CHAPTER 5

BUK1213
ENTROPY, FREE ENERGY AND EQUILIBRIUM

NURLIN BINTI ABU SAMAH nurlin@ump.edu.my 0123439534

1

In order to predict the spontaneity of a process, we need to know two things about the system. 1. The change in enthalpy, which equivalent to (E from most processes. is nearly

2. The entropy (S), which is measure randomness or disorder of a system

of

the

WHAT IS ENTROPY??
A quantitative measure of microscopic disorder for a system. A measure of molecular disorder, randomness in a system Increasing entropy means increasing disorder and randomized motion The universe tends towards more random, disorganized states.

Concept: Nature tends from order to disorder in isolated systems. This tells us that the right hand box of molecules happened before the left.

SECOND LAW OF THERMODYNAMIC

The second law of thermodynamics states that process occur in a certain direction, not in any direction. A process will not occur unless it satisfies both the first and the second law of thermodynamics.

THE CONCEPTS OF SECOND LAW OF THERMODYNAMIC:

1. Explain the origin of the spontaneity of physical and chemical change. 2. Show how to define, measure and use entropy to discuss spontaneous changes quantitatively 3. Introduce the Gibbs energy

SECOND LAW OF THERMODYNAMICS

The Second Law of TD is one of the most important generalizations in science. It is important in Chemistry because it tell us whether a process/reaction will occur in the forward/reverse direction.

The Second Law of TD 1. Explains the origin of the spontaneity of physical and chemical changes. 2. Tells whether a reaction/process will occur in the forward or reverse direction. 3. Tells the direction of processes in the universe

SPONTANEOUS AND NON-SPONTANEOUS CHANGE

Spontaneous process (Irreversible): A process that results in a change, from one state to another, in an irreversible way.     Do not require a driving force in order to bring about the process. Do not relate to the rate of the process. Associated to a decrease in the quality of energy (wirr< w rev) e.g precipitation reaction when solutions of sodium chloride and silver nitrate are mixed.

Anything that happens in the universe that results in an irreversible change in state is spontaneous.

Non Spontaneous (Reversible Change):  Requires a driving force for the process to occur, hence it is non spontaneous.  Truly reversible process all forces would be perfectly balanced. There would be no driving force for the system to move.  A change that can be brought about only by doing work.  e.g reduced gas volume

PROCESS 1

PROCESS 2

Process 1: First Law fulfilled Elastic ball - initial potential energy - converted into kinetic energy - converted back to original potential energy.

PROCESS 1

PROCESS 2

Process 2: Why doesnt the egg bounce? Initial and final states are not the same - seem to have lost energy!

First Law: we cannot lose energy - where did the energy go?  Converted into random molecular motion and heat  Ended up with a more disorganized form of matter First Law of Thermodynamics: 1. The energy of the universe is constant 2. When one form of energy is converted to another, the total energy is conserved 3. Gives no clue on which processes will not. occur and which will

4. Does not tell the direction in which a process can occur spontaneously.

Example of spontaneous processes: 1. Gases expand spontaneously into vacuum (unless some sort of work is done to bring about the reverse change) 2. Heat is always transferred from a hot body to a cold body 3. H2 (g) reacts with O2 (g) in the presence of catalyst to form water*: 3H2(g) + O2(g) 6H2O(l)
o fH

= -286 kJ mol-1

*Reverse process non spontaneous

Using the First law  U and H associated with a spontaneous reaction can be calculated  U and H can also be calculated for the reverse reaction, does not occur spontaneously. Neither the sign nor the magnitude of way the reaction will go. U and H tells which

The direction of a reaction can be obtained from the Second Law of Thermodynamic

Dispersal of Energy Spontaneous changes are accompanied by dispersal of energy into a more disordered form. Bouncing ball:  Ball does not return to original height, the energy redistributed to molecules in the floor and ball as heat Ball eventually comes to rest, losing all energy into thermal motion of atoms in the floor the reverse process will never occur!

Heated floor and ball:  Molecules and atoms in the floor (and ball) undergo thermal (random) motion  For the ball to spontaneously bounce, it require a spontaneous localization of motion, to create an upwards motion of all of the atoms a virtually impossible process

(a)

(b)

Second Law and Entropy The Second law is used to identify spontaneous change and can be quantified in terms of entropy, S

ENTROPY (S)
The second law of thermodynamics leads to the definition of a new property called entropy, a quantitative measure of microscopic disorder for a system. A measure of molecular disorder, randomness in a system Increasing entropy means increasing disorder and randomized motion The universe tends towards more random, disorganized states.

The entropy change in the universe ((Suniv) for any process is sum of the entropy change in the system ((Ssys)and in the surroundings ((Ssurr). Mathematically, we can express the second law of thermodynamic as follows

For a spontaneous process: For an equilibrium process:

(Suniv = (Ssys + (Ssurr > 0 (Suniv = (Ssys + (Ssurr = 0

For the spontaneous process, the second law says that (Suniv must be greater than zero but it does not place a restriction on either (Ssys or (Ssurr . For an equilibrium process, (Suniv is zero.

ENTROPY CHANGE IN SYSTEM

To calculate (Suniv, we need to know both (Ssys and (Ssurr . e.g aA + bB
p

cC

dD

The standard entropy of reaction (Sorxn is given by

(Sorxn = [cSo(C) + dSo(D)] - [aSo(A) + bSo(B)]

or in general using nSo(products) - mSo(reactants) The standard entropy values of a large number of compounds have been measured in J/K . mol

Table1: Standard Entropy Values (So) for Some Substances at 25oC (Inorganic Substances)
Substances Ag(s) Ag+(aq) Br2(l) Br-(aq) CaCO3(s) CaO(s) CO2(g) Cl2(g) H2(g) HCl(g) So (J/K.mol) 42.7 73.9 152.3 80.7 92.9 39.8 213.6 223 131 187 Substances H2O(l) H2O(g) HBr(g) NH4+(aq) NH4Cl(s) N2(g) NH3 (g) NH3 (aq) O2(g) O3(g) So (J/K.mol) 69.9 188.7 198.48 112.8 94.56 191.5 193.0 111.3 205.0 110.88

EXAMPLE
From the absolute entropy values in Table 1, calculate the standard entropy changes for the following reactions at 25oC.

(a) CaCO3(s)

CaO(s)

CO2(g)

(b) N2(g) + 3H2(g) p (c) H2(g) + Cl2(g) p

2NH3(g) 2HCl(g)

Reasoning and Solutions

We can calculate (So by using equation (a) CaCO3(s)
p

CaO(s)

CO2(g)

(Sorxn = [So(CaO) + So(CO2)] - [So(CaCO3)] = [(1 mol)(39.8 J/K.mol) + (1 mol)(213.6 J/K.mol)] -(1 mol)(92.9 J/K.mol) = 160.5 J/K

Thus when1 mol of CaCO3 decomposes to form 1 mole of CaO and 1 mole of gaseous CO2, there is an increase in entropy equal to 160.5 J/K

(b)

N2(g) + 3H2(g) p

2NH3(g)

(Sorxn = [2So(NH3)] - [So(N2)] + [3So(H2)] = [(2 mol)(193 J/K.mol)] [(1 mol)(192 J/K.mol)] +(1 mol)(131 J/K.mol)] = -199 J/K

Result shows that when 1 mole of gaseous nitrogen reacts with 3 moles of gaseous hydrogen to form 2 moles of gaseous ammonia, there is a decrease in entropy equal to -199 J/K

(c) H2(g) + Cl2(g) p

2HCl(g)

(Sorxn = [2So(HCl)] - [So(H2)] + [So(Cl2)] = [(2 mol)(187 J/K.mol)] [(1 mol)(131 J/K.mol)] +(1 mol)(223 J/K.mol)] = 20 J/K

Thus the formation of 2 mole of gaseous HCl from 1 mole of gaseous H2 and 1 mole of gaseous Cl2 results in a small increase in entropy equal to 20 J/K

The results of example are consistent with results observed for many other reactions. Taken together , they support the following general rules: (a) If a reaction produces more gas molecules than it consume [Example (a)], (So is positive (b) If the total number of gas molecules diminished [Example (b)], (So is negative (c) If there is net charge in the total number of gas molecules [Example (c), then (So may be positive or negative, but relatively small numerically

These conclusions make sense given that gases invariably have greater entropy than liquids and solids. For reactions involving only liquids and solids, predicting the sign of (So is more difficult, but in many such cases an increase in the total number of molecules and/or ions is accompanied by an increase in entropy The following example shows how knowing the nature of reactants and products makes it possible to predict entropy changes.

EXAMPLE
Predicts whether the entropy change of the system in each of the following reactions is positive or negative. (a) 2H2(g) + O2(g)
p

2H2O(l)

(b) NH4Cl(s) p

NH3(g) + HCl(g)

(c) H2(g) + Br2(g) p 2HBr(g)

Reasoning and Solutions

We follow the above rules for determining the changes in entropy (a) Two gases combine to form a liquid. Therefore, (S is negative Because the solid is converted to two gaseous products, (S is positive We see that the same number of moles of gas is involved in the reactants as in the products. Therefore we cannot predict the sign of (S, but we know the change must be quite small

(b)

(c)

DON T GIVE UP & PLEASE DO ALL THE CALCULATIONS OR EXAMPLES IN MY LECTURE NOTES!!!!
GOOD LUCK!!!!