Thermodynamics

《Basic chemistry》

6.5 Chemical Equilibrium

《Basic chemistry》
Relating ∆𝒓 𝑮⊖
𝒎 to the Equilibrium Constant

⊖ ⊖ ⊖
∆𝒓 𝑮𝒎 (𝑻) = ∆𝒓 𝑯𝒎 (𝟐𝟗𝟖. 𝟏𝟓 𝐊) − 𝑻∆𝒓 𝑺𝒎 (𝟐𝟗𝟖. 𝟏𝟓 𝐊)

Under conditions that are nonstandard state, we must

use ∆𝒓 𝑮𝒎 rather than ∆𝒓 𝑮⊖
𝒎 to predict the reaction.

How to calculate ∆𝒓 𝑮𝒎 when the

substance is not in standard state?
 Reaction quotient

⊖
The relationship between ∆𝒓 𝑮𝒎 and ∆𝒓 𝑮𝒎 is:
∆𝒓 𝑮𝒎 = ∆𝒓 𝑮⊖
𝒎 + 𝑹𝑻𝒍𝒏𝑱
where R is the gas constant (8.314 J·mol-1·K-1), T is the absolute
temperature, J is the reaction quotient.
𝒑 𝒑
1. For gas, 𝑱 = , ∆𝒓 𝑮𝒎 = ∆𝒓 𝑮⊖
𝒎 + 𝑹𝑻𝒍𝒏 ⊖
𝒑⊖ 𝒑
𝒄 ⊖ 𝒄
2. For solute, 𝑱 = , ∆𝒓 𝑮𝒎 = ∆𝒓 𝑮𝒎
+ 𝑹𝑻𝒍𝒏 ⊖
𝒄⊖ 𝒄
⊖
3. For pure substance, 𝑱 = 𝟎 , ∆𝒓 𝑮𝒎 = ∆𝒓 𝑮𝒎
 Reaction quotient

aA + bB ＝ cC＋ dD
𝒄 𝒅
𝒑𝑪 𝒑𝑫
For gas 𝒑⊖ 𝒑⊖
∆𝒓 𝑮𝒎 = ∆𝒓 𝑮⊖
𝒎 + 𝑹𝑻 𝒍𝒏 𝒂 𝒃
𝒑𝑨 𝒑𝑩
𝒑⊖ 𝒑⊖
𝒄𝑪 𝒄 𝒄𝑫 𝒅

⊖ 𝒄⊖ 𝒄⊖
For solution ∆𝒓 𝑮𝒎 = ∆𝒓 𝑮𝒎 + 𝑹𝑻 𝒍𝒏 𝒂 𝒃
𝒄𝑨 𝒄𝑩
𝒄⊖ 𝒄⊖
 Reaction quotient

aA + bB ＝ cC＋ dD

∆𝒓 𝑮𝒎 = ∆𝒓 𝑮⊖
𝒎 + 𝑹𝑻𝒍𝒏𝑱
𝒗𝑩 𝒗𝑩
⊖ 𝒑𝑩 𝒄𝑩
= ∆𝒓 𝑮𝒎 + 𝑹𝑻 𝐥𝐧 ෑ ⊖ ෑ ⊖
𝒑 𝒄
𝑩 𝑩

∆𝒓 𝑮𝒎 can be used to predict the spontaneity of an irreversible

reaction, or the direction of a reversible reaction in any condition.
 Reaction quotient

Most reactions cannot react completely, only part of the

reactants can be converted into products.
The reactions that can proceed in two opposite directions at the
same time under the same conditions, called reversible
reactions, using “⇌” to replace “=” or “”.

e.g. 2N2 + 3H2 2NH3

Usually the reaction proceeds from left to right is called a forward
reaction, right to left is called a reverse reaction.
 1. The concept of Equilibrium

v
vfor
Equilibrium state

vrev
Time
When the speed of the forward reaction is equal to the reverse reaction, the
concentration of reactants and products will keep constant, call equilibrium state.
Such a state will be break when changing the conditions, and the reaction will
continue till a new equilibrium state.
 1. The concept of Equilibrium

𝒑𝑩 𝒗𝑩 𝒄𝑩 𝒗𝑩
Equilibrium constant 𝑲⊖ = ς𝑩 ⊖ ς𝑩 ⊖
𝒑 𝒆𝒒 𝒄 𝒆𝒒

At equilibrium, ∆𝒓 𝑮𝒎 = 𝟎, 𝑲⊖ is equal to J, then

∆𝒓 𝑮𝒎 = ∆𝒓 𝑮⊖
𝒎 + 𝑹𝑻𝒍𝒏𝑲 ⊖ =𝟎

⊖
Law of chemical equilibrium: ∆𝒓 𝑮𝒎 = −𝑹𝑻𝒍𝒏𝑲⊖
Example 9
(1) N2(g) + 3H2(g) ⇌ 2NH3(g)
(2) Sn2+(aq) + 2Fe3+(aq) ⇌ Sn4+(aq) + 2Fe2+(aq)
(3) ZnS(s) + 2H3O+(aq) ⇌ Zn2+(aq) + H2S(g) + 2H2O(l)
 peq  NH3  / p 
2

(1) K 
 peq  N 2  / p    peq  H 2  / p 
3

ceq  Sn  / c   ceq  Fe  / c
2
4+ 2+

(2) K     
ceq  Sn 2+  / c   ceq  Fe3+  / c
2

   
ceq  Zn 2+  / c    peq  H 2S / p 
(3) K     
ceq  H3O  / c 
2
+
 
2. Equilibrium constant
When a reversible reaction reaches the equilibrium state, it
means the conversion of reactants to products has reached the
maximum value.

𝑲⊖ can be determined experimentally.

When 𝑲⊖ is large, it means the concentration of products is

pretty high compared with the reactants. Thus the conversion
rate is high.

The higher 𝑲⊖ is, the larger conversion rate is.

Only temperature changes alter the 𝑲⊖ .
3. Calculation rules of equilibrium constant

1. Using ∆𝒓 𝑮⊖
𝒎
⊖
∆𝒓 𝑮𝒎 = −𝑹𝑻𝒍𝒏𝑲⊖
⊖
a. ∆𝒓 𝑮𝒎 (𝟐𝟗𝟖. 𝟏𝟓 𝑲) = σ𝑩 𝒗𝑩 ∆𝒇 𝑮⊖
𝒎 (𝑩, 𝟐𝟗𝟖. 𝟏𝟓 𝑲)

b. ∆𝒓 𝑮⊖
𝒎 (𝑻) = ∆ 𝑯
𝒓 𝒎
⊖
(𝟐𝟗𝟖. 𝟏𝟓 𝑲) − 𝑻∆ ⊖
𝒓 𝒎 (𝟐𝟗𝟖. 𝟏𝟓 𝑲)
𝑺

2. Using several 𝑲⊖ of different reactions

a. 2N2 + 3H2 2NH3 𝑲⊖
𝟏
𝟏
𝑲⊖
𝟐 = 𝑲⊖
𝟏
𝟐
N2 + 3/2H2 NH3 𝑲⊖
𝟐
 Calculation rules of equilibrium constant

2. Using several 𝑲⊖ of different reactions

b. 2N2 + 3H2 2NH3 𝑲⊖ ⊖ 𝟏

𝟏 𝑲𝟐 = ⊖
2NH3 2N2 + 3H2 ⊖
𝑲𝟐 𝑲𝟏

c. H3PO4 + H2O H3O+ + H2PO4- 𝑲⊖

𝟏
⊖
H2PO4 -+ H2O H3O+ + HPO42- 𝑲𝟐
H3PO4 + 2H2O 2H3O+ + HPO42- 𝑲⊖
𝟑

(3) = (1) + (2) 𝑲⊖

𝟑 = 𝑲 ⊖
𝟏 ∙ 𝑲 ⊖
𝟐
 The Reaction Direction: Comparing J and 𝑲⊖

To predict the direction of a reaction, we need to compare the

current state ( J ) with the equilibrium state ( 𝑲⊖ ).
𝒗𝑩 𝒗𝑩 𝒗𝑩 𝒗𝑩
𝒑𝑩 𝒄𝑩 𝒑𝑩 𝒄𝑩
𝑱=ෑ ⊖ ෑ ⊖ 𝑲⊖ =ෑ ⊖ ෑ ⊖
𝒑 𝒄 𝒑 𝒆𝒒
𝒄 𝒆𝒒
𝑩 𝑩 𝑩 𝑩

1. J < 𝑲⊖ , the reaction shift in the forward direction,

2. J > 𝑲⊖ , the reaction shift in the reverse direction.
3. J = 𝑲⊖ , the reaction is at equilibrium.
 Example 10

At 298.15 K, the 𝑲⊖ of the reaction Pb2+(aq) + Sn(s) ⇌ Pb(s) + Sn2+(aq)

is 𝑲⊖ = 2.2, please predict the direction under following conditions:
(1) c(Pb2+) = c(Sn2+) = 0.10 mol·L-1.
(2) c(Pb2+) = 0.10 mol·L-1, c(Sn2+) = 1.0 mol·L-1
2+
c(Sn ) / c 0.10 /1
(1) J1  2+
  1.0
c(Pb ) / c 0.10/1
J < 𝑲⊖ , shift in the forward direction.
1.0 /1
(2) JJ 2   10
0.10/1
J < 𝑲⊖ , shift in the reverse direction.
《Basic chemistry》
4. Altering Equilibrium Conditions: Le Châtelier’s Principle

• If we change the conditions (temperature, pressure,

concentration), how will a reaction shift?

If a system equilibrium experiences a change,

it will shift its equilibrium to try to

the Le Châtelier’s Principle can only be used in

an equilibrium system.
 A. Effect of a change in concentration

Le Châtelier’s Principle: If a system equilibrium experiences a change,

it will shift its equilibrium to try to compensate for the change.
𝒄𝑪 𝒄 𝒄𝑫 𝒅

𝒄⊖ 𝒄⊖
aA(aq) + bB(aq) ⇌ cC(aq) + dD(aq) 𝑱= 𝒂 𝒃
𝒄𝑨 𝒄𝑩
𝒄⊖ 𝒄⊖
At equilibrium, J = 𝑲⊖ .
1) When increase the concentrations of reactants, the J will fall
immediately, then J < 𝑲⊖ , the reaction shift to the right.
2) When increase the concentrations of product, then J increase
and J > 𝑲⊖ , the reaction shift to the left.
 B. Effect of a change in pressure - 1

Le Châtelier’s Principle: If a system equilibrium experiences a change,

it will shift its equilibrium to try to compensate for the change.
𝒄 𝒅
𝒑𝑪 𝒑𝑫
𝒑⊖ 𝒑⊖
aA(g) + bB(g) ⇌ cC(g) + dD(g) 𝑱= 𝒂 𝒃
𝒑𝑨 𝒑𝑩
𝒑⊖ 𝒑⊖
At equilibrium, J = 𝑲⊖ .
1) When increase the pressure of reactants, the J will falls
immediately, then J < 𝑲⊖ , the reaction shift to the right.
2) When increase the pressure of products, then J increase and J >
𝑲⊖ , the reaction shift to the left.
 B. Effect of a change in pressure - 2

If we increase the pressure of the whole system by reducing the

volume of the vessel, or by adding inert gas, the reaction shift
toward the direction with fewer moles of gas.
e.g. Increase the pressure

2N2(g) + 3H2(g) ⇌ 2NH3 (g) →

H2 (g) + I2 (g) ⇌ 2HI (g) No change

H2CO3 (aq) ⇌ H2O (l) + CO2(g) ←

 C. Effect of a change in temperature

Only temperature changes will alter 𝑲⊖ .

From ∆𝐫 𝑮⊖
𝒎 = −𝑹𝑻 𝐥𝐧 𝑲 ⊖

∆𝐫 𝑮⊖
𝒎 = ∆ 𝑯
𝐫 𝒎
⊖
− 𝑻∆ 𝑺⊖
𝐫 𝒎

⊖ ⊖
Then −𝑹𝑻 𝐥𝐧 𝑲⊖ = ∆𝐫 𝑯 𝒎 − 𝑻∆𝐫 𝑺𝒎
⊖ ⊖
∆𝐫 𝑺𝒎 ∆𝐫 𝑯 𝒎
𝐥𝐧 𝑲⊖ = −
𝑹 𝑹𝑻
 C. Effect of a change in temperature

In different temperature T1 and T2, with equilibrium

constants 𝑲⊖𝟏 and 𝑲 ⊖
𝟐 :

∆𝐫 𝑺⊖ ∆𝐫 𝑯⊖ ∆𝐫 𝑺⊖
𝒎 ∆ 𝑯
𝐫 𝒎
⊖
𝐥𝐧 𝑲𝟏⊖ =
𝒎
−
𝒎
(𝟏) 𝐥𝐧 𝑲𝟐⊖ = − (𝟐)
𝑹 𝑹𝑻𝟏 𝑹 𝑹𝑻𝟐

𝑲⊖
𝟐 ∆𝐫 𝑯 ⊖
𝒎 𝟏 𝟏
(2) – (1) 𝐥𝐧 ⊖
= −
𝑲𝟏 𝑹 𝑻𝟏 𝑻𝟐

K (T2 )  r H m T2  T1 
Van’t Hoff equation: ln 
K (T1 ) RT1 T2
 C. Effect of a change in temperature

K (T2 )  r H m T2  T1 
Van’t Hoff equation: ln 
K (T1 ) RT1 T2

For an endothermic reaction (∆𝒓 𝑯⊖

𝒎 > 0), a temperature rise will increase 𝑲⊖.

For an exothermic reaction (∆𝒓 𝑯⊖

𝒎 < 0), a temperature rise will decrease 𝑲⊖.
 D. Effect of a catalyst

A···B···C
Energy

Without catalyst

Ea With catalyst
K···A+BC
KA···B···C
Ea,2
Ea,1 KA+BC
A+BC
AB+C
O Reaction process
A catalyst can speed up the reaction by lowering the activation
energy, but it has no effect on 𝑲⊖ .
《Basic chemistry》
Summary of the disturbances
Disturbance Net direction of the reaction Effect on value of 𝑲⊖
Increase (reactant) Toward formation of product None
Concentration
Decrease (reactant) Toward formation of reactant None

Increase p Toward formation of less mole gas None

Pressure
(Volume)
Decrease p Toward formation of more mole gas None
⊖
Increases if ∆𝑟 𝐻𝑚 >0
Increase T Toward absorption of heat ⊖
Decrease if ∆𝑟 𝐻𝑚 <0
Temperature ⊖
Increases if ∆𝑟 𝐻𝑚 <0
Decrease T Toward release of heat ⊖
Decrease if ∆𝑟 𝐻𝑚 >0
Catalyst None None
24
《Basic chemistry》

Summary of Thermodynamics
 Key Point

1. Wp-V = -peΔV, ΔU = Q + W, H = U + pV
∆𝒓 𝑯
2. ∆𝒓 𝑯𝒎 ：∆𝒓 𝑯𝒎 =
∆𝝃
3. Calculation of 𝚫𝐫 𝑯⊖𝒎
1. Hess’s law: 2. Using ∆𝒇 𝑯⊖
𝒎:

∆𝒓 𝑯 ⊖
𝒎 = ෍ 𝒗 ⊖
𝑩 𝒇 𝒎 (𝑩)
∆ 𝑯
𝑩
 Key Point

4. Predict the direction of reaction: (rGm)T,p ≤ 0, or ∆𝑺 > 𝟎

5. Calculation of ∆𝑺
∆𝑯(𝐬𝐲𝐬)
∆𝑺 = ∆𝑺𝐬𝐲𝐬 + ∆𝑺𝐬𝐮𝐫 = ෍ 𝒗𝑩 𝑺⊖
𝒎 (𝑩) − >𝟎
𝑻
𝑩
6. Calculation of 𝚫𝒓 𝑮⊖
𝒎

𝚫𝐫 𝑮⊖
𝒎 𝟐𝟗𝟖. 𝟏𝟓 𝐊 = ෍ 𝒗 ⊖
𝑩 𝐟 𝒎,𝑩 𝟐𝟗𝟖. 𝟏𝟓 𝐊
𝚫 𝑮
𝑩
𝚫𝐫 𝑮⊖
𝒎 𝑻 = 𝚫 𝑯
𝐫 𝒎
⊖
𝟐𝟗𝟖. 𝟏𝟓 𝐊 − 𝑻𝚫 ⊖
𝐫 𝒎 𝟐𝟗𝟖. 𝟏𝟓 𝐊
𝑺
 Key Point

7. Calculation of ∆𝒓 𝑮𝒎
⊖
∆𝒓 𝑮𝒎 = 𝜟𝐫 𝑮𝒎 𝑻 + 𝐑𝐓 𝒍𝒏 𝑱
𝒗𝑩 𝒗𝑩
𝒑𝑩 𝒄𝑩
𝑱=ෑ ⊖ ෑ ⊖
𝒑 𝒄
𝑩 𝑩

8. Calculation of 𝑲⊖
𝒗𝑩 𝒗𝑩
𝒑𝑩 𝒄𝑩
∆𝒓 𝑮⊖ ⊖ 𝑲⊖ =ෑ ⊖ ෑ ⊖
𝒎 = −𝑹𝑻𝒍𝒏𝑲 𝒑 𝒆𝒒
𝒄 𝒆𝒒
𝑩 𝑩
𝑲⊖
𝟐 ∆𝐫 𝑯⊖
𝒎 𝟏 𝟏
𝐥𝐧 = −
𝑲⊖
𝟏
𝑹 𝑻𝟏 𝑻𝟐
《Basic chemistry》

Key Point

9. Predict the direction of a reversible reaction using 𝑲⊖

1. J < 𝑲⊖ , the reaction shift in the forward direction,
2. J > 𝑲⊖ , the reaction shift in the reverse direction.
3. J = 𝑲⊖ , the reaction is at equilibrium.

29
 Homework

P57：1，2，17

P69：2
Thanks for Watching