Equilibrium

Nothing ever changes. Does it?

1/28/15

Phase Equilibrium
The laws of thermodynamics determine equilibrium
between phases.
.The fundamental fact of phase equilibrium is that at
equilibrium the chemical potential of any substance must
have the same value in all phases in which that
substance appears.

1/28/15

Phase Equilibrium
Phase:

1/28/15

a portion of a system
or an entire system
wherein the intensive
properties do not
change abruptly as a
function of position.
One of the many
homogeneous portions
of a heterogeneous
system

A heterogeneous system
3

Equilibrium
between phases

1/28/15

Nonequilibrium phases

At constant temperature and pressure, any substance

tends to move spontaneously from a phase of higher
chemical potential to a phase of lower chemical potential.
1/28/15

Gibbs Phase Rule

The Gibbs phase rule gives the number of independent
intensive variables in a simple system that can have a
number of phases and components.
The equilibrium thermodynamic state of a single-phase
simple system with c components is specified by the
values of c + 2 thermodynamic variables, at least one of
which must be an extensive variable.
All other equilibrium variables are dependent variables.
1/28/15

The coexistence of two phases in equilibrium

implies that:
This means that the two intensive variables
needed to describe the state of a system are
now related and no longer independent.

1/28/15

Thermodynamic Cat says: The Gibbs phase

rule is one of the most elegant deductions of
the whole of chemical thermodynamics and
one of the truly great generalizations of the
physical sciences.

Where f is the:
Degrees of freedom
Variance
the number of independent intensive
variables in a simple system that can have a
number of phases and components.
1/28/15

But how do we count the

number of components? Is
number of components =
number of chemical
species?
Actually,
NO!

1/28/15

Components
Chemically independent species
The number of components is equal to the number of
chemical species present minus the number of
relations that constrain the amounts of the species
Relations due to chemical equilibrium;
a relation due to a requirement of electrical neutrality (which
we always assume to exist);
relations due to the way the system was prepared (such as a
specification that two substances are in their stoichiometric
ratio)
my

Wise
sensei, is
this true?

1/28/15

Son,

10

Example:
Determine the number of components in:
An aqueous solution containing Na+, Cl, and
Br.
An aqueous solution containing Na+, K+, Li+,
Cl, and Br.
A gaseous system containing NO2 and N2O4
at chemical equilibrium with each other.
An aqueous solution containing Ca2+ ions and
Cl ions.
3, 5, 1, 2
1/28/15

11

Phase equilibria in one-component systems

f = 1 1 + 2 = 2 (one component, one phase)
Temperature and pressure can both be independent and any point

in a plot of the T-P graph can represent a possible intensive

state of the system

f = 1 2 + 2 = 1 (one component, two phases)

The pressure must be a function of the temperature, and is
represented by a coexistence curve.

f = 1 3 + 2 = 0 (one component, three phases)

This three-phase state is represented by a triple point at which three
coexistence curves intersect.
1/28/15

12

Examples:
A system composed of solid sucrose in equilibrium with an aqueous
solution of sucrose.
SO2, SO3, and O2 in a one-phase gaseous system, with the
chemical reaction among these substances at equilibrium
Ice and liquid water.
CO, O2, and CO2 in a single gas phase, with no catalyst present so
that the chemical reaction cannot equilibrate, and with each
substance added separately.
An aqueous solution of acetic acid. Make a list of the major species
present in the solution.
1/28/15

13

Waters phase diagram

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14

If helium has
many different
phases, cursed
humans also
have different
phases.

1/28/15

15

Clapeyron equation

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16

Example
Estimate the pressure on a system of liquid and solid
water if the equilibrium melting temperature is equal to
0.100C. The density of ice is 0.917 g/cm 3, the density
of liquid water is 1.000 g/cm3, and the molar enthalpy
change of fusion is 6008 J/mol.
14.3 atm

Integrate the Clapeyron equation for a solidsolid or

liquidsolid phase transition under the assumption that
Vm is constant and that Hm(T) = Hm(T1) + CP,m(T
T1) where CP,m is constant.

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17

Clausius-Clapeyron Equation
The ClausiusClapeyron equation is obtained by
integrating the Clapeyron equation in the case that one
of the two phases is a vapor (gas) and the other is a
condensed phase (liquid or solid).
We make two approximations:
(1) that the vapor is an ideal gas, and
(2) that the molar volume of the condensed phase is negligible
compared with that of the vapor (gas) phase.

These are both good approximations

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18

Clausius-Clapeyron equation

This is NOT the Clausius-Clapeyron equation

1/28/15

19

Example
Calculate the enthalpy change of vaporization of water
given the following values:
Vapor pressure of water at 25.0C = 23.756 torr
Vapor pressure of water at 100.0C = 760.0 torr

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20

Gibbs Energy and Phase Transitions

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21

Classification of Phase Transitions

Phase transitions are classified according to the partial derivatives of
the Gibbs energy
Ordinary phase transitions such as vaporizations etc are called firstorder phase transitions.

This means that at least one of the first derivatives and is discontinuous
at the phase transition.

1/28/15

22

 Given the relationships below, at the discontinuity the

Cp,m and T must have a singularity, a point where it
becomes infinite.

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23

Second order phase

transitions

A transition wherein both of the first

derivatives of the Gibbs energy are
continuous but at least one of the
second derivatives is discontinuous.
The order of a phase transition must
be determined experimentally
through careful measurements of the
isothermal compressibility and heat
capacity at the phase transition.
An example of a second-order phase
transition is the transition between
normal and superconducting states
1/28/15

24

Other kinds of transitions

Paramagnetic-toferromagnetic transitions
in some magnetic
materials
Order-disorder transitions
in certain alloys such as
beta brass

1/28/15

25

Lambda transition
This takes place when the heat capacity rises
smoothly toward infinity instead of rising
abruptly
Example: transition between normal, liquid
helium I, and liquid helium II.

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26

Surfaces
Many of the thermodynamic equations discussed are
valid only when surface contributions to the energy
can be neglected.
Although this is ordinarily an excellent approximation,
there is a significant contribution to the energy of a
liquid by the surface of the phase in the case of a
small droplet or a liquid in a small capillary tube.
Many products and reactions involve surface effects,
such as colloids, biological cell membranes,
lubrication, corrosion, adhesion, detergency,
lubrication, and electrochemical cell reactions.
1/28/15

27

Energy attributed to a surface

The surface contribution to the energy of a liquid is
primarily due to intermolecular attractions.
Although this is ordinarily an excellent approximation,
there is a significant contribution to the energy of a
liquid by the surface of the phase in the case of a
small droplet or a liquid in a small capillary tube.
Many products and reactions involve surface effects,
such as colloids, biological cell membranes,
lubrication, corrosion, adhesion, detergency,
lubrication, and electrochemical cell reactions.
1/28/15

28

Nanoscale Thermodynamics
Thermodynamic
properties change as
objects become smaller,
significantly so in
nanoscale.
Melting point and
enthalpy of fusion
decreases as the size of
a nanoparticle decreases.
Thermodynamics
becomes less and less
applicable as particle
sizes become smaller.
1/28/15

29

Nanoparticles
In nanoparticles and
other nanoscale objects,
their properties begin to
depend more and more
on surface effects,
electrostatic interactions,
molecular interactions,
and even quantum
mechanics.

From
http://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.abstractDetail/abstract/7136/report/F30
http://cheed.nus.edu.sg/~cheleejy/Gallery.html

Nanoparticles

From
http://upload.wikimedia.org/wikipedia/commons/6/6b/ColloidalGold_aq.png
http://www.topnews.in/files/stained-glass.jpg
Buzea, 2007

31

Nanoparticles: Fabrication

Gas phase methods

Vapor deposition synthesis
Mechanical processes
Liquid phase methods

From
http://cheed.nus.edu.sg/~cheleejy/Gallery.html
http://www.ptl.ethz.ch/research/res_top_FSP
http://www.manmadediamondinfo.com/cvd.shtml
http://www.cuttingtoolssite.com/2011/02/25/ball-milling-2/

32

Nanoparticles: Applications

From
http://www-ibmc.u-strasbg.fr/ict/vectorisation/nanotubes_eng.shtml
http://www.voyle.net/Extra%202005%20Images/21-01-2005-2.jpg
http://www.pharmacy.ac.uk/uploads/pics/Drug_Delivery_Polymer.jpg
http://www.bridgat.com/files/antiUV_agent.jpg
http://ic.tweakimg.net/ext/i/imagenormal/1265797330.jpeg

33

Nanoparticles: Classification

From
Buzea, 2007

34

Quantum dots
Inorganic semiconductor nanocrystals.
Have many possible applications due to their optical
properties.
In solar cells, biosensors and bioimaging, LEDs, quantum
computing

Interphase region
The 3-D region of contact
between 2 phases wherein
molecules interact with
molecules of both phases
is called the interfacial
layer, surface layer, or
interphase region.
This region is a few
molecules thick if ions are
not present.
This region is a transition
region between the two
bulk phases and is not
homogeneous
1/28/15

36

Colloids
A colloid or disperse phase is a dispersion of
small particles of one material in another.
This means typically around less than 500 nm
particles.
In general, colloidal particles are aggregates of
numerous atoms or molecules.
Kinds of colloids
Sol solid in liquid
Aerosol liquid in gas
Emulsion liquid in liquid

1/28/15

37

Colloids
Colloids are
thermodynamically
unstable with respect to
the bulk, but kinetically
nonlabile
Even though colloids
appear to attract each
other to coalesce into
larger particles, there are
factors that oppose these.
A major source of kinetic
nonlability of colloids is
the electrical double layer
1/28/15

38

Colloids
The theory of the stability of
colloids is known as the DLVO
theory, which assumes that there is
a balance between the repulsive
interaction between the charges of
the electric double layers on
neighboring particles and the
attractive interactions arising from
van der Waals interactions
between the molecules in the
particles.

1/28/15

39

 The Gibbs phase rule allows phase diagrams to be

understood.
The Clausius and ClausiusClapeyron equations govern
the curves in phase diagrams.
Thermodynamics allows analysis of the stability of
phases in systems.
Surface effects must be included in a complete
thermodynamic treatment, but are usually negligible.
1/28/15

40

Chemical Equilibrium
1. The principles of thermodynamics determine the state of chemical
equilibrium for any reaction.
2. The equilibrium constant expression of elementary chemistry is
equal to a constant at constant temperature when it is expressed in
terms of activities.
3. The principle of Le Chatelier can predict how a chemical system at
equilibrium responds to changes in temperature, pressure, or
amounts of substances.
4. The coupling of biochemical reactions can be understood through
thermodynamics and the use of postulated mechanisms.
1/28/15

41

Zerg at chemical equilibrium.

Zumdahl1/28/15
Chapter 2

42

1/28/15

43

At constant T and P

= extent of reaction

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44

We now have the expression of G for our

reaction system as a function of the extent of
reaction at constant T and P
1/28/15

45

Want equilibrium?
Join the Marines!

1/28/15

46

1/28/15

47

 Where activity can be defined as:

The activity is a dimensionless

quantity that is equal to unity if
the substance is in its standard
state.

1/28/15

48

 For every mole of reaction

1/28/15

49

Gibbs Energy Change at a definite composition

Q is called the activity quotient. The factors for the

reactants have negative exponents.

1/28/15

50

At equilibrium:

Leading to:
Which gives us:

1/28/15

51

This is one of the

greatest or most
significant equations
in science

1/28/15

An article in
Scientific American
states that this is
one of the only two
equations you
should know

52

Reactions involving gases and pure solids or

liquids
We know that
So for an ideal gas reaction:

We define this as the pressure equilibrium constant, or

Kp

1/28/15

53

Example:
Consider the reaction: 0 = 2NO2(g) N2O4(g)
Calculate the value of G at 298.15 K.

4.729 kJ/mol

Calculate the value of K at 298.15 K.

0.148

Calculate the equilibrium pressure of a system that initially

consists of 1.000 mol of N2O4 and that is confined in a fixed
volume of 24.46 L at 298.15 K. Assume ideal gases.
1.174 atm

fG (NO2) = 51.258 kJ/mol

fG (N2O4) = 97.787 kJ/mol

1/28/15

54

HINT: It is always the case that when a quadratic equation is solved in a

The Equilibrium Condition (Chem Rxn)

aA + bB

cC + dD

The same equilibrium state

is achieved whether
starting with pure reactants
or pure products.
The equilibrium state can
change with temperature.

The Equilibrium State (Chem Rxn)

H2O (g) + CO (g) H2 (g) + CO2 (g)

Change
[CO] to PCO
[H2O] to PH2O
etc

Chemical Reactions and Equilibrium

As the equilibrium state is approached, the

forward and backward rates of reaction
approach equality. At equilibrium the rates
are equal, and no further net change occurs
in the partial pressures of reactants or
products.

Fundamental characteristics of equilibrium states:

1. No macroscopic evidence of change.
2. Reached through spontaneous processes.
3. Show a dynamic balance of forward and backward processes.
4. Same regardless of the direction from which they are approached.
5. No change over time.

Arrows: Chemical Symbolism

Use this in an
equilibrium expression.

Use this to indicate

resonance.

Chemical Reactions and Equilibrium

The equilibrium condition for every reaction can be
described in a single equation in which a number, the
equilibrium constant (K) of the reaction, equals an
equilibrium expression, a function of properties of the
reactants and products.
H2O(l)

H2O(g) @ 25oC

K = 0.03126
H2O(l)

H2O(g) @ 30oC

K = 0.04187

Temperature (oC) Vapor Pressure (atm)

15.0
0.01683
17.0
0.01912
19.0
0.02168
21.0
0.02454
23.0
0.02772
25.0
0.03126
30.0
0.04187
50.0
0.1217

Law of Mass Action (1)

Partial pressures and concentrations of products appear in the
numerator and those of the reactants in the denominator.
Each is raised to a power equal to its coefficient in the
balanced chemical equation.

aA + bB

ifconcentrations

ifgases

PC PD
a
b
PA PB
c

cC + dD

C D K
a
b
A B
c

Law of Mass Action (2)

1. Gases enter equilibrium expressions as partial pressures, in
atmospheres. E.g., PCO2
2. Dissolved species enter as concentrations, in molarity (M)
moles per liter. E.g., [Na+]
3. Pure solids and pure liquids are represented in equilibrium
expressions by the number 1 (unity); a solvent taking part in a
chemical reaction is represented by unity, provided that the
solution is dilute. E.g., I2(s) I2(aq) [I2 (aq) ] = K

I 2 ( s ) I 2 (aq )
[ I 2 (aq )] [ I 2 (aq )]
K

[ I 2 ( aq )]
[ I 2 ( s )]
1

Activities
The concept of Activity (i-th component)
= ai = Pi / P reference

H2O (l)
PH2O

H2O (g) Kp = P H2O

=K

@ 25oC Kp = 0.03126 atm

Pref is numerically equal to 1

Pref
K = 0.03126
The convention is to express all pressures in atmospheres
and to omit factors of Pref because their value is unity. An
equilibrium constant K is a pure number.

The Equilibrium State

H2O (g) + CO (g) H2 (g) + CO2 (g)

PH 2 PCO 2
Kp
PH 2 O PCO

The Equilibrium Expressions

aA + bB

cC + dD

In a chemical reaction in which a moles of species A and b moles of

species B react to form c moles of species C and d moles of species D,
The partial pressures at equilibrium are related through

K = PcCPdD/PaAPbB

Write equilibrium expressions for the

following reactions

3 H2(g) + SO2(g) H2S(g) + 2 H2O(g)

2 C2F5Cl(g) + 4 O2(g) Cl2(g) + 4 CO2(g) + 5 F2(g)

Heterogeneous Equilibrium

Gases and
Solids

CaCO3(s)

CaO(s) + CO2(g)

K=PCO2
K is independent of the amounts
of CaCO3(s) or CaO(s)

Heterogeneous Equilibrium
Liquids

H2O(l)

H2O(g)
K=PH2O

Solutions

I2(s)

I2(aq)
K=[I2]

Relationships Among the Ks of Related Reactions

#1: The equilibrium constant for a reverse reaction is always
the reciprocal of the equilibrium constant for the
corresponding forward reaction.

K for

K rev

aA + bB
#1
#2

cC + dD

2 H2 (g) + O2 (g)
2 H2O (g)

or K for K rev 1
versus

2 H2O (g)

cC + dD

(PH2O)2
(PH2)2(PO2) = K1

2 H2 (g) + O2 (g) (PH2) (PO22)

(PH2O)
2

= K2

aA + bB

K1 = 1/K2

Relationships Among the Ks of Related Reactions

# 2: When the coefficients in a balanced chemical
equation are all multiplied by a constant factor, the
corresponding equilibrium constant is raised to a power
equal to that factor.
#1
#3

2 H2 (g) + O2 (g)
H2 (g) + O2 (g)
(PH2O)
(PH2)(PO2)

2 H2O (g) Rxn 1

H2O (g)

= K3

(PH2O)2
(PH2)2(PO2) = K1

Rxn 3 = Rxn 1 times 1/2

K3 = K1

Relationships Among the Ks of Related Reactions

# 3: when chemical equations are added to give a new
equation, their equilibrium constants are multiplied to
give the equilibrium constant associated with the new
equation.
2 BrCl (g) Br2 (g) + Cl2 (g)
wrong arrow

Br2 (g) + I2 (g) 2 IBr (g)

wrong arrow

(PBr2)(PCl2)
(PBrCl)2

(PIBr)2
o
=
K
=
0.051
@
25
C
2
(PBr2) (PI2)

2 BrCl (g) + I2 (g) 2 IBr (g) + Cl2(g)

wrong arrow

(PBr2)(PCl2)
(PBrCl)2

= K1 = 0.45 @ 25oC

(PIBr)2
X (P ) (P ) = K1K2 = K3
Br2
I2

= K1K2
= (0.45)(0.051)
=0.023 @ 25oC

Calculating Equilibrium Constants

Consider the equilibrium
4 NO2(g)
2 N2O(g) + 3 O2(g)
The three gases are introduced into a container
at partial pressures of 3.6 atm (for NO 2), 5.1 atm (for N2O), and 8.0 atm
(for O2) and react to reach equilibrium at a fixed temperature. The
equilibrium partial pressure of the NO 2 is measured to be 2.4 atm.
Calculate the equilibrium constant of the reaction at this temperature,
assuming that no competing reactions occur.
4 NO2(g) 2 N2O(g) + 3 O2(g)
initial partial pressure (atm)
change in partial pressure (atm)
equilibrium partial pressure (atm)

Calculate the equilibrium constant of the reaction at this temperature,

assuming that no competing reactions occur.
4 NO2(g) 2 N2O(g) + 3 O2(g)
initial partial pressure (atm)

3.6

5.1

change in partial pressure (atm)

4x

equilibrium partial pressure (atm)

2.4

+2x
5.1 + 2x

+3x
8.0 + 3x

5.1 + 2(0.3 atm) = 5.7 atm N2O

3.6 4x = 2.4 atm NO2;

x = 0.3 atm
(PN2O)2(PO2)3
K=
(PNO2)4

8.0

8.0 + 3(0.3 atm) = 8.9 atm O2

=

The compound GeWO4(g) forms at high temperature in the reaction

2 GeO (g) + W2O6(g) 2 GeWO4(g)
Some GeO
(g) and W2O6 (g) are mixed. Before they start to react, their partial
pressures both equal 1.000 atm. After their reaction at constant
temperature and volume, the equilibrium partial pressure of
GeWO4(g) is 0.980 atm. Assuming that this is the only reaction that
takes place, (a) determine the equilibrium partial pressures of
GeO and W2O6, and (b) determine the equilibrium constant for
the reaction.

pressure (atm)

2 GeO (g) + W2O6 (g) 2 GeWO4(g) initial partial

1.000
1.000
0

change in partial pressure (atm)

equilibrium partial pressure (atm)

2x

+2x

(a) determine the equilibrium partial pressures of GeO and W2O6, and
(b) determine the equilibrium constant for the reaction.
pressure (atm)

2 GeO(g) + W2O6(g) 2 GeWO4(g) initial partial

1.000
1.000
0

change in partial pressure (atm)

2x

equilibrium partial pressure (atm) 1.000 2x

0 + 2x = 0.980 atm GeWO4;

x = 0.490 atm

(PGeWO4)2
K = (P )2(P
=
)
GeO
W2O6

x
1.000 x

+2x
0.980

1.000 2(0.490) = 0.020 atm GeO

1.000 0.490 = 0.510 atm W2O6

Skip Solving quadratic equations

Will utilize approximation method
Systems that have small equilibrium
constants.
Assume x (the change in concentration) is
small (less than 5%) of the initial
concentration.

A vessel holds pure CO (g) at a pressure of 1.282 atm and a temperature of

354K. A quantity of nickel is added, and the partial pressure of CO (g)
drops to an equilibrium value of 0.709 atm because of the reaction
Ni (s) + 4CO (g) Ni(CO)4 (g)
Compute the equilibrium constant for this reaction at 354K.

PNi(CO)4
4

(PCO ) [Ni(s)]

PNi(CO)4
(PCO ) 4 (1)

Ni (s) + 4CO (g) Ni(CO)4 (g)

Construct an ICE table

P CO (atm) P Ni(CO)4 (atm)

initial partial pressure (atm)

1.282
change in partial pressure (atm)
-4x
equilibrium partial pressure (atm)
0.709

At equil. Pco=

0
+1x
x

x = PNi(CO)4 =

Equilibrium Calculations
At a particular temperature, K = 2.0 x 10-6 mol/L for the
reaction
2CO2 (g)

2CO (g) + O2 (g)

If 2.0 mol CO2 is initially placed into a 5.0-L vessel, calculate

the equilibrium concentrations of all species.
2CO2 (g)
initial partial pressure (mol/L) 0.4
0
change in partial pressure (mol/L)
2x
equilibrium partial pressure (mol/L) 0.4 -2x

2CO (g) + O2 (g)

0
+2x

+1x
2x

1x

At a particular temperature, K = 2.0 x 10-6 mol/L for the reaction

2CO2 (g)

2CO (g) + O2 (g)

If 2.0 mol CO2 is initially placed into a 5.0-L vessel, calculate the equilibrium
concentrations of all species.

2CO2 (g)

2CO (g) + O2 (g)

initial partial pressure (mol/L)

0.4
0
change in partial pressure (mol/L)
2x
equilibrium partial pressure (mol/L) 0.4 -2x
2

Kp =

+1x
2x

[CO] [O 2 ]
(2 x) ( x)
= 2.0x10-6
2
[CO 2 ]
(0.40 2 x) 2

assume 2x << 0.40

2.0x10-6 =

0
+2x

(2x) 2 (x)
x = 4.3x10-3M
2
(0.40)

check assumption
2x 2(4.3x10-3)
=
x 100 = 2.2%
0.40
0.40
assumpiton valid, less than 5%

1x

At a particular temperature, K = 2.0 x 10-6 mol/L for the reaction

2CO2 (g)

2CO (g) + O2 (g)

If 2.0 mol CO2 is initially placed into a 5.0-L vessel, calculate the equilibrium
concentrations of all species.

2CO2 (g)

initial partial pressure (mol/L)

0.4
0
change in partial pressure (mol/L)
2x
equilibrium partial pressure (mol/L) 0.4 -2x

[CO]2 [O 2 ]
-6
Kp =
=
2.0x10
[CO 2 ]2
(2 x ) 2 ( x)

2
(0.40 2 x)[CO]
= 2x = 2(4.3 x 10

-3

2CO (g) + O2 (g)

0
+2x

+1x
2x

1x

[CO 2 ] = 0.40 - 2x =
= 0.40 - 2(4.3x10-3 ) = 0.39M

-3
-3 = 8.6 x 10 M

x = 4.3x10 M

-3

[O 2 ] = x = 4.3 x 10 M

Non-Equilibrium Conditions:
The Reaction Quotient (1)
forward

aA bB reverse cC dD

PC PD
a
b
PA PB
c

PC PD
a
b
PA PB
c

wrong arrow

?
Q K

K (the Equilibrium Constant) uses equilibrium

partial pressures
Q (the reaction quotient) uses prevailing partial
pressures, not necessarily at equilibrium

The Reaction Quotient (2)

wrong
forward

arrow
aA bB reverse cC dD

PC c PD d
PA a PB b

?
QK

PC c PD d
PA a PB b

If Q < K, reaction proceeds in a

forward direction (toward
products);
If Q > K, reaction proceeds in a backward direction
(toward reactants);
If Q = K, the reaction is in equilibrium.

The equilibrium constant for the reaction P4(g) 2 P2(g) is

1.39 at 400oC. Suppose that 2.75 mol of P4(g) and 1.08 mol of
P2(g) are mixed in a closed 25.0 L container at 400oC. Compute
Q(init) (the Q at the moment of mixing) and state the direction in
which the reaction proceeds.

PP 2 2
K 1.39
1
PP 4

?
Q K

PV nRT

K = 1.39 @ 400oC; nP4(init) = 2.75 mol; nP2(init) = 1.08 mol

PP4(init) = nP4(init)RT/V

= [(2.75mol)(0.08206 atm L mol-1 K-1)(273.15+400oC)]/(25.0L)

PP2(init) = nP2(init)RT/V

= [(1.08mol)(0.08206 atm L mol-1 K-1)(273.15+400oC)]/(25.0L)

= 6.08 atm
= 2.39 atm

Q=

Henri Louis Le Chtelier (1850-1936)

Highlights
1884 Le Chatelier's Principle: A system in
equilibrium that is subjected to a stress
reacts in a way that counteracts the stress
If a chemical system at equilibrium
experiences a change in concentration,
temperature or total pressure the
equilibrium will shift in order to minimize
that change.
Industrial chemist involved with industrial
efficiency and labor-management
relations

Moments in a Life
Le Chatelier was named "chevalier"
(knight) of the Lgion d'honneur in 1887,
decoration established by Napolon
Bonaparte in 1802.

Challenge my
moustache? I
think not!

Effects of External Stresses on Equilibria:

Le Chteliers Principle
A system in equilibrium that is subjected to a
stress reacts in a way that counteracts the stress.
Le Chteliers Principle provides a way to predict the
response of an equilibrium system to an external
perturbation, such as
1. Effects of Adding or Removing Reactants or Products
2. Effects of Changing the Volume (or Pressure) of the System
3. Effects of Changing the Temperature

Effects of Adding or Removing Reactants or Products

PCl5(g)

PCl3(g) + Cl2(g)

K = 11.5 @ 300oC = Q

add extra PCl5(g)

add extra PCl3(g)
remove some PCl5(g)
remove some PCl3(g)

A system in equilibrium that is subjected to a stress reacts in a

way that counteracts the stress. In this case adding or
removing reactants or products

Effects of Changing the Volume of the System

PCl5(g)
1 mole

PCl3(g) + Cl2(g)
1+1 = 2 moles

Lets decrease the volume of the reaction container

Less room :: less amount (fewer moles)
Shifts reaction
to restore equilibrium
Lets increase the volume of the reaction container
More room :: more amount (greater moles)
Shifts reaction
to restore equilibrium

A system in equilibrium that is subjected to a

stress reacts in a way that counteracts the stress.
In this case a change in volume

Volume Decreased

Volume Increased

(Pressure Increased)

(Pressure Decreased)

V reactants > V products

Equilibrium shift right

(toward products)

Equilibrium Shifts left

(toward reactants)

V reactants < V products

Equilibrium Shifts left

(toward reactants)

Equilibrium shift right

(toward products)

V reactants = V products

Equilibrium not affected

Equilibrium not affected

2 P2(g)
P4 (g)
PCl5(g)
PCl3(g) + Cl2(g)
CO (g) +H2O (g)

CO2 (g) + H2 (g)

Boyles Law:
PV = Constant
A system in equilibrium that is subjected to a stress reacts in a way
that counteracts the stress. In this case a change in volume (or
pressure)

Effects of Changing the Temperature

Endothermic: heat is aborbed by a reaction
Reactants + heat gives Products
Exothermic: heat is liberated by a reaction
Reactants gives Products + heat
A system in equilibrium that is subjected to a stress reacts
in a way that counteracts the stress. In this case a change
in temperature

Effects of Changing the Temperature

Endothermic: absorption of heat by a reaction
Reactants + heat gives Products
Lets increase the temperature of the reaction, what
direction does the equilibrium reaction shift
Lets decrease the temperature of the reaction

Effects of Changing the Temperature

Exothermic: heat liberated by a reaction
Reactants Products + heat
Lets increase the temperature of the reaction
Lets decrease the temperature of the reaction

A system in equilibrium that is subjected to a stress reacts

in a way that counteracts the stress. In this case a change
in temperature

Temperature Raised

Temperature Lowered

Endothermic
Reaction
(absorb heat)

Equilibrium shift right

(toward products)

Equilibrium Shifts left

(toward reactants)

Exothermic
Reaction
(liberate heat)

Equilibrium Shifts left

(toward reactants)

Equilibrium shift right

(toward products)

If a forward reaction is exothermic,

forward

aA bB cC dD Heat
Then the reverse reaction must be endothermic
reverse

cC dD Heat aA bB

aA bB reverse cC dD

forward

Driving Reactions to Completion/ Increasing Yield

Industrial Synthesis of Ammonia (Haber)

N2 (g) + 3H2 (g) 2NH3 (g)
Forward reaction is exothermic
What conditions do we need to increase the yield, i.e.,
produce more ammonia?

V reactants >
V products
Exothermic
Reaction
(liberate heat)

Volume Decreased

Volume Increased

(Pressure Increased)

(Pressure Decreased)

Equilibrium shift
right
(toward products)
Temperature Raised

Equilibrium Shifts left

(toward
reactants)
Temperature Lowered

Equilibrium Shifts left Equilibrium shift right

(toward
(toward
reactants)
products)

Problem
Hello Kitty has concocted a vile gas, 2(g), to combat the forces of
Kerokeropi the Green. This gas is harmless, but when in contact with
sunlight, it decomposes into the toxic nerve gas 2(g) and the harmless
liquid (l).
22(g) 2(g) + 4(l)
At equilibrium, the partial pressures of 2(g) and 2(g) are 0.02 and 0.87
atm at 32C, the usual temperature in Isengard.
Determine the gas equilibrium constant of the reaction.
Determine the standard reaction Gibbs energy of the reaction.
In Rohan, the temperature is a cooler 27C and when Sarumans UrukHai warriors deployed the gas there, the partial pressures of2(g)
and 2(g) are 0.057 and 0.76 atm at equilibrium.
Determine the standard reaction Gibbs energy of the reaction when it
93
takes place in Rohan.
What is the standard reaction enthalpy change of the reaction?

Thank you for listening!

1/28/15

94