RECALL: Physical Chemistry 1

First law of Thermodynamics: Law of Conservation of Energy

dU = dq + dw

Second law of Thermodynamics: Unidirectionality

dS = dqrev/T

Third Law of Thermodynamics: Entropy of a crystalline solid

Scrystalline0K = 0

* Zeroth Law of Thermodynamics: Thermal equilibrium

System A = System B = System C
U; Internal energy
- Energy associated with the random, disordered motion of molecules

H ≡ U + PV; Enthalpy
- Heat change associated at constant pressure

A ≡ U – TS; Helmholtz energy, “arbeit or work function”

- Maximum work accompanying a process at constant temperature (dwmax = dA)

G ≡ H – TS; G is Gibbs free energy

- Maximum non-expansion (non-PV) work at constant temperature and pressure
DG = wmax - wPV
BASIC EQUATIONS OF THERMODYNAMICS
Exact differentials

dU = TdS – PdV (fundamental equation)

dH = TdS + VdP

dA = - SdT – PdV

dG = VdP - SdT
SUMMARY
State Function Exact Differential Maxwell Relation
U dU = TdS - PdV =-

H dH = TdS + VdP =

A dA = - PdV - SdT =

G dG = VdP - SdT =-
CHEMICAL EQUILIBRIUM
EQUILIBRIUM

- A state in which there are no observable changes as time goes by

- The state wherein the concentrations of the individual reactants and

products remain constant with time

- At the state of equilibrium, there is dynamic motion involved on the

molecules (dynamic equilibrium)
For systems at equilibrium:
rate of forward reaction = rate of reverse reaction
Physical Equilibrium Systems
Chemical Equilibrium Systems
 
Recall that for an ideal gas, the Gibbs free energy changes as the pressure is altered.

(isothermal conditions)

= G2 – G1 =

If the gas is initially at standard state (P = 1 bar), then

= G - Go =

The Gibbs free energy equation at any pressure P (expressed in bars) is

G = Go +

For one mole of a gas, G = Gm so that the molar Gibbs free energy expression becomes

Gm = Go +
 For
one mole of real gases, P therefore, the molar Gibbs free energy equation
becomes

Gm = Gmo + , where f is termed as fugacity

When the fugacity of a real gas undergoes a change, it is already termed as activity
such that
Gm = Gmo + ; wherein = a (activity)

therefore, Gm = G mo +
For ideal gases, Gmo = Go + (in bar)
 

Gm is also known as the chemical potential (Gm = µ), thus, for an ideal gas, the
equation can be rewritten as

µ = µo +

The chemical potential gives the change in the Gibbs energy per unit change in the
number of moles of an ideal gas at constant pressure and temperature.

µA =
REACTION ISOTHERM
For the gas reaction a A (g) + b B (g) = c C (g), the change in G is

DG = c GC – (a GA + b GB)

In terms of the chemical potential

DG = c µC – (a µA + b µB)

The molar Gibbs energy for each of the substances in the reactions are:
GmA = GAo + RT ln (PA)
GmB = GBo + RT ln (PB)
GmC = GCo + RT ln (PC)

* Pressure is expressed in bar

REACTION ISOTHERM
 The molar Gibbs energy for each of the substances in the reactions are:
GmA = GAo + RT ln (PA)
GmB = GBo + RT ln (PB)
GmC = GCo + RT ln (PC)

Thus, the Gibbs free energy change for the reaction is

DG = c [GCo + RT ln (PC)] -

Rearranging,

DG = [c GCo – (a GAo + b GBo)] + RT [c ln (PC) – a ln (PA) – b ln (PB)]

 ln
DG o
REACTION ISOTHERM
DG = [c GCo – (a GAo + b GBo)] + RT [c ln (PC) – a ln (PA) – b ln (PB)]

 ln
DGo

DG = DGo + RT ln
 

Reaction isotherm – gives the free energy change of a reaction when the
reactants and products are not at the standard state.

* Pressure expressed in bar

THE EQUILIBRIUM CONSTANT
If the reaction is at equilibrium, DG = 0, so that

DGo = - RT ln
 

cannot be determined Thermodynamic equilibrium constant Kp

experimentally (can be determined experimentally)

DGo Kp
Spontaneous reaction <0 >1
Non-spontaneous reaction >0 <1
Reaction equilibrium =0 =1
EXERCISE 1
1. Write the equilibrium constant expression for the reaction
N2 (g) + 3H2 (g) 2NH3 (g)

2. Refer to the reaction above. If the equilibrium pressures of the

reactants and products at a certain temperature are
2
PNH = 2.9  10 atm
3

PN = 8.9  101 atm

2

PH = 2.9  10 3 atm
2

What is the value for the equilibrium constant Kp?

[3.9 x 104]
EXERCISE 2
3. For the ozone formation reaction, the change in the standard Gibbs
energy at 25oC is 326.4 kJ mol-1. Calculate the equilibrium constant of this
reaction.
3O2 (g) 2O3 (g)

4. At 25.0oC, the equilibrium constant for the reaction

CO(g) + H2O(g) CO2(g) + H2(g)
is 1.00 x 10-5 and ΔSo is 41.8 J K-1 mol-1. Calculate ΔGo and ΔHo at 25oC.

[6.52 x 10-58; 28.5 kJ mol-1 and 41.0 kJ mol-1]

UNITS OF THE EQUILIBRIUM CONSTANT
Thermodynamic equilibrium constant – one related with DGo, which is denoted by Kpo
- dimensionless quantity

Practical equilibrium constant – denoted by Kp

- has units which depend on the type of reaction it refers to
- has the same value as Kpo

Reaction Unit of Kp
SO2 (g) + ½ O2 (g) SO3 (g) bar1/2
N2O4 (g) 2NO2 (g) bar
CO2 (g) + H2 (g) CO (g) + H2O (g) none
EXERCISE 3
Write the corresponding units for the following reactions:

Reaction Unit
2NOBr (g) 2NO (g) + Br2 (g)
2CH4 (g) C2H6 (g) + H2 (g)
4HCl (g) + O2 (g) 2Cl2 (g) + 2H2O (g)
PROPERTIES OF THE EQUILIBRIUM CONSTANT
1. Kp involves the pressures and the concentrations of the products and the reactants when the system
is at equilibrium.

2. Kp provides an index of the extent to which the reaction proceeds under the given conditions
Kp >> 1, formation of product is favored; K p << 1, formation of reactant is favored; K p = 0, equilibrium state

3. The value for Kp is not affected by changes in concentration or pressure in the equilibrium mixture, as
long as temperature is maintained.

4. The expression for Kp and its value vary with the way the reaction equation is written.

5. The behavior of Kp is different from that of the thermodynamic functions such as DG because of the
logarithmic relationship that exists between the two.

6. If a reaction can be expressed as the sum of two or more reactions, the equilibrium constant for the
overall reaction is given by the product of the equilibrium constants of the individual reactions.
 4. Variation of Kp with how the chemical reaction is written:

Reaction Kp Kp at 525 K

1.92 bar

[0.521 bar-1; 0.271 bar-2]

5. Summary of the behavior of Kpo vs DGo

Kp (reverse) = [Kp (forward)-1]

EXERCISE 4
For the ammonia synthesis reaction N2 (g) + 3H2 (g) 2NH3 (g)
the KP at 500oC is 7.11 x 10-5 bar-2.

Evaluate the KP at 500oC for the following equations:

a) ½ N2 (g) + 3/2 H2 (g) NH3 (g)

b) 2NH3 (g) N2 (g) + 3H2 (g)
c) 6NH3 (g) 3N2 (g) + 9H2 (g)

[8.43 x 10-3 bar-1; 1.41 x 104 bar2; 2.78 x 1012 bar6]

EXERCISE 5

[1.6 x 109; 200]

6. Reactions that are expressed as sums of two or more
elementary steps
EXERCISE 6
The following equilibrium constants have been determined for the ionization of
carbonic acid at 25oC.

a. Write the overall chemical reaction for the ionization of H 2CO3

b. Write the resulting equilibrium constant expression
c. Calculate the equilibrium constant

[2.0 x 10-17]
CONCENTRATION EQUILIBRIUM CONSTANT
-• K  p can also be expressed in terms of concentration terms

In terms of molarity (mol L-1):

Kp = Kc (RT)Dng

where =

In terms of mole fraction, X:

Kp = Kx (P)Dng

where =

*Dn is the difference in the number of moles of products and reactants

EXERCISE 7
For the ammonia synthesis reaction N2 (g) + 3H2 (g) 2NH3 (g): the Kp at
298 K and 1 bar total pressure is 6.0 x 10-5 bar-2

a. What is KC for this reaction?

b. What is KX for this reaction?

[3.60 x 10-8; 6.0 x 10-5]

HOW TO DETERMINE THE EQUILIBRIUM
CONSTANT?
 Determine the concentration or partial pressure of each reactant and
product in equilibrium

 Measure one component, then use stoichiometric relationship

expressed through the balanced chemical equation
How to measure the amount of products or
reactants?
•  The amount (i.e, concentration) of the amounts of products or reactants formed can

be possibly done through non-destructive, physicochemical methods

 Spectrophotometry
 Potentiometry
 Conductimetry
 Refractometry

 The measurement of physical properties of the equilibrium mixture (i.e. pressure, total density) can
also be used, because these are usually related with the concentration
Ex. =
How will I know that the state has already
reached a state of equilibrium?
 Monitor continuously with time, then a steady-state
value of the property being measured (i.e concentration,
partial pressure) is an indication that the system is
already at equilibrium.

Ex.
What can the equilibrium constant expression tell us?
The equilibrium constant expression can predict the direction of the reaction to
obtain equilibrium.
EXERCISE 8

[Shift to the right]

EXERCISE 9

[Shift to the left]

CALCULATING EQUILIBRIUM
CONSTANTS/EQUILIBRIUM CONCENTRATIONS
Dissociation reactions
- Measured through the degree of dissociation (a), which
expresses the fraction of the reactant that has dissociated in
the equilibrium mixture.
- Monitored using the I-C-E method.
CALCULATING EQUILIBRIUM
CONSTANTS/EQUILIBRIUM CONCENTRATIONS
Ex. For the reaction
SbCl5 (g) = SbCl3 (g) + Cl2 (g)

SbCl5 was found to be 71.8% dissociated at 248 oC and 1 bar.

What would be the equilibrium constant for the reaction? The volume of
the flask is 1 L.

[1.83]
EXERCISE 10

[49]
EXERCISE 11

[0.0025 M, 0.025 M, 0.175 M, 0.175 M]

REACTION EQUILIBRIA INVOLVING SOLIDS
- The system CaCO3 (s) = CaO (s) + CO2 (g) involves a
heterogenous equilibrium system.

- For heterogenous equilibrium systems, only the gaseous

compounds enter into the expression for the equilibrium
constant. Pure solid or liquid phases are disregarded in
writing the expression for Kp, such that
Kp = PCO2
FACTORS AFFECTING EQUILIBRIUM
1. Effect of temperature

2. Effect of pressure

3. Effect of concentration

4. Effect of inert gases

5. Effect of the addition of catalysts

EFFECT OF TEMPERATURE ON Kp
 -
Kp is a function of temperature.

- The equation which relates Kp vs temperature is called van’t Hoff

equation
EFFECT OF TEMPERATURE ON Kp
 Indefinite integration of the van’t Hoff equation

will lead to

where c is an integration constant.

EFFECT OF TEMPERATURE ON EQUILIBRIUM
 

- slope of the line when ln Kp vs 1/T is plotted

Behavior of Kp with temperature changes: depends on the sign of DHo

- For exothermic reactions, DHo < 0. If temperature is decreased, Kp becomes lower
- For endothermic reactions, DHo > 0. If temperature is increased, Kp becomes higher
EXERCISE 12
For the reaction
N2 (g) + O2 (g) = 2NO (g)

The standard enthalpy of reaction, DHo is 182 kJ/mol, and Kp1 is 4.08 x
10-4 at 2000 K. Calculate the value of Kp2 at 2500 K.

[36.0]
EFFECT OF PRESSURE ON EQUILIBRIUM
 - The value of Kp is independent of the pressure at which the equilibrium is
established.

=0

- However, even if the equilibrium constant is unaffected by pressure, the

pressures or concentrations of the individual components of the equilibrium
mixture is altered if the total pressure of the system is changed.

- This effect is predicted by applying the Le Chatelier’s principle.

EXERCISE 13
Predict the shift in equilibrium for each of the following reactions.

Reactions Total Pressure Shift in equilibrium

N2 (g) + 3H2 (g) = 2NH3 (g) Increase
H2 (g) + CO2 (g) = CO (g) + H2O (g) Decrease
SbCl5 (g) = SbCl3 (g) + Cl2 (g) Increase
2NaHSO4 (s) = Na2S2O7 (s) + H2O (g) Decrease
2O3 (g) = 3O2 (g) Increase
EFFECT OF INERT GASES ON EQUILIBRIUM
- Does not affect Kp, but affects the composition of the equilibrium
mixture.

- There are two conditions: (1) at constant volume, and (2) at constant
pressure
EFFECT OF INERT GASES ON EQUILIBRIUM
At constant volume, the total pressure of the equilibrium is increased but
the partial pressures of the reaction components remain unchanged.

Conclusion: The addition of inert gases at constant volume does not

have an effect on the equilibrium system.
EFFECT OF INERT GASES ON EQUILIBRIUM
At constant pressure, the added inert gas accounts for part of the fixed
total pressure. Therefore, the partial pressures of the reaction
components are reduced.

Conclusion: The addition of the inert gas under a condition of constant

total pressure leads to a lowering of the sum of the partial pressures of
the reaction components, resulting in a shift in the position of the
equilibrium.
EXERCISE 14
At 248oC and 1 bar pressure, 1 mole of SbCl5 is 71.8% dissociated according
to the reaction:

SbCl5 (g) = SbCl3 (g) + Cl2 (g)

The equilibrium constant for the reaction under these conditions was
calculated to be 1.064 bar. If N2 (g) will be added in the equilibrium mixture
and has a partial pressure of 0.4 bar, what is the degree of dissociation of
SbCl5 under the same conditions of temperature and total pressure?

[80%]
EFFECT OF CATALYSTS ON EQUILIBRIUM
Catalysts
- do not change the value for Kp;
- do not affect the shift the position of an
equilibrium system; and
- will just make the system reach
equilibrium faster

A catalyst only lowers the Ea for both forward

and reverse reactions.
EXERCISE 15
EXERCISE 16
EXERCISE 17
Consider the following equilibrium system involving SO 2, Cl2,
and SO2Cl2 (sulfuryl dichloride):

SO2 (g) + Cl2 (g) SO2Cl2(g)

Predict the shift in equilibrium position if (a) Cl 2 gas were

added to the system; (b) SO2Cl2 were removed from the
system; (c) SO2 were removed from the system.
EXERCISE 18
Heating solid sodium bicarbonate in a closed vessel
establishes the following equilibrium:

2NaHCO3 (s) + Na2CO3 (s) H2O(g) + CO2(g)

What would happen to the equilibrium position if

(a) some of the CO2 were removed from the system;
(b) some solid Na2CO3 were added to the system;
(c) some of the solid NaHCO3 were removed from
the system? The temperature remains constant.
EXERCISE 19
Consider the following equilibrium systems:
(a) A 2B ΔH° = 20.0 kJ/mol
(b) A + B C ΔH° = -5.4 kJ/mol
(c) A B ΔH° = 0.0 kJ/mol

Predict the change in the equilibrium constant that would occur

in each case if the temperature of the reacting system were
raised.
EXERCISE 20
What effect does an increase in pressure have on each
of the following systems at equilibrium?
(a) A (s) 2B (s)
(b) 2A (l) B (l)
(c) A (s) B (g)
(d) A (g) B (g)
(e) A (g) 2B (g)