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Thermodynamics and Chemical Equilibrium

This document provides an overview of thermodynamics and chemical equilibrium. It discusses the first and second laws of thermodynamics, Gibbs free energy, and how the equilibrium constant relates these concepts. Examples are provided for calculating standard enthalpies, Gibbs free energies, and equilibrium constants of reactions. Le Châtelier's principle and how temperature changes can shift chemical equilibria are also summarized.

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210 views40 pages

Thermodynamics and Chemical Equilibrium

This document provides an overview of thermodynamics and chemical equilibrium. It discusses the first and second laws of thermodynamics, Gibbs free energy, and how the equilibrium constant relates these concepts. Examples are provided for calculating standard enthalpies, Gibbs free energies, and equilibrium constants of reactions. Le Châtelier's principle and how temperature changes can shift chemical equilibria are also summarized.

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Dotan Nutod
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UNIT 2.

Thermodynamics and chemical equilibrium : Class notes

1. Review of systems and laws of thermodynamics


2. Gibbs Free Energy
3. Equilibrium Constant

Lecture 2
Dr. Clare Robinson
Examples of open and closed systems
Review of laws of thermodynamics
First law of thermodynamics: any change in heat of a system or work
done by the system changes the internal energy of a system
dU = dQ + dW

For constant pressure system the change in enthalpy (extensive


property) is equal to heat adsorbed by the system
dH = dQ

Tells us energy is conserved but does not tell us about spontaneous or


reversibility of a process (i.e. chemical reaction)
Review of laws of thermodynamics
Second law of thermodynamics:
Systems move from a more ordered state to more random state
Entropy (S) is a measure of disorder

A process will occur (spontaneous) if it increases the total entropy of the universe:
S total
0
t
For a reversible process:
Stotal
=0
t
But you need to consider change in entropy (S) of the universe (system and surroundings)
Example for Second Law of Thermodynamics
Ice dissolving is an example of the second law of thermodynamics

BUT why then does water freeze below 0 C?


Examples of extensive and intensive properties
Intensive quantity: independent of amount of material in a system (not additive)

Extensive quantity: dependent on amount of material in a system (additive)


Gibbs Free Energy (G)
Gibbs free energy: links the first and second laws by combining enthalpy and
entropy
G= H – TSsys

• Measure of reversibility and spontaneity


dG = 0 for reversible reactions
dG  0 for spontaneous reactions

• Both S and G are related to reversibility and spontaneity but advantage of G is that
it only considers changes in the system and not also from surroundings
Defining zero (reference) levels
• H = 0 and G = 0 for each element in its standard state when the element is in
the physical state (g, l or s) at which it is most stable under standard conditions
(25  C and 1 bar)

• Entropy approaches 0 as T approaches 0K (Third law of thermodynamics)

• Parameters at standard state are indicated by superscript:


• e.g., H, G, S
Properties of formation
• Thermodynamic properties for the formation of chemical species
from elements at their standard states are tabulated

• Partial molar enthalpy of formation

• Partial molar entropy of formation

• Partial molar Gibbs energy of formation


Example 1: Enthalpy of reaction
Calculate heat released if methane gas is combusted:
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g)
Example 2: Enthalpy of reaction
Calculate heat released if silver chloride (AgCl(s)) dissolves:
Standard enthalpy of reaction
∆𝐻𝑟° = °
𝑣𝑖 𝐻𝑓,𝑖 Standard enthalpy of reaction
(kJ/mol)

• Subscript f denotes formation (chemical species at its standard state)

• 𝜈i = reaction stochiometric coefficient of species i


Convention: 𝜈i is negative for reactants and positive for products

• H i = partial molar enthalpy of species i (kJ/mol)


Standard enthalpy of reaction
In general, for reaction:
aA+bB = cC+dD

° ° ° ° ° °
∆𝐻𝑟 = 𝜈𝑖 𝐻𝑓,𝑖 = 𝑐𝐻𝑓,𝐶 + 𝑑𝐻𝑓,𝐷 − 𝑎𝐻𝑓,𝐴 − 𝑏𝐻𝑓,𝐵

Each term on right hand side can be found in standard thermodynamic tables
(e.g., Appendix 3, Stumm and Morgan)
What do these mean?
• ∆𝐻𝑟° < 0 reaction is exothermic (heat is generated)

°
• ∆𝐻𝑟 >0 reaction is endothermic (heat is absorbed)
Standard Gibbs free energy and entropy of reaction

°
∆𝐺𝑟° = 𝑣𝑖 𝐺𝑓,𝑖 Standard Gibbs free energy of reaction (kJ/mol)

°
∆𝑆𝑟° = 𝑣𝑖 𝑆𝑓,𝑖 Standard entropy of reaction (kJ/mol)

Based on definition of G:
∆𝐺𝑟° = ∆𝐻𝑟° − 𝑇∆𝑆𝑟°
What do these mean?
• ∆𝑆𝑟° < 0
• ∆𝑆𝑟° > 0

°
• ∆𝐺𝑟<0
°
• ∆𝐺𝑟 >0

What is required for a reaction to be reversible?


Example 1: Gibbs free energy of reaction
• What is the standard Gibbs free energy of reaction for (AgCl(s)) dissolution?
What does this mean?
Gibbs free energy and reactions
What if the species in a reaction are not at standard state?

For reaction, a A + b B = c C + d D

Gr = Gr + RT ln
o  c
C D  d

A B
a b
Equilibrium constant
• At equilibrium: ∆𝐺𝑟 = 0

0 = Gro + RT ln
C c
Dd
So this is also

A B
Constant for a a b constant at
given reversible equilibrium
reaction

• Equilibrium constant defined as:


c d 0 c d
Keq =
{C} {D} G = − RT
r
Q=
{C
ln K}eq {D}
a b a b
{ A} {B} { A} {B}
 G 0r 
K eq = exp  − 
 RT 
 
Example 2: Gibbs free energy of reaction
CaCO3(s) = Ca2+ + CO32-
Calculate the equilibrium constant (Keq)?
Example 3: Gibbs free energy of reaction:
CaCO3(s) = Ca2+ + CO32-
with [Ca2+] = 0.1 mM, [CO32-] = 1 M, 0.1 M NaCl
Calculate Gibbs free energy of reaction ( ∆𝐺𝑟)?
Working with reactions
• For a generic reaction:
aA+bB=cC+dD
C D  C    D 
c d c c d d

Keq = = a C D

 A B  A  A  B  B
a b a b b

• Write equilibrium expression for:


Pb(OH)2(s) = Pb2+ + 2 OH-
Examining Equilibrium Constants
Magnitude of Keq
Keq >> 1
Keq > 1
Keq < 1
Keq << 1
Reaction Quotient
Simplest method to determine which way a reaction will proceed is to calculate the reaction
quotient (Q)
aA+bB = cC+dD
{C}c {D}d {C}c {D}d
Keq = a b
Q= a b
{ A} {B} { A} {B}
Keq dictates the relationship Q reflects the conditions
of products and reactants at of the system at a given time.
equilibrium

Q = K eq
Q  K eq
Q  K eq
Example: Reaction Quotient
A water sample has a Ca2+ concentration of 20 mg/L and a F- concentration of 0.1
mg/L. Calculate the reaction quotient (Q).

Will CaF2(s) dissolve or precipitate, or is water in equilibrium with respect to CaF2(s)?

Given: Ksp = 5.14 x 10-12


Ignore activity corrections
Manipulating equilibrium expressions: Adding reactions

S(s) + O2(g) = SO2(g)


SO2(g) + 1/2 O2(g) = SO3(g)

NET EQUATION
S(s) + 3/2 O2(g) = SO3(g)
Manipulating equilibrium expressions: Changing coefficients

S(s) + 3/2 O2(g) = SO3(g)

2 S(s) + 3 O2(g) = 2 SO3(g)


Manipulating equilibrium expressions: Changing direction
S(s) + O2(g) = SO2(g)

SO2(g) = S(s) + O2(g)


Example: Manipulating equilibrium expressions

Calculate Keq for reaction


Pb(OH)2(s) + 2 H+ = Pb2+ + 2 H2O

Given that :
Pb(OH)2(s) = Pb2+ +2 OH- Ksp = 10-10.9
Keq = 1/Kw=1014
H+ + OH- = H2O
Le Châtelier’s Principle

If a system at equilibrium is disturbed by


a change in temperature, pressure, or
the concentration of one of the
chemical species, the system will shift
its position to counteract the effect of
the disturbance. N2 + 3 H2 = 2 NH3
Effect of Temperature Change
Temperature has a significant effect on most reactions

Reaction rates generally increase with an increase in temperature (i.e., increase in rate
constant). Therefore, equilibrium is established sooner.

Equilibrium constant Keq also varies with temperature


Effect of Temperature Change
• For endothermic reactions increasing the temperature is analogous to adding more
reactant
" heat"+ reactants = products (H is positive)

Increasing temperature causes equilibrium to shift to right to counteract change.

“heat” does not appear in the equilibrium constant expression but this change
results in a larger Keq
Effect of Temperature Change
For exothermic reactions increasing the temperature is analogous to adding more
product
reactants = products + " heat" (H is negative)

Increasing temperature causes equilibrium to shift to left to counter the change.

“heat” does not appear in the equilibrium-constant expression but this change results in
a smaller K

35
Effect of Temperature Change: Example
CO(g) + 3H2(g) = CH4(g) + H2O(g)

Is this reaction exothermic or endothermic?

36
Effect of the temperature on Keq
• Derived from van’t Hoff equation
standard (0)
enthalpy of the
0
H  1 1 
reaction
K eq ,T2
=  − 
r
ln
K eq ,T1 R  T1 T2 
  H  1 1 
0

= K eq ,T1 exp   − 
r
K eq ,T2
 R  T1 T2  
Example: Effect of the temperature on Keq
CaCO3(s) = Ca2+ (aq) + CO32- (aq)

What is Ksp for calcite at T = 278 K?


• Calcium carbonate accumulation in oceans
• More soluble at lower temperature and higher pressure
• What does this means with respect to global carbon cycle?
Example: Le Châtelier’s Principle
2 SO2(g) + O2(g) = 2 SO3(g) ΔHR < 0

Effect on equilibrium mixture when…


(a) O2(g) is added?
(b) reaction is heated?
(c) catalyst is added?
(d) SO3(g) is removed?
(e) total P is increased by adding a noble gas?
(f) volume of container is doubled?

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