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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
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ENTROPY
CONTENTS
Spontaneous changes Free enthalpy and entropy Second Law of Thermodynamics
Change of state
Is a reaction spontaneous? - worked examples
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
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
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.
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
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.
Spontaneous reaction Non-spontaneous reaction (will be spontaneous in reverse direction) The system is in equilibrium
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
liquids boil ionic solids dissolve in water the number of gas molecules increases the temperature increases
all chemical and physical changes involve an overall increase in entropy SOLIDS MELT
all chemical and physical changes involve an overall increase in entropy LIQUIDS BOIL
all chemical and physical changes involve an overall increase in entropy IONIC SOLIDS DISSOLVE IN WATER
all chemical and physical changes involve an overall increase in entropy THE MOLES OF GAS INCREASE
Particles in gases move in a random way. The more gas molecules there are, the greater the degree of randomness.
all chemical and physical changes involve an overall increase in entropy THE TEMPERATURE INCREASES
If
DG = ZERO
then and
DH = T DS DS = DH T
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)
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)
highly exothermic (Lattice Enthalpy) more order in a solid mostly due to the high value of lattice enthalpy
(3)
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
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
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
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
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
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)
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)
+ -
+
+ 0