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Chemical Equilibrium Clean

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9 views21 pages

Chemical Equilibrium Clean

Uploaded by

andreamcarthur2
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CH6: Chemical

equilibrium
Gibbs energy minimum
• Consider the reaction: A B (isomerization) suppose that dξ of A
converts to B so dnA = -dξ and dnB = +dξ (ξ is called the extend of
reaction). From chapter 5, at constant P and T. so . The reaction
Gibbs energy (ΔrG) can also be defined as the slope of Gibbs energy
with respect to the extend of reaction:
∆ 𝑟 𝐺=𝜇 𝐵 −𝜇 𝐴
• < 0 the forward reaction is spontaneous
• > 0 the reverse reaction is spontaneous
𝜇𝐵 < 𝜇𝐴
• = 0 the reaction is at equilibrium

𝜇𝐵 > 𝜇𝐴

We define reaction quotient (Q):


so
𝜇 𝐵 =𝜇 𝐴
At equilibrium: so and
ξ
Where K is Q calculated at equilibrium
Δ 𝑟 𝐺𝜃 =− 𝑅𝑇𝑙𝑛𝐾

Δ 𝑟 𝐺𝜃
<0
>0
=0
• In general, for a reaction such as ,

Note that activities are dimensionless numbers.

State Measure Approximation for


activity (aJ)
Solute molality mJ/(1 mol/kg)
molarity [J]/(1 mol/L)
Gas phase Partial pressure PJ/(1 bar)
• Consider the reaction CaCO3(s) CaO(s) + CO2(g). Calculate K

DfGθ (CO2(g)) = 394.4 kJ/mol


DfGθ (CaO(s)) = 603.3 kJ/mol
DfGθ (CaCO3(s)) = 1129.1 kJ/mol
• Use the thermodynamic data below to calculate ΔrG for the following
reaction when the partial pressures of NOCl, NO and Cl2 are 2.00 bar,
1.00 × 10-3 bar and 1.00 × 10-3 bar, respectively. Is this reaction
spontaneous in the forward or the reverse direction under these
conditions?
2 NO( g )  Cl2 ( g )  2 NOCl( g )

 f G NO(g) Cl2(g) NOCl(g)


kJ/mol
87.6 0 66.1
• Consider the following reactions

What is the expression for K for each reaction?


The relationship between
equilibrium constants
• Note that any form of concentration is acceptable here!

• If all components are perfect gases,


If all substances have activity coefficient close to 1, then,

• and : change in number of moles of gas


• What is the relationship between K and Kc for the following reaction?
𝑁 2 ( 𝑔 ) +3 𝐻 2 ( 𝑔 ) ⇌ 2 𝑁 𝐻 3 (𝑔)
Molecular interpretation of the
equilibrium constant
𝑆 𝐵 > 𝑆 𝐴Or Δ 𝑟 𝑆 ( 𝐴→ 𝐵 ) >0 𝑆 𝐵 < 𝑆 𝐴Or Δ 𝑟 𝑆 ( 𝐴→ 𝐵 ) <0
𝜃
Δ 𝑟 𝐺 =− 𝑅𝑇𝑙𝑛𝐾

Energy
Energy
Entropy
and
Δ 𝑟 𝐺𝜃 =∆ 𝑟 𝐻 𝜃 − T Δ 𝑟 𝑆𝜃
A B A B
Energy

Δ 𝑟 𝐻 ( 𝐴→ 𝐵 ) < 0 Δ 𝑟 𝐻 ( 𝐴→ 𝐵 ) > 0
Enthalpy

Energy
A
B

A
B
Reaction progress Reaction progress
• Use the following thermodynamic data to calculate K at 298 K
𝑁 2 ( 𝑔 ) +3 𝐻 2 ( 𝑔 ) ⇌ 2 𝑁 𝐻 3 (𝑔)
(kJ/mol) J/(mol K)
H2 130.684
N2 191.16
NH3 -46.11 192.45

Chapter 6A
The response of equilibria to the
conditions (Le Chatelier’s principle)
• and so
so
• If Reaction proceeds towards reactants
• If Reaction proceeds towards products
• Note that K only depends on temperature
• Consider the reaction
How will each of the following change the direction of the process?
a) Addition of NH3
b) Addition of H2
The response to temperature
• Endothermic reactions: increased temperature favors the products,
increases K
• Exothermic reactions: increased temperature favors the reactants,
decreases K
• Van’t Hoff equation: or
• or
• The data below show the temperature variation of the equilibrium
constant of the reaction
Calculate standard reaction enthalpy

T(K) 350 400 450 500


Keq 3.98×10-4 1.41×10-2 1.86×10-1 1.48
T(K) 350 400 450 500
Keq 3.98×10-4 1.41×10-2 1.86×10-1 1.48
ln(Keq) -7.82906 -4.26158 -1.68201 0.392042
1/T (1/K) 0.002857 0.0025 0.002222 0.002
1000*1/T (1/K) 2.857143 2.5 2.222222 2

0 f(x) = − 9.57901639711602 x + 19.595072404357


2 R² = 0.999642770471524
2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3
-1

-2

-3
ln(K)

-4

-5

-6

-7

-8

-9 The slope is -9.6×103 so =-(- 9.6×103)×R= 80 kJ/mol


1000*1/T(1/K)
• For reaction , at 298 K, K=6.1×105 and ΔfHθ (NH3(g)) = -46.1 kJ/mol.
What is K at 500K?
(answer = 0.18)
• Iron metal is produced commercially by reducing iron(III) oxide in iron ore
with carbon monoxide:
• Fe2O3(s) + 3 CO(g) → 2 Fe(s) + 3 CO2(g)
a) Calculate the equilibrium constant for this reaction at 25 °C.
b) Calculate ΔG for a reaction mixture in which and .
c) In which direction is the reaction spontaneous?
Fe2O3(s) CO(g) Fe(s) CO2(g)
ΔH°f(kJ/mol) –824.2 –110.5 0 –393.5
S°[J/(K • mol)] 87.4 197.6 27.3 213.6
• Calculate the ratio of B to A in an equilibrium mixture of A and B?

In which direction will the reaction be spontaneous if PA = 2.01 bar and


PB = 3.55 bar

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