CHEMICAL EQUILIBRIUM

KP = KC if ng = 0 no need to solve equation but use

Reaction Units of KP = ng (atm )D approximation.
Units of KC = ng (M )D In 1st case [R]eq  0
A In 2nd case [P]eq  0
Reversible Irreversible KP = f er H /RT
Ab  Degree of dissociation, 
Reaction reaction
both KP & KC depend only on temperature n P m V
  
Reversible Reaction: for given reaction. n0 P0 m0 V0
 For pure solids & pure liquids (solvent): # n, P, m, V  mols, partial pressure,
 KC not very large or very small.
Active mass = 1 [Kinetically] mass, partial volume of reactant
 Both R and P present at equilibrium.
Activity = 1 [thermodynamically] respectively.
 R and P stability comparable.
Density % dissociation = % reactant converted to
Irreversible Reaction: Molarity = = Constant
Molar mass product = 100 
 KC >>> 1  Reaction Quotient (QC/QP) #   1 [Equality for irreversible reaction]
 [P] >>> [R] at equilibrium. Used to find direction of reaction mixture – Pgas Vgas ngas
 Stability P >>> R Fwd./Bwd.  X gas   
PT VT nT
At equilibrium for reaction mix. properties like QC < KC or QP < KP  FWD.
For a reacting mixture of 'n' gases :
P, V, T, n, magnetism, colour, density become QC > KC or QP > KP  BWD. m
constant. QC = KC or QP = KP  Equilibrium 2VDmix = Mavg. = xm
i1
i i

 For gaseous reactions. QP = QC ng (RT)ng

 If • Mavg. & VDmix is a function of mixture
KP = KC ng (RT )D
 [KP >>> 1 or KC >>> 1] composition.
KP > KC if ng > 0
or • For mixture of reacting gas Mavg. changes
KP < KC if ng < 0
 [KP <<< 1 or KC <<< 1] & becomes constant at equilibrium.
Ashwani Tyagi | Insta: ashwanityagi.iitr | Twitter: @ashwani_iitr | Telegram: t.me/chemistryatjee | Whatsapp: 7042916164
 CHEMICAL EQUILIBRIUM

• Mavg. (or VDmix)   KP or KC depend on the way of writing a Case II: Total P increased (or V decreased)
1 reaction: If ng > 0  backward
moles of gases in mixture I. R  P; KC, KP If ng < 0  forward
P  R; 1/ KC, 1/ KP If ng = 0  no effect
(VD)i M i nf Pf II. C  D; KC' , KP'
    Case III: V Increased
(VD)f Mf ni Pi  R + C  P + D; KCKC' or KPKP'  Same effect as P decreased
Used to find '' from Mavg or VD data for III. R – C  P – D; If ng > 0  forward
reactions with ng  0 K K If ng < 0  backward
or R + D  P + C ; C' or P'
• On going FWD. KC KP If ng = 0  no effect
If ng > 0 IV. nR  nP; (KC)n or (KP)n Case IV: T Increased
P n  Relative Humidity (R.H.) If r H > 0  forward
Mavg.  VD   Partial pressure of water vapour  If r H < 0  backward
If ng < 0 P n    100 T decreased
 Aqueous tension 
Mavg.  VD  If r H > 0  backward
If RH < 100%  Partial pressure <
If ng = 0 P, n, Mavg.,VD = Constant If r H < 0  forward
Aqueous tension  Unsaturated air
 For a reaction with ng  0 Case V: Using Catalyst
sample
 depends on – KP or KC, Temperature, No effect on KC, KP or equilibrium
If RH < 100%  Saturated air sample
Initial concentration, Initial moles, Initial concentration
 Le chetelier Principle
pressure, volume of vessel Only time required to attain equilibrium is
Case I: [R] increased  Forward shift lesser.
 For a reaction with ng = 0;
[P] increased  Backward shift Case VI : Adding inert gas at constant V.
 depends only on - KP or KC,
 If R or P is pure solid / Pure liquid  No  No effect
Temperature
effect.

Ashwani Tyagi | Insta: ashwanityagi.iitr | Twitter: @ashwani_iitr | Telegram: t.me/chemistryatjee | Whatsapp: 7042916164
 CHEMICAL EQUILIBRIUM
Case VII: Adding inert gas at constant Standard State Exception: M.P. of H2O decrease on
Pressure Gas  Ideal gas increasing pressure
 Same effect as Pressure decrease or  Van't Hoff Equation :
volume increase Activity=Partial pressure = 1 bar  1 atm. d[lnK P ]  r H  H A
 ; n K P   r  n f ;
Thermodynamics state of Equilibrium: Solute  Ideal solution dT RT 2 RT Ab
Activity = concentration = 1M
 Gmix  Minimum K P2  rH  1 1 
Solid/Liquid  Pure activity = 1 log    
  rG  0  Q contains activity of species i.e., partial K P1 2.303R  T1 T2 
  VPGP =  VRGR pressure in bar (or atm) for gas molarity for
 If rG < 0  VPGP <  VRGR solute is unity for solid or liquid. Endothermic Exothermic
 Reaction shifts forward to attain  At equilibrium rG = 0 & Q = Keq Reaction Reaction
equilibrium. rG = – RTln keq
Keq. = e–rG / RT
If rG > 0   VPGP >  VRGR
 For gaseous homogeneous reaction,
 Reaction shifts backward to attain rG = –RT ln KP
equilibrium. For homogeneous reaction in solution
If rG = 0  Equilibrium state phase
 rG = rG + RT ln(Q) rG = –RT ln KC
rG = Standard Gibbs energy of reaction  BP, MP & Sublimation point all increase in
(when all Reactants & Products are in increasing pressure
standard states)

Ashwani Tyagi | Insta: ashwanityagi.iitr | Twitter: @ashwani_iitr | Telegram: t.me/chemistryatjee | Whatsapp: 7042916164