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ENTROPY & FREE ENERGY

A guide for A level students

KNOCKHARDY PUBLISHING

2008
SPECIFICATIONS

ENTHALPY CHANGES
INTRODUCTION This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards. Individual students may use the material at home for revision purposes or it may be used for classroom teaching if an interactive white board is available. Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at...

www.knockhardy.org.uk/sci.htm
Navigation is achieved by...
either or clicking on the grey arrows at the foot of each page using the left and right arrow keys on the keyboard

ENTROPY
CONTENTS
Spontaneous changes Free enthalpy and entropy Second Law of Thermodynamics

Change of state
Is a reaction spontaneous? - worked examples

FREE ENERGY & ENTROPY


SPONTANEOUS CHANGES - occur in one particular direction and not the other

- take place without the need for work


Exothermic reactions are usually spontaneous - this is because they go from higher to lower enthalpy

FREE ENERGY & ENTROPY


SPONTANEOUS CHANGES - occur in one particular direction and not the other

- take place without the need for work


Exothermic reactions are usually spontaneous - this is because they go from higher to lower enthalpy

However ... Why should reactions with a positive DH value take place spontaneously ? (some salts dissolve readily in water and the solution gets colder, not hotter)

ENDOTHERMIC
Energy is put in to overcome the electrostatic attraction between ions

FREE ENERGY & ENTROPY


SPONTANEOUS CHANGES - occur in one particular direction and not the other

- take place without the need for work


Exothermic reactions are usually spontaneous - this is because they go from higher to lower enthalpy

However ... Why should reactions with a positive DH value take place spontaneously ? (some salts dissolve readily in water and the solution gets colder, not hotter)

ENDOTHERMIC
Energy is put in to overcome the electrostatic attraction between ions

EXOTHERMIC
Energy is released as the ions are attracted to polar water molecules

FREE ENERGY & ENTROPY


SPONTANEOUS CHANGES - occur in one particular direction and not the other

- take place without the need for work


Exothermic reactions are usually spontaneous - this is because they go from higher to lower enthalpy

However ... Why should reactions with a positive DH value take place spontaneously ? (some salts dissolve readily in water and the solution gets colder, not hotter)

ENDOTHERMIC

EXOTHERMIC

If the energy released when the ions dissolve is less than that put in to break up the lattice, the overall process will be ENDOTHERMIC and the temperature of the solution will drop.

FREE ENERGY & ENTROPY


SPONTANEOUS CHANGES - occur in one particular direction and not the other

- take place without the need for work


Exothermic reactions are usually spontaneous - this is because they go from higher to lower enthalpy

However ... Why should reactions with a positive DH value take place spontaneously ? (some salts dissolve readily in water and the solution gets colder, not hotter) This must mean that energy has to be put in for the reaction to take place

FREE ENERGY & ENTROPY


SPONTANEOUS CHANGES - occur in one particular direction and not the other

- take place without the need for work


Exothermic reactions are usually spontaneous - this is because they go from higher to lower enthalpy

However ... Why should reactions with a positive DH value take place spontaneously ? (some salts dissolve readily in water and the solution gets colder, not hotter) This must mean that energy has to be put in for the reaction to take place The answer is that enthalpy change DH does not give the full story. Free energy changes, DG, give a better picture.

FREE ENERGY & ENTROPY


FREE ENERGY (G) A reaction is only spontaneous if it can do work - it must generate free energy A negative DG indicates a reaction capable of proceeding of its own accord

FREE ENERGY & ENTROPY


FREE ENERGY (G) A reaction is only spontaneous if it can do work - it must generate free energy A negative DG indicates a reaction capable of proceeding of its own accord

DG < 0 (- ive) DG > 0 (+ ive) DG = 0

Spontaneous reaction Non-spontaneous reaction (will be spontaneous in reverse direction) The system is in equilibrium

FREE ENERGY & ENTROPY


FREE ENERGY (G) A reaction is only spontaneous if it can do work - it must generate free energy A negative DG indicates a reaction capable of proceeding of its own accord

DG < 0 (- ive) DG > 0 (+ ive) DG = 0

Spontaneous reaction Non-spontaneous reaction (will be spontaneous in reverse direction) The system is in equilibrium

ENTROPY (S) Entropy (symbol S) is a measure of the disorder of a system The more the disorder, the greater the entropy If a system becomes more disordered, the value of DS is positive Values tend to be in JOULES - not kJ

DS = Sfinal - Sinitial

THE SECOND LAW


The Second Law of Thermodynamics is based on entropy and states that

Entropy tends to a maximum


This infers that...

all chemical and physical changes involve an overall increase in entropy

THE SECOND LAW


The Second Law of Thermodynamics is based on entropy and states that

Entropy tends to a maximum


This infers that...

all chemical and physical changes involve an overall increase in entropy

Entropy increases when solids melt

liquids boil ionic solids dissolve in water the number of gas molecules increases the temperature increases

THE SECOND LAW


The Second Law of Thermodynamics is based on entropy and states that

Entropy tends to a maximum


This infers that...

all chemical and physical changes involve an overall increase in entropy SOLIDS MELT

Entropy increases when

Regular arrangement of particles in solids

Less regular arrangement; more disorder in liquids

THE SECOND LAW


The Second Law of Thermodynamics is based on entropy and states that

Entropy tends to a maximum


This infers that...

all chemical and physical changes involve an overall increase in entropy LIQUIDS BOIL

Entropy increases when

Irregular arrangement; some disorder in liquids

Random nature and disorder of particles in a gas

THE SECOND LAW


The Second Law of Thermodynamics is based on entropy and states that

Entropy tends to a maximum


This infers that...

all chemical and physical changes involve an overall increase in entropy IONIC SOLIDS DISSOLVE IN WATER

Entropy increases when

Regular arrangement in an ionic crystal lattice

Ions dissociate in water; there is less order

THE SECOND LAW


The Second Law of Thermodynamics is based on entropy and states that

Entropy tends to a maximum


This infers that...

all chemical and physical changes involve an overall increase in entropy THE MOLES OF GAS INCREASE

Entropy increases when

Particles in gases move in a random way. The more gas molecules there are, the greater the degree of randomness.

THE SECOND LAW


The Second Law of Thermodynamics is based on entropy and states that

Entropy tends to a maximum


This infers that...

all chemical and physical changes involve an overall increase in entropy THE TEMPERATURE INCREASES

Entropy increases when

Lower temperature; less energy

Higher temperature; more energy and more disorder

FREE ENERGY & ENTROPY


Free energy, enthalpy and entropy are related ... Special case DG = DH - TDS

For a reversible reaction at equilibrium the value of DG is zero

If

DG = ZERO

then and

DH = T DS DS = DH T

This occurs during changes of state (melting, boiling etc)

FREE ENERGY & ENTROPY


Free energy, enthalpy and entropy are related ... Special case DG = DH - TDS

For a reversible reaction at equilibrium the value of DG is zero

If

DG = ZERO

then and

DH = T DS DS = DH T

Worked Example Calculate the entropy change when water turns to steam at 100C (373K). The enthalpy of vaporisation of water is +44 kJ mol-1 DS = DH T = + 44 kJ mol -1 373 K = + 118 J K -1 mol -1
(+ive as gases have more disorder)

Entropy change values are much smaller than enthalpy change values; they tend to be in Joules rather than kJ

IS A REACTION SPONTANEOUS?
A reaction should be spontaneous if DG is negative, so ... Work out if it is exothermic (DH -ive) or endothermic (DH +ive) Is there an increase in disorder ? Is the temperature high or low ? If YES then DS will be positive. This can affect the value of TDS

IS A REACTION SPONTANEOUS?
A reaction should be spontaneous if DG is negative, so ... Work out if it is exothermic (DH -ive) or endothermic (DH +ive) Is there an increase in disorder ? Is the temperature high or low ? If YES then DS will be positive. This can affect the value of TDS

General examples If DH is ive If DH is +ive and and DS is +ive DS is -ive then then DG must be negative DG must be positive

IS A REACTION SPONTANEOUS?
Specific examples

DG = DH - TDS
(1) H2(g) DH DS DG + F2(g) > 2HF(g)

- ive 0 - ive

highly exothermic process same number of gas molecules must be negative (taking 0 away from a negative number)

IS A REACTION SPONTANEOUS?
Specific examples

DG = DH - TDS
(2) Na+(g) DH DS DG + Cl(g) > NaCl(s)

- ive - ive - ive

highly exothermic (Lattice Enthalpy) more order in a solid mostly due to the high value of lattice enthalpy

IS A REACTION SPONTANEOUS?
Specific examples

DG = DH - TDS
(3) NH4NO3(s) > NH4+(aq) + NO3(aq) DH DS DG +ive +ive - ive endothermic (the solution goes colder) more disorder as lattice breaks up if T is high or the value of DS is big enough

IS A REACTION SPONTANEOUS?
Specific examples - summary
(1) H2(g) DH DS DG (2) Na+(g) DH DS DG + F2(g) > 2HF(g)

- ive 0 - ive +

highly exothermic process same number of gas molecules must be negative (taking 0 away from a negative number) > NaCl(s)

Cl(g)

- ive - ive - ive

highly exothermic (Lattice Enthalpy) more order in a solid mostly due to the high value of lattice enthalpy

(3)

NH4NO3(s) > NH4+(aq) + NO3(aq)


DH DS DG +ive +ive - ive endothermic (the solution goes colder) more disorder as lattice breaks up if T is high or the value of DS is big enough

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reaction ? Give reasons for your decision. What is the sign of DG? a) CaCO3(s) > CaO(s) + CO2(g)

DG = DH -

T DS

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reaction ? Give reasons for your decision. What is the sign of DG? a) CaCO3(s) > CaO(s) + CO2(g)

DG = DH +
Endothermic

T DS
+ +
increase in the number of gas molecules

Temperature is ALWAYS positive

Because DS is positive; TDS must be positive DH is positive (very endothermic reaction) For DG to be NEGATIVE, TDS must be bigger than DH This is more likely with a higher temperature The reaction is more likely to be spontaneous if heated

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reaction ? Give reasons for your decision. What is the sign of DG? b) NH3(g) + HCl(g) > NH4Cl(s)

DG = DH -

T DS

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reaction ? Give reasons for your decision. What is the sign of DG? b) NH3(g) + HCl(g) > NH4Cl(s)

DG = DH Exothermic

T DS
+
decrease in the number of gas molecules

Temperature is ALWAYS positive

Because DS is negative; TDS must be negative DH is negative For DG to be negative TDS must be less negative than DH This is more likely if the value of T is lower The higher the temperature the less likely that the reaction will proceed

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reactions ? Give reasons for your decision. What is the sign of DG? c) Na(s) > Na(g) (Equivalent to Enthalpy of Atomisation)

DG = DH -

T DS

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reactions ? Give reasons for your decision. What is the sign of DG? c) Na(s) > Na(g) (Equivalent to Enthalpy of Atomisation)

DG = DH +
Endothermic

T DS
+ +
increase in the number of gas molecules

Temperature is ALWAYS positive

Because DS is positive; TDS must be positive DH is positive For DG to be NEGATIVE, TDS must be bigger than DH This is more likely with a higher temperature so the reaction Solids are more likely to become gases if heated

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reactions ? Give reasons for your decision. What is the sign of DG? d) C6H12(l) + 9O2(g) > 6CO2(g) + 6H2O(g)

DG = DH -

T DS

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reactions ? Give reasons for your decision. What is the sign of DG? d) C6H12(l) + 9O2(g) > 6CO2(g) + 6H2O(g)

DG = DH COMBUSTION is exothermic

T DS
+ +
increase in the number of gas molecules

Temperature is ALWAYS positive

Because DS is positive; TDS must be positive DH is negative Taking a +ive value away from a ive value must give a ive value DG must be NEGATIVE so the reaction is SPONTANEOUS

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reactions ? Give reasons for your decision. What is the sign of DG? e) C(s) + O2(g) > CO2(g)

DG = DH -

T DS

IS A REACTION SPONTANEOUS?
What is the sign of the entropy change in the following reactions ? Give reasons for your decision. What is the sign of DG? e) C(s) + O2(g) > CO2(g)

DG = DH COMBUSTION is exothermic

T DS
+
very small
no change in the number of gas molecules

Temperature is ALWAYS positive

DS is very small (could be ive or +ive) TDS will therefore not be a large number DH will be have a relatively large negative value Taking a small +ive value away from a ive value must give a ive value DG must be NEGATIVE so the reaction is SPONTANEOUS

ANSWERS
What is the sign of the entropy change (DS) in the following reactions ? Give reasons for your decision. a) CaCO3(s) > CaO(s) + CO2(g) b) NH3(g) + HCl(g) > NH4Cl(s)

c) Na(s) > Na(g)


d) C6H12(l) + 9O2(g) > 6CO2(g) + 6H2O(g) e) C(s) + O2(g) > CO2(g)

ANSWERS
What is the sign of the entropy change (DS) in the following reactions ? Give reasons for your decision. a) CaCO3(s) > CaO(s) + CO2(g) b) NH3(g) + HCl(g) > NH4Cl(s)

+ -

more gas molecules

fewer gas molecules


goes from solid to gas more gas molecules similar moles of gas

c) Na(s) > Na(g)


d) C6H12(l) + 9O2(g) > 6CO2(g) + 6H2O(g) e) C(s) + O2(g) > CO2(g)

+
+ 0

ENTROPY & FREE ENERGY


The End

2009 JONATHAN HOPTON & KNOCKHARDY PUBLISHING