Chapter 2

Chemical Equilibrium
2.1. Some definitions
2.1.1. Reversible reaction
- Reaction that proceed in only one derection called one derection reaction
Example:
- Reversible reaction: the reaction that do not go completion and that can
occur in both derections
aA + bB ↔ cC + dD
↔: indicates that the reaction is reversible
Example: N2 + 3H2 ↔ 2NH3
When the rate of A and B react to form C and equal the rate of C and D
react to form A and B, the system is at equilibrium
2.1. Some definitions
2.1.2. The chemical equilibrium state
- The chemical equilibrium state is characteristic of reversible
reaction, at which concentration of reactants and products no
longer change with time
- The chemical equilibrium state is achieved when the rate of the
foward and reverse reactions are equal (vf=vr)
2.2. Equilibrium constants
Consider a reversible reaction: aA + bB ↔ cC + dD (A, B, C, D are gas)
For the reaction at a perticular temp T
𝑃𝐶𝑐 ∗𝑃𝐷
𝑑
𝐾𝑝 = ( )
𝑃𝐴𝑎 ∗𝑃𝐵𝑏 eq
Pi: is partial pressure of i subtance at equilibrium state
𝐶𝐶𝑐 ∗𝐶𝐷
𝑑
𝐾𝐶 = ( )
𝐶𝐴𝑎 ∗𝐶𝐵𝑏 eq
Ci: is concentration of i subtance at equilibrium state
𝑐 𝑑
𝑛𝐶 ∗𝑛𝐷
𝐾𝑛 = ( 𝑎 ∗𝑛𝑏 )eq
𝑛𝐴 𝐵
ni: the number of mole of i at equilibrium state
The relation between equilibrium constants
• We have: PV=nRT, →P=nRT/V=CRT, →Pi=CiRT

𝑃𝐶𝑐 ∗𝑃𝐷
𝑑
𝐶𝐶𝑐 ∗𝐶𝐷
𝑑
𝑐+𝑑 −(𝑎+𝑏) = 𝐶𝐶𝑐 ∗𝐶𝐷
𝑑
∆𝑛 = 𝐾 ∗ (𝑅𝑇)∆𝑛
𝐾𝑝 = = 𝑏 (𝑅𝑇) (𝑅𝑇) 𝐶
𝑃𝐴𝑎 ∗𝑃𝐵𝑏 𝐶𝐴𝑎 ∗𝐶𝐵 𝐶𝐴𝑎 ∗𝐶𝐵
𝑏

𝑃𝑖 𝑛𝑖 𝑛𝑖
• We have, =σ → 𝑃𝑖 = σ 𝑛𝑖
*P
𝑃 𝑛𝑖
𝑃𝐶𝑐 ∗𝑃𝐷
𝑑 𝑐 𝑑
𝑛𝐶 ∗𝑛𝐷 𝑃 ∆𝑛 𝑃 ∆𝑛
𝐾𝑝 = 𝑏= ∗( σ ) = 𝐾𝑛 ∗( σ )
𝑃𝐴𝑎 ∗𝑃𝐵 𝑎 ∗𝑛𝑏
𝑛𝐴 𝐵 𝑛𝑖 𝑛𝑖
Where: ∆𝑛: total mole number of gas (products)- total mole number of
gas (reactants)
P: total pressure of the system at equilibrium state
Σni: total of mole number of the system at equilibrium state
 𝑃 ∆𝑛
• 𝐾𝑝 = 𝐾𝐶 ∗ (𝑅𝑇)∆𝑛 = 𝐾𝑛 ∗( σ )
𝑛𝑖
• When ∆n=0, 𝐾𝑝 = 𝐾𝐶 = 𝐾𝑛
• Note:
- 𝐾𝑝 , 𝐾𝐶 are only depend on T and characteristic of reaction.
When T=const, 𝐾𝑝 , 𝐾𝐶 =const
- 𝐾𝑛 depends on T, P and σ 𝑛𝑖
- The equilibrium constants has no units
- The reaction has solid reactants, there is no solid in the
formular of K
Example 1. Write equilibrium constant of the reaction
N2(g) + 3H2(g) ↔ 2NH3(g)
2 2
𝑃𝑁𝐻3 [𝑁𝐻3 ]2 𝑛𝑁𝐻3
𝐾𝑝 = 3 ; 𝐾𝐶 = ; 𝐾𝑛 = 3
𝑃𝑁2 ∗𝑃𝐻 [𝑁2 ]∗[𝐻2 ]3 𝑛𝑁2 ∗𝑛𝐻
2 2
Example 2. Calculate ∆n for following reactions
1. N2(g) + 3H2(g) ↔ 2NH3(g) ∆n=2-(1+3)=-2
2. H2(g) + Cl2(g) ↔ 2HCl ∆n= 2-(1+1)=0
3. CaCO3(s) ↔ CaO(s) + CO2(k) ∆n=1-0=1
Example 3. Write equilibrium constant of the reaction
CaCO3(s) ↔ CaO(s) + CO2(k) is a heterogeneuos eq, there is no CaCO3 and
CaO in K
Kp=PCO2; KC=[CO2]; Kn=nCO2
Example 4. Consider the eq: 2BrCl (g) ↔ Br2(g) + Cl2(g)
At initial time, the mole number BrCl =2 mole, Br2=1 mole, KC=5 (1000K), V=10l
Calculate Kp, Kn

2BrCl (g) ↔ Br2(g) + Cl2(g)

t=0 2/10 (M) 1/10 (M) 0
React 2x x x
t=teq (0,2-2x) (0,1+x) x
𝐶𝑙2 𝐵𝑟2 (0,1+𝑥)∗𝑥
𝐾𝐶 = 2 = 2 =5
[𝐵𝑟𝐶𝑙] [0,2−2𝑥]
x=[Cl2]=0,075 M; [Br2]= (0,1+x) =0,175M; [BrCl]=(0,2-2x)=0,05M
PBrCl=[BrCl]RT=0,05*0,082*1000=
PBr2=[Br2]RT=0,175*0,082*1000
PCl2=[Cl2]RT=0,075*0,082*1000
nCl2=0,75 mole; nBr2= (0,1+x)*10 =1,75mole; nBrCl=0,5 mole
2.3. Relationship between ∆Go and K
Consider the eq: aA + bB ↔ cC + dD (A, B, C, D are gases)
𝑃𝐶𝑐 ∗𝑃𝐷
𝑑
∆G= ∆Go+RTln (1)
𝑃𝐴𝑎 ∗𝑃𝐵𝑏
PA, PB, PC, PD: particular pressure at the calculation time
When the reaction reach to the equilibrium state, ∆G=0,
𝑃𝐶𝑐 ∗𝑃𝐷
𝑑
→ ∆Go+RTln =0;
𝑃𝐴𝑎 ∗𝑃𝐵𝑏
𝑃𝐶𝑐 ∗𝑃𝐷𝑑
→ ∆Go=-RTln ( ) =-RTlnKp (2)
𝑃𝐴𝑎 ∗𝑃𝐵𝑏 eq
𝑃𝐶𝑐 ∗𝑃𝐷
𝑑 𝑄𝑝
Replace (2) in (1): ∆G= -RTlnKp +RTln =RTln (3)
𝑃𝐴𝑎 ∗𝑃𝐵𝑏 𝐾𝑝
𝑃𝐶𝑐 ∗𝑃𝐷
𝑑
Where: Qp= (Pi: particular pressure at the calculation time)
𝑃𝐴𝑎 ∗𝑃𝐵𝑏
2.4. Evaluation of K at different temparature
• The Van’t Hoff equation:
𝐾𝑝𝑇 ∆𝐻 𝑜 1 1
2
ln = −
𝐾𝑝𝑇 𝑅 𝑇1 𝑇2
1
𝐾𝑝𝑇1 , 𝐾𝑝𝑇2 : 𝐾𝑝 𝑎𝑡 𝑇1, 𝑇2 𝑜𝑓 𝑡𝑒𝑚𝑝𝑎𝑟𝑎𝑡𝑢𝑟𝑒
∆𝐻 𝑜 : 𝑡ℎ𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑒𝑛𝑡ℎ𝑎𝑛𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑖𝑛𝑐𝑎𝑠𝑒 𝑡ℎ𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑇 𝑖𝑠 𝑛𝑜𝑡 𝑚𝑢𝑐ℎ)
2.5. Factors that effect to the chemical equilibrium
• Le Chatelier’s principle: If an external stress is applied to a system at
equilibrium, the system adjusts in such a way that the stress is
partically off set
1. Change in concentration
FeCl3 + NH4CNS ↔ Fe(CNS)3 + NH4Cl
red (like blood)
- When the concentration of FeCl3, or NH4CNS, or both increase, eq shift
from left to right, so you can see the color of red darker because the
concentration of Fe(CNS)3 increase
- When the concentration of NH4Cl, eq shift from right to left, so you can
see the color of red lighter
CaCO3 (s) ↔ CaO(s) + CO2(g)
2. Change in volume or pressure
(Applied for gases system)
*PV=nRT → P=(n/V)RT
C=n/V → the influence of volume to the eq is similar to the influence of
concentration
*We only consider about the change of general pressure of a gases system
- When P decrease, eq shift to the increasing the mole of gases direction
- When P increase, eq shift to the decreasing the mole of gases direction
- If the number of mole of gases are not change, P does not influence to the
eq
Ex: N2(g) + 3H2(g) ↔ 2NH3(g) ; H2(g) + Cl2(g) ↔ 2HCl(g)
3. Change in temparature
• When temparature increase, favors an edothermic reaction
• When temparature decrease, favors an exothermic reaction
2NO2(g) ↔ N2O4(g) ∆H<0
brown colorless
• Kreverv=1/K
 [𝐻2 𝑆]2 [8.7/12]2
𝐾𝐶 = =
[𝐻2 ] [𝑆2 ] [2.5/12]2 [1.35 ∗ 10−5 /12]
2
• Kp=PCO2=0.105
• Kp=KC*(RT)∆n → KC= Kp *(RT)-∆n =0.105*(0.082*623)-1
 N2(g) + 3H2(g) ↔ 2NH3(g)
t=0 0.6 M 0.76 0.48
React x 3x 2x
t=teq (0.6-x) (0.76-3x) (0.48+2x)
[𝑁𝐻3 ]2 (0.48 + 2𝑥)2
𝐾𝐶 = 3
= 3
= 1.2
[𝐻2 ] [𝑁2 ] 0.76 − 3𝑥 (0.6 − 𝑥)
→x
 H2(g) + CO2(g) ↔ H2O(g) + CO (g)
t=0 0.16 M 0.16 M 0 0
React x x x x
t=teq (0.16-x) (0.16-x) x x
[𝐻2 𝑂][𝐶𝑂]
𝐾𝐶 =
[𝐻2 ] [𝐶𝑂2 ]
a. H2(g) + CO2(g) ↔ H2O(g) + CO (g)
[𝐻2 𝑂][𝐶𝑂] [0.04][0.05]
𝐾𝐶 = = =
[𝐻2 ] [𝐶𝑂2 ] [0.045] [0.086]

b. H2(g) + CO2(g) ↔ H2O(g) + CO (g)

t=0 0.045 M 0.5 0.04 0.05
React x x x x
teq (0.045-x) (0.5-x) (0.04+x) (0.05+x)
Chapter 3. Solution and solution of electrolytes
3.1. Concentration units
a. Percent by mass (C%): is the ratio of the mass of a solute to the
mass of solution, multiplied by 100%
Ex: solution of C12H22O11 10% mean that, there are 10 g
C12H22O11 in 100 g solution
b. Molarity (CM):
Ex: solution of NaOH 0.1M mean that there are 0.1 mole of
NaOH in 1 l of solution
3.2. Principle of solubility
3.2.1. Type of solutions
Saturated solution
3.2.2. A view of the solution process
There are 3 steps
- Separation of sonvent molecules (∆H1)
- Entail the separation of solute molecules (∆H2)
- The sonvent and solute mix (∆H3)
∆Hsol=∆H1 + ∆H2 + ∆H3
∆Hsol>0,
∆Hsol<0
 3.2.3. The effect of temparature of solubility
• For solid subtances:
Solutes + Sonvent ↔ Solution
∆Hsol>0, T increase, the solubility increase
∆Hsol<0, T increase, the solubility decrease
• For gases:
Solutes (gases) + Sonvent (water) ↔ Solution ∆Hsol<0
 3.2.4. The solution of electrolytes
• Electrolytes are subtances that in solution, electrolytes dissociate into ions
• Acid, Base, Salts are electrolytes
HCl → H+ + Cl-
Ba(OH)2 → Ba2+ + 2OH-
Na2SO4 → Na+ + SO42-
- Strong electrolytes: are subtances that dissociate completely into ions in solution
Ex: strong acid, strong base, suluble salts
- Weak electrolytes: are subtances that dissociate partically into ions in solution
(At eq, nodissociated molecules of weak electrolytes exist with their ions)
Ex: weak acid (HCN, HNO2, H2S, H3PO4, H2CO3....), weak base (NH3), poorly
electrolytes (AgCl, BaSO4, ...)
HCN ↔ H+ + CN-
3.3. Bronsted acid-base theory
3.3.1. Concept of acid-base by Bronsted
- Bronsted acid is a subtance which is capable donating proton (H+)
and a Bronsted base is a subtance which is capable accepting
proton (H+)
- Ex:
HCl + H2O → H3O+ + Cl-
acid base
NH4+ + H2O ↔ H3O+ + NH3
acid base
NaOH → Na+ + OH-
OH- + H+ → H2O
NH3 + H2O ↔ NH4+ + OH-
3.3.2. The acid-base properties of water
• Water has ability to act either as an acid and as a base, it is very weak electrolyte
2H2O ↔ H3O+ + OH-
[𝐻3 𝑂+ ][𝑂𝐻 − ] −16
𝐾𝐶 = = 1.8 ∗ 10
[𝐻2 𝑂]2
(T=298K)
1000
18 𝑚𝑜𝑙
[H2O]= = 55,56
1 𝑙
+ − −
→ KH2O= 𝐻3 𝑂 𝑂𝐻 = 10 14 (T=298K) (*)
(*) apply for water and solution which sonvent is water
- In water (neutral environment), [H3O+]=[OH-]=10-7mol/l
- In acid solution [H3O+]>10-7mol/l
- In base solution, [OH-]>10-7mol/l, →[H3O+]<10-7mol/l
3.3.3. pH- a measure of acidity
• pH=-lg[H+]
• At 25 oC:
- Neutral solution: pH=7
- Acid solution: pH<7
- Base solution: pH>7
3.3.4. Strength of acids and bases
- Strong acids and bases are strong electrolytes which dissociate
completely in water into ions
- Weak acids and bases: we consider by acid and base constant (Ka,
Kb)
- For weak acid HA
HA + H2O ↔ A- + H3O+
Ka=[A-][H3O+]/[HA]
- For weak base B
B + H2O ↔ BH+ + OH-
Kb=[BH+ ][OH-]/[B]
- For a conjugate acid-base: HA/A- (CH3COOH/CH3COO-,
NH4+/NH3....)
HA + H2O ↔ A- + H3O+
Ka=[A-][H3O+]/[HA] (1)
A- + H2O ↔ HA + OH-
Kb=[HA][OH-]/[A-] (2)
From (1) and (2): Ka * Kb = {[A-][H3O+]/[HA]}*{[HA][OH-]/[A-]}
=[H3O+][OH-]=10-14
Ex: Ka (CH3COOH)=1.8*10-5 →Kb (CH3COO-)= 10-14/ 1.8*10-5=
3.3.5. Calculate pH of some acids and bases
solution
1. Strong mono acid solution HA (Ca mol/l)
HA → H+ + A- (1)
H2O ↔ H+ + OH- (2)
When Ca>3.17*10-7 mol/l, ignore the [H+] (2)
[H+]=Ca → pH = -lgCa
2. Strong mono base solution MOH (Cb mol/l)
MOH→ M+ + OH- (1)
H2O ↔ H+ + OH- (2)
When Cb>3.17*10-7 mol/l, ignore the [OH-] (2)
[OH-]=Cb → pOH = -lg[OH-]=-lgCb
pH=14-pOH=14+lgCb
3. Weak mono acid solution HA (Ca mol/l)
HA ↔ H+ + A- (1)
H2O ↔ H+ + OH- (2)
+ If Ca*Ka>10-12 , ignore (2)
HA ↔ H+ + A-
t=0 Ca 0 0
Eq Ca-x x x
Ka =[A-][H3O+]/[HA]=x2/(Ca-x)
→ x → pH=-lgx
+ If Ca*Ka>10-12 and Ca/Ka>100 → Ca>>x→ Ca-x=Ca →x=sqrt(Ka*Ca)

→ pH=-1/2lg Ka-1/2lgCa
4. Weak mono base solution B (Cb mol/l)
B + H2O ↔ BH+ + OH- (1)
H2O ↔ H+ + OH- (2)
+ If Cb*Kb>10-12 , ignore (2)
B + H2O ↔ BH+ + OH-
t=0 Cb 0 0
Eq Cb-x x x
Kb =[BH+][OH-]/[B]=x2/(Cb-x)
→ x → pOH=-lgx → pH=14+lgx
+ If Cb*Kb>10-12 and Cb/Kb>100 → Cb>>x→ Cb-x=Cb →x=sqrt(Kb*Cb)

→ pOH=-1/2lg Kb-1/2lgCb→ pH=14+1/2lg Kb+1/2lgCb

3.3.6. Poor electrolytes solution
• AgCl, BaSO4, Mg(OH)2, Fe(OH)3, Ag2CrO4, CaCO3....
• In general, consider the poor electrolyte solution AnBm
AnBm (s) ↔ nAm+ + mBn-
At equilibrium state (T=const): K=[Am+]n *[Bn-]m= TAnBm
• Relationship between TAnBm and s (mol/l)
AnBm (s) ↔ nAm+ + mBn-
s (mol/l) ns ms
TAnBm= [Am+]n *[Bn-]m=(ns)n(ms)m→s=
• Ex
Ag2CrO4(s) ↔ 2Ag+ + CrO42-
TAg2CrO4=([Ag+]2[CrO42-])eq
Ag2CrO4(s) ↔ 2Ag+ + CrO42-
s(mol/l) 2s s
TAg2CrO4=([Ag+]2[CrO42-])eq=(2s)2(s)=4s3
• The condition to form and dilute the poor electrolytes AnBm
- The condition to form: [Am+]n*[Bn-]m >TAnBm
- The condition to dilute : [Am+]n*[Bn-]m <TAnBm
Ex: Mixing 2 solutions of Mg(NO3)2 0.002 M and NaOH 0.01 M
with the equal volume. Does the Mg(OH)2(s) appear ?
[Mg2+]=0.002/2=0.001 M
[OH-]=0.01/2=0.005 M
[Mg2+]*[OH-]2 commpare with TMg(OH)2