Criteria for Spontaneous Change

Suppose a System is in Thermal Equilibrium with its Surroundings at temperature, Tsurr. When there is
a change in state then there is a transfer of energy in the form of heat (q) between the System and the
Surrounding.
Then, according to the 2nd Law, the Clausius inequality for Spontaneous Change is:

Again, accorrding to the 1st Law, we can write:

TsurrdS – (dU- δw) > 0
TsurrdS – (dU + pextdV) > 0
Combining the two laws, assuming only pV work, gives the following general criterion for
spontaneous change:

* Equilibrium is reached when there no possible change of State that would satisfy this
inequality
**We would now use this general criterion under specific condition to get the
Thermodynamic paramters
 Criteria for Spontaneous Change
Transfer of energy in the form of heat (q) between the System and the Surrounding
when there is a change in state at CONSTANT VOLUME and CONSTANT ENERGY

Let us first consider an ISOLATED SYSTEM (q = w = 0, ∆U = 0)

Since, dU = 0 and dV = 0, therefore from the general criterion
above, we have ⇒

And the EQULIBRIUM for an ISOLATED SYSTEM is then achieved when the
ENTROPY is MAXIMIZED.
Therefore, at the MAXIMUM ENTROPY, No spontaneous changes can further occur

System + thermal reservoir

Let us now consider a proccess under constant ENTROPY and
constant Volume.
Since, dS = 0 and dV = 0, therefore from the general criterion above,
we have ⇒

At constant S and V, the EQULIBRIUM is achieved when the ENERGY

(T,V)
is MINIMIZED.
 Criteria for Spontaneous Change

Now let‛s begin considering cases that are experimentally more controllable
Let us now consider a proccess under constant T = TSurr and constant Volume
dU – TdS < 0 ⇒ d(U – TS) < 0
By definition: A = (U – TS), the Helmholtz Free Energy
Then the criterion for spontaneity under constant T = Tsurr and constant V.

**Therefore, for a spontaneous process under constant V and constant T=Tsurr,

Equilibrium is achieved when the Helmholtz free energy is MINIMIZED

Let us now considera proccess under constant T = TSurr and c onstant Pressure = pext
(dU + pdV – TdS) < 0 ⇒ d(U + pV – TS) < 0
By definition: G = (U + pV – TS), the Gibbs Free Energy
(can also be written as G = A + pV and G = H – TS )
Then is the criterion for spontaneity under constant T=Tsurr and constant p=pext.

**Therefore, for a spontaneous process under constant p=pext and constant T=Tsurr,
Equilibrium is achieved when the Gibbs free energy is MINIMIZED
We defined:
Helmholtz Energy: A = U − TS
Gibbs Free Energy: G = H −TS also, G = A + PV
Entropy Change Derived from the Fundamental Equations of U & H
 These are the Maxwell Relations

 P   T   T   V 
       
 S V   V  S  P  S  S  P

The first two are little used.

 S   P   S   V 
         
  V  T   T V  P  T  T  P
The last two are extremely valuable.

The equations relate the isothermal pressure and Isobaric volume

variations of entropy to measurable properties that can be obtained
from an EQUATION OF STATE.
Dependence of state functions (U, H, and and S) on T , p, and V

;; ; ;;
Prove or Find the following :
;
 Gibbs Free Energy
Properties of the Gibbs Free Energy
G of a state decreases with in increase in T G of a state increases with in increase in T
and is a measure of the Entropy of the state and is a measure of the Volume of the state
Anomalous expansion of
Water
THERMODYNAMICS
OF OPEN SYSTEM
 THERMODYNAMICS OF
OPEN SYSTEM
Limitations of of the Fundamental Equation of Chemical Thermodynamics

This equation is not applicable when:

• System composition is changing due to exchange of matter with
surroundings (open system)
• An irreverrsible chemical reaction takes place
• An irreversible inter-phase transport of matter takes place

CONCLUSION: We need new sets of Fundamental Equations of Chemical

Thermodynamics to deal with OPEN SYSTEMS
 Multicomponent Systems, Partial Molar Quantities, and the
Chemical Potential
So far we ve worked with fundamental equations for a closed (no mass change) system with
no composition change. We had the following:

• How does this change if we allow the composition of the system to change? Like in a
chemical reaction or a biochemical process?

• Consider Gibbs free energy of a 2-component system G (T,P,n1,n2 )

We define the chemical
potential, µi of species i

µι(T, P,n ) is an intensive variable

 OPEN SYSTEM
When exchange of matter is allowed
between the System and the
Surrounding, the composition can
change. We then have to modify the
Fundamental Equations

The modifications give rise to NEW sets of Fundamental Equations for

OPEN systems
Chemical potential, µi , is the
rate of change of the
thermodynamic potential with
respect to change in the
NUMBER of species, ni , of type
i where (i = 1, N)

These are applicable to single phase, multi-component open system in thermal and mechanical
equilibrium and with ONLY pV (i.e., expansive) work done.
SIMPLE MIXTURE
Partial Molar Quantities

Partial Molar Volume

The Thermodynamics of Mixing

 Chemical Potential for a Mixture of Ideal Gases

Let's show this in a system that has ONE component and TWO parts .
For example: a solid and a liquid phase, or for the case of a cell placed in salt
water, conside the water in the cell versus the water outside the cell in the salt
water solution.
What will happen for the cell placed in a salt water solution?

The Cell will die as water would flow from inside the cell to the outside into the
salt solution (this is what we call osmotic pressure)

The chemical potential and its downhill drive to Equilibrium will be the guiding
principle for our Study of Phase Transition, Chemical Reactions , and various
Biochemical processes
 SIMPLE MIXTURE: Partial Molar Volume
Volume in Simple mixtures: b) Real Mixtures : Interactions Exists
• Imagine a huge volume of water, and add 1 mol H2O.
The volume will increase by 18 cm3, because 18 cm3 mol-1 is the molar volume of water

Now, add 1 mol H2O to a huge volume of pure

• ethanol. The volume will increase by 14 cm3
mol-1, which is the partial molar volumeof
water in pure ethanol. The reason for the
different increase is that the volume occupied
by a given number of water molecules depends
on the identity of the molecules that surround
them.
• In general, the partial molar volume of a
substance A in a mixture is the change in
volume per mole of A added to a large volume
of the mixture.

• The partial molar volumes of the components

of the mixture vary with composition because The partial molar volumes of water and
the environment of each type of molecule ethanol at 25°C.
changes as the composition changes from pure Note the different scales (water on the
A to pure B. left, ethanol on the right).
 SIMPLE MIXTURE: Partial Molar Volume
Volume in Simple mixtures: b) Real Mixtures : Interactions Exists
SIMPLE MIXTURE: Partial Molar Volume
 Gibbs- Duhem Equation and Partial Molar Volumes of
Water and Ethanol in Mixture

Significance: The chemical potential (or, any

other Partial Molar Quantity) of one
component cannot change independently of
the other components

Therefore, according to Gibbs-Duhem Equation, the Partial Molar Volume of H2O

decreases, and that of Ethanol increases in a mixture
Numerical on Partial Molar Volumes
Assignment