Atkins & de Paula: Elements of Physical Chemistry 6e: Chapter 7: Chemical Equilibria: The Principles

Atkins & de Paula
Atkins & de Paula: Elements of

Physical Chemistry 6e
Chapter 7: Chemical equilibria:

the principles
©Oxford University Press, 2013. All rights reserved.

Chemical Reaction - The Equation
• Reaction equation for A reacting with B forming C and D

A+ B → C+ D (1) - general expression of a reaction
vAA + vBB = vCC + vDD (2) - quantitative representation of a reaction
vAA + vBB ⇄ vCC + vDD (3) - representing an equilibrium controlled reactio
• Reaction stoichiometry
– vA, vB, vC and vD are numbers, called stoichiometry coefficients
– The concept of mole (the number of molecules) in a chemical reaction
– Determination of stoichiometry coefficients - balancing equation (equal number o
each atom on both sides of the equation)
e.g. 2NO + O2 = 2NO2 we have: 2 N, 4 O on both side
Q. For the same reaction can we write the equation as
4 NO + 2 O2 = 4NO2 or
NO + ½O2=NO2 ?
Atkins & de Paula: Elements of Physical Chemistry 6e

Direction of a Reaction
Q. A reaction: A + B → C + D. Will it proceed in the direction indicated?
Is there a general way to know reaction direction?
A. We can tell from the change of Gibbs free energy in a reaction, ΔG
for a reaction at ∆GT ° < 0 reaction can proceed (we don’t know how fast it will be!)

constant T, P, ∆GT ° = 0 reaction at equilibrium (no change in system - ‘dead’ state)
we have ∆G ° > 0 reaction will NOT proceed (or can proceed backward!)
 T
The 2nd Law of Thermodynamics - Processes occur in a direction of decreasing
quality of energy.
We need to study reaction system in terms of energies and their changes
• The energies associated with a reaction system
– Many energy terms, a, U, H, G, - all depend on 4 basic parameters: P, T, V, S
– Usually P, T, V are specified by given reaction conditions. S is related to the
substances in the reaction (reactants/products) and reaction conditions (P, T, V)
– Knowing P, T, V and S, all other energy terms can be determined. The most
important ones in relation to chemical reactions are H and G.

Entropy of Reaction System
Entropy definition dS = dQ/T meaning: at T, change of S is proportional to

change of heat.
Entropy calculation
Basis of S calculation: 3rd Law of thermodynamics: S = 0 at absolute T = 0.
Assign standard entropy of a substance (1 mole, at 1 atm. 25°C) as
298 𝐶𝐶
0 𝑝𝑝
𝑆𝑆298 = � 𝑑𝑑𝑑𝑑
0 𝑇𝑇
(S°298 value of common substances are available in most chemistry / chem. Eng. handbooks.)
The entropy change in a reaction at T, p This term becomes zero if there is no
phase change during the reaction
reaction: vAA + vBB D vCC + vDD
𝑇𝑇
0 0 0 𝑑𝑑𝑑𝑑 𝑄𝑄𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝
∆𝑆𝑆𝑇𝑇0 =� 𝜈𝜈𝑖𝑖 𝑆𝑆𝑖𝑖,𝑇𝑇 −� 𝜈𝜈𝑖𝑖 𝑆𝑆𝑖𝑖,𝑇𝑇 , Δ𝑆𝑆𝑖𝑖,𝑇𝑇 = 0
𝑆𝑆298 + � Δ𝐶𝐶𝑝𝑝,𝑖𝑖 +
𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟
298 𝑇𝑇 𝑇𝑇𝑗𝑗
If a reaction is adiabatic, it can only proceed when ΔS>0 (reaction reaches
equilibrium when ΔS=0).
Usually S analysis of a reaction system is complicated and inconvenient to use.
Enthalpy of Reaction System
Enthalpy definition
H = U+ pV ⇒ dH = dU + pdV + Vdp = S dT + Vdp
ΔH = ΔU + Δn RT (gas, g-l, g-s, g-s,l phase at constant p and T)
ΔH = ΔU (liquid, or solid (dV = 0))
Enthalpy calculation
Standard enthalpy of formation, Hf0
Assign H°f of all stable substances (O2, N2, CO2 H2O etc.) at 298K & 1atm
as 0 (not at 0K as for S) (H°298 values of common substances are available
in most chemistry / chem. eng. handbooks.)
Enthalpy of combustion, Hc -Often used for combustion process, similar
to enthalpy of formation
Enthalpy change when 1 mole of substance combusted completely
(reacted completely with O2).

Enthalpy of Reaction System
The enthalpy change in a reaction at T, p

reaction: vAA + vBB ⇄ vCC + vDD
0 0
∆𝐻𝐻𝑇𝑇0 = � 𝜈𝜈𝑖𝑖 𝐻𝐻𝑖𝑖,𝑇𝑇 − � 𝜈𝜈𝑖𝑖 𝐻𝐻𝑖𝑖,𝑇𝑇
The ΔH of phase transformations including
In which g-l-s or crystalline phase change
𝑇𝑇
0 0
Δ𝐻𝐻𝑖𝑖,𝑇𝑇 = 𝐻𝐻298 + � Δ𝐶𝐶𝑝𝑝,𝑖𝑖 𝑑𝑑𝑑𝑑 + � Δ𝐻𝐻𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝
298
ΔH is a direct measure of the reaction heat associated with a reaction (if only
chemical energy change exists). When ΔH < 0 - the reaction is exothermic
and when ΔH > 0 is the reaction is endothermic.
Reaction heat is of critical importance in reaction engineering (reactor and
process design).

Gibbs Free Energy of Reaction System
Gibbs Free Energy definition

G = U + pV − TS = H − TS ⇒ ΔG = ΔH − T ΔS = − S ΔT + VΔp
Gibbs free energy calculation
Standard Gibbs free energy, G2980
Similar to S0 and H0, the standard Gibbs free energy of formation of a
substance, G0, is defined at reference state of T=298 K and p = 1 atm
(G°298 values of common substances are available in most chemistry / chem. eng. handbooks.)
The enthalpy change in a reaction at T, p
reaction: vAA + vBB ⇄ vCC + vDD
0 0
∆𝐺𝐺𝑇𝑇0 = � 𝜈𝜈𝑖𝑖 𝐺𝐺𝑖𝑖,𝑇𝑇 − � 𝜈𝜈𝑖𝑖 𝐺𝐺𝐻𝐻𝑖𝑖,𝑇𝑇
0 0 0
In which Δ𝐺𝐺𝑖𝑖,𝑇𝑇 = Δ𝐻𝐻𝑖𝑖,𝑇𝑇 − 𝑇𝑇Δ𝑆𝑆𝑖𝑖,𝑇𝑇 (value of each individual substance)
or, ΔGT0 can be determined directly from Δ𝐺𝐺𝑇𝑇0 = Δ𝐻𝐻𝑇𝑇0 − 𝑇𝑇Δ𝑆𝑆𝑇𝑇0 (value from
overall reaction)

Gibbs Free Energy of Reaction System
ΔG° is one of the most important thermodynamics properties for a chemical
reaction system. - It determines the direction of reaction to proceed
for a reaction at ∆GT ° < 0 reaction can proceed (we don’t know how fast it will be!)

constant T, p, ∆GT ° = 0 reaction at equilibrium (no further change in system)
we have ∆G ° > 0 reaction will NOT proceed (or can proceed backward!)
 T
• ΔG0 < 0 is the pre-condition which MUST be met for any process (not limited
to chemical reaction systems) to occur (spontaneous process).
• ΔG0 < 0 indicates a specified reaction has tendency to proceed; however, it
CANNOT tell how fast that reaction will occur - reaction kinetics tell the
reaction rate.
• A process/reaction proceeds always in the direction of MINIMISING Gibbs
free energy. This is a very important concept.
• A process/reaction will stop at ΔG0 = 0, this is called equilibrium state.

Important Notes about ΔS, ΔH and ΔG
ΔS, ΔH and ΔG are widely used in analysing various systems. Our current
discussion of these function is limited to the application to a reaction system.
A clear definition of the reaction conditions is necessary before start calculation
of these properties.
There are many ways these thermodynamic properties can be determined.
Only most commonly used ones in relation to a chemical reaction are given.
It is very important to understand the study a chemical reaction by means of
thermodynamics tells only state - a ‘snapshot’ of system, and how a process
proceeds from one state to another (reversible-irreversible, with or without work
done / exchange heat with surrounding). There is no factor of time involved.

Gibbs energy minimum
Extent of reaction (ξ ):
The amount of reactants being converted to products. Its unit is mole.
In a very general way, the extent of reaction is calculated as
dξ = dnA/vA
(where vA is the stoichiometric number of the reactant A, which is
negative for the reactant!!)
Why do we need a new quantity?
Consider a generic reaction: 2A ↔ 3B
The amount of A consumed is different from the amount of B produced. Which
number should be used in the report?
Consider: A ↔ B
Assume an infinitesimal amount dξ of A turns into B,
dnA = -dξ
On the other hand, dnB = dξ
Gibbs energy minimum
Example 1: N2(g) + 3H2(g) ↔ 2NH3(g)

When the extent of reaction changes from ξ = 0 to ξ = 1.0 mole,
what are the changes of each reagent?
Solution: identify vj:
v(N2) = -1; v(H2) = -3; v(NH3) = 2.
since dξ = 1.0 mole,
dn(N2) = -1x1.0 mole = -1.0 mole,
dn(H2) = -3x1.0 mole = -3.0 moles,
dn(NH3) = 2x1.0 mole = 2.0 moles,
Example 2: CH4(g) + Cl2(g) ↔ CHCl3(l) + HCl(g),

in which the amount of reactant Cl2(g) decreases by 2 moles. What is
the extent of the reaction?
Solution:
Gibbs energy
Variation of Gibbs energy during a reaction process

The reaction Gibbs energy: ΔrG
The slope of the Gibbs energy plotted against the extent of reaction:
𝜕𝜕𝐺𝐺
∆𝑟𝑟 𝐺𝐺 =
𝜕𝜕𝜕𝜕 𝑝𝑝,𝑇𝑇
here Δr signifies a derivative
• A reaction for which ΔrG < 0 is called exergonic.
• A reaction for which ΔrG > 0 is called endergonic.
• ΔrG < 0, the forward reaction is spontaneous.
• ΔrG > 0, the reverse reaction is spontaneous.
• ΔrG = 0, the reaction is at equilibrium!!!

The reaction Gibbs energy
Molecular interpretation of the minimum in the reaction Gibbs energy
Gibbs energy of the system

decreases as the reaction progress
Gibbs energy of a system consisting

of different portions of reactants
and products

Calculation of reaction Gibbs energy
Consider the reaction : A ↔ B

initial amount: nA0 nB0
final amount: nAf nBf
Ginitial = μBnB0 + μAnA0
Gfinal = μBnBf + μAnAf
ΔG = Gfinal - Ginitial = (μBnBf + μAnAf ) – (μBnB0 + μAnA0 )
= μB(nBf- nB0) + μA (nAf - nA0) = μBΔξ + μA(-Δξ)
= (μB - μA )Δξ
𝜕𝜕𝐺𝐺
∆𝑟𝑟 𝐺𝐺 = = 𝜇𝜇𝐵𝐵 − 𝜇𝜇𝐴𝐴
𝜕𝜕𝜕𝜕 𝑝𝑝,𝑇𝑇
• When μA > μB, the reaction (A → B) is spontaneous.
• When μB > μA, the reverse reaction (B → A) is spontaneous.
• When μB = μA, the reaction is spontaneous in neither direction (equilibrium
condition).
Description of equilibrium
Perfect gas equilibrium : A(g) ↔ B(g)

ΔrG = μB – μA
Δ𝑟𝑟 𝐺𝐺 = 𝜇𝜇𝐵𝐵𝜃𝜃 + 𝑅𝑅𝑅𝑅 ln 𝑝𝑝𝐵𝐵 − 𝜇𝜇𝐴𝐴𝜃𝜃 + 𝑅𝑅𝑅𝑅 ln 𝑝𝑝𝐴𝐴
𝜃𝜃
𝑝𝑝𝐵𝐵
= Δ𝑟𝑟 𝐺𝐺 + 𝑅𝑅𝑅𝑅 ln = Δ𝑟𝑟 𝐺𝐺 𝜃𝜃 + 𝑅𝑅𝑅𝑅 ln 𝑄𝑄
𝑝𝑝𝐴𝐴
Q ( pB /pA ) is a reaction quotient
At equilibrium, ΔrG = 0, therefore
0 = Δ𝑟𝑟 𝐺𝐺 𝜃𝜃 + 𝑅𝑅𝑅𝑅 ln 𝐾𝐾 → 𝑅𝑅𝑅𝑅 ln 𝐾𝐾 = − ∆𝑟𝑟 𝐺𝐺 𝜃𝜃
(K is used to denote the ratio of partial pressures at equilibrium)
Note: The difference in standard molar Gibbs energies of the products and
reactants is equal to the difference in their standard Gibbs energies of
formation, thus,
Δr Gθ = Δf Gθ(B) - Δf Gθ(A)

Equilibrium of a general reaction
Example: 2A + B ↔ C + 3D
The reaction Gibbs energy, ΔrG, is defined in the same way as discussed
earlier :
Δ𝑟𝑟 𝐺𝐺 = Δ𝑟𝑟 𝐺𝐺 𝜃𝜃 + 𝑅𝑅𝑅𝑅 ln 𝑄𝑄
where the reaction quotient, Q, has the form:
Q = activities of products/activities of reactants in a compact expression
𝑄𝑄 = ∏ 𝛼𝛼𝑗𝑗 𝑣𝑣𝑗𝑗
vj are the corresponding stoichiometric numbers; positive for products and
negative for reactants.
vA = -2; vB = -1; vC = 1; vD = 3

Justification
∆ G=∆ G r r
θ
+ RT ln Q
Justification of the equation : dG = ∑μjdnj

Assuming that the extent of reaction equals dξ,
one gets dnj = vjdξ
then dG = ∑μjdnj = ∑μjvjdξ
(dG/dξ) = ∑ujvj  ΔrG = ∑μjvj
because μj = μjθ + RT ln (aj)
ΔrG = ∑{vj(μjθ + RT ln (aj))}
= ∑(vjμjθ) + ∑vj(RT ln (aj))
= ΔrGθ + RT ∑ ln(aj)vJ
= ΔrGθ + RT ln (∏(aj)vj) = ΔrGθ + RT ln (Q )
∆ r Gθ = ∑ v∆
Pr oducts
f G θ
− ∑ v∆
Re ac tan ts
f G θ

reaction quotient
Again, we use K to denote the reaction quotient at an equilibrium point,

K = Qequilibrium = (∏ajvj)equilibrium
K is called thermodynamic equilibrium constant. Note that until now K is
expressed in terms of activities)
Example: calculate the quotient for the reaction: A + 2B ↔ 3C + 4D

Solution: first, identify the stoichiometric number of each reactant:
vA = -1, vB = -2, vC = 3, and vD = 4.
𝑎𝑎𝐶𝐶3 𝑎𝑎𝐷𝐷4
𝑄𝑄 =
𝑎𝑎𝐴𝐴 𝑎𝑎𝐵𝐵2
At the equilibrium condition:
𝑎𝑎𝐶𝐶3 𝑎𝑎𝐷𝐷4
𝐾𝐾 =
𝑎𝑎𝐴𝐴 𝑎𝑎𝐵𝐵2

Equilibrium Constants
Example 1. Consider a hypothetical equilibrium reaction

A(g) + B(g) ↔ C(g) + D(g)
While all gases may be considered ideal. The following data are available for
this reaction:
Compound μθ(kJ mol-1)
A(g) -55.00
B(g) -44.00
C(g) -54.00
D(g) -47.00
Calculate the value of the equilibrium constant Kp for the reaction at 298.15K.
Solution:

Equilibrium Constants
Example 2: Using the data provided in the data section, calculate the standard
Gibbs energy and the equilibrium constant at 25oC for the following reaction
CH4(g) + Cl2(g) ↔ CHCl3(g) + HCl(g)
Solution: (chalkboard)
ΔfGθ(CHCl3, g) = -73.66 kJ mol-1
ΔfGθ(HCl, g) = - 95.30 kJ mol-1
ΔfGθ(CH4, g) = - 50.72 kJ mol-1

Thermodynamic equilibrium constant K
• K is a dimensionless quantity.
• K can be expressed in terms of fugacity for gas phase reactions or activities
for aqueous phase reactions.
• Gas phase: Fugacity is a dimensionless quantity and equals to the numerical
value of partial pressure expressed in bar, i.e. f j = pj/pθ where pθ = 1 bar).
• Aqueous phase:
1. Neutral solution: the activity, a, is equal to the numerical value of the
molality, i.e. bj/bθ where bθ = 1 mol kg-1.
2. Electrolyte solution: The activity shall now be calculated as αj = γj*bj/bθ ,
where the activity coefficient, γ, denotes distance from the ideal system
where there is no ion-interactions among constituents.

Chemical Reaction - The Equilibrium
For a chemical reaction vAA + vBB ⇄ vCC + vDD

when 𝐺𝐺𝑇𝑇0 = 0, we say the reaction is in chemical reaction equilibrium
• What is a chemical reaction equilibrium?
NH4
Example 1: NH3(aq)+H2O(l) ⇄ NH4+(l)+OH-(aq)
At constant T and p, when t → ∞
𝑁𝑁𝐻𝐻4+ 𝑂𝑂𝐻𝐻 − NH3
= 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
𝑁𝑁𝑁𝑁3 𝐻𝐻2 0 t
Example 2: 2NO(g) + O2(g) ⇄ 2NO2(g)
reaction quotient
At constant T and p, when t → ∞ NO2
2
𝑝𝑝𝑁𝑁𝑁𝑁 2
NO
2 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 O2
𝑝𝑝𝑁𝑁𝑁𝑁 𝑃𝑃𝑂𝑂2
t
• The concentration of a gas is usually measured as partial pressure
• At an equilibrium the reaction quotient becomes constant

Chemical Reaction - The Equilibrium
Chemical reaction equilibrium

vAA + vBB ⇄ vCC + vDD
– An equilibrium is a state at which no further change is possible under that
specific set of reaction system parameters
– An equilibrium is a dynamic process, meaning that the rate of forward
reaction is equal to that of reverse
– At equilibrium 𝐺𝐺𝑇𝑇0 = 0, i.e
0 0 0 0
∆𝐺𝐺𝑇𝑇0 = � 𝜈𝜈𝑖𝑖 𝐺𝐺𝑖𝑖,𝑇𝑇 − � 𝜈𝜈𝑖𝑖 𝐺𝐺𝑖𝑖,𝑇𝑇 = 0 ⇒ � 𝜈𝜈𝑖𝑖 𝐺𝐺𝑖𝑖,𝑇𝑇 = � 𝜈𝜈𝑖𝑖 𝐺𝐺𝑖𝑖,𝑇𝑇
𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟
– Any change of reaction parameters will redefine a system leading to a new

equilibrium, which may not be the same as that before the change
– Kp indicates only the relation between the partial pressures of reactants and
products at equilibrium, how fast a reaction proceed is controlled by
reaction kinetics.

Equilibrium Constant
Definition of equilibrium constant, K

The equilibrium constant is the reaction quotient at 𝐺𝐺𝑇𝑇0 = 0.
Expressions of equilibrium constant for various reactions
2
𝑝𝑝𝑁𝑁𝑁𝑁
– gas phase 2NO(g) + O2(g) ⇄ 2NO2(g) 𝐾𝐾𝑝𝑝 = 2
2
𝑝𝑝𝑁𝑁𝑁𝑁 𝑃𝑃𝑂𝑂2
– gas-solid phase CaCO3(s) ⇄ CaO (s)+CO2(g) 𝐾𝐾𝑝𝑝 = 𝑃𝑃𝐶𝐶𝑂𝑂2
𝑁𝑁𝐻𝐻4+ 𝑂𝑂𝐻𝐻−
– liquid phase NH3(aq)+H2O(l) ⇄ NH4+(l)+OH-(aq) 𝐾𝐾𝑐𝑐 =
𝑁𝑁𝑁𝑁3 𝐻𝐻2 0
– liquid-solid Cu(OH)2(s) ⇄ Cu2+(aq)+2OH- (aq) 𝐾𝐾𝑐𝑐 = 𝐶𝐶𝐶𝐶2+ 𝑂𝑂𝐻𝐻 − 2
– gas-liquid NH3(g)+H2O(l) ⇄ NH4OH(aq) 𝐾𝐾𝑝𝑝 = 1/𝑃𝑃𝑁𝑁𝑁𝑁3

𝜈𝜈𝐶𝐶 𝜈𝜈𝐷𝐷 𝜈𝜈 𝜈𝜈
𝐶𝐶 𝐷𝐷 𝑝𝑝𝐶𝐶 𝐶𝐶 𝑝𝑝𝐷𝐷𝐷𝐷
– general vAA + vBB ⇄ vCC + vDD 𝐾𝐾𝑐𝑐 = 𝜈𝜈𝐴𝐴 𝜈𝜈𝐵𝐵 = 𝜈𝜈 𝜈𝜈
𝐴𝐴 𝐵𝐵 𝑝𝑝𝐴𝐴𝐴𝐴 𝑝𝑝𝐵𝐵𝐵𝐵
Equilibrium constant, Kp, and Gibbs free energy DG

A gas phase reaction vAA + vBB ⇄ vCC + vDD
At equilibrium, assuming all the gases follow the ideal gas law at p = 1 atm,
ΔG°=∑(viG°i)prod− ∑(viG°i)reac=0 and at any p(≠1) ΔG= ∑(viGi)prod− ∑(viGi)reac=0
When reaction occurs at constant temperature (isothermal reaction)
Intergration
dG=Vdp −SdT T=const
dG=Vdp PV=RT
dG=RTdp/p ΔG=RT ln(p/p0)
G° is defined at p0=1 atm, so that ΔG=G −G°=RT ln(p/1) → Gi=Gi°+RT lnpi
∑(vi(G°i+RT ln(pC pD))prod − ∑(vi (G°i+RT ln(pA pB))reac=0
∑(viG°i)prod − ∑(vi G°i)reac= −[∑(viRT ln(pC pD))prod − ∑(vi RT ln(pA pB))reac]
𝜈𝜈𝑐𝑐 𝜈𝜈𝐷𝐷 𝜈𝜈 𝜈𝜈
𝑝𝑝𝑐𝑐 ⁄𝑎𝑎𝑎𝑎𝑎𝑎 𝑝𝑝𝐷𝐷 ⁄𝑎𝑎𝑎𝑎𝑎𝑎 𝑝𝑝𝑐𝑐 𝐶𝐶 𝑝𝑝𝐷𝐷𝐷𝐷
Δ𝐺𝐺 0 = −𝑅𝑅𝑅𝑅 ln 𝜈𝜈𝐴𝐴 𝜈𝜈𝐵𝐵
= − 𝑅𝑅𝑅𝑅 ln 𝜈𝜈 𝜈𝜈
𝑝𝑝𝐴𝐴 ⁄𝑎𝑎𝑎𝑎𝑎𝑎 𝑝𝑝𝐵𝐵 ⁄𝑎𝑎𝑎𝑎𝑎𝑎 𝑝𝑝𝐴𝐴𝐴𝐴 𝑝𝑝𝐵𝐵𝐵𝐵
𝜈𝜈 𝜈𝜈
𝑝𝑝𝑐𝑐 𝐶𝐶 𝑝𝑝𝐷𝐷𝐷𝐷
– By definition: 𝐾𝐾𝑝𝑝 = 𝜈𝜈 𝜈𝜈 ΔG0 = − RT ln Kp
𝑝𝑝𝐴𝐴𝐴𝐴 𝑝𝑝𝐵𝐵𝐵𝐵

Equilibrium constant, Kc, and Gibbs free energy ΔG

Ideal solution (liquid and solid) Pi - vapor pressure of component i
Raoult’s law pi=xipi* or xi=pi / pi* where xi - mole fraction of component i in solution
Pi* - equil. vapor pressure of pure component i
Thus for a solution we can also write Gi = (Gi° + RT ln xi) (compare to gas
Gi=Gi°+RT lnpi) which lead to, in a similar way, the relation between ΔG and Kc,
𝜈𝜈𝐶𝐶 𝜈𝜈𝐷𝐷 𝜈𝜈𝐶𝐶 𝐷𝐷 𝜈𝜈𝐷𝐷
𝑥𝑥𝑐𝑐 𝑥𝑥𝐷𝐷 𝐶𝐶
Δ𝐺𝐺 0 = −𝑅𝑅𝑅𝑅 ln 𝜈𝜈𝐴𝐴 𝜈𝜈𝐵𝐵 = −𝑅𝑅𝑅𝑅 ln 𝜈𝜈𝐴𝐴 𝐵𝐵 𝜈𝜈𝐵𝐵 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑐𝑐
𝑥𝑥𝐴𝐴 𝑥𝑥𝐵𝐵 𝐴𝐴
Summary of G calculation for ideal gas and solution
• For a pure substance at constant T and p, G = G°+ RT ln p (1)
• For a mixture of ideal gas at const T and p, G = ∑Gi = ∑(Gi°+ RT ln pi) (2-1)
• For a mixture of ideal solution at const T and p, G = ∑Gi = ∑(Gi°+ RT ln xi) (2-2)
 For a situation that a mixture (gas or solution) under concern is not ideal,
the pi or xi cannot be related to G by expressions (2-1) & (2-2). How do you
calculate G?

Real mixture (Non ideal substances)

For a real gas: pi,real ≠ pi,ideal, we define the effective pressure (called fugacity) f,
𝑝𝑝
𝑓𝑓𝑖𝑖 = 𝑖𝑖,𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟�𝑝𝑝𝑖𝑖,𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 or pi,real = fi pi,ideal.
For a real solution: : pi,vap,real ≠ pi,vap,ideal, we define the effective concentration, ai,
𝑝𝑝
a is called activity : 𝑎𝑎𝑖𝑖 = 𝑖𝑖,𝑣𝑣𝑣𝑣𝑣𝑣,𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟�𝑝𝑝𝑖𝑖,𝑣𝑣𝑣𝑣𝑣𝑣,𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 or pi,vap,real = ai pi,vap,ideal.
– Chemical potential, μ
Using the same relation of G with pi and xi for ideal gas and solution, but G is
replaced by a new term, μ, called chemical potential , representing the non-
ideal situation
ideal gas Gi= Gi°+RT lnPi real gas: μi = μi°+ RT ln pi,real = μi°+RT ln fipi,ideal
ideal solution Gi=Gi°+RT ln xi real solution: μi= μi°+RT lnxi,real = μi°+RT ln aixi,ideal
 Values of f and a for real gases and solutions can be found from literature
 Chemical potential can also be used to describe an ideal gas or solution, i.e.
G = μ. i.e. for ideal gas μi = μi°+ RT ln pi and for ideal solution μi= μi°+RT ln xi

A chemical reaction, if in equilibrium (Δμ = 0)

vAA + vBB ⇄ vCC + vDD
𝜈𝜈 𝜈𝜈
𝑝𝑝𝑐𝑐 𝐶𝐶 𝑝𝑝𝐷𝐷𝐷𝐷
ideal gas Δ𝐺𝐺 0 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑝𝑝 or Δ𝜇𝜇0 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑝𝑝 where 𝐾𝐾𝑝𝑝 = 𝜈𝜈 𝜈𝜈
𝑝𝑝𝐴𝐴𝐴𝐴 𝑝𝑝𝐵𝐵𝐵𝐵
𝜈𝜈 𝜈𝜈 𝜈𝜈 𝜈𝜈 𝜈𝜈 𝜈𝜈
𝑓𝑓𝑐𝑐 𝐶𝐶 𝑓𝑓𝐷𝐷 𝐷𝐷 𝑝𝑝𝑐𝑐 𝐶𝐶 𝑝𝑝𝐷𝐷𝐷𝐷 𝑓𝑓𝑐𝑐 𝐶𝐶 𝑓𝑓𝐷𝐷 𝐷𝐷
real gas Δ𝜇𝜇0 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑓𝑓 where 𝐾𝐾𝑓𝑓 = 𝜈𝜈 𝜈𝜈 𝜈𝜈 𝜈𝜈 = 𝜈𝜈 𝜈𝜈 𝐾𝐾𝑝𝑝
𝑓𝑓𝐴𝐴 𝐴𝐴 𝑓𝑓𝐵𝐵 𝐵𝐵 𝑝𝑝𝐴𝐴𝐴𝐴 𝑝𝑝𝐵𝐵𝐵𝐵 𝑓𝑓𝐴𝐴 𝐴𝐴 𝑓𝑓𝐵𝐵 𝐵𝐵
𝐶𝐶 𝜈𝜈𝐶𝐶 𝐷𝐷 𝜈𝜈𝐷𝐷
ideal solution Δ𝐺𝐺 0 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑐𝑐 or Δ𝜇𝜇0 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑐𝑐 where 𝐾𝐾𝑝𝑝 = 𝜈𝜈𝐴𝐴 𝐵𝐵 𝜈𝜈𝐵𝐵
𝐴𝐴
𝜈𝜈 𝜈𝜈 𝜈𝜈 𝜈𝜈
𝑎𝑎𝑐𝑐 𝐶𝐶 𝑎𝑎𝐷𝐷𝐷𝐷 𝐶𝐶 𝜈𝜈𝐶𝐶 𝐷𝐷 𝜈𝜈𝐷𝐷 𝑎𝑎𝑐𝑐 𝐶𝐶 𝑎𝑎𝐷𝐷𝐷𝐷
real solution Δ𝜇𝜇0 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑎𝑎 where 𝐾𝐾𝑎𝑎 = 𝜈𝜈 𝜈𝜈 𝜈𝜈𝐴𝐴 𝐵𝐵 𝜈𝜈𝐵𝐵 = 𝜈𝜈 𝜈𝜈 𝐾𝐾𝑐𝑐
𝑎𝑎𝐴𝐴𝐴𝐴 𝑎𝑎𝐵𝐵𝐵𝐵 𝐴𝐴 𝑎𝑎𝐴𝐴𝐴𝐴 𝑎𝑎𝐵𝐵𝐵𝐵
When solids or liquids are present either as reactants or products, their vapour
pressures, at constant T, are usually constant - thus can be included in the Kp
without appearing in the expression.
e.g. CaCO3(s) = CaO(s) + CO2 (g) Kp = pCaO pCO2/pCaCO3 ⇒ Kp’=PCO2

The equilibrium constant, K, is a function of temperature

Δ𝐺𝐺 0 Δ𝜇𝜇0
Δ𝐺𝐺 0 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾 ⇒ 𝐾𝐾 = exp − or Δ𝜇𝜇0 = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾 ⇒ 𝐾𝐾 = exp −
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅
The effect of inert on the equilibrium composition - depending on the reaction
stoichiometry : Δv = vC + vD - vA - vB
Δv < 0 : adding an inert cause the equilibrium to shift to more reactants
Δv = 0 : adding an inert has no effect on the equilibrium composition
Δv > 0 : adding an inert push the equilibrium to shift to more products
When Δv > 0, a high p push the equilibrium to the direction of more
completion, and visa verse
The expression of equilibrium constant depends on the way reaction equation is written
– For a reverse reaction its equilibrium constant
vAA + vBB ⇄ vCC + vDD vCC + vDD ⇄ vAA + vBB
– For reaction equation written with different stoichiometry coefficient
2NO(g) + O2(g) ⇄ 2NO2(g) NO(g) + ½ O2(g) ⇄ NO2(g)
The expression of equilibrium constant depends on the way reaction equation is written
– For a reverse reaction its equilibrium constant
vAA + vBB ⇄ vCC + vDD vCC + vDD ⇄ vAA + vBB
𝜈𝜈 𝜈𝜈 𝜈𝜈 𝜈𝜈 𝜈𝜈 𝜈𝜈 −1
𝑝𝑝𝐶𝐶𝐶𝐶 𝑝𝑝𝐷𝐷𝐷𝐷 𝑝𝑝𝐴𝐴𝐴𝐴 𝑝𝑝𝐵𝐵𝐵𝐵 𝑝𝑝𝐶𝐶 𝐶𝐶 𝑝𝑝𝐷𝐷𝐷𝐷 −1
𝐾𝐾𝑝𝑝,𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 = 𝜈𝜈 𝜈𝜈 , 𝐾𝐾𝑝𝑝,𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝜈𝜈 𝜈𝜈 = 𝜈𝜈 𝜈𝜈 = 𝐾𝐾𝑝𝑝,𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
𝑝𝑝𝐴𝐴𝐴𝐴 𝑝𝑝𝐵𝐵𝐵𝐵 𝑝𝑝𝐶𝐶 𝐶𝐶 𝑝𝑝𝐷𝐷𝐷𝐷 𝑝𝑝𝐴𝐴𝐴𝐴 𝑝𝑝𝐵𝐵𝐵𝐵
–For reaction equation written with different stoichiometry coefficient
2NO(g) + O2(g) ⇄ 2NO2(g) NO(g) + ½ O2(g) ⇄ NO2(g)
2
𝑝𝑝𝑁𝑁𝑁𝑁 𝑝𝑝𝑁𝑁𝑁𝑁2 1/2
𝐾𝐾𝑝𝑝 = 2 2 , 𝐾𝐾′𝑝𝑝 = 1/2
= 𝑃𝑃
𝑝𝑝
𝑝𝑝𝑁𝑁𝑁𝑁 𝑃𝑃𝑂𝑂2 𝑃𝑃𝑁𝑁𝑁𝑁 𝑝𝑝𝑂𝑂2

Activities of Solids and Pure Liquids
• α(solid) = 1 and α(pure liquid) = 1 (!!!)

• Illustration: Express the equilibrium constant for the heterogeneous reaction
NH4Cl(s) ↔ NH3(g) + HCl(g)
• Answer:
In term of fugacity (i.e. thermodynamic equilibrium constant):
Kp =
In term of molar fraction (this one is not a thermodynamic equilibrium
constant): Kx =

Estimate reaction compositions at
equilibrium
• Example 1: Given the standard Gibbs energy of reaction H2O(g) → H2(g) +
1/2O2(g) at 2000 K is + 135.2 kJ mol-1, suppose that steam at 200 kpa is
passed through a furnace tube at that temperature. Calculate the mole
fraction of O2 present in the output gas stream.
• Solution: (details will be discussed in class)
lnK = - (135.2 x 103 J mol-1)/(8.3145 JK-1mol-1 x 2000K)
= - 8.13037
K = 2.9446 x 10-4
1/2
𝑝𝑝𝑂𝑂2 /𝑝𝑝𝜃𝜃 𝑝𝑝𝐻𝐻2 𝑝𝑝𝜃𝜃
𝐾𝐾 = 𝑝𝑝𝐻𝐻2 𝑂𝑂 𝑝𝑝𝜃𝜃
ptotal = 200 kpa

assuming the mole fraction of O2 equals x
pO2 = x ptotal,
pH2 = 2(x ptotal)
pH2O = ptotal – pO2 – pH2 = (1-3x) ptotal
Equilibrium in biological systems
Biological standard state: pH = 7.

For a reaction: A + vH+(aq) ↔ P
𝜃𝜃
𝑏𝑏𝑃𝑃
Δ𝑟𝑟 𝐺𝐺 = Δ𝑟𝑟 𝐺𝐺 + 𝑅𝑅𝑅𝑅 ln 𝜈𝜈
𝑏𝑏𝐴𝐴 𝑏𝑏𝐻𝐻+
1 𝑏𝑏𝑃𝑃
Δ𝑟𝑟 𝐺𝐺 = Δ𝑟𝑟 𝐺𝐺 𝜃𝜃 + 𝑅𝑅𝑅𝑅 ln + 𝑅𝑅𝑅𝑅 ln
𝐻𝐻+ 𝜈𝜈 𝑏𝑏𝐴𝐴
the first two terms of the above equation form ΔrG‡
ΔrG‡ = ΔrGθ + 7 vRT ln10,
ΔrG‡ is defined as Standard reaction Gibbs energy for biochemical systems
A better practice is to transfer the above equation into
ΔrGθ = ΔrG‡ − 7vRT ln10,
and then recognizes v is the stoichiometric number of H+.

Equilibrium in biological systems
Example: For a particular reaction of the form A → B + 2H+ in aqueous

solution, it was found that ΔrGθ = 20kJ mol-1 at 28oC. Estimate the value of ΔrG‡.
Solution:
ΔrG‡ = ΔrGθ − 7vRT ln10
here the stoichiometric number of H+ is 2, i.e. v = 2
ΔrG‡ = 20 kJ mol-1 − 7(2)(8.3145x10-3 kJ K-1mol-1)x(273+ 28K) ln10
= 20 kJ mol-1 − 80.676 kJ mol-1
= − 61 kJ mol-1
(Notably, when measured with the biological standard, the standard Gibbs
energy of reaction becomes negative.!
A transition from endergonic to exergonic process. )

Molecular Interpretation of equilibrium
Two factors affect the thermodynamic equilibrium constant:

(1) Enthalpy, and (2) Entropy.
Boltzmann distribution is independent of the nature of the particle.
Response of equilibria to reaction
conditions
The response of equilibria to reaction conditions
• Equilibria may respond to changes in pressure, temperature, and
concentrations of reactants and products.
• The equilibrium constant is not affected by the presence of a catalyst.
How equilibria respond to pressure?
• The thermodynamic equilibrium constant K is a function of the standard
reaction Gibbs energy, ΔrGθ .
• Standard reaction Gibbs energy ΔrGθ is defined at a single standard
pressure and thus is independent of the pressure used in a specific reaction.
• The thermodynamic equilibrium constant is therefore independent of
reaction pressure. Such a relationship can be expressed as:
𝜕𝜕𝐾𝐾
=0
𝜕𝜕𝑝𝑝 𝑇𝑇

conditions
• Although the thermodynamics equilibrium constant K is independent of
pressure, it does not mean that the equilibrium composition is independent
of the pressure!!!
• Example: Consider a gas phase reaction 2A(g) ↔ B(g)
assuming that the mole fraction of A equals xA at equilibrium,
then xB = 1.0 – xA,
1.0 − 𝑥𝑥𝐴𝐴 𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 /𝑝𝑝𝜃𝜃 (1.0 − 𝑥𝑥𝐴𝐴 )𝑝𝑝𝜃𝜃
𝐾𝐾 = =
𝑥𝑥𝐴𝐴 𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 /𝑝𝑝𝜃𝜃 2 𝑥𝑥𝐴𝐴2 𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
because K does not change, xA must change in response to any
variation in ptotal!!!

Le Chatelier’s Principle
A system at equilibrium, when subject to a

disturbance, responds in a way that tends
to minimize the effect of the disturbance.
The above statement suggests that if the
total pressure of a system is increased, the
system will shift to the direction that will
have smaller number of molecules, i.e.
smaller pressure.
3H2(g) + N2(g) ↔ 2NH3(g).

Le Chatelier’s Principle
Example: Predict the effect of an increase in pressure on the Haber reaction,

3H2(g) + N2(g) ↔ 2NH3(g).
Solution: According to Le Chatelier’s Principle, an increase in pressure will favor
the product.
prove:
2
𝑝𝑝𝑁𝑁𝐻𝐻3
2
𝑥𝑥𝑁𝑁𝐻𝐻 𝑝𝑝2
3 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
2
𝑥𝑥𝑁𝑁𝐻𝐻3
𝐾𝐾𝑥𝑥
𝐾𝐾 = = = =
𝑝𝑝𝑁𝑁2 𝑝𝑝𝐻𝐻3 2 3
𝑥𝑥𝑁𝑁2 𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑥𝑥𝐻𝐻32 𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑥𝑥𝑁𝑁2 𝑥𝑥𝐻𝐻32 𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
2 2
𝑝𝑝𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
Therefore, to keep the thermodynamic equilibrium constant K unchanged, the
equilibrium mole fractions Kx must change by a factor of 4 if the pressure ptotal is
doubled.

conditions
The response of equilibria to temperature
According to Le Chatelier’s Principle:
Exothermic reactions: increased temperature favors the reactants.
Endothermic reactions: increased temperature favors the products.
The van’t Hoff equation:
𝑑𝑑 ln 𝐾𝐾 ∆𝑟𝑟 𝐻𝐻𝜃𝜃
𝑎𝑎 =
𝑑𝑑𝑑𝑑 𝑅𝑅𝑇𝑇 2
𝑏𝑏 =−
𝑑𝑑(1/𝑇𝑇 ) 𝑅𝑅

Derivation of the van’t Hoff equation
∆𝑟𝑟 𝐺𝐺 𝜃𝜃
ln 𝐾𝐾 = −
𝑅𝑅𝑅𝑅
• Differentiate ln K with respect to temperature
𝑑𝑑 ln 𝐾𝐾 1 𝑑𝑑(∆𝑟𝑟 𝐺𝐺 𝜃𝜃 /𝑇𝑇)
=−
𝑑𝑑𝑑𝑑 𝑅𝑅 𝑑𝑑𝑑𝑑
• Using Gibbs-Helmholtz equation
𝑑𝑑(∆𝑟𝑟 𝐺𝐺 𝜃𝜃 /𝑇𝑇) ∆𝑟𝑟 𝐻𝐻𝜃𝜃
=− 2
𝑑𝑑𝑑𝑑 𝑇𝑇
thus
=
𝑑𝑑𝑑𝑑 𝑅𝑅𝑇𝑇 2
• Because d(1/T)/dT = −1/T2:
=−
𝑑𝑑(1/𝑇𝑇 ) 𝑅𝑅

van’t Hoff equation
For an exothermic reaction, ΔrHθ < 0,

𝑑𝑑 ln 𝐾𝐾
thus 𝑑𝑑𝑑𝑑 < 0, suggesting that
increasing the reaction temperature
will reduce the equilibrium constant.

Applications of the van’t Hoff equation
• Provided the reaction enthalpy, ΔrHθ, can be assumed to be independent of

temperature, eqn. 7.23b (or 9.26b in 7th edition) illustrates that a plot of – lnK
against 1/T should yield a straight line of slope ΔrHθ/R .
• Example: The data below show the equilibrium constant measured at
different temperatures. Calculate the standard reaction enthalpy for the
system.
T/K 350 400 450 500
K 3.94x10-4 1.41x10-2 1.86x10-1 1.48
Solution:
1/T 2.86x10-3 2.50x10-3 2.22x10-3 2.00x10-3
− ln K 7.83 4.26 1.68 -0.39


Self-test : The equilibrium constant of the reaction

2SO2(g) + O2(g) ↔ 2SO3(g)
is 4.0x1024 at 300K, 2.5x1010 at 500K, and 2.0x104 at 700K. Estimate the
reaction enthalpy at 500K.
Solution : discussion:
1. Do we need a balanced reaction equation here?
2. What can be learned about the reaction based on the information
provided?
3. Will the enthalpy become different at 300K or 700K?

K at different temperatures
The equilibrium constant at temperature T2 can be obtained in terms of the

known equilibrium constant K1 at T1.
Since the standard reaction enthalpy is also a function of temperature, when
integrating the equation 9.26b from T1 to T2, we need to assume that ΔrHө is
constant within that interval.
𝐾𝐾2 1/𝑇𝑇2
∆𝑟𝑟 𝐻𝐻𝜃𝜃 1
� 𝑑𝑑 ln 𝐾𝐾 = − � 𝑑𝑑
𝐾𝐾1 1/𝑇𝑇1 𝑅𝑅 𝑇𝑇
∆𝑟𝑟 𝐻𝐻𝜃𝜃 1 1
so ln 𝐾𝐾2 − ln 𝐾𝐾1 =− − (7.24)
𝑅𝑅 𝑇𝑇2 𝑇𝑇1
Equation 7.24 provides a non-calorimetric method of determining standard

reaction enthalpy. (Must keep in mind that the reaction enthalpy is actually
temperature-dependent!)

K at different temperatures
Example, The Haber reaction

N2(g) + 3H2(g) ↔ 2NH3(g)
At 298 K, the equilibrium constant K = 6.1x105. The standard enthalpy of
formation for NH3 equals -46.1 kJ mol-1. What is the equilibrium constant at
500K?
Answer: First, calculate the standard reaction enthalpy, ΔrH ө,
ΔrH ө = 2ΔfH ө(NH3) − 3 ΔfH ө(H2) − ΔfH ө(N2)
= 2(− 46.1) – 3(0) − 1(0)
= − 92.2 kJ mol-1
then ln(K2) – ln(6.1x105) = (−1/8.3145)(− 92.2x103 J mol-1) (1/500 – 1/298)
ln(K2) = − 1.71
K2 = 0.18
Despite the decrease in equilibrium constant as a result of temperature
increase, yet in industrial production it is still operated at an elevated
temperature (kinetics vs thermodynamics)
temperature dependence of the
equilibrium constant
Practical Applications of the Knowledge of the temperature dependence of the
equilibrium constant
(i) M(s) + 1/2O2(g) → MO(s)
(ii) 1/2C(s) + 1/2O2(g) → 1/2CO2(g)
(iii) C(s) + 1/2O2(g) → CO(g)
(iv) CO(g) + 1/2O2(g) → CO2(g)
This is carried out based on two criteria
(1) Gibbs energy is a state quantity and
thus can be added or subtracted directly.
(2) When the standard reaction Gibbs
energy is negative, the forward reaction
is favored (i.e. K > 1).
Standard reaction Gibbs energy is
sometimes referred as Free Gibbs energy.


Atkins & de Paula: Elements of Physical Chemistry 6e: Chapter 7: Chemical Equilibria: The Principles

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Atkins & de Paula: Elements of Physical Chemistry 6e: Chapter 7: Chemical Equilibria: The Principles

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Atkins & de Paula

Atkins & de Paula: Elements of

Chapter 7: Chemical equilibria:

©Oxford University Press, 2013. All rights reserved.

• Reaction equation for A reacting with B forming C and D

Atkins & de Paula: Elements of Physical Chemistry 6e

Atkins & de Paula: Elements of Physical Chemistry 6e

Entropy definition dS = dQ/T meaning: at T, change of S is proportional to

Atkins & de Paula: Elements of Physical Chemistry 6e

The enthalpy change in a reaction at T, p

Atkins & de Paula: Elements of Physical Chemistry 6e

Gibbs Free Energy definition

Atkins & de Paula: Elements of Physical Chemistry 6e

Atkins & de Paula: Elements of Physical Chemistry 6e

Atkins & de Paula: Elements of Physical Chemistry 6e

Example 1: N2(g) + 3H2(g) ↔ 2NH3(g)

Example 2: CH4(g) + Cl2(g) ↔ CHCl3(l) + HCl(g),

Variation of Gibbs energy during a reaction process

Atkins & de Paula: Elements of Physical Chemistry 6e

Atkins & de Paula: Elements of Physical Chemistry 6e

Molecular interpretation of the minimum in the reaction Gibbs energy

Gibbs energy of the system

Gibbs energy of a system consisting

Atkins & de Paula: Elements of Physical Chemistry 6e

Consider the reaction : A ↔ B

Perfect gas equilibrium : A(g) ↔ B(g)

Atkins & de Paula: Elements of Physical Chemistry 6e

Atkins & de Paula: Elements of Physical Chemistry 6e

Justification of the equation : dG = ∑μjdnj

Atkins & de Paula: Elements of Physical Chemistry 6e

Again, we use K to denote the reaction quotient at an equilibrium point,

Example: calculate the quotient for the reaction: A + 2B ↔ 3C + 4D

Atkins & de Paula: Elements of Physical Chemistry 6e

Example 1. Consider a hypothetical equilibrium reaction

Atkins & de Paula: Elements of Physical Chemistry 6e

Atkins & de Paula: Elements of Physical Chemistry 6e

Atkins & de Paula: Elements of Physical Chemistry 6e

For a chemical reaction vAA + vBB ⇄ vCC + vDD

Atkins & de Paula: Elements of Physical Chemistry 6e

Chemical reaction equilibrium

– Any change of reaction parameters will redefine a system leading to a new

Atkins & de Paula: Elements of Physical Chemistry 6e

Definition of equilibrium constant, K

– liquid-solid Cu(OH)2(s) ⇄ Cu2+(aq)+2OH- (aq) 𝐾𝐾𝑐𝑐 = 𝐶𝐶𝐶𝐶2+ 𝑂𝑂𝐻𝐻 − 2

– gas-liquid NH3(g)+H2O(l) ⇄ NH4OH(aq) 𝐾𝐾𝑝𝑝 = 1/𝑃𝑃𝑁𝑁𝑁𝑁3

Equilibrium constant, Kp, and Gibbs free energy DG

Atkins & de Paula: Elements of Physical Chemistry 6e

Equilibrium constant, Kc, and Gibbs free energy ΔG

Atkins & de Paula: Elements of Physical Chemistry 6e

Real mixture (Non ideal substances)

Atkins & de Paula: Elements of Physical Chemistry 6e

A chemical reaction, if in equilibrium (Δμ = 0)

Atkins & de Paula: Elements of Physical Chemistry 6e

The equilibrium constant, K, is a function of temperature

Atkins & de Paula: Elements of Physical Chemistry 6e

• α(solid) = 1 and α(pure liquid) = 1 (!!!)

Atkins & de Paula: Elements of Physical Chemistry 6e

ptotal = 200 kpa

Biological standard state: pH = 7.

Atkins & de Paula: Elements of Physical Chemistry 6e

Example: For a particular reaction of the form A → B + 2H+ in aqueous

Atkins & de Paula: Elements of Physical Chemistry 6e

Two factors affect the thermodynamic equilibrium constant: