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■■ predict whether the entropy change for a given ■■ predict the effect of temperature change on the
process is positive or negative spontaneity of a reaction given standard enthalpy
and entropy changes.
cambridge international a level chemistry
Introduction
about 150 years ago, many scientists thought that all chemical
reactions gave off heat to the surroundings. they thought that
all chemical reactions were exothermic. we now know this not
true. many chemical reactions and processes are endothermic.
enthalpy changes alone cannot help us predict whether or not a
reaction will occur. if we want to predict this, we need to consider
the entropy change of the reaction.
the term entropy was first given by German physicist rudolf
clausius in 1865. From experimental results, he suggested a
relationship between entropy change (∆S), the energy transferred
reversibly from the surroundings (q) and the temperature (T):
q
ΔS = __
T
Figure 23.1 Potassium reacts spontaneously
with water.
Figure 23.2 The spontaneous mixing of helium atoms ( ) with argon atoms ( ).
Chapter 23: Entropy and Gibbs free energy
We can make a model to show how, during a There are eight different ways of arranging the three
spontaneous process, the entropy of the system increases. molecules between two gas jars. We can express this as:
Figure 23.2 shows a system of two flasks connected by
a stopcock. One flask contains helium and the other number of molecules
contains argon. These gases do not react.
When the stopcock is opened, the gas atoms move 2 × 2 × 2 = 23 = 8
spontaneously by diffusion. After mixing, the gases are
mixed up and there is more disorder than before mixing.
two gas jars
The entropy has increased.
Each of these ways is equally likely (probable). So the
Diffusion and number of ways chance that all the molecules will stay in gas jar A is 1 in
We can show that the molecules in a vapour diffuse by 8. Similarly, the chance that all three molecules will move
chance by thinking about the probability of finding them over to gas jar B is 1 in 8. The molecules diffuse because
at one place at any one time. Consider the simplified there are more ways of them being spread out than
model shown below. remaining in the same place.
partition If we started with five molecules in gas jar A, the
number of ways of arranging the molecules is 25 = 32
1
2 3 different ways. If we scaled this up to the numbers of
gas jar A gas jar B gas molecules that we might find in a container in the
laboratory, the number of ways of arranging the
The three molecules in gas jar A cannot move into gas molecules is extremely large; for example, for a million
jar B. molecules between two gas jars it would be 21 000 000, a
In this model we assume that: number that is too large for your calculator to deal with.
■■ there are only a few molecules in gas jar A So diffusion happens because there is an overwhelming 351
■■ there are no other particles present likelihood of it taking place as a result of the large number
■■ the molecules move randomly and change directions of ways of arranging the molecules. The idea of the
when they collide. ‘number of ways’ of arranging either molecules or the
After we remove the partition, the molecules can move energy within molecules dictates whether the changes
randomly not only within gas jar A but also into gas jar that take place are the ones that are most likely to happen.
B. There are three molecules and two places in which they This applies to chemical reactions as well as to physical
can be (gas jar A and gas jar B). The number of ways of processes such as diffusion.
arranging the molecules after removing the partition is
Question
shown in Figure 23.3.
1 a For this question refer back to Figure 23.3. If
there are four molecules in the gas jar on the left,
1 2
3
1
3
2 how many ways of arranging the molecules are
there when the partition is removed?
b What is the probability of finding all four
1 2 2 1
3 3 molecules in the right-hand gas jar?
c Which of the following changes are likely to
3
be spontaneous?
2 3 1 1 2
i sugar dissolving in water
ii the smell from an open bottle of aqueous
3 1 2 3 ammonia diffusing throughout a room
2 1
iii water turning to ice at 10 °C
iv ethanol vaporising at 20 °C
Figure 23.3 The eight possible arrangements of molecules
after removing the partition between the gas jars. v water mixing completely with cooking oil
vi limestone (calcium carbonate) decomposing
at room temperature
Cambridge International A Level Chemistry
Figure 23.5 The change in entropy as a substance melts and we should expect an increase of entropy of the system
then boils. because there are a greater number of moles of gas
molecules in the products (5 molecules) than in the
When a liquid changes to a vapour: reactants (2 molecules). In addition, there are two
■■ the irregular arrangement of particles in the liquid which different product molecules but only one type of reactant
are close together and rotating changes to molecule. This also contributes to a greater disorder in
■■ an irregular arrangement of particles, which are free to the products compared with the reactants. The system
move around rapidly because they are far apart from becomes energetically more stable when it becomes
each other. more disordered.
In the reaction
Question
N2(g) + 3H2(g) 2NH3(g) 353
2 Explain the difference in the entropy of each of the
we should expect a decrease in the entropy of the
following pairs of substances in terms of their state
and structure.
system because there is a reduction in the number of gas
molecules as the reaction proceeds. So the entropy change
a Br2(l) S —
O
= 151.6 J K–1 mol–1
of the system is negative. The reactants, hydrogen and
and I2(s) S —
O
= 116.8 J K–1 mol–1 nitrogen, are more stable than the product, ammonia.
b H2(g) S —
O
= 130.6 J K–1 mol–1
and CH4(g) S —
O
= 186.2 J K–1 mol–1 Question
—
c Hg(l) S O
= 76.00 J K–1 mol–1 3 For each of the following reactions, suggest whether
and Na(s) S —
O
= 51.20 J K–1 mol–1 the entropy of the reactants or the products will be
d SO2(g) S —
O
= 248.1 J K–1 mol–1 greater or whether it is difficult to decide. Explain
your answers.
and SO3(l) S —
O
= 95.60 J K–1 mol–1
a NH3(g) + HCl(g) NH4Cl(s)
b S(l) + O2(g) SO2(g)
Entropy changes in reactions c 2Mg(s) + CO2(g) 2MgO(s) + C(s)
In a chemical reaction, if we compare the entropies of d 2Li(s) + Cl2(g) 2LiCl(s)
the reactants and products, we can try to explain the e H2O(g) + C(s) H2(g) + CO(g)
magnitude of the entropy change and whether or not it f 2HI(g) H2(g) + I2(g)
increases or decreases. We will assume that gases have
g 2K(s) + 2H2O(l) 2KOH(aq) + H2(g)
high entropy and solids have low entropy. If there is a
change in the number of gaseous molecules in a reaction, h MgCO3(s) MgO(s) + CO2(g)
there is likely to be a significant entropy change. This is
Cambridge International A Level Chemistry
ΔS —Osystem = S — —
products – S reactants
O O
Chapter 23: Entropy and Gibbs free energy
ΔS —
O
= ________
reaction
MgO(s) = 26.90, Na(s) = 51.20, NaCl(s) = 72.10, surroundings T
NH4NO3(s) = 151.1, N2O(g) = 219.7, O2(g) = 205.0)
–(–1 270 200)
a 2H2O2(l) 2H2O(l) + O2(g) = ___________
298
c H2(g) + F2(g) 2HF(g) ΔH —O
reaction
6 Calculate the total standard entropy change in each
= –271.1 kJ mol–1 of the following reactions using the standard molar
carried out at standard temperature entropy values given here.
d Si(s) + 2H2(g) SiH4(g) ΔH —
O (Values for S —
O
in J K–1 mol–1: C(graphite) = 5.700,
reaction
= +34.30 kJ mol–1 C2N2(g) = 242.1, C 3H8(g) = 269.9, CO2(g) = 213.6,
carried out at –3 °C H2(g) = 130.6, H2O(l) = 69.90, H2S(g) = 205.7,
N2(g) = 191.6, O2(g) = 205.0, P(s) = 41.10,
P4O10(s) = 228.9, S(s) = 31.80)
Calculating total entropy change a S(s) + H2(g) H2S(g)
The total entropy change is given by: ΔH —
reaction = –20.6 kJ mol
O –1
ΔS —total
O
= ΔS —Osystem + ΔS —Osurroundings b 2C(graphite) + N2(g) C2N2(g)
—
ΔH reaction = +307.9 kJ mol–1
O
The total entropy change for the examples given above for d C 3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)
the reaction of calcium with oxygen and the combustion ΔH — –1
reaction = –2219.2 kJ mol
O
So:
ΔS —
O —
O —
O
total = ΔS system + ΔS surroundings
= –208.4 + 4262.4 equilibrium
ΔS —
O –1
total = +4054.0 J K mol
–1
Increase in entropy
ΔS —
O
system = –5.2 J K–1 mol–1
ΔS —
O –1
surroundings = +2987.6 J K mol
–1
So:
ΔS —
O —
O —
O
total = ΔS system + ΔS surroundings
Pure N2O4 Pure NO2
= –5.2 + 2987.6
ΔS —
O –1
total = +2982.4 J K mol
–1
Figure 23.6 The total entropy change, ΔS —
O
total, when N2O 4 is
You can see that in both of these worked examples, converted to an equilibrium mixture of NO2 and N2O4 and NO2
the large positive entropy change of the is converted to the same equilibrium mixture.
surroundings has more than compensated for
the negative entropy change of the system. The
As mixing proceeds, the rate of increasing disorder
total entropy change is positive and the reactions
decreases as more and more NO2 molecules are formed
are feasible.
from N2O4. At some stage in the reaction, the rate of the
Chapter 23: Entropy and Gibbs free energy
ΔS —total
O
= –67.8 J K–1 mol–1 the entropy change of the system is negative. But the
large negative value of the enthalpy change more than
Reaction at 550 K compensates for the negative entropy change of the system
– 72 300 because it causes the term –ΔH — reaction/T to have a high
O
ΔS —Osurroundings = _______
550 positive value. So the total entropy change is positive
= –131.5 J K–1 mol–1 and the reaction, once started, is spontaneous. In highly
Cambridge International A Level Chemistry
Derivation
Gibbs free energy can easily be derived from the equation
relating total entropy to the entropy changes of system and
surroundings.
As:
ΔS —total
O ΔH —O
= ΔS —Osystem – _____
T
Multiplying by –T: –TΔS —total O
= –TΔS —Osystem + ΔH —O
— —
The term –TΔS system + ΔH is equivalent to the Gibbs
O O
Figure 23.7 Gibbs free energy is named after American free energy change of the reaction system ΔG —O .
scientist Josiah Willard Gibbs, who applied the concept of So –TΔS —total
O
= ΔG —O and so ΔG —O = ΔH —O – TΔS —Osystem.
entropy and ‘applied energy’ changes to chemical reactions
and physical processes.
Gibbs free energy and spontaneous
Gibbs free energy reactions
For a reaction to be spontaneous, ΔS —total
O
must be
What is Gibbs free energy? positive. The value of T is always positive on the absolute
In determining whether a chemical reaction is likely to (kelvin) temperature scale. So applying these signs to
be spontaneous we use the quantity Gibbs free energy the relationship ΔG —O = –TΔS —total
O
, the value of ΔG must
change, ΔG. The Gibbs free energy change is given by be negative for a reaction to be spontaneous. So, when a
the relationship: spontaneous reaction occurs at constant temperature and
pressure, the Gibbs free energy decreases. If the value of
ΔG = –TΔStotal ΔG is positive, the reaction is not spontaneous.
Chapter 23: Entropy and Gibbs free energy
reaction if we know:
b CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
■■ the entropy change of the system in J K–1 mol–1 ΔH — –1
r = –890.3 kJ mol
O
(Values for S —
O
in J K–1 mol–1: CO2(g) = +213.6,
ZnCO3(s) = +82.4, ZnO(s) = +43.6) Temperature change and reaction
Step 1 Convert the value of ΔH —
O –1 spontaneity
r to J mol :
For a reaction to be spontaneous, ΔG must be negative.
+71.0 × 1000 = 71 000 J mol–1
The temperature can influence the spontaneity of a
Step 2 Calculate ΔS —
O
system:
reaction. We can deduce this by considering the Gibbs free
ΔS — — — energy as a combination of two terms in the relationship
system = S products – S reactants
O O O
359
= S—O
[ZnO(s)] + S —
O
[CO2(g)] – S —
O
[ZnCO3(s)] ∆G = ∆Hreaction – T∆Ssystem
= 43.6 + 213.6 – 82.4
first second
ΔS —
O
system = +174.8 J K–1 mol–1 term term
Step 3 Calculate ΔG —
O
: Assuming that the value of ΔH reaction does not change
ΔG —
O
= ΔH — —
reaction – TΔS system
O O
much with temperature, we can see that the value of
000 – 298 × (+174.8)
= 71 TΔSsystem may influence the value of ΔG.
ΔG —
O
= +18 909.6 J mol–1 ■■ For an exothermic reaction, the first term (ΔHreaction) has a
= +18.9 kJ mol–1 (to 3 significant figures) negative value.
As the value of ΔG —
O
is positive, the reaction is not – If the value of ΔSsystem is positive, the second term
spontaneous at 298 K. (–TΔSsystem) is negative and the reaction will be
spontaneous because both ΔHreaction and –TΔSsystem
are negative. So ΔG is negative.
Question
– If the value of ΔSsystem is negative, the second term is
8 Calculate the standard Gibbs free energy of reaction positive. The reaction is likely to be spontaneous if the
in each of the following using the standard molar temperature is low because ΔHreaction is more likely to
entropy values given. Express your answers to 3 have a greater negative value than the positive value of
significant figures in kJ mol–1, and in each case state the second term. So ΔG is negative. If the temperature
whether the reaction is spontaneous or not under is very high, the second term may be positive enough
standard conditions. to overcome the negative value of ΔHreaction and
(Values for S —
O
in J K–1 mol–1: Ag2CO3(s) = 167.4, make ΔG positive. So the reaction is less likely to be
Ag2O(s) = 121.3, CH4(g) = 186.2, Cl2(g) = 165, spontaneous at a higher temperature. This mirrors
CO2(g) = 213.6, H2(g) = 130.6, HCl(g) = 186.8, what we know about the effect of temperature on
H2O(l) = 69.9, Mg(s) = 37.2, MgCl2(s) = 89.6, equilibrium: for an exothermic reaction, a higher
Na(s) = 51.2, Na2O2(s) = 95.0, O2(g) = 205.0) temperature shifts the position of equilibrium in favour
of the reactants.
Cambridge International A Level Chemistry
■■ For an endothermic reaction, the first term (ΔHreaction) has Comparing Gibbs free energy values
a positive value.
Table 23.2 shows some values for some standard molar
– If the value of ΔSsystem is negative, the second term is Gibbs free energy changes of formation.
positive. The reaction will not occur because both
You learnt in AS Level that the standard enthalpy
terms are positive, making the value of ΔG positive.
change of an element is zero. Similarly, the standard
– If the value of ΔSsystem is positive, the second term is Gibbs free energy change of formation of an element is
negative. The reaction is unlikely to be spontaneous if
zero. Many compounds in the solid state
the temperature is low because ΔHreaction is more likely
have high negative values of Gibbs free energy change of
to have a greater positive value than the negative
value of the second term. So ΔG is positive. If the
formation. Many gases and liquids have standard Gibbs
temperature is very high, the second term may be free energy change values that are negative but many
negative enough to overcome the positive value of others, such as ethene, have positive values. The standard
ΔHreaction and make ΔG negative. So the reaction is Gibbs free energy change of formation also depends on
—
more likely to be spontaneous at a higher temperature. the state. For example, ΔG Of [H2O(l)] is – 237.2 kJ mol–1 but
This mirrors what we know about the effect of —
ΔG f [H2O(g)] is – 228.6 kJ mol–1.
O
ΔG — —
O —
= ΔH reaction – TΔS system
O O
ΔG —
O
ΔG —
O
1 2
000 – 1200 × (+174.8)
= 71
000 – 209 760
= 71 elements in their
ΔG — –1 standard states
= –139 kJ mol
O
As the value of ΔG —
O Figure 23.8 A free energy cycle for calculating the standard
is negative, the reaction is
spontaneous at 1200 K. Gibbs free energy of reaction. The dashed line shows the
indirect (two-step) route.
— —
Substance ΔG Of / kJ mol–1 Substance ΔG Of / kJ mol–1
carbon (s) 0 water (l) –237.2
calcium (s) 0 methanol (l) –166.4
bromine (l) 0 chlorobenzene (l) +93.6
helium (g) 0 water (g) –228.6
calcium oxide (s) –604.0 ethane (g) +68.2
calcium carbonate (s) –1128.8 ammonia (g) –16.5
magnesium oxide (s) –569.4 magnesium ion, Mg2+ (aq) –454.8
zinc sulfide (s) –201.3 carbonate ion, CO32– (aq) –527.9
Table 23.2 Standard molar Gibbs free energy changes of some solids, liquids, gases and aqueous ions. The states are shown as
state symbols after each substance.
Chapter 23: Entropy and Gibbs free energy
of sodium hydrogencarbonate. ΔG —
O
reaction
— — —
= 2 × ΔG Of [H2O(l)] – {2 × ΔG Of [H2(g)] + ΔG Of [O2(g)]} 361
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)
= 2 × (–273.2) – 0 + 0
The relevant Gibbs free energy values are: —
—
ΔG reaction = –546.4 kJ
O
ΔG Of [NaHCO3(s)] = –851.0 kJ mol–1
The value of ΔG —
O
reaction is negative. So under standard
—
O
ΔG f [Na2CO3(s)] = –1044.5 kJ mol–1 conditions, the reaction is spontaneous.
—
ΔG Of [CO2(g)] = –394.4 kJ mol–1
—
ΔG Of [H2O(l)] = –237.2 kJ mol–1
The Gibbs free energy cycle is shown in Figure 23.9. Gibbs free energy and work
Gibbs free energy change can be thought of as part of the
∆G reaction enthalpy change that is needed to do work. If we rearrange
2 NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)
the equation ΔG = ΔH – TΔS as ΔH = ΔG + TΔS, we can
∆G f [Na2CO3(s)]
2 ∆G f NaHCO3(s) ∆G1 ∆G2
regard the +TΔS part as being the energy unavailable to do
+∆G f [CO2(g)]
work because it is involved with the disorder of the system.
+∆G f [H2O(l)]
The ΔG part is free energy that is available to do work, e.g.
2Na(s) + 2C(graphite) + 3O2(g) + H2(g) driving the charge in electrochemical cells.
Gibbs free energy change and direction ■■ The reaction can be regarded as not being feasible
(spontaneous) at all if the value of ΔG —
O
reaction is high and
of chemical change positive, e.g. +60 kJ mol–1.
Gibbs free energy of formation is a measure of the stability
of a compound. The more negative the value of ΔG —Of , the
greater the stability of the compound. It is unlikely to Question
decompose. If ΔG —Of is positive, the compound is likely to be
unstable with respect to its elements. For example: 9 Calculate the standard Gibbs free energy change
of reaction in each of the following using the
_ 1 H (g) + _1 I (s) HI(g) ΔG —Of [HI(g)] = +1.7 kJ mol–1 standard molar values for Gibbs free energy
2 2 2 2
change given here. In each case, comment on
The Gibbs free energy change of reaction is also a whether the reaction is spontaneous or not, under
measure of the feasibility of a reaction. Reactions with standard conditions.
negative values of ΔG —
reaction are likely to be feasible
O
(Values for G — –1
in kJ mol : C 3H8(g) = –23.4,
O
(spontaneous), whereas those with positive values are less CO2(g) = –394.4, Fe2O3(s) = –742.2, H2O(l) = –273.2,
likely to be spontaneous. H2O2(l) = –120.4, MgO(s) = –569.4, NaCl(s) = –384.2,
■■ When a system is in chemical equilibrium and the amounts NH4NO3(s) = –184.0, N2O(g) = +104.2)
of products and reactants balance, the value of ΔG — O
reaction a 2H2O2(l) 2H2O(l) + O2(g)
—O
is zero (ΔG reaction = 0).
The products predominate if the value of ΔG — O b NH4NO3(s) N2O(g) + 2H2O(g)
■■ reaction has a
fairly low negative value, e.g. –10 kJ mol . –1
c 2Mg(s) + O2(g) 2MgO(s)
■■ The reactants predominate if the value of ΔG — O
reaction has a
slightly positive value, e.g. +10 kJ mol . –1 d C 3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)
■■ The reaction can be regarded as complete if the value of e 3Mg(s) + Fe2O3(s) 3MgO(s) + 2Fe(s)
–1
ΔG —reaction is high and negative, e.g. – 60 kJ mol .
O
362
Summary
■ ntropy (S) is related to the degree of randomness ■ Solids generally have smaller entropies than liquids,
or disorder in a system. The greater the disorder, the and liquids have smaller entropies than gases.
greater the entropy.
■ A knowledge of the structures and states of
—
■ tandard molar entropy (S O ) is the entropy the reactants and products helps us to make
when the substance is in its normal state at 298 K generalisations about whether the entropy of the
and 105 Pa. reactants or products is greater.
■ In a chemical reaction, the system is the chemical ■ The total entropy change in a reaction is given by
reactants and products themselves and the ΔStotal = ΔSsystem + ΔSsurroundings
surroundings is everything not involved in the
system, e.g. the air around the reaction vessel. ■ The entropy change in the system is given by
ΔSsystem = ΔSproducts – ΔSreactants
■ A system becomes energetically more stable when it
becomes more disordered ■ The entropy change in the surroundings is given
■ A spontaneous change is one that, once started, by ΔSsurroundings = –ΔHreaction/T, where T is the
tends to continue to happen. temperature in kelvin.
■ A spontaneous change involves an increase in ■ An increase in temperature makes the entropy
total entropy (ΔS is positive). If a reaction is change of the surroundings less negative.
not spontaneous, there is a decrease in entropy
■ tandard Gibbs free energy of formation is
(ΔS is negative). the Gibbs free energy change when 1 mole of a
■ The entropy increases as a substance changes state compound is formed from its elements in their
from solid to liquid to gas. normal states under standard conditions.
Chapter 23: Entropy and Gibbs free energy
■ standard Gibbs free energy of reaction is the Gibbs the enthalpy change of reaction and entropy
free energy change when the amounts of reactants change of the system by the relationship
—
O —
O —
O
shown in the stoichiometric equation react under ΔG reaction = ΔG products – ΔG reactants
standard conditions to form the products. ■ The Gibbs free energy change of formation of an
■ Gibbs free energy is related to the enthalpy change element is zero.
of reaction and entropy change of the system by the ■ spontaneous (feasible) chemical changes involve a
—
O —
O —
O
relationship ΔG = ΔH reaction – TΔS system decrease in Gibbs free energy (ΔG is negative).
■ The Gibbs free energy change of a reaction can ■ Chemical reactions tend not to be spontaneous if there
be calculated from Gibbs free energy changes is an increase in Gibbs free energy (ΔG is positive).
of formation using the relationship is related to
End-of-chapter questions
1 Graphite and diamond are both forms of carbon. Their standard molar entropies are:
ΔS —
O –1 –1 —
O –1
graphite = 5.70 J K mol , ΔS diamond = 2.40 J K mol
–1
a i Suggest why the standard molar entropy of graphite is greater than that of diamond. [2]
ii Calculate the entropy change of the process Cgraphite Cdiamond at 298 K [1]
iii Explain why you would be unlikely to make diamonds from graphite at atmospheric
temperature and pressure. [1]
b The standard molar enthalpy change for Cgraphite Cdiamond is +2.00 kJ mol–1.
i Calculate the total entropy change for this reaction at 25.0 ºC. [4]
ii Explain why you would be unlikely to make diamonds from graphite at atmospheric
temperature and pressure. [1]
c Graphite reacts with oxygen to form carbon dioxide. Would you expect the entropy of the
products to be greater or less than the entropy of the reactants? Explain your answer. [1]
Total = 10
2 3268 kJ are required to change 1 mole of ethanol into its gaseous atoms.
a Calculate the entropy change of the surroundings during this process when it is carried out at 150 °C. [3]
b Explain why the total entropy change of this reaction is likely to be negative. [2]
c When ethanol undergoes combustion, carbon dioxide and water are formed.