm2

1SC2 710. 7.11 7.12 A

(a) 2CO(g) +O,(8)= 2C0,(g)
K,> K, (b) C(s)+ H,O(g) Co(g)+ H,(g)
(50,) 4L WROLAA WAA F0UA 3 AG PCI(g) fACA T GIOTN

448,g)
,g)+ ,g) 2HI(g)
U A I N,(g)+ 3H,(g)*2NH,(g), AH = -22.4 kJ