Contents

1. Introduction
2. Factors affect chemical equilibrium
3. Determination of Equilibrium constant
4. Ideal solutions and real solutions
Chapter 6 5. Chemical equilibrium in real gases
6. Chemical equilibrium in real solutions
7. Chemical equilibrium in heterogeneous systems

1. Introduction 1. Introduction
Equilibrium state Equilibrium constant
• For a reaction in gas phase: aA + bB = dD
• T= constant
• P= constant GT = d -a
D A- b B

Since: i = 0i(T) + RTlnPi (assume ideal gases)

[ or fully: i = 0i(T) + RTln(Pi atm /1atm) ]
Equilibrium State
(Keq)

0 0 0 PDd
dG < 0 dG =0 GT (d D a A b B ) RT ln a b
PA .PB
[ Note: Pi unit: atm]
 1. Introduction 1. Introduction
Equilibrium constant Equilibrium constant

PDd • Equilibrium constant:

0 0 0
GT (d D a A b B ) RT ln d
PAa .PBb PD
GT0 RT ln K P
KP ( P ) eq a b
0 PA .PB eq
GT G T RT ln P (Van’t Hoff’s equation)
• Since G0T depends only on T
G0T : Gibbs energy change of the reaction at 1 atm, Kp depends only on T
depending only on temperature (= GT when =1)

• At equilibrium ( GT =0): GT0 RT ln( )

P eq GT GT0 RT ln P GT RT ln P

KP

1. Introduction 1. Introduction
Equilibrium constant Equilibrium constants
• For reaction in gas phase: aA + bB = dD
• Determination of reaction direction: GT RT ln P

KP
PDd CDd
KP KC
T,P = constant PAa .PBb C Aa .CBb eq
eq

Forward reaction xDd nDd

Kp > GT < 0 Kx Kn
P
occurs x .xBb
a
A eq n Aa .nBb eq

Reverse reaction
Kp < P GT > 0 occurs • Note:
Pi is actually Pi(atm)/1(atm);
Kp = P GT = 0 Equilibrium Ci is actually Ci(M)/1(M);
ni is actually ni(mol)/1(mol);
Unit of Kp, KC, Kx, Kn is [ ] (no unit)
 1. Introduction 1. Introduction
Equilibrium constants Equilibrium constants
n
• For reaction in gas phase: aA + bB = dD KP K C .( RT ) n
K x .P n
Kn .
P
• Relationships: ni eq

PDd CDd xDd nDd

KP KC Kx Kn Since KP depends only on Temperature then:
PAa .PBb eq
C Aa .CBb x .xBb
a
A nAa .nBb
eq eq eq - Kc depends only on T
- Kx depends on T and P
n
n n P - Kn depends on T, P and total of moles ( ni)
KP K C .( RT ) K x .P Kn .
ni eq

n= mole change of gaseous substances = d-a-b - If n = 0 then KP = Kc = Kx = Kn

P (atm): Reaction pressure
T (K) : Reaction temperature
R = 0.082

1. Introduction 1. Introduction
Example Example
• Solution:
a. Determine Kp , KC of following reaction at 400 0C,
1atm: COCl2 = CO + Cl2 ( n=1+1-1= 1)
Initial 0,1 mol 0 0
COCl2 = CO + Cl2 Reacted y mol y y
Given: 0,1 mol COCl2 occupies 6,73L (at equilibrium).
Equil. (0,1-y) mol y y
b. Which reaction direction of the following mixtures:
1/ 0,5 mol COCl2 ; 0,3 mol CO ; và 0,2 mol Cl2
2/ 0,8 mol COCl2 ; 0,1 mol CO ; và 0,1 mol Cl2 ni = 0,1+y (mol)
 1. Introduction 1. Introduction
Example Example
b. Reaction direction: comparing KP and P

Ideal gas EOS: ni = 0,1 + y = PV/(RT) P

n
nCO .nCl 2 P
n

y = 0,022 mol P n .
ni nCOCl 2 ni
n n
P nCO .nCl 2 P Mixture 1: 0.5 mol COCl2 ; 0,3 mol CO ; and 0,2 mol Cl2
KP Kn .
ni eq
nCOCl 2 eq
ni
1
n 1 0,3.0,2 1 Reverse reaction
nCO .nCl 2 P y2 1 . 0,12 0,0509 KP
KP . . 0,0509 P
0,5 1 occurs
nCOCl 2 ni cb
0,1 y 0,1 y

KP 0,0509 4
KC n
9,23.10
( RT ) 0,082.673

1. Introduction 1. Introduction
Example Comments on equilibrium constants
b. Reaction direction: comparing KP and P i. A reaction can proceed in the forward direction or reverse
direction depending on the initial composition.
n n ii. All reactions are reversible. A reaction is considered
P nCO .nCl 2 P
P n . completion when its equilibrium constant is very large
ni nCOCl 2 ni
reactants’ concentration is negligible in the equilibrium
Mixture 2: 0,8 mol COCl2 ; 0,1 mol CO ; and 0,1 mol Cl2 mixture.
iii. A reaction can proceed to completion if a product is
removed from the equilibrium mixture (in precipitation,
0,1.0,1 1
1
Forward reaction evaporation, or weak electrolyte).
P . 0,0125 0,0509 KP occurs
0,8 1
 2. Factors affect chemical equilibrium
Effect of temperature
G H
G0298 KP (298) – Gibbs-Helmholtz equation: T T P T2

– Van’t Hoff equation: GT0 RT ln K P

G H
T T P T2 RT ln K P H0 ln K P H0
T T P T2 T P RT 2

0 KP (T) ? – Because of insignificant effect of pressure on H

T and KP:
d ln K P H H
d ln K P H ln K P dT I
dT RT 2 RT 2
dT RT 2

2. Factors affect chemical equilibrium 2. Factors affect chemical equilibrium

Effect of temperature Effect of temperature
d ln K P H
d ln K P H dT RT 2
– Endothermic reactions: H >0 d ln K P
RT 2
0
dT dT
T increases KP increases Reaction shifts to
–Endothermic reactions ? FORWARD direction (Endothermic direction)
(Le Chatelier principle)
–Exothermic reactions ?
– Exothermic reactions : H <0

T increases KP decreases Reaction shifts to

REVERSE direction (Endothermic direction)
(Le Chatelier principle)
 2. Factors affect chemical equilibrium 2. Factors affect chemical equilibrium
Effect of temperature Effect of temperature

d ln K P H • Example: C (r) + CO2 (k) = 2CO (k)

dT RT 2 – Given: KP (1000K) = 1,85, H (averg)= 41130 cal/mol,
– For a small temperature change ( H=const): Total pressure: P=1atm

Determine equilibrium compositions of gas phase

K P,T2 H 1 1
ln at 1000K and 1200K
K P,T1 R T2 T1

2. Factors affect chemical equilibrium 2. Factors affect chemical equilibrium

Effect of temperature Effect of total pressure
• Solution:
– Gas phase consists of CO and CO2 : – For condense phase reaction (liquid/ solid):
Mole fraction of CO : x Mole fraction of CO2 : (1-x) negligible effects
– Equilibrium constant: 2 2 2
PCO n xCO 1 x
KP K x .P .1
PCO2 xCO2 1 x – For gas phase reaction: At specific T, KP = const
– At 1000 K: KP,1000 =1,85 x= 0,72
n
– At 1200 K: KP K x .P
K P,T2 H 1 1 K P ,1200 41.130 1 1
ln ln
K P,T1 R T2 T1 K P ,1000 1,987 1200 1000

KP,1200 = 58,28 x = 0,98

 2. Factors affect chemical equilibrium 2. Factors affect chemical equilibrium
Effect of total pressure Effect of inert components

KP K x .P n – In solution: At a specific temperature

n
KC K n .V const
IF n > 0: When P increases Kx decreases
Adding inert/solvent V increase:
Equil. Shifts to REVERSE side
• IF n > 0: Kn increases Equil. shifts to FORWARD side
(reduce number of moles) (increase number of moles)
IF n < 0: When P increases Kx increases • IF n < 0: Kn decreases Equil. shifts to REVERSE side
Equil. Shifts to FORWARD side (increase number of moles)
(reduce number of moles) • IF n = 0: KC = Kx no effect

IF n = 0: KP = Kx no effect

2. Factors affect chemical equilibrium 2. Factors affect chemical equilibrium

Effect of inert components Effect of inert components
n
– Ideal gases: At a specific temperature, pressure RT
n KP Kn. const
P P RT V eq
KP Kn. const
ni eq
ni eq
V Adding inert/solvent at constant pressure V increase:
• IF n > 0: Kn increases Equil. Shifts to FORWARD side
(increase number of moles)
n • IF n < 0: Kn decreases Equil. Shifts to REVERSE side
RT (increase number of moles)
KP Kn. const
V eq • IF n = 0: Kp = Kx no effect
 2. Factors affect chemical equilibrium 2. Factors affect chemical equilibrium
Effect of inert components Effect of inert components

Ex: C (s) + CO2 (g) = 2CO (g) Solution: a. C (r) + CO2 (k) = 2CO (k) ( n= 2-1=1)
Initial (mol) 1 0
Given KP (1000K) = 1,85. Determine equilibrium Equilibrium (mol) 1-y 2y
compositions at 1000 K, 0,1atm: ( ni = 1-y+2y=1+y)
n 1
a. Pure CO2 reacts with excess C. P (2 y ) 2 0,1 y= 0,906
KP Kn . 1,85 .
ni 1 y 1 y
b. Equi-molar mixture (CO2 + N2) react with eq

excess C.
At equilibrium: CO/CO2 = 2y/(1-y) = 19,3

2. Factors affect chemical equilibrium 2. Factors affect chemical equilibrium

Effect of inert components Effect of initial composition
Solution : b. C (r) + CO2 (k) = 2CO (k) ( n= 2-1=1) – Yield (h%): mole fraction of products in the
Initial (mol) 1 0 equilibrium mixture.
Equil. (mol) 1-y 2y
– Conversion ( ): A= nA reacted/nAinitial

ni = 1-y+2y+1=2+y
n 1 Maximum equilibrium yield is obtained at stoichiometric
P (2 y ) 2 0,1 y= 0,953 compositions.
KP Kn. 1,85 .
ni eq
1 y 2 y

Equilibrium conversion of a reactant will increase if the

At equilibrium: CO/CO2 = 2y/(1-y) = 40,6
concentrations of the other reactants increase.
 2. Factors affect chemical equilibrium 2. Factors affect chemical equilibrium
Effect of initial composition Effect of initial composition
– Ex: – Ex: O2 + N2 = 2NO KP = 1 at 1500K.
N2 + 3H2 = 2NH3
Initial: a b 0 (mol)
Equilibrium: a-y b-3y 2y (mol) Initial composition h (%) O2 N2

Yield: 2y 2y
h% 100% 100% 3 mol O2 + 3 mol N2 33,33 0,33 0,33
(a y ) (b 3 y ) 2 y a b 2y

5 mol O2 + 2 mol N2 28,57 0,20 0,50

y 3y
Conversion: N2 và H2
a b 2 mol O2 + 5 mol N2 28,57 0,50 0,20

3. Determination of Equilibrium constant 3. Determination of Equilibrium constant

Determine (Pi) or (Ci) at equilibrium state. (i) Measure the change of physicochemical
parameters such as pressure, volume,
– Note:
density, color, conductivity, …which
• Determine (Pi) or (Ci) at equilibrium state: check
change due to the reaction.
forward and reverse direction.
• Quench (rapid cooling) or inhibitor addition may be
used to make sure that the equilibrium is stable.
3. Determination of Equilibrium constant 3. Determination of Equilibrium constant

(ii) Via equilibrium constant of other related GT0 RT ln K P

reactions.
– Calculate G0T :
example: (1) C (r) + O2 = CO2 T2 T
GT2 GT1 dT
(2) 2CO + O2 = 2CO2 • Gibbs-Helmholtz equation: ( HT1 CP dT )
T2 T1 T1 T1
T2
(3) 2C (r) + O2 = 2CO
• Chomkin-Svartsman equation:
GT H 298 T . S298 T . ai M i
Rx(3) = 2* Rx(1) – Rx(2) • Reduced Gibbs energy:

Kp (3) = KP2(1) . KP-1(2)

GT0 H 00 T . g p.u

3. Determination of Equilibrium constant 4. Ideal solutions and real solutions

Solution??
• From measurement of electromotive force • Solution: A solution is a homogeneous
(E) mixture; that is, a solution is a one-phase
nFE0 system with more than one component. The
0 0
G nFE ln K P phase may be solid, liquid, or gas:
RT
– Solid solution
– Liquid solution (or solution)
Where: E0 : Standard electromotive force of the battery
F : Faraday constant
– Gas solution (gas mixture)
n : number of exchanged electrons
4. Ideal solutions and real solutions 4. Ideal solutions and real solutions
Solution?? Solution composition
• Solvent - Solutes • (molar) concentration (Ci)
• Solution types: • Molarity (mi): moles solute/ 1 kg
– Ideal solutions solvent
– Ideally (infinite) dilute solutions • Weight percent (wi)
– Real solutions • Volume percent (vi)
• Non-electrolyte solutions • Mole fraction (xi): mole percent the
• Electrolyte solutions (will be discussed in course solvent mole fraction is greater than
“Physical Chemistry 2”) the mole fraction of each solute.

4. Ideal solutions and real solutions 4. Ideal solutions and real solutions
Solution composition Mixing quantities
• Example: A solution is prepared by dissolving 555.5 g • Mixing volume change:
of sucrose, C12H22O11, in 750 mL of water and diluting
with water to a final volume of 1.0000 L. The density of
the final solution is found to be 1.2079 g/cm3. Find the V V*= xi.Vi
sucrose mole fraction, molality, and weight percent
mixV = V- V*
in this solution.

• Similarly:
(Answers: 0.04289, 2.488 mol/kg, 45.99%.)
mixH = H- H*
mixS = S- S*

mixG = G- G*
 4. Ideal solutions and real solutions 4. Ideal solutions and real solutions
Mixing quantities Mixing quantities

(Similar)

Others:

4. Ideal solutions and real solutions 4. Ideal solutions and real solutions
Ideal solution (ideal mixture) Ideal solution (ideal mixture)
• A solution where the molecules
mixV =0
of the various species are so
similar to one another that
replacing molecules of one
species with molecules of another mixU =0
species will not change the spatial
structure or the intermolecular mixH =0
interaction energy in the solution.
mixG = RT(n1lnx1+ n2lnx2)
• Examples:
benzene–toluene,
n-C7H16–n-C8H18,
C2H5Cl–C2H5Br,
C(CH3)4–Si(CH3)4.
4. Ideal solutions and real solutions 4. Ideal solutions and real solutions
Ideally (infinite) dilute solution Ideally (infinite) dilute solution

• Solvent: x1 1 ; Solutes: xj 0
• solute molecules interact essentially only
with solvent molecules.
• Chemical potential:
Solvent: 1 = *i (T, P) + RT.lnx1
Solutes: j = f(T, P) + RT.lnxj

4. Ideal solutions and real solutions 4. Ideal solutions and real solutions
Real solutions Real solutions
Activity (a): A function of mole fraction (x ) or concentration (C ).
i i Determine activity coefficients:
The ideal solution relation can be used for real solutions by replacing the (xi)
• By experimental works
or (Ci) by the activity (ai) of that component.
• By activity coefficient models: Margules, Van Laar,
id UNQUAC, NRTL, Wilson, UNIFAC,…
i = i0(T) + RTlnxi (ideal solutions)
0
i = i (T) + RTlnai (real solutions)

ai
i
xi
 4. Ideal solutions and real solutions 4. Ideal solutions and real solutions
Real solutions Real solutions
• Margules model (simple): • Van Laar model (more accurate):

(A: constant from

experiments) ( : available for some
common solutions)

(Application: 2-component system: non-polar or weakly polar compounds)

(Application: 2-component system: non-polar or weakly polar compounds)

4. Ideal solutions and real solutions 5. Chemical equilibrium in real gases

Real solutions
– Ideal gas relation:
• Example: PV = RT (n=1 mol)
Using the Van Laar model, determine the water activity
coefficient of the water-acetone mixture containing 25
– Real gas relations:
mol% water at 25 °C.
2
Given : For solution acetone (1) – water (2) at 25 oC: RT a (PT Van der Walls)
= 1.89
P a, b: constants
V b V
= 1.66
– Fugacity – Pressure
0
i = i (T) + RTlnPi (ideal gas)
0
i = i (T) + RTlnfi (real gas)
 5. Chemical equilibrium in real gases 5. Chemical equilibrium in real gases
Real gases
=
– Fugacity coefficient: f
• Ideal gases : = 1 P =
• Real gases: 1 (Depend on T, P and gases)
• (High pressure, low temperature) big difference between f
and P
• (Low pressure, high temperature) small difference between
f and P
– Equilibrium const:

fi = i.Pi Kf = K .KP

5. Chemical equilibrium in real gases 5. Chemical equilibrium in real gases

Given data: T, P, ni0
– Equilibrium constant: 0
G T RT ln K f
Calculating Kf
Exactly!!! (Accept, Proving is complicated)

Guesting K ni(eq)
– Fugacity coefficient: Y
fi
i Kf K .K P N
K (new)/K -1
Pi Calculating Kp K =K (new)
=0

Kf : Depend on Temperature : Kf= exp(- G0T /RT)

Calculating equilibrium Pi
: Depend on Temperature and Partial Pressure (Pi)
Calculating ( i) Calculating K (new)
Require iterative calculation to obtain the equilibrium composition
 6. Chemical equilibrium in real solutions 6. Chemical equilibrium in real solutions
Given data: T, P, ni0
– Equilibrium constant: GT0 RT ln Ka
Calculating Ka
Exactly!!! (Accept, Proving is complicated)

Guesting K ni(eq)
– Activity coefficient: Y
ai
i Ka K .K x N (new)/K
xi K =K (new) K -1
Calculating Kx
=0

Ka : Depend on Temperature : Ka= exp(- G0T /RT)

Calculating equilibrium xi
: Depend on Temperature and concentration
K , Kx: Depend on Temperature and concentration. (new)
Calculating ( i) Calculating K
Require iterative calculation to obtain the equilibrium composition

7. Chemical equilibrium in heterogeneous systems 7. Chemical equilibrium in heterogeneous systems

• Chemical equilibrium:
– Chemical potentials in gas phase: i = 0 (T)
i + RTlnPi • If the substances in liquid, solid phase are insoluble
– Chemical potentials in liquid/solid phase : * (T)
i = i + RTlnxi in each other (not form a solution), then xi = 1
Chemical equilibrium: KP,x = ( P,x)eq
their value does not affect Keq: KP,x = ( P)eq

• Ex: Fe2 O3 (s) + 3CO (g) = 2Fe (s) + 3 CO2 (g)

• Example: Fe2 O3 (s) + 3CO (g) = 2Fe (s) + 3 CO2 (g)
2 3
xFe PCO 2
x Fe 3
PCO 3
PCO
K P, x 2
3 K P, x 2
KP 2

xFe2O3 .PCO 3
xFe2O3 .PCO 3
PCO
eq eq eq
 7. Chemical equilibrium in heterogeneous systems

• Ex: CaCO3 (s) = CaO (s) + CO2 (g)

– Equil. Const.: KP = (PCO2)eq depend only on T.

– When T increases, (PCO2)eq increases.
– When (PCO2)eq = (PCO2)atmosphere Dissociation temperature
(CaCO3 Tdis = 512oC) END
– When (PCO2)eq = 1 atm Decomposition temperature
(CaCO3 Tdecomp. = 880oC)