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CHAPTER 4

Chapter 19

Spontaneous Processes

Thermodynamics

question: can a reaction occur?

First Law of Thermodynamics: energy is

conserved.

Any process that occurs without outside

intervention is spontaneous.

When two eggs are dropped they

spontaneously break.

The reverse reaction is not spontaneous.

We can conclude that a spontaneous process

has a direction.

Prentice Hall 2003

Chapter 19

Spontaneous Processes

A

direction is not spontaneous in the

opposite direction.

The direction of a spontaneous process

can depend on temperature: Ice turning

to water is spontaneous at T > 0C, Water

turning to ice is spontaneous at T < 0C.

Chapter 19

Spontaneous Processes

Chapter 19

Spontaneous Processes

Reversible and Irreversible Processes

When 1 mol of water is frozen at 1 atm at 0C to

form 1 mol of ice, q = Hvap of heat is removed.

To reverse the process, q = Hvap must be added

to the 1 mol of ice at 0C and 1 atm to form 1

mol of water at 0C.

Therefore, converting between 1 mol of ice and

1 mol of water at 0C is a reversible process.

Allowing 1 mol of ice to warm is an irreversible

process. To get the reverse process to occur,

the water temperature must be lowered to 0C.

Prentice Hall 2003

Chapter 19

Processes

A

and forth between states along the same

path.

heat flow between two objects that have almost

infinitesimal change in temperature.

A

simply be reversed to restore the system

and its surroundings to their original states.

Heat can not flow from the colder object to the

hotter one.

Prentice Hall 2003

Chapter 19

Processes

Irreversible process

Chapter 19

Processes

Chemical

reversible.

In any spontaneous process, the

path between reactants and

products is irreversible.

Thermodynamics gives us the

direction of a process. It cannot

predict the speed at which the

process will occur.

Prentice Hall 2003

Chapter 19

of a Gas

Consider

connected by a closed stopcock. One flask

is evacuated and the other contains 1 atm

of gas.

The final state: two flasks connected by an

open stopcock. Each flask contains gas at

0.5 atm.

The expansion of the gas is isothermal (i.e.

constant temperature). Therefore the gas

does no work and heat is not transferred.

Prentice Hall 2003

Chapter 19

The

Spontaneous

Expansion of a

Gas

The Spontaneous

Expansion of a Gas

of a Gas

Consider

there are two gas molecules in the

flasks.

Before the stopcock is open, both

gas molecules will be in one flask.

Once the stopcock is open, there is a

higher probability that one molecule

will be in each flask that both

molecules being in the same flask.

Prentice Hall 2003

Chapter 19

of a Gas

When

much more probable that the molecules

will distribute among to the two flasks

than all remain in only one flask.

Chapter 19

Second Law of

Thermodynamics

Any irreversible process results in an

overall increase in entropy, whereas

a reversible process results in no

overall change in entropy

Chapter 19

of Thermodynamics

Entropy

Entropy, S, is a measure of the

disorder of a system.

Spontaneous reactions proceed to

lower energy or higher entropy.

In ice, the molecules are very well

ordered because of the H-bonds.

Therefore, ice has a low entropy.

Prentice Hall 2003

Chapter 19

of Thermodynamics

Entropy

As ice melts, the intermolecular

forces are broken (requires energy),

but the order is interrupted (so

entropy increases).

Water is more random than ice, so

ice spontaneously melts at room

temperature.

Prentice Hall 2003

Chapter 19

of Thermodynamics

Entropy

There is a balance between energy and

entropy considerations.

When an ionic solid is placed in water

two things happen:

the water organizes into hydrates about the

the ions in the crystal dissociate (the

hydrated ions are less ordered than the

crystal, so the entropy increases).

Prentice Hall 2003

Chapter 19

Entropy

of Thermodynamics

Entropy

Generally, when an increase in

entropy in one process is associated

with a decrease in entropy in

another, the increase in entropy

dominates.

Entropy is a state function.

For a system, S = Sfinal - Sinitial.

If S > 0 the randomness increases,

if S < 0 the order increases.

Chapter 19

of Thermodynamics

Entropy

Suppose a system changes reversibly

between state 1 and state 2. Then, the

change in entropy is given by

qrev

Ssys

(constant T )

T

at constant T where qrev is the amount of heat

phase change occurs at constant T with the

reversible addition of heat.)

Prentice Hall 2003

Chapter 19

of Thermodynamics

The Second Law of Thermodynamics

The second law of thermodynamics explains

why spontaneous processes have a direction.

In any spontaneous process, the entropy of the

universe increases.

S univ. S syst . S surr .

sum of the change in entropy of the system

and the change in entropy of the surroundings.

Entropy is not conserved: Suniv is increasing

Chapter 19

of Thermodynamics

The Second Law of Thermodynamics

For a reversible process:

S univ. S syst . S surr . 0

For a irreversible process:

S univ. S syst . S surr . 0

Note: the second law states

that the entropy

of the universe must increase in a

spontaneous process. It is possible for the

entropy of a system to decrease as long as

the entropy of the surroundings increases.

For an isolated system, Ssys = 0 for a

reversible process and Ssys > 0 for a

spontaneous process.

Prentice Hall 2003

Chapter 19

of Entropy

A

that is less ordered than a solid.

Any process that increases the

number of gas molecules leads to an

increase in entropy.

When NO(g) reacts with O2(g) to

form NO2(g), the total number of gas

molecules decreases, and the

entropy decreases.

Prentice Hall 2003

Chapter 19

of Entropy

There

vibration (the shortening and lengthening of

bonds, including the change in bond angles),

rotation (the spinning of a molecule about

some axis).

Chapter 19

of Entropy

Energy

translate, vibrate or rotate.

The more energy stored in translation,

vibration and rotation, the greater the

degrees of freedom and the higher the

entropy.

In a perfect crystal at 0 K there is no

translation, rotation or vibration of

molecules. Therefore, this is a state of

perfect order.

Prentice Hall 2003

Chapter 19

of Entropy

Third

entropy of a perfect crystal at 0 K is

zero.

Entropy changes dramatically at a

phase change.

As we heat a substance from

absolute zero, the entropy must

increase.

If there are two different solid state

forms of a substance, then the

Chapter 19

of Entropy

Chapter 19

of Entropy

Boiling

corresponds to a much

greater change in entropy than

melting.

Entropy will increase when

liquids or solutions are formed from

solids,

gases are formed from solids or liquids,

the number of gas molecules increase,

the temperature is increased.

Prentice Hall 2003

Chapter 19

Reactions

Absolute

complicated measurements.

Standard molar entropy, S: entropy of a

substance in its standard state. Similar in

concept to H.

Units: J/mol-K. Note units of H: kJ/mol.

Standard molar entropies of elements are not

zero.

For a chemical reaction which produces n

moles of products from m moles of reactants:

S nS products mS reactants

Chapter 19

For

of the universe must increase.

Reactions with large negative H values

are spontaneous.

How to we balance S and H to predict

whether a reaction is spontaneous?

Gibbs free energy, G, of a state is

G H TSat constant

a process occurring

temperature

G H TS

For

Chapter 19

There

If G = 0 then reaction is at equilibrium and no net

If G > 0 then the forward reaction is not

spontaneous. If G > 0, work must be supplied

from the surroundings to drive the reaction.

For

decreases to a minimum (equilibrium) and

then increases to the free energy of the

products.

Chapter 19

Chapter 19

Consider

from nitrogen and hydrogen:

N2(g) + 3H2(g)

Initially

2NH3(g)

spontaneously (Q < Keq).

After some time, the ammonia will

spontaneously react to form N2 and

H2 (Q > Keq).

At equilibrium, G = 0 and Q = K eq.

Prentice Hall 2003

Chapter 19

Standard Free-Energy Changes

We can tabulate standard free-energies of

formation, Gf (c.f. standard enthalpies of

formation).

Standard states are: pure solid, pure liquid, 1 atm

(gas), 1 M concentration (solution), and G = 0 for

elements.

G fora

mG f reactants

Gprocess

nGisf given

productsby

quantity G for a reaction tells us whether a

mixture of substances will spontaneously react to

produce more reactants (G > 0) or products (G

< 0).

The

Chapter 19

Temperature

Focus

on G = H - TS:

negative.

If H > 0 and S < 0, then G is always

positive. (That is, the reverse of 1.)

If H < 0 and S < 0, then G is negative at

low temperatures.

If H > 0 and S > 0, then G is negative at

high temperatures.

it may occur too slowly to be observed.

Even

Chapter 19

Temperature

Chapter 19

Equilibrium Constant

that G and K (equilibrium

constant) apply to standard

conditions.

Recall that G and Q (equilibrium

quotient) apply to any conditions.

It is useful to determine whether

G any

RT lnconditions

Q

substancesG

under

will

react:

Recall

Chapter 19

Equilibrium Constant

At

equilibrium, Q = K and G = 0, so

G G RT ln Q

0 G RT ln K eq

G RT ln K eq

From

If G = 0, then K = 1.

If G > 0, then K < 1.

Prentice Hall 2003

Chapter 19

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